JP2002542331A - Curable composition - Google Patents

Abstract

(57) Abstract: A backbone polymer component having a plurality of linked curable residues, wherein the polymer comprises monomer residues, each monomer residue comprising a monomer residue having at least two reactive groups. One is curable, but is affected by radiation from one state to another, characterized in that at least one of the remaining groups is non-reactive under the conditions under the reaction forming the polymer. Transformable polymers that can change.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a curable composition and a method for producing the curable composition. The present invention also relates to polymers for use in such compositions and to methods for making such polymers. Further, the present invention relates to an article comprising the curable composition and a method for using the article.

In particular, the present invention relates to “convertible” adhesive compositions. That is, an adhesive composition that is susceptible to change from a tacky state to a less tacky or even non-tacky state can reduce the peel strength of the adhesive composition. In particular, the invention also relates to “convertible” curable compositions. That is, a curable composition that is susceptible to change from a fluid or flexible state to a solid or poorly flexible or hard state can be used, thereby increasing the strength of the curable composition.

[0003] Adhesive products, such as adhesive surgical or medical dressings and bandages, usually consist of a pressure-sensitive adhesive layer. However, when removing conventional adhesive dressings and / or bandages, they often cause localized trauma to the patient. Accordingly, it has long been desired to provide an adhesive dressing that can reduce the peel strength of the adhesive, for example, by making it possible to change from a tacky state to a less tacky or non-tacky state. Such "convertible adhesives" cause less local trauma when removing the dressing than conventional adhesives.

[0004] Convertible adhesives are known. For example, U.S. Pat.Nos. 5,032,637, 5,352,516, 4,331,576 and 5,182,323 describe adhesives that change to a less tacky state upon contact with water, i.e., convertible adhesives. I have. However, such adhesives are used, for example, in wound dressings and are unsuitable when a patient's wound needs to be kept dry.

[0005] UV convertible adhesives are described in US Pat. Nos. 4,286,047, 4,968,559 and 5,118,567 and in Japanese Patent 3,043,988. Such adhesives have the disadvantage of producing undesirable side effects because they require high doses of UV radiation or must be used with photoinitiators. Exposing patients to large amounts of ultraviolet radiation is still undesirable. Accordingly, there is a need for convertible adhesives that can reduce the peel strength by low doses of UV radiation or, preferably, by visible light radiation.

In our International Patent Publication WO 97/06836, we described a convertible adhesive formulation. It consists in particular of a modified acrylic adhesive based on a copolymer of a free-radical adhesive vinyl component functionalized by an alkyl acrylate, acrylic acid and / or an adhesive component bonded to the copolymer. Such adhesive components include those derived from anthracene, cinnamate, maleimide, coumarin, acrylate and / or methacrylate. One problem with the use of such components is the difficulty of synthesis and their relatively strong adhesive properties.

[0007] Polymerization of conventional methacrylate-functionalized convertible adhesives includes: a) firstly to produce polymers having sufficiently high molecular weights to be used as medical adhesives, and b) secondly functionalized adhesives. It is necessary to use a multi-step pre-process to react the functionalized component with the main polymer chain. Curable products such as curable orthopedic prostheses and bandages usually consist of a body or layer of conventional material or a radiation-sensitive and curable material, respectively. However, when such bandages are applied, they often cause inconvenience to the patient or the applicator. Accordingly, there is provided a curable prosthetic device and a bandage that can be easily changed by changing the strength of the curable component from a fluid or flexible state to a solid or poorly flexible or hard state. It has long been desired to do so. Such "convertible curable" bandages have less application disadvantages than conventional curable bandages.

[0008] Convertible curable bandages are known. There are curable bandages, eg, convertible curable bandages, which become inflexible, for example, by contact with water. However, such sclerotic dressings are used as orthopedic splint dressings and are unsuitable when the patient's break needs to be kept dry.

[0009] UV-convertible curable bandages are known. However, such curable bandages have the disadvantage of requiring high doses of UV radiation or having undesirable side effects because they need to be used with photoinitiators. Exposing a patient to large amounts of ultraviolet radiation is undesirable. Therefore, there is a need for a convertible curable bandage in which the increase in intensity can be effected by low doses of UV radiation or, preferably, by visible light radiation. One problem with the use of such materials is the difficulty of synthesis and their relatively aggressive biological properties.

[0010] Polymerization of conventional convertible curable materials includes: a) firstly to produce polymers having sufficiently high molecular weights as they are used as orthopedic curable materials; and b) secondly, functionalized components. It is necessary to use a multi-step pre-process to react with the main polymer chain.

We have surprisingly found a curable material that can be converted, especially when exposed to electromagnetic radiation, in particular actinic radiation, ie visible or UV light radiation. This convertible curability has better curing properties than known convertible curable materials and does not require a multi-step preliminary step.

Thus, according to a first aspect of the present invention, a convertible curable composition comprising a convertible polymer comprising a skeletal polymer component having a plurality of curable components bonded to a skeletal polymer component, the curable composition being curable by radiation. Offer things. The polymer consists of monomer residues, each monomer residue consisting of a monomer residue having at least two reactive groups. At least one of the reactive groups is curable, but is non-reactive under conditions where at least one of the remaining groups is under a polymer forming reaction.

As used herein, the term “curable” refers to the ability, by addition or condensation, of binding or crosslinking a convertible polymer to increase the molecular weight of the polymer to which the component is attached. means.

When the polymer is an adhesive or a component of an adhesive composition, it changes the adhesive or composition from a tacky state to a less tacky or non-tacky state (ie, Can be converted). This is done by producing polymers with increased molecular weight.

When the polymer is a constituent of the curable material or composition, it changes the material or composition from a fluid or flexible state to a solid or less flexible or rigid state. (Ie, can be converted). This is done by attaching or cross-linking the convertible polymer to produce a polymer of increased molecular weight.

As used herein, the phrase “curable, but at least one of the remaining groups is non-reactive under conditions that effect the polymer-forming reaction” includes: a) as defined above. B) exhibit reactive groups that are significantly non-reactive under the reaction conditions to form a polymer for each of the remaining groups. Groups that react in this manner by a different mechanism than each of the remaining groups, and are therefore non-reactive during polymerization, are beneficial because they promote a more selective reaction.

Also, less desirably, all groups react by essentially the same mechanism, while the remaining groups are curable but significantly more reactive than non-reactive groups. Under conditions in which the curable, but at least one of the remaining groups is under a polymer forming reaction, the non-reactive groups or their respective groups are preferably free radical reactive groups. It is preferably curable but non-reactive under conditions in which each of the remaining groups is under addition or condensation which causes polymerization.

As used herein, the term “free radical reactive group” means any group that can be added to another group by free radical rearrangement.

Thus, according to one embodiment of the first aspect of the present invention, there is provided a convertible adhesive composition that can be changed from tacky to poorly tacky by radiation. The composition comprises a convertible polymer as defined above in connection with the first aspect of the invention.

According to another embodiment of the first aspect of the present invention, there is provided a convertible curable composition that may also be affected by radiation to change from a fluid or flexible state to a solid or less flexible state. provide. The composition comprises a convertible polymer as defined above in connection with the first aspect of the invention.

[0021] Yet another embodiment of this aspect of the invention is characterized in that the polymer consists of monomer residues. The monomers each consist of at least two reactive groups. At least one of those groups is free radical reactive ("curable"), while at least one of the remaining groups is non-reactive under the conditions under which the polymer is formed.

The convertible polymer may form the sole curable component of the curable composition, or may be mixed with other curable materials, for example, in the curable composition of the present invention. The convertible polymer may have adhesive properties, in which case it may form the only adhesive component of the adhesive composition, or may be mixed with other adhesives.

In such convertible adhesive compositions of the present invention, the convertible polymer need not have adhesive properties per se. In that case it is mixed with one or more adhesives.

In another embodiment of this aspect of the invention, there is provided a convertible adhesive composition of the invention. It is characterized in that it consists of the above-mentioned non-adhesive convertible polymer mixed with an adhesive convertible polymer as described above or a non-convertible adhesive.

For simplicity, all characteristic polymers of the composition according to the invention are hereinafter referred to as “convertible polymers”.

According to a second aspect of the present invention, there is provided a convertible polymer that is capable of changing from one state to another affected by radiation. It consists of a backbone polymer chain with multiple curable residues attached to it. The polymer consists of monomer residues, each of which consists of at least two reactive groups. At least one of them is reactive ("curable"), but at least one of the remaining groups is non-reactive under conditions that effect a polymer forming reaction.

The monomer residue is preferably a photocurable monomer residue. By this word,
A component capable of performing a reaction induced by electromagnetic waves, especially actinic radiation. Such components often require at least one free radical initiator to initiate the reaction under the influence of radiation. Such initiators are described below. An example of such a reaction is, for example, photocuring which increases the molecular weight of the polymer to which the component is attached.

The monomer residues form a backbone polymer chain with a pendant curable component,
The polymerization is triggered in a single step by the addition or condensation of reactive groups within the monomer. This obviates the need for the prior art in which a polymer consisting of the backbone polymer component is formed and then the precursor of the monomer residues is chemically bonded to the backbone polymer component.

The convertible adhesive composition of the present invention preferably has a peel strength in the non-tacky state of at most 50%, preferably 25% or 20%, especially 10% of the peel strength in the tacky state. The convertible curable composition of the present invention, in a solid or poorly flexible state,
At least 200% of the bending strength in the flowable or flexible state, preferably 400 or 500
%, Especially 1000%.

[0030] Any monomer that can react to form the backbone polymer component and leave a curable but non-reactive component can be used to form the polymer component. This can occur, for example, by forming a polyadduct or polycondensate of the monomeric precursor of the residue.

Preferred convertible polymers include polyurethanes and poly (alkenylene (poly) s having a free radical curable acryloyl or methacryloyl component.
Cycloalkyl) s. Poly (alkenylene (poly) cycloalkyl) s are particularly preferred as the material forming the backbone polymer chains.

The term “poly (alkenylene (poly) cycloalkyl)” refers to monomers that are suitably functionalized derivatives of polycycloalkenes, including similar comonomers optionally substituted with polycycloalkenes ) Is included. At least one of them may be a copolymer of one or more polycycloalkenes composed of an acrylate-based curable component. Such alkenylene (poly) cycloalkyl convertible polymers may be formed from the corresponding polycycloalkene monomer by a ring opening metathesis polymerization reaction.

For example, an ethenylene cyclopentyl polymer, an alkenylene (poly) cycloalkyl polymer containing a curable acryloxy or methacryloxy group and any other inert substituents, such as alkoxycarbonyl (ester) groups, is , A) norbornenyl acrylate or methacrylate and b) optionally inertly substituted norbornene by ring-opening metathesis polymerization. The acryloxy or methacryloxy groups remain curable and do not react under conditions where the respective bicycloalkene groups are under a polymerization reaction.

[0034] Any polycycloalkene species can be: a) capable of ring-opening metathesis polymerization; and b) consist of at least one group, for example one or two groups, each of which is curable. If the cycloalkene group is unreactive under the conditions under which such a reaction occurs, it is suitable as a monomeric precursor for the backbone polymer residue.

Suitable polycycloalkene monomer species include those capable of ring-opening metathesis polymerization, wherein the skeletal cyclic component has from 2 to 4 rings, each of which is independently It has from 3 to 8 carbon atoms and is optionally substituted with one or more oxa groups. The monomers preferably have two or three rings each having 4 to 7 carbon atoms and are unsubstituted. The species may be, for example, a norbornene derivative.

Suitable monomeric precursors of the residue include any of the following: a) curable, but b) non-reactive under conditions where each of the polycycloalkene groups is under a ring-opening metathesis polymerization reaction. Including. Such suitable groups have at least one, often one, free radical active group, which does not react like other functional groups do to form the main polymer component. Such groups include acryloyl or methacryloyl.

Preferred monomers of this type include, for example, 5-acryloxy,
Alkenoate monoesters and alkenoate diesters such as methacryloxy-, 5,6-diacryloxy- and 5,6-di (methacryloxy) -norbornene, in particular mono- and bis-C _3-6 alkenoyl Oxy-C _6-10 bi to tetra-cycloalkene; for example, polycycloalkenyl-2′-C _1-6 alk-1′-ene-1 such as norbornen-5-yl-2′-acryloyl or methacryloyl acetate '-Yl-C _1-6 alkanoate; and, for example, 5- (2'-acryloxyethoxycarbonyl)-, 5- (2'-methacryl-oxyethoxycarbonyl)-, 5,6-bis (2'-acryl (Oxyethoxycarbonyl)-and 5,6
- bis (2'-methacryloxyethoxy - carbonyl) - polycycloalkenyl substituted with free radically active alkene functional group in the alkyl group such as norbornene - mono - and bis -C _1-6 alkanoic C _1-6 alkyl ester And mixtures thereof. Wherein the 5- and 6-substituents are each independently in exo- or endo- orientation.

Particularly preferred are 5-acryloxy-, 5-methacryloxy-, 5,6-diacryloxy-; and 5,6-di (methacryloxy) -norbornene; and 5
-(2'-acryloxyethoxycarbonyl)-, 5- (2'-methacryloxyethoxycarbonyl)-, 5,6-bis (2'-acryloxyethoxycarbonyl)-and 5,6-bis (2'- Methacryloxy-ethoxycarbonyl) -norbornene; and mixtures thereof. Provided that the 5- and 6-substituents are each independently
Exo- or endo-orientation.

Preferred polymers are 5-acryloxy-, 5-methacryloxy-, 5,6-
Diacryloxy- and 5,6-di (methacryloxy) -norbornene; and 5
-(2'-acryloxyethoxycarbonyl)-, 5- (2'-methacryloxyethoxycarbonyl)-, 5,6-bis (2'-acryloxyethoxycarbonyl)-and 5,6-bis (2'- Methacryloxy-ethoxycarbonyl) -norbornene, provided that the 5- and 6-substituents independently include both homopolymers and copolymers, which are exo- or endo-oriented.

[0040] The amount of this monomer residue present in the convertible curable composition may vary. This depends, inter alia, on the amount of tack required for the convertible polymer when converting from tacky to less tacky or non-tacky. Thus, the amount of monomer residues present in the convertible curable composition is from 0.4 to 50%, preferably from 0.4 to 40%, more preferably from 0.4 to 20% by weight of the polymer.
% By weight.

The polymer may be a copolymer of a monomer or a monomer containing a curable component and one or more polycycloalkene species, at least one of which is, for example, one or two, consisting of other groups.

[0042] Such groups are often inert, for example carbonyl groups and derivatives thereof, such as esters, especially C _6-12 alkyl esters, such as 2-ethylhex-1-yloxycarbonyl, and amino groups; And derivatives thereof, such as ester derivatives; and derivatives of two such groups on adjacent cyclic carbon atoms, such as lactones. Preferred groups are C _6-12 alkyl ester group, in particular 2-Echiruhekisu-1-yl oxycarbonyl.

Poly (alkenylene (poly) cycloalkyl) adhesive polymers, especially pressure-sensitive adhesives (
Among the PSA) polymers, a preferred polymer is a polycycloalkene monomer in which the comonomer is inertly substituted (PSA functional group) copolymers, the substituents of which are selected for their ability to promote tackiness. As such an example, a carboxyl ester group, in particular branched C _1-12 alkyl esters such as 2-Echiruhekisu-1-yl oxycarbonyl.

Preferred monomers of this type are polycycloalkenyl-mono- and bis-C _1-6 Alkanoic C_6-12Branched alkyl esters such as 5- (2'-ethylhexyl)
1-yloxycarbonyl)-and 5,6- (2'-ethylhex-1-yloxy
(Cyclocarbonyl) -norbornene; and mixtures thereof. Where 5- and
The 6-substituents are each independently in exo- or endo- orientation.

Particularly preferred PSA functional monomers are those that contain at least two PSA functional groups present in the monomer. Particularly preferred polymers are 5-acryloxy-, 5-methacryloxy-, 5,
6-diacryloxy- and 5,6-di (methacryloxy) -norbornene; and 5- (2'-acryloxyethoxycarbonyl)-, 5- (2'-methacryloxyethoxycarbonyl)-, 5,6- Bis (2'-acryloxyethoxycarbonyl)-
And 5,6-bis (2′-methacryloxyethoxycarbonyl) -norbornene;
And copolymers of any of their mixtures with any of 5- (2'-ethylhex-yloxycarbonyl)-and 5,6-bis (2'-ethylhex-1-yloxycarbonyl) -norbornene and mixtures thereof including. However, the 5- and 6-substituents in all monomers are each independently in exo- or endo- orientation.

Examples include those which consist of 50% by weight, preferably 40% by weight, more preferably 20% by weight of the monomer species of the polymer and comprise one or two curable components.

In norbornene and structurally related monomers substituted by a functional group, the nature of the monomer, and thus of the polymer, may also be a substituent of the curable component or, for example, a tackifier or cohesion improving substituent. , Depending on the orientation of any of the functional substituents. They are in norbornene at the 5- and 6-position, for example
Endo-, exo-, bis (endo)-and endo-exo-, optionally in the 7-position, may be bi-oriented. As a sticky but cohesive PSA, for example,
5-exo and 6-exo substitutions are preferred.

Suitable polyurethanes for use as convertible polymers in the curable compositions include: a) polyesters, preferably polyfunctional isocyanate-reactive compounds such as polyethers, diols, aminols and / or diamines, and B) a polyisocyanate, such as a di-isocyanate, and b) a polyester, preferably a polyfunctional isocyanate-reactive compound such as a polyether, diol, aminol and / or diamine, and / or a curable but containing hydroxy or isocyanate groups ( (Suitably) can be derived from polyisocyanates such as di-isocyanates which have at least one reactive group which is not active under the conditions under reaction.

For example, polyurethane polymers containing unreacted cured acryloxy or methacryloxy groups include: a) between acryloxy- or methacryloxy-diol and b) diisocyanate, or less commonly, i) acrylic It may be formed by a urethane polymerization reaction between oxy- or methacryloxy-diisocyanate and ii) a diol.

Suitable polyether diols include polyoxyalkylene diols whose alkylene contains 2 to 4 carbon atoms, such as polyoxyethylene, polyoxypropylene and polyoxytetramethylene diol and mixtures thereof. Such polyether diols may suitably have a molecular weight of from 1000 to 8000, preferably from 1500 to 6000. The preferred polyether diol for forming use in the present invention is polyoxypropylene diol. A suitable diol of this type has an average molecular weight of 2025, is known as PPG2025, and is available from the British Drug House.

Another suitable diol is a block copolymer of polypropylene glycol and ethylene oxide that has hydrophilic groups and is available from Dow Chemical Inc. and is commercially available as Dowfax 63N10 ™. Polyoxymethacryloxy-diol residues can be used to make the curability formed therefrom moisture permeable. Can be used to

Suitable polyether diols which have at least one reactive group which is curable but which is non-reactive under the conditions of the reaction of hydroxy with isocyanate groups (suitably) are polyoxyalkylene / (Meth) acryloxyalkylene copolymer diol. In these, the alkylene groups are each independently
It contains 2 to 4 carbon atoms, none of which has two oxy groups.

Examples include copolymers of polyoxyethylene, polyoxypropylene and polyoxytetramethylenediol and mixtures thereof with (meth) acryloxy-propylene and -tetramethylenediol and mixtures thereof. (Meth) acryloxy-diols can be produced by esterifying the corresponding triol.

The diisocyanate used to form the polyurethane is suitably 1
. It has an isocyanate functionality of 6 to 2.05. They preferably have an isocyanate functionality of about 2.0. Suitable diisocyanates include aliphatic (including cycloaliphatic) and aromatic diisocyanates. Preferred diisocyanates include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and 4,4'-dicyclohexylmethyl diisocyanate. The latter is a preferred diisocyanate and a suitable type is known as DesmodurW ™ available from Bayer.

[0055] The polyurethane can optionally include a chain extender. Suitable chain extenders are
Includes diols such as ethanediol and butanediol, dialkenes, for example ethylene dialkenes, and water. The molar ratio of diol or diol and dialkene residues to diisocyanate residues in the polyurethane is suitably from 0.6 to 0.8: 1, preferably from 0.6 to 0.8: 1.
5 to 0.75: 1, for example, 0.7: 1.

The remainder of the free isocyanate groups may, for example, react with hydroxy group-containing groups present as chain terminators. Although curable, the amount of non-reactive monomer residues present in the convertible curable composition may vary. This will depend on the amount of tack desired for convertible curability, especially when changing from a tacky to a less tacky or non-tacky state. Thus, the amount of monomer residues present in the convertible curable composition is less than 1% of the polymer.
Up to 5% by weight, preferably up to 10%, more preferably up to 7%. Mono-ols, which are tackifiers, can be used to react with free isocyanate groups of the polyurethane. Such mono-alcohols include hydrogenated monohydroxy sticky residues, for example, hydrogenated abiethyl alcohol.

[0057] The hydrophilic polyurethane can be formed by a suitable choice of polyether diol. Such polyurethanes may be hydrated, in which case the hydrate is 35-95% by weight of water, suitably 50-92% by weight, preferably 70-90% by weight.
, More preferably 75 to 85% by weight. The degree of water absorption can be measured by impregnating with water for 24 hours, taking into account the known weight of the polyurethane. The hydrated polymer is removed from the water, the excess water is removed by gently blotting with water absorbent paper, and the hydrated polyurethane is then weighed. The water absorption (% by weight) of the polyurethane can then be calculated as (weight of hydrated polyurethane-weight of dry polyurethane) x 100 / weight of hydrated polyurethane.

If the polymer comprises a polyurethane curable, it may be a slightly crosslinked or linear polyurethane curable. The convertible curable compositions of the present invention will often include or be used in combination with at least one free radical initiator responsive to electromagnetic radiation. Any conventionally known free radical photoinitiator may be used. Particularly preferably, in the composition according to the invention, an initiator which responds to light with a wavelength longer or shorter than visible light may be used, but one which responds to visible light radiation.

Thus, the free radical initiators include titanocene photoinitiators; dye-co-initiator systems such as thionin and triethanoalkene and dye-borate systems. Other than the above, a dye-peroxide system and a 1,2-diketone / co-initiator system,
Examples include camphorquinone and tertiary alkenes. A preferred free radical initiator is bis (hapto-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyr-1-yl) phenyl, which is marketed in the UK by Ciba Geigy as Lilgacure 784 ™ ] -Titanocene initiators such as titanim.

Initiators that react with ultraviolet light can be used, and such initiators include Rilgacure 651 (benzyldimethyl ketal) or lirgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-. Irgacure such as morpholino-propan-1-one) or Uvaton such as Uvaton 8302 (2,2-diethoxy-1,2-diphenylethanone). The convertible curable composition of the present invention is preferably provided with a photoinitiator.

According to a third aspect of the present invention, mixing the convertible curable polymer of the present invention with other conventional components of a curable composition and optionally at least one other curable material. A method for producing a curable composition as described above is provided.

According to one embodiment of the third aspect of the present invention, other conventional components of the curable composition,
There is provided a process for producing an adhesive composition as described above, characterized by mixing a non-convertible adhesive with an adhesive convertible polymer or non-adhesive convertible polymer as described above.

In a fourth aspect of the present invention, there is provided a method for producing a convertible polymer according to the present invention, characterized by reacting a monomer precursor of a residue in the polymer skeleton. The monomer has at least two reactive groups, one of which is curable, but non-reactive under conditions where at least one of the remaining groups is under a polymer forming reaction. Attachment of the monomers to form residues in the backbone is preferably effected via ring-opening metathesis polymerization of the polycycloalkene and / or via isocyanate-isocyanate reactive group addition. Such reactions can be performed under appropriate conventional reaction conditions. In particular, in one embodiment of this feature, a) a norbornenyl (meth) acrylate monomer precursor of the (meth) acryloxy-substituted ethenylenecyclopentyl residue in the polymer; b) optionally at least A process for the preparation of a poly ([meth] acryloxy-substituted ethenylenecyclopentyl) convertible curable and in particular adhesive polymer as described above, characterized by reacting norbornene with one other substituent, is provided. You.

Further, the polyisocyanate and a) at least two isocyanate-reactive groups and b) at least one which is curable but is non-reactive under the conditions under which the isocyanate reacts with the isocyanate-reactive groups There is provided a process for producing a polyurethane convertible polymer as described above, characterized by reacting with at least one compound consisting of two reactive groups.

The monomers for this polymer are: a) no curable but non-reactive groups, and b) the corresponding intermediates derivable to them, with the derived precursor of that group. It can be manufactured by induction. These precursors of the monomers may contain, for example, hydroxy groups that can be esterified with curable acid derivatives. For example, norbornenyl acrylate or methacrylate can be made by conventional acrylation or methacrylation of norborneol with acryloyl or methacryloyl chloride, respectively.

Similarly, diol monomers having at least one acryloyl or methacryloyl group can be prepared by conventional acrylation or methacrylation of a suitable polyol with acryloyl or methacryloyl chloride, respectively. The precursor may contain a reactive primary amine group. The amine may be similarly derivatized to provide monomers having groups that are curable but are unreactive under the conditions under the respective polymerization reaction of the remaining groups.

As mentioned above, preferred monomer residues include a photocurable component. Preferred curing components also change the curable composition from one state to another, as described above, by producing polymers of increased molecular weight by free-radical bonding or crosslinking of the convertible polymer. Including those that cause Such curing can be initiated by visible or longer or shorter wavelength light, such as infrared or ultraviolet light.

While it is preferred that the curable residue react via irradiation, it is most desirable that the reaction of the curable group be initiated by visible light. Therefore, the wavelength of the light used is 70
It is preferably smaller than 0 nm, for example, between 400 nm and 700 nm. The light dose used may vary depending on the convertible curable composition and is typically greater than 0.4 mWcm ^-2 when using UV light. If a visible light convertible curable composition is used, ambient light may be used, and thus the dose may be varied.

As noted above, the convertible curable compositions of the present invention may also be blended with conventional curable compositions to produce convertible curable mixtures.

The curable compositions of the present invention are particularly advantageous in the production of curable tapes, bandages, dressings and prosthetic devices. The term "dressing" includes wound dressings. The term "bandage" includes medical and orthopedic applications, such as those for applying splints or casting bandages. The curable composition can also be used in the manufacture of other conventional products that require the curable composition. Thus, according to the present invention, there is provided the use of a composition in the manufacture of a curable article, as described above.

Preferred curable compositions of the present invention include pressure-sensitive curable compositions (PSAs) and are particularly advantageous in the manufacture of adhesive tapes, bandages and dressings. The term "dressing" includes wound dressings. The curable composition can also be used in the manufacture of other conventional products that require peelable adhesive properties, such as masking tapes, stencils, and the like. Thus, according to the present invention, there is provided the use of the composition in the manufacture of an adhesive dressing, bandage or tape, as described above.

Preferred curable compositions of the present invention include curable compositions for orthopedic bandages and prostheses and are particularly advantageous in the production of curable tapes and bandages. the term"
"Bandage" includes hardenable orthopedic splint dressings and other hardenable tapes for orthopedic applications. Curable compositions can also be used in the manufacture of other conventional products that require curable materials. Thus, according to the present invention, there is provided the use of the composition in the production of a curable bandage or tape, as described above.

The products comprising the curable compositions of the present invention are also novel per se. Thus, according to a further feature of the present invention, there is provided a curable product comprising a curable composition, as described above. Tapes, bandages and dressings comprising the curable compositions of the present invention are also novel per se. Thus, according to a further aspect of the present invention there is provided a curable product comprising a backing layer, wherein the backing layer is substantially coated on at least one surface with a curable composition as described above. You.

In one embodiment of this aspect of the present invention, an adhesive dressing comprising a backing layer, wherein the backing layer is substantially coated on at least one surface with an adhesive composition as described above. Is provided. Suitably, the backing layer has a thickness of between 0.375 mm and 1.25 mm, more suitably between 0.45 mm and 1.0 mm and preferably between 0.50 mm and 0.875 mm, for example, 0.825 mm. You may have.

In another embodiment of this aspect of the invention, the backing layer is characterized in that at least one surface thereof is substantially coated and / or impregnated or encapsulated with a curable composition as described above. A curable tape or bandage comprising a backing layer is provided. Suitably, the backing layer has a thickness of between 0.375 mm and 1.25 mm, more suitably between 0.45 mm and 1.0 mm and preferably between 0.50 mm and 0.875 mm, for example, 0.825 mm. You may have.

The convertible curable compositions of the present invention will begin to change from one state to another once the curing reaction has been initiated by any susceptible radiation. Thus, for storage stability, the cured product should be in a form that prevents the onset of the curing reaction.

Thus, if the exposure to the appropriate radiation is sufficient to initiate the reaction, with or without photoinitiator in the curable composition, the curable composition in the curable product will have sufficient It should be shielded from radiation by an occlusive material. ("Closed" means that the material closes over the wavelength range over which the curable composition is convertible and / or absorbed by the photoinitiator.)

[0078] Particularly preferred curable compositions of the present invention are those that respond to visible light radiation. Therefore, it is particularly preferred that any occlusive composition blocks visible light radiation. Thus, for example, the product can be stored in a closed pouch. In the case of a tape, dressing or bandage, for example, a roll may be provided with an occlusive backing or covering layer, and if not a roll, one or more occlusive release liners on the curable composition. .

All such products, especially those which are sensitive to visible light, are exposed to a curable solvate, for example: a) to facilitate removal of the adhesive product from any substrate to which it has been applied. B) The curable product on any substrate that is being applied should be adapted to facilitate curing.

In the case of an adhesive product comprising a backing layer, the backing layer preferably comprises: a) a removable closable layer to facilitate its removal from any substrate to which it has been applied. b) It preferably comprises a transparent, ie transparent or translucent layer having the adhesive composition on the side not facing the closing layer.

Particularly preferred are closure layers that are opaque to visible light, and permeable layers that transmit visible light. The occlusive layer is preferably continuous, but the permeable layer may be a continuous layer or any type of discontinuous layer. The latter includes a perforated layer and a complete net layer in which the area of the gap in the net is greater than the area of the material of the layer.

This includes all intermediate structures in the structures described herein. The adhesive coating may be a continuous coating or a discontinuous coating, for example, an adhesive that has a pattern spread over the continuous surface of the backing layer. If the backing layer comprises a permeable layer, the adhesive may form a coating over the permeable layer, and the coating may be continuous or discontinuous. The occlusive layer should, of course, be sufficiently overlaid with the adhesive composition. The occlusive and permeable layers may be reversibly laminated together in any manner.

For example, the occlusive layer may be adhesively bonded to the permeable layer. If adhesively bonded, the peel strength of the bonded adhesive must be less than that of the convertible adhesive composition in its tacky form. In use, the adhesive products of the present invention, especially dressings, can be applied to the skin of a patient. If it is desired to remove or remove the product, the occlusive layer can be removed. The adhesive on the substrate, particularly the skin-facing surface of the permeable layer, can be exposed to a suitable source of electromagnetic radiation, preferably visible radiation. It can then be exposed to a suitable source of electromagnetic radiation, especially visible light. After a period of time, the peel strength of the adhesive will decrease so that the clear layer can be removed from the substrate, especially the patient's skin.

Thus, according to the present invention, a) a backing layer consisting of a removable occlusive layer and a permeable layer between the occlusive layer and the adhesive layer; and b) convertible as described above. An adhesive product comprising a backing layer and an adhesive layer as described above, particularly a dressing, characterized by an adhesive layer comprising an adhesive composition, is provided. Any conventionally known occlusive and permeable materials can be used for the adhesive product of the present invention, especially the backing layer of the dressing. Preferred adhesive products, in particular dressings, are film-like, for example thin film-like backing layers, ie both the occlusive and permeable layers consist of or are films.

However, other backing layers, such as a textile layer, may be considered suitable. The adhesive product of the invention, in particular the dressing, can be manufactured using conventional methods known per se. According to a further feature of the present invention there is provided a method of using the adhesive product of the present invention. It is characterized in that a part of the adhesive product having the adhesive composition of the present invention is brought into adhesive contact with a substrate.

The method comprises: a) removing the occlusive layer from the product, and then b) irradiating the adhesive composition through the permeable layer to render the adhesive composition less tacky. Removal of such products consisting of an occlusive layer and a permeable layer can be included. The dressings of the present invention are particularly useful in treating wounds. Thus, according to a further feature of the present invention, there is provided a method of treating a wound in a patient, characterized in that the dressing of the present invention is adhesively adapted to the wound.

The method comprises: a) removing the occlusive layer from the product, and then b) irradiating the adhesive composition through the permeable layer to render the adhesive composition less tacky. Removal of such dressings consisting of an occlusive layer and a permeable layer can be included.

The curable products of the present invention include curable tapes and bandages, particularly orthopedic splint bandages. These have a backing layer, as described above, which is substantially coated and / or impregnated or encapsulated on at least one surface with the curable composition. To facilitate its transfer to any substrate to be applied, the dressing preferably has a removable occlusive layer laminated over the backing layer. If the at least one side of the dressing has a curable composition, it is usually on the side facing the occlusive layer. Particularly, it is preferable that the layer is a closing layer that is visible light closing property.

Preferably, the occlusive layer is continuous. The curable composition may be present at least in part as a continuous coating or, for example, a discontinuous coating that may be spread in a pattern on a continuous surface of the dressing. If the dressing has a backing layer impregnated or encapsulated with the composition, the impregnation or encapsulation may also be continuous or discontinuous. The closable layer should, of course, be sufficiently laminated with the curable composition.

The suitable layers of the occlusive layer and the backing layer or bandage may be reversibly bonded together in any manner. For example, the closable layer may be adhesively bonded to the backing layer or surface.

In use, the sclerosing product of the present invention, especially an orthopedic splint dressing, is usually applied around a patient's fracture. Often, once applied, the occlusive layer may be removed. The curable composition on and / or in the backing layer can then be exposed to a suitable source of electromagnetic radiation, preferably visible light. After a predetermined time, the flexural strength of the curable composition is such that the bandage remains in place and the substrate,
In particular, it will increase to allow the patient to support the fracture.

Thus, according to the present invention, there is provided a sclerosing orthopedic product, especially an orthopedic splint bandage, comprising a bandage having the sclerosing composition of the present invention, as described above. It is characterized in that the product has a removable occlusive layer on at least one side of the bandage. Any conventionally known occlusive layer can be used in the curable products of the present invention, particularly in orthopedic splint dressings. Preferred curable products, especially orthopedic splint dressings, are comprised of a film-like, eg, thin film, closure layer. However, other backing layers, such as a textile layer, are considered suitable.

[0093] Any of the materials known in the art can be used for the backing layer of the curable products of the present invention, especially orthopedic splint dressings. A preferred curable product, especially an orthopedic splint dressing, comprises a woven fabric, for example, a thin woven backing layer. However, other backing layers, such as a film layer, may be suitable. The orthopedic splint dressing of the present invention desirably has a longitudinal elastic stretch due to the presence of elastic fibers in the backing layer. As used herein, the term "
"Fiber" relates to the yarn material used when the yarn consists of mono- or multifilaments. Elongation at a given load and the load required to provide a constant elongation can be calculated from the bending of the backing layer under test.

Thus, for example, the backing layer is or comprises woven or knitted fibers of inelastic and elastic fibers, the elastic fibers being incorporated in the backing layer in the longitudinal direction. Inelastic fibers have a low modulus of elasticity, for example, where each filament has 1
. Fibers having a rate of less than 38 × 10 ⁸ Pa. The elastic fiber is a low-density fiber, that is, each filament has 2.07 × 10 ¹⁰ Pa (
Fibers having a rate of less than 3 × 10 ⁶ psi, more suitably less than 1.38 × 10 ¹⁰ Pa (2 × 10 ⁶ psi) and preferably less than 6.90 × 10 ⁹ Pa (10 ⁵ psi). You may.

In another aspect of the present invention, a suitable visible light curable orthopedic splint dressing comprising a textile backing layer coated and / or impregnated or encapsulated with the curable composition of the present invention. Provided. The backing layer is made of inelastic fibers and elastic fibers, and the elastic fibers are incorporated in the backing layer in the length direction. Inelastic fibers have a low modulus of elasticity, ie, each filament is a fiber having a modulus of less than 1.38 × 10 ⁸ Pa. The rest of the knitted backing layer consists of or contains polymer fibers such as polypropylene, polyester, polyamide and polyethylene. The low modulus fiber may have a modulus of less than 6.90 × 10 ⁷ Pa (10 ⁴ psi). Preferred fibers are formed from polypropylene and may be employed as multifilament or monofilament fibers. A second preferred fiber is a polyester comprising multifilament or monofilament polyethylene terephthalate fibers.

The use of such a thread results in a particularly durable casting bandage. The curable products, in particular bandages, of the present invention can be manufactured using conventional methods known per se. According to a further feature of the present invention there is provided the use of a curable product of the present invention. It is characterized in that a curable product comprising the curable composition of the present invention is brought into contact with a substrate.

The dressings of the present invention are particularly useful for treating fractures. Thus, according to a further feature of the present invention, there is provided a method of treating a patient's fracture, comprising applying the bandage of the present invention around a fracture. The method comprises a closable layer, by a) removing the closable layer from the product, and then b) irradiating the curable composition in the dressing to make it a solid or poorly flexible state. This includes the application of such products.

The dressing system of the present invention is particularly useful in treating fractures. Many medical agents are suitable for incorporation into the curable compositions of the present invention. In medical medicine, local anesthetics such as xylocaine, bacteriostats such as silver nitrate, antibacterials and antibiotics whose preferred forms are silver sulfadiazine and chlorhexidine salts, topical steroids, enzymes, tissue stimulants, coagulants and anticoagulants. It refers to pharmacologically active agents, including agents such as coagulants and fungicides. Other agents such as emollients can also be added.

The present invention will now be described with reference to the accompanying drawings and examples. In FIG. 1, the dressing (1) comprises a backing layer (2) and an adhesive layer (3) of a convertible pressure-sensitive adhesive (PSA) of the invention having pendant acryloxy groups. The backing layer (2) consists of an occlusive layer (4) and a permeable layer (5) between the occlusive layer (4) and the adhesive layer (3). The dressing may optionally include a suitable carrier layer and a protective layer.

In use, the dressing (1) is adhered to the patient's skin when the adhesive layer (3) is in a sticky form. If it is desired to remove the dressing (1) from the patient, the occlusive layer is removed and the permeable layer (5) and thus the adhesive layer (3) is exposed to visible light. Visible light causes photoinitiation to initiate free-radical crosslinking of the PSA through pendant acryloxy groups, resulting in loss of its tack in the adhesive layer. The time required to complete this reaction may vary, for example, from 1 to 15 minutes. The dressing is then removed with reduced trauma to the patient.

Referring now to FIG. 2, the medical dressing (10) is shown to adhere to the patient's skin (20). The dressing (10) consists of a wound facing absorbent layer (30) underneath the protective backing layer (40). On opposing edges (50, 60), the backing layer (40) is provided with an adhesive layer (70) consisting of a convertible polymer having groups that can crosslink under the influence of UV or visible light.

The backing layer (40) is provided with a cover (80) releasably secured to the backing layer (40) by a weak adhesive (90). Alternatively, the cover (80) may be laminated to the backing layer (40). To facilitate removal, cover (80
) Is laminated on the backing layer at its edges (100, 110).

If it is desired to remove the dressing from the patient's skin, the cover (80) is grasped firmly at its edges (100, 110) and peeled from the backing layer (40). This exposes the adhesive layer (70) to UV or visible light radiation. This irradiation acts to cure the convertible polymer in the adhesive layer. This causes the adhesive layer (70) to lose its tack to such an extent that after a predetermined time (depending on the adhesive used) the dressing can be removed without causing trauma to the patient. Removal of the cover (80) should not itself cause removal of the dressing prior to conversion.

Accordingly, the peel strength of the adhesive (90) to which the cover (80) adheres to the backing layer is greater than that of the adhesive layer (70) to which the dressing (10) adheres to the patient's skin. It is substantially smaller. The adhesive (70) loses tackiness when exposed to UV or visible light. Thus, the adhesive layer (70) is preferably not exposed to light for a substantial period of time when the dressing (10) is applied to a patient. Therefore, the adhesive layer (70
) May be provided on the surface with a release paper (not shown) that is initially opaque to UV and visible light and can be easily removed from the adhesive to prepare the dressing for use.

According to FIG. 3, the bandage (11) comprises a backing layer (21) impregnated and coated with a layer (31) of the convertible curable composition of the invention having pendant acryloxy groups.
)including. The dressing (21) has an occlusive layer (41) on the layer (31). The bandage may optionally be provided with a suitable protective layer. In use, when the curable composition (including layer (31)) is in a flexible form, a bandage (11) is applied around the patient's break and a closable layer (41) is applied.
The curable composition is exposed to visible light and removed. Visible light causes the photoinitiator to initiate free-radical crosslinking of the curable composition through the pendant acryloxy groups, thereby increasing the flexural strength of the curable composition.

The time required to complete this reaction may vary, for example, from 1 to 15 minutes. The bandage is then left in place to support the patient's break.

Referring to FIG. 4, the medical bandage (110) is shown around the breakage point (210) of the patient. The dressing (110) is applied to the patient over a conventional protective underlying dressing (310) and has the converted curable composition of the present invention having pendant acryloxy groups that crosslink under the influence of UV or visible light. A backing layer (410) impregnated and covered with a layer (710) of the same. The preparation and testing of an adhesive composition for suitable use as an adhesive layer in a convertible adhesive dressing is shown in the following examples.

D. Example 1 Synthesis of Monofunctional Monomer Exo and Endo-Noriborn-2-en-5-ylmethanol (I) (5
. 53 g) was dissolved in chloroform (about 30 ml), and acryloyl chloride (3.9 g) (II) was added. The mixture was heated to reflux and then maintained at 50 ° C. for 15 hours. The chloroform was then evaporated, leaving a pale yellow liquid, and the structure (M.1) was identified by nmr as a mixture of exo and endo-noriborn-2-en-5-ylmethyl acrylate.

D. 2 Synthesis of Bifunctional Monomer Endo, exo-5,6-bis (chlorocarbonyl) noriborn-2-ene (III
) (6.06 g: 0.0276 mol) and 2-hydroxy-ethyl methacrylate (IV) (HEMA) (7.2 g: 0.0554 mol) were mixed in a 100 ml round bottom flask. The mixture was stirred. After 1-2 minutes, an exothermic reaction began and gas evolved (hydrogen chloride). The mixture was heated in a water bath at 50 ° C. and stirred for about 90 minutes. The ¹ H / ¹³ C nmr spectrum of the sample evaporated in vacuo (30 minutes) shows the reaction forming the endo, exo-5,6-bis (methacryloxyethoxycarbonyl) noriborn-2-ene (M.2). Is shown.

D. 3 Synthesis of Nonfunctional Monomer 2-Ethylhexanol (33.0 g) and exo-noriborn-2-ene-5,6-dicarboxylic anhydride (20.8 g) were dissolved in toluene (30% solid) in toluene. Heated for 5 hours. Concentrated sulfuric acid (1 ml) was added. The reaction mixture was refluxed for another 48 hours. Product endo, exo-5,6-bis (2-ethylhexyloxycarbonyl)
Noriborn-2-ene (M.3) was isolated from the reaction mixture by rotary evaporation of the solvent in vacuo. The product was confirmed as pure by ¹ H and ¹³ C nmr.

E. 1 Copolymerization of monofunctional and nonfunctional monomers (M.3) (4.5 g) and (M.1) (0.5 g) in chloroform at 40 w /
Mix at w% solids. The monomer was degassed with argon for 5 minutes before adding the initiator, Grubbs' catalyst (bis (tricyclohexylphosphine) -benzylidene-ruthenium (IV) dichloride) (25 mg). The mixture was stirred at 20 ° C. for 15 hours. ¹ H nmr (CDCL ₃ ) of the syrup-like evaporated sample indicated the presence of acrylate groups and polymerization had occurred.

E. 2 Copolymerization of bifunctional and nonfunctional monomers D. (M.2) from Example 2 (0.55 g) and D. (M.3) from 3 (4
. 45 g). The polymerization was carried out under the conditions as in 1. The final viscosity was clearly higher than at the beginning. ¹ H nmr indicates that polymerization has occurred and that methacrylate groups are present.

F. 1. Crosslinking and Testing of Functionalized Polymers 1 and E.I. Two (about 5 g) of the 40% syrup of the polymer were each separately mixed with Irgacure 651 photoinitiator (about 5% by weight of the polymer) to dissolve it. The product film was produced on silicon release paper and the solvent was distilled off. The tacky film was coated with a clear Melinex sheet and half was irradiated in a UV cabinet for 3 minutes.

Irradiation results

[Table 1]

The results clearly demonstrate that the novel adhesive compositions of the present invention are good.
They can be much more controllable compared to the prior art.

[Brief description of the drawings]

FIG. 1 is a sectional view of a dressing of the present invention.

FIG. 2 is a cross-sectional view of a further dressing embodiment of the present invention when used on a patient.

FIG. 3 is a cross-sectional view of the bandage of the present invention.

FIG. 4 is a cross-sectional view of a further bandage embodiment of the present invention when used on a patient.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN , IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZWF terms (reference) 4C081 AA04 AC04 BB04 DC12 4J004 AA11 AA14 AB01 AB07 CA04 CA06 CB01 CC03 DB02 EA06 FA09 4J027 AA08 AG01 CB10 CC05 CD07 4J040 EF001 EL011 GA01 GA05 GA07 GA13 HB13 HB18 HB21 HD19 HD38 HD41 JB08 JB09 KA13 MA10 MA14 MB03 NA02 PA20

Claims (12)

[Claims] 1. A polymer comprising a backbone polymer component having a plurality of linked curable residues, wherein the polymer comprises monomer residues, each monomer residue comprising a monomer residue having at least two reactive groups. One is curable, but changes from one state to another under the influence of radiation, characterized in that at least one of the remaining groups is non-reactive under the conditions under the reaction forming the polymer Convertible polymer. 2. The polymer of claim 1 which is adhesive and can change from tacky to poorly tacky under the influence of radiation. 3. The polymer of claim 1 which is a curable material that can be affected by radiation to change from a fluid or flexible state to a solid or poorly flexible or hard state. 4. A convertible composition curable by radiation, comprising the convertible polymer of claim 1. 5. The convertible composition according to claim 4, comprising a convertible polymer according to claim 2 or a mixture of the convertible polymer according to claim 1 and a non-convertible adhesive. . 6. A convertible adhesive composition, which comprises the convertible polymer of claim 3. 7. The polymer backbone, wherein the monomer is at least two reactive groups, one of which is adhesive, but at least one of the remaining groups is non-reactive under the conditions that react to form the polymer. 2. The process according to claim 1, wherein the precursor of the monomer of the residue is reacted. 8. A mixture of the convertible polymer of claim 2 or a non-convertible adhesive with the non-convertible adhesive of claim 1, which is non-adhesive, with other conventional components of the curable composition. The method for producing an adhesive composition according to claim 5. 9. A curable product comprising the curable composition of claim 4. 10. A curable product having a backing layer, wherein the backing layer is substantially coated and / or impregnated or encapsulated on at least one surface with the curable composition of claim 4. 11. An adhesive dressing having a backing layer, wherein the backing layer is substantially coated on at least one surface with the adhesive composition of claim 5. 12. A curable tape or bandage having a backing layer, wherein the backing layer has at least one surface substantially coated and / or impregnated or encapsulated with the curable composition of claim 6. .