Vinylaromatic block copolymers and enclosing structures

 

(57) Abstract:

The copolymers for radiation curing the molten adhesive composition with the General formula (AB)p(IN)q1X, where a is polyvinylpyrolidine block IN1and B represents the same or different polybutadiene blocks with additional content of 1,2-vanilovich units, and X is the remainder of the polyvalent agent combinations, and full of apparent molecular mass of blockcopolymer according to the gel chromatography is in the range from 100000 to 500000. The content of 1,2-vinyl units in the polybutadiene blocks is 25-70 wt.%, the maximum active centers (m) agent in a combination of X ranges from 3 to 6, where the values of p and q are in the range from 1.5 to m, provided that the average value of the sum of the values of p and q is less than m, and the effectiveness of the combination is less than 90%, and the average full content vinylaromatic links in the specified blockcopolymer is in the range from 10 to 50 wt.%. The copolymers provide improved properties as radiation-curable adhesive, sealant or coating compositions, and Noteridae adhesive, sealant or coating compositions, sabreena refers to vinylaromatic the copolymers and adhesive, sealing or coating compositions comprising these copolymers. More specifically, the invention relates to copolymers containing at least one unit derived from vinylaromatic monomers, and at least one block derived from butadiene, and to an adhesive, sealant or coating compositions containing these copolymers. It was found that these compounds effectively otverzhdajutsja under the action of radiation.

Such copolymers and radiation-curable adhesive, sealing and coating compositions are known, for example, from PCT application published as WO 93/24547.

In this application WO 93/24547 describes block copolymers (AB)p(B)qX, where A denotes polyvinylpyrolidine block and B is a polybutadiene block, where essentially the disclosed X represents a tetravalent residue combining substances, such as SiCl4, SnCl4or DEAP, or polyvalent combining agent, such as divinylbenzene, forming multicare radial block copolymers with a large number of circuits (6 < n < 20), moreover, these copolymers have average total content vinylaromatic monomers from 7 to 35 wt. % and full of apparent molecular m is specified publication WO 93/24547 explicitly favoured cetirizinum the copolymers, with the preferred structure (AB)2(B)2X, where the segments have the same apparent molecular weight. In the above publication contains the values of p and q, which is the numerical averages, corresponding to the formation of mixtures chetyrehtomnik radial block copolymers, where the actual values of p and q vary from 0 to maximum functionality combining agent.

It should be borne in mind that this reaction is the simultaneous combination of two living types of circuits is determined by the necessity of polybutadiene chains with the content of vinyl groups (arising 1,2-polymerization of 1,3-butadiene in the range of 35-70 wt.%, which, as you know, is achieved by polymerization in the presence of simple ether, and that is usually the preferred alternative processes combinations, using polyvalent combining agents and then adding living intermediate polymer chains, as follows, for example, from European Patent Application 0314256 and U.S. patent N 5212249, are unacceptable, because, according to experts in this field, preferably more disordered, statistical distribution.

In the European AI:

(a) contact of the first living polymer containing a single terminal reactive group, with a combination agent containing many functional groups, which react with reactive terminal groups, and the number of the specified first living polymer practically corresponds to the stoichiometric part of the total number of functional groups in the sense that the reaction between the said first polymer and combining the agent proceeds substantially to the end;

(b) contact in the later stages of one or more living polymer that is different from the specified first living polymer and from each other and having a reactive end group, with a corresponding reaction product from each preceding stage until the reaction is completed all functional groups combining agent and

(C) allocation received asymmetric radial polymer.

This method preferably is carried out for a combination of four chains selected from polymers containing only polymerized conjugate diolefin, and copolymers comprising at least one monoalkylamines hydrocarbon blakolmer and cruets way to obtain asymmetric radial polymers, in accordance with which sequentially carry out the different polymer chains with polimerizuet combining agent, preferably the silicone combining the agent with up to 12 functional centers. The implementation of contact at the final stage of this method, which is often, but not necessarily always, will be the second stage of the method, carried out in the presence of polar compounds, which, as is known, increases the content of vinyl groups in the dual diolefines the polymer during its polymerization. Obtained in accordance with this method, the polymers have a more narrow relative distribution chains obtained in some asymmetric radial polymers and significantly higher yield of product having the desired ratio of polymer chains. The most preferred polimerizuet combining agents containing 3 or 4 functional groups.

It should be borne in mind that in the case of the simultaneous combination of both types of boundary obtained living polymer chains AB-Li and B'-Li, having a molar ratio of about 1 and tetravalent combining agent in the mixture of the individual molecules of the copolymers will be (AB)4X(B1)2is 37,5% regardless of molecular weight, so 100% matching copolymers will have a mass average functionality equal to their numerical average functionality, that is, both will be equal functionality used combining agent (p+q).

Similarly, in the case of the simultaneous combination of the two previously prepared living polymer chains AB-Li and B1-Li, having a molar ratio of about 1.0 and, for example, hexavalent combining agent in accordance with previously determined in a known manner, in real mixtures are individual block-copolymer molecules, such as (AB)6X, (AB)5(B1)X, (AB)4(B1)2X,

(AB)3(B1)3X, (AB)2(B1)4X, AB(B1)5X and (B1)6X, with 31% of the desired (AB)3(B1)3X, provided that the effectiveness of the combination is 100%, that is busy all existing primary functional centers.

It should be borne in mind that due to more stringent requirements in respect of environmental protection and achieve high efficiency, adhesive, coating or sealing compositions of vinylaromatic and paired que is improved sustained fashion, the minimum viscosity of the molten composition in combination with a sufficiently high sensitivity to UV - and E-rays, which can increase the processing speed and performance, or use more weak radiation, and to avoid the complications that arise in the allocation of blockcopolymer of the polymeric binder.

As a result of intensive studies and experiments were suddenly discovered copolymers that provide improved properties as radiation-curable adhesive, sealant or coating compositions, and Noteridae adhesive, sealant or coating compositions, which are applicable for labels, tapes, and articles time to time.

In accordance with one aspect of the present invention offers a special, made with the desired properties of the copolymers (AB)p(B1)qX, where A is poly (vinylaromatic) block and B and B1- polybutadiene blocks, in which the content of the attached vinyl due to 1,2-polymerization ranges from 25 to 70 wt.% and preferably, from 45 to 70 wt.%, where X is the polyvalent residue combining the agent with a maximum of active centers (m) in the range of 3-6, where Srednekanskaya values of p and q nah is 90%, and preferably, greater than 55%, and the average total content vinylaromatic of monomer units (often referred to as full content limits vinylaromatic of monomer units) for these copolymers is in the range from 10 to 50%, and preferably in the range from 10 to 30%, and their total apparent molecular mass determined gel chromatography GPC is in the range of from 100000 to 500000.

Preferably, the sum of the values of p and q is greater than 1.5, more preferably greater than 2.

The effectiveness of combinations, in the sense in which it is used in the text of the description, means the efficiency defined by the GPC method total process combinations.

Specialists in this field it is obvious that the sum of p and q is actually determined by the effectiveness of the combination of (ES).

In accordance with a particularly preferred embodiment of the invention the efficiency of the combination is equal to from 60 to 85%, more preferably from 70 to 84%, and most preferably, from 70 to 82%.

The above copolymers can be involved in bonding, sealing and coating compositions, radiation curing in their final form, but also in the compositions, properties:

the optimal balance between UV-reaction activity and viscosity of the melt due to the high molecular weight poly(conjugated diene) and a content of vinyl groups in one radial structure;

the distribution of the components of the individual molecules, some of which are particularly suitable due to their UV sensitivity (high molecular weight), while smaller molecules presumably determine the high stickiness before or after UV curing;

the mixture of copolymers have substantially lower melt viscosity in full adhesive composition at normal temperature processing.

As defined GPC effectiveness of the combination of (ES) is usually expressed on a mass basis, this means that the nominal ES is always less than a certain method gel chromatography GPC.

Usually defined GPC effectiveness of the combination depends on the molecular weight of the obtained product, while the nominal value of ES (molar number) it does not depend on.

In the radial multicanal block copolymers of the present invention (AB)pX(B1)qactually will contain a set of individualism, what functionality is used combining agent.

For example, radial multicanal blockcopolymers composition derived from a tetravalent combining agent, will include the following 14 types of molecular structures:

(AB)0X(B1)1, (AB)1X(B1)0,

(AB)0X(B1)2, (AB)1X(B1)1,

(AB)2X(B1)0, (AB)0X(B1)3,

(AB)1X(B1)2, (AB)2X(B1)1,

(AB)3X(B1)0, (AB)0X(B1)4,

(AB)1X(B1)3, (AB)2X(B1)2,

(AB)3X(B1)1, (AB)4X(B1)0.

Similarly, radial multicanal block copolymers derived from hexavalent combining agent, in fact, will include 27 different individual molecules.

And finally, the molar fraction distribution of incomplete patterns (AB)pX(B1)qdescribed by the equation:

Fm[i,j] = (miri(1-r)m-iai(ij) aj(i-a)i-j,

where m means the functionality used combining agent CA and thus the maximum number of chains.

r is the nominal ES, divided by 100.

a is equal to the ratio p/(p+q).

The above formula describes the overall distribution of types of macromolecules such asymmetric radial polymers.

Preferably, the corresponding Srednekanskaya values of p and q in the radial multicash the copolymers is equal to at most m-1,5, where m represents the maximum functionality combining agent.

More preferably, the radial multicare the copolymers derived from trivalent or tetravalent combining agents.

A-blocks in these copolymers typically have an apparent molecular weight in the range from 5000 to 50000, preferably from 7,000 to 20,000 and most preferably from 9,000 to 15,000. B and B1the blocks in these copolymers may have the same or different apparent molecular weight ranging from 15,000 to 250,000, and preferably from 20000 to 100000.

The copolymers of the present invention preferably have a total apparent molecular weight in the range of 150,000 to 350,000.

The content of vinyl groups in the poly(butadiene) chain blocks is preferably 45-70%.

The copolymers present the aromatic monomer in the presence of an organolithium initiator RLi and preferably alkyllithium initiator, containing 4 to 6 carbon atoms, to obtain a living polymer ALi;

(b) carrying out the polymerization of predominantly butadiene with a living polymer ALi and at the predetermined time with organolithium initiator RLi with a mixture of living polymers A-B-Li and B1Li, where the segments B and B1may be the same or different molecular weight [M], M[B] M[IN1] depending on the exact moment you add RLi, where the butadiene is polymerized 1,2 - containing vinyl groups from 25 to 70% and where the initiator RLi added in such a quantity, in which the molar ratio of initiator RLi to the living polymer ALi is in the range of 0.42-2.20 per cent;

(c) implementation of a combination of a mixture of living polymers A-B-Li and B1Li obtained from polyfunctional combining agent.

The expression "predominantly butadiene used in the text of this description, means that at the stage (b) polymerization can also be used butadiene containing small amounts of other conjugated dienes or vinylaromatic monomers (less than 5 wt.%).

Similarly, the expression "predominantly monovinylacetylene monomer" and "predominantly styrene used in the text of this opinionsthe conjugated dienes or other vinylaromatic monomers, usually less than 5 wt%.

Preferably, at the stage of polymerization (a) is used primarily monomer styrene.

In accordance with one of preferred examples of embodiment of the invention uses a trivalent or tetravalent combining substance, such as tennispalatsi, tetrachlorosilane (SiCl4), tetramethoxysilane, (Si(OMe)4), diethylacetal, dimethyladipate-glycolate-propyl-trimethoxysilane, and the like, preferably gpts or tennispalatsi.

In accordance with the previously defined method can also be applied hexaphenyldisilane (hexavalent) combining substances, for example, bis(trichlorosilyl)alkane, in which albanova group contains 2-10 carbon atoms, or bis(tralkoxydim)alkanes, alkane which meets the definition above, and the alkoxy group contains 1-4 carbon atoms, compounds of General formula (R1-O)3Si-R2-O-R2-Si(OR1)3where R1-Allenova group with 1-4 carbon atoms and R2-Allenova group with 2-10 carbon atoms. Preferred hexaphenyldisilane combining agents are 1,2 bis(trimethoxysilyl)ethane, 1,2-bis(trichlorosilyl)ethane and 3,3'- oxinitride Halogens.

The molar ratio between the initiator RLi and living polymer ALi at the stage (b) is typically set in the range from 0.88 to 1.12, preferably in the range from 0.95 to 1.05, and most preferably as close as possible to 1.0 to obtain nominally x-chain blockcopolymer containing on average x/2 AB blocks and x/2 B1blocks; and x is equal to the number of chains p+q.

It is obvious that in the polymerization of predominantly butadiene at the stage (b) apply the modifier, which causes an increase in the content of vinyl groups (25-70%). It was found that the content of vinyl groups in the specified range increases UV and (or) E-the radiation sensitivity of the final composition.

As modifiers suitable for this purpose can be applied ethers, amines and other bases Lewis, and more preferred dialkylamide ethers of glycols. The most preferred such modifiers as simple diakidoy ether of ethylene glycol, containing the same or different terminal alkoxy groups and randomly containing alkyl Deputy for the average ethylene radical, such as monoglyme, diglyme, diethoxyethane, 1,2-diethoxypropane, 1 ethoxy, 2-tert-butoxide, of which the most preferable one I had, in which R represents an aliphatic, cycloaliphatic, aromatic or alkyl substituted aromatic hydrocarbon group with the number of carbon atoms of 1-20, preferably 1-12. Particularly preferred organolithium initiators are alkyllithium initiators containing from 4 to 6 carbon atoms. Accordingly, examples of preferred organolithium initiators can serve one or more compounds selected from the group consisting of utility, n-properity, isopropylate, n-utility, second-utility, tert-octillery, n-docility, n-docility, n-agaility, phenyl-lithium, 2-afterlite, 4-butylaniline, cyclohexylethyl, 4-cyclopentylmethyl and the like, of which particularly preferred is a second-utility.

Specialists in this field it is obvious that the effectiveness of the combination can be adjusted by selection of the molar relationship between the combining agent and the total amount of living polymer chains. This ratio is usually equal to 1,05-1,2.

It was found that a distinct advantage of the copolymers of the present invention manifests itself in the attractive properties of these polymers when selecting them from polymer idunno was revealed, implemented with the application of the above groups of the copolymers according to the present invention

(a) a low viscosity hot melt at normal temperature processing blockcopolymers melted adhesives, which makes them extremely attractive for low-temperature applications, such as labels, tapes, and articles time to time;

(b) in combination with a simple structure of copolymers that can be obtained with variable efficacy of the combination in the range from 70 to 85% and therefore has a relatively low cost;

(c) special sensitivity to UV radiation that best meets modern trends to increase the processing speed of the final composition and(or) reduction of specific energy radiation per unit surface area, in contrast to the previously established properties, for example, the known copolymers with four chains;

(d) after curing the adhesive composition containing block copolymers, can be achieved preferred resistance to high temperatures;

(e) there is no need for a separate cross-linking agents, i.e. substances, such as acrylates, and this significantly reduces the risk for tagaet urgent need for the exclusion of air under UV irradiation.

It should be borne in mind that another aspect of the present invention is an adhesive, preferably an adhesive in the melt, sealing or coating compositions, which, depending on the final destination arbitrarily radiation can be cured. More specifically, these adhesive compositions in the form of melts include the previously described sensitive to UV and (or) E-the radiation block copolymers with one or more conventional fillers, such as resin, improves adhesion, oil filling and / or plasticizer, oil, waxes, antioxidants, photoinitiator (in the case of UV-radiation curing) and arbitrarily resin together with monovinylacetylene block.

The block copolymers does not seem sufficient adhesive or sticky. Therefore, in adhesive compositions, it is often desirable to introduce a resin that increases the stickiness, which is compatible with the elastomeric blocks of polybutadiene.

Preferably, in the adhesive compositions according to the present invention includes a resin that increases the stickiness, which has a low level of unsaturation, allowing the use of low-dose radiation for curing the adhesive composition, preferably the unsaturation of less than 5%, more preferred to use a mixture of resins, with usually different levels of unsaturation and different softening temperatures, but they are less preferred due to possible uncontrolled side reactions.

Examples of resins that increase the stickiness that can be used in the adhesive compositions of the present invention include saturated resins, ester resins, polyterpenes, in primary forms, serpentinely resin and polymerized mixture of olefins or their mixtures with gidrirovanie resins, which are preferred.

The total amount of the resin or resins that increase stickiness, is typically 10-300 parts per 100 parts of blockcopolymer, preferably 50-200 parts per 100 parts of copolymer.

Arbitrarily can be added modifying resin, i.e. a resin which is compatible with poly(vinylaromatic) blocks. Preferably, choose such a modifying resin, which slightly slows down the process of radiation curing in the alignment of the molecular levels with polybutadiene blocks. It is believed that the inhibitory effect of the modifying resin on the process of radiation curing irrelevant if the time required for complete curing, less than half the time, the cat is valuated according to the method, disclosed in U.S. patent N 3917607. Typically, the softening temperature of the resin must be above the 100oC when determining by ASTM method E28.

Substances to increase the stickiness chosen for their ability to enhance the adhesion of the elastomer block and on their compatibility with the elastomeric block.

Examples of resins used, enhancing the adhesiveness can serve as ESCOREZTMseries 5300; REGALITETMR91, R101, S100, S260; REGALREZTM1018, 3103, 6108, 5095; ZONATACTM105 LITE; HERCULES MBG 264, etc.

Adhesive, sealant or coating compositions of the present invention may also include plasticizers, such as filler rubber or mixture of oils to provide wetting and / or adjusting the viscosity. These plasticizers are well known in the art and can include highly paraffinic or naphthenic oils, and aromatic oils. These plasticizers include not only the usual plasticizers, but also cover the use of olefin oligomers and low molecular weight polymers, such as vegetable and animal oil and their derivatives. You can apply oil with a relatively high boiling point and preferably contains only a small proportion of aromati the mi oils are, for example, SHELLFLEXTM451; 4510; RISELATM68; ONDINATM68; PRIMOLTM352; WITCOTM260, and the like, of which oil brands ONDINA, RISELA and PRIMOL known as non-aromatic oils. As oligomers can be used in polypropylene, polybutylene, hydrogenated polyisoprene, hydrogenated polybutadienes, and the like, having an average molecular weight ranging from about 200 to about 10,000.

Vegetable and animal oils include esters of glycerol and fatty acids and polymerization products of their.

The applied amount of plasticizers and oils can vary from 0 to 500 m h/ 100 m h/ blockcopolymer, preferably 0-150 100 hours of blockcopolymer and more preferably 5-120mm 100 hours of blockcopolymer.

The mixture can also include various petroleum waxes that give the adhesive compositions of fluidity in the molten state and elasticity utverzhdennym adhesive compositions, and also serve as a wetting component to bind the cellulose fibers. The term "petroleum waxes" applies to both paraffin and microcrystalline waxes having a melting point in the range of about 54-107oC, as well as synthetic waxes, such as HB ranging from 0 to about 100 at 100 hours polymer, preferably from 0 to about 15 per 100 g polymer.

It should be borne in mind that the best results (that is, a satisfactory cure can be achieved with the minimum dose of radiation) are obtained when plasticizers and oils, like adhesive resins are characterized by low levels of unsaturation, preferably less than 5%, more preferably less than 1%. In addition, preferably the minimum content of aromatic groups.

Adhesive, sealant or coating compositions can additionally include standard additives, such as stabilizers, pigments, fillers and the like, but the compositions preferably should not contain other additives and impurities which have an adverse effect on the adhesive, sealant or coating ability of the composition and especially on their high temperature characteristics.

Typically, commercially available compounds to add stabilizers and antioxidants to protect components against degradation during preparation and application of adhesives, but this should not adversely affect the radiation curing of the polymer.

It is often more effective to use a mixture of stanima certain sterically difficult phenols, ORGANOMETALLIC compounds, aromatic amines, aromatic phosphites and sulfur-containing compounds.

Examples of effective types of these substances can serve as phenolic antioxidants, tizaidine and Tris(neilyoung phenyl)phosphites.

Examples of industrial antioxidants can serve as "IRGANOX 565" 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)- 1,3,5-triazine, "IONOL" 2,6-di-tert-butyl-4-METHYLPHENOL, "IRGANOX 1010" tetrakis-ethylene-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)methane, "IONOX330" 3,4,6-Tris(3,5-di-tert-butyl-para-hydroxybenzyl)-1,3,5 - trimethyl-benzene and POLYGARD HR" Tris(2,4-di-tert-butylphenyl)FOSFA.

Usually in bonding, sealing or coating compositions include about 0.01 to 5.0 wt.% one or more antioxidants.

Adhesive, sealant or coating compositions of the present invention can be obtained by mixing block copolymers, resins, improves adhesion and other desirable ingredients at an elevated temperature, for example, at about 160oC (melt) in a Z blade mixer or extruder or other mixer of conventional type for this purpose.

Adhesives of the present invention is particularly suitable for cooking in here during processing, less than a hundred thousandth CP, and adequate safety, up to several hours at a temperature of processing approximately 150 - 180oC. the Preferred method of treatment consists in the use of the extruder for mixing the adhesive composition and feed supply mouthpiece, as described in U.S. patent N 3984509.

As previously indicated, the compositions of the present invention can be cured depending on their destination. This curing is carried out under the action of ionizing radiation of high energy, for example, electron beam or UV radiation.

Electron beam radiation (E) or ionizing radiation high energy, which is used when carrying out the reaction of cross-linking can be obtained from any appropriate source, such as from a nuclear reactor, electron guns, resonant accelerator, the electron accelerator of the van de Graph, electron accelerator type Linear, betatron, a synchrotron, cyclotron, and similar sources. These sources will cause ionizing radiation, such as electrons, protons, neutrons, deuteron, gamma rays, X-rays, alpha particles and beta particles.

The stitching is conveniently carried out at room temperature, but when it is installed, when applying UV-radiation is not required to completely remove the air. Therefore, it is no longer necessary to carry out the stitching UV radiation composition placed on the type sandwiched between the substrates, for example, when the composition is used as a connecting layer between the substrates, or to conduct it in a sealed equipment, completed after vacuum inert atmosphere containing no oxygen.

Specialists in this field it is obvious that the possibility of a specified radiation curing in oxygen-containing atmosphere, such as air, means a considerable reduction of costs for the implementation of this process.

The radiation dose required for satisfactory curing depends mainly on the type and concentration of the applied blockcopolymer and level of unsaturation of the composition. Acceptable dose electron beam irradiation are in the range from 0.5 to 8 Mrad, preferably from about 4 to 8 Mrad, and more preferably about 6 to 8 Mrad.

Adhesive compositions preferably utverjdayut under the action of UV radiation for a time sufficient to generate the required number of crosslinking bonds. the tion to UV light (photoinitiator), on 100 wt. hours of blockcopolymer. Can be used any known UV sensitizers.

Preferred photoinitiators are selected from the group consisting of:

(1) at least one benzophenone of the General formula (I)

< / BR>
where R1-R8independently represent hydrogen or alkyl with 1-4 carbon atoms, preferably methyl, and R7and/or R8in addition, there may be an alkoxy group with carbon atoms of 1 to 4, and where n takes the values 0,1 or 2, optionally in combination with at least one tertiary amine,

(2) at least one structurae carbonyl compound in which a carbonyl group is directly linked with at least one aromatic nucleus, preferably the General formula (II):

< / BR>
where R9, R10, R11each may represent hydrogen, alkyl with 1-4 carbon atoms or alkylthio group with 1-4 carbon atoms, and (3) and a mixture of (1) and (2).

Examples of acceptable compounds of formula (I) can serve as benzophenone, 2,4,6-trimethylbenzene, 4-methylbenzophenone, 4 - methylbenzophenone and eutectic mixture of 2,4,6-trimethylbenzene and 4-methylbenzophenone (ESACURETMTZT) and 2,2-dimethoxy-1,2-diphenyl what measures UVEKRYLTM7100.

The compounds of formula (2) include such as, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1, commercial name IRGACURETM907.

Examples of acceptable mixtures (3) serve a mixture of 15 wt.% a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone and 4-isopropylthioxanthone and 85 wt.% a mixture of 2,4,6-trimethylbenzoquinone and 4-methylbenzophenone. The commercial name of such a mixture is ESACURETMH.

Photoinitiator any one of the above types (1), (2) and (3) can also be used in combination with other photoinitiators, such as, for example, UVECRYL R. Particularly useful is a mixture of benzophenone and specified UVECRYL R.

In the preferred embodiment of the present invention photoinitiator chosen from the group consisting of (i) benzophenone, (ii) a mixture of benzophenone and tertiary amines containing carbonyl group, which is directly connected with at least one aromatic nucleus, (iii) 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropan-1 (IRGACURE 907), (iv) 2,2-dimethoxy-1,2-diphenylethane-1 (IRGA-CURE 651), from which (iii) and (iv) are the most preferred.

It should be borne in mind that the duration of exposure will depend on the women curing (bonding) layer and so on. Photoinitiator preferably may be included in the amount of 1-10 wt. hours at 100 wt. hours of blockcopolymer and, more preferably, in the amount of 1-5 wt. h

In principle for the formation of cross-links in the block-copolymer composition of the present invention can use any source of UV radiation having the emission spectrum with one or more maxima in the wavelength range of 200-500 nm. Particularly suitable as UV sources bulbs melting, in particular the lamp H and D (linear power of 118 watts/cm and 236 W/cm), although it is also possible to use combinations of lamps D and H.

UV irradiation may be carried out in a known manner. Appropriate way, for example, is a sample preparation or in the form of a layer of hot melt or in the form of a coating layer from a solution and UV irradiation while moving the specified pattern with a certain velocity (expressed in metres per minute m/min) under a UV source. If necessary, the irradiation may be repeated one or more times, for example, passing again the sample under UV source or under two or more lamps, installed in series to provide the necessary cure. The lower total dose irradiation and satisfactory curing, the better the curing ability of the specified pattern.

The preferred use of the present composition is in preparation sensitive to the contraction of the adhesive tape (EIC) or in the production of labels. Sensitive to the contraction of the adhesive tape includes a flexible sheet lining and a layer of an adhesive composition of the present invention, deposited on one main surface of sheet lining. Sheet lining may be a plastic film, paper or any other suitable material, and the film may include various other layers and coatings, such as primers, coatings, greases and similar materials used in production are sensitive to the contraction of the adhesive films.

In accordance with another aspect of the present invention relates to molten adhesive compositions for use in the production of single use, such as napkins.

These molten adhesive compositions include block copolymers of the present invention, preferably, such copolymers, in which q is zero. The adhesive composition typically further comprises a resin, a reinforcing adhesion, and, optionally, a plasticizer. Preferred Sora. Like other adhesive compositions also may be other additives, such as antioksidanty and similar components, preferably in an amount of not more than 20 wt.%

The invention is additionally illustrated by the following examples, which however should not be construed as limiting the scope of the present invention.

Example 1 for the production of polymer P1

Cyclohexane, styrene, and butadiene previously passed through a column of AlcoaTMwith alumina to remove possible stabilizers and traces of water. The column was activated at 350oC in a stream of nitrogen. The reactor tube was also purged with nitrogen. In a reactor with a volume of 300 liters, equipped with a screw agitator with a speed of 120 rpm./min, after loading 180 l of cyclohexane at 40oC was added 5 kg of styrene and the reaction mixture was heated to 45oC, after which was added 330 ml of 1.4 mol) secondary utility.

The first sample of the reaction mixture were taken one hour after conducting the polymerization at 50oC and analyzed by the method of GPC-UV detection (actual maximum molecular weight = 11410).

Added second portion of the styrene weight 1,542 kg to obtain the desired molecular mA the analysis of the second sample by the method of GPC-UV, taken after a sufficient reaction time. The reaction mixture was cooled to 40oC (the actual maximum molecular weight = 14520).

After adding 225 ml of 1.4 mol) secondary utility added 63,18 ml diethoxypropane (DEP) and then 29,85 kg of butadiene.

The supply of butadiene started at 40oC. for 20 minutes after the start of feeding the reactor was heated to 70oC, and during this time the reactor was filed 7,00 kg of butadiene (artificial adiabatic process). The remainder of the butadiene (22,85 kg) was administered isothermal at 70oC. After the filing of the butadiene reaction continued for 10 minutes

The sample was selected after completion of the reaction and analyzed (apparent maximum molecular weight = 97150). Living polymers combined with 43,53 ml gamma-gpts.

After the reaction combinations within 60 minutes the reaction was stopped by adding 9 ml of methanol. The mixture was cooled to 0oC, and a sample of the polymer P1 was selected for analysis. (GPC+UV+IR analysis: the content of HPS in the UV 2,95, the effectiveness of a combination of 85%, a content of vinyl groups is 49.0%, a styrene content of 18.8%, the apparent molecular mass: 254300 - 258600.

The reaction mixture was transferred into a mixer, was added to 0.4 hours to 100 hours POL is Ali.

Then in the coagulator was added in 800 l of demineralized water and was carried out by coagulation with steam at 105oC. the Coagulated crumb rubber and steam condensate was cooled to 30oC, crumb was separated from water and dried in an air dryer at 50oC until the water content of approximately 0.2%.

Comparative Example 1 Preparation of polymer RA

In the first reactor of 5 liters was filled with 3 l of cyclohexane, which was purged with nitrogen for half an hour. After adding 150 g of the styrene content of the reactor was titrated at room temperature for 12 wt.% solution of second-utility (BuLi) in cyclohexane to remove any impurities that are present in the reaction mixture. Then add the 15.6 mmole utility, and raised the temperature to 50oC, and was maintained at this level. After about 30 min received block politicality, and the contents of the reactor were transferred to the second reactor with a volume of 10 l, which is pre-loaded with about 3 liters of cyclohexane, purged with nitrogen for half an hour, and a variable number diethoxyethane modifier and 350 g of butadiene, pre-titrated with a solution of utility.

The temperature was raised to 50oC. In the second reactor was made different, advance, and is>Then the temperature in the second reactor was raised to 80oC and maintained at this level, was added to 7.7 mmole SiCl4and spent the reaction mix for about 30 minutes.

It was found that the effectiveness of the combination of (ES) is equal to 96%, while the content of vinyl groups in the polybutadiene is 54%.

After about two hours, was added 10 g of 2,6-di-tert.-butyl - 4-methylphenyl. Then deleted the steam solvent, and the polymer (Pa) was dried in an oven at 60oC for 5-6 hours.

Example 2 production of polymer P2

To 18 l of cyclohexane at 50oC was added 250 g of styrene after adding 20 mmol secondary utility. The reaction was terminated after 40 minutes. Then add 8 ml of 1,2-diethoxypropane (DEP). Was the temperature of the reactor to 60oC, and then added 20 mmol secondary utility. Then to the reaction mixture gradually over 15 minutes, was added to the butadiene in the number 1414 Polymerization was carried out at 60oC for 120 minutes. Then for a combination of living chains were added to 1.96 ml of bis(trimethoxysilyl)ethane (BTME). After cooling the reaction mixture to 20oC, after 12 hours, was added 20 ml of ethanol.

The polymer stabilized with 0.2 is small crumbs. Product P2 were analyzed according to ASTM D3536. Content vanilovich groups was determined by IR spectrum according to ASTM D3677.

Example 3 for the production of polymer P3

To 18 l of cyclohexane at 50oC was added 225 g of styrene, after adding 21 mmole secondary utility. The reaction was terminated after 40 minutes. Then add 14 ml of 1,2-diethoxypropane (DEP). Was the temperature of the reactor to 70oC, and then added 21 mmol secondary utility. Then to the reaction mixture slowly over 20 minutes, was added to the butadiene in the number 1275, Polymerization was carried out at 70oC for 60 minutes. Then for a combination of living chains were added 2,12 ml of bis(trimethoxysilyl)ethane (BTME). After cooling the reaction mixture to 20oC, after 12 hours, was added 20 ml of ethanol. The polymer stabilized with 0.2 g BHT/100 g polymer and 0.4 h Polygard/100 g polymer was separated by steam distillation, obtaining a white powder. Product P3 was analyzed according to ASTM D3536. The content of vinyl groups was determined by IR-spectroscopy, described in the ASTM D3677.

Example 4. The production of polymer P4

To 18 l of cyclohexane at 50oC was added 225 g of styrene after adding 21.5 mmole secondary utility. The reaction was completed after 40 minutes. Then, there was added 13 ml of 1,2-dieta minutes added butadiene in the number 294, Polymerization was carried out at 70oC for 30 minutes. Then he added, 21.5 mmole Deut-utility and 1 ml of DEP and immediately gradually over 13 minutes was added 981 g of butadiene. The polymerization was carried out at 70oC for 60 minutes. Then for a combination of living chains were added 2,19 mmole of bis(tri - methoxysilyl)ethane (BTSE). After cooling the reaction mixture to 20oC, 12 hours, was added 20 ml of ethanol.

The polymer stabilized with 0.2 g BHT/100 g polymer and 0.4 h Polygard/100 g polymer was separated by steam distillation, obtaining a white powder. Product P4 were analyzed according to ASTM D3536. The content of vinyl groups was determined by the method of IR-spectroscopy, described in ASTM D3677.

Comparative example 2 production of polymer Pb with 6 chains

To 18 l of cyclohexane at 50oC was added 200 g of styrene after adding 22 mmol secondary utility. The reaction was completed after 40 minutes. Then added the 4.7 ml of 1,2-diethoxypropane (DEP). The reactor temperature was set equal to the 30oC and added 44 mmole Deut-utility. Then to the reaction mixture was gradually added within 40 min 1800 g of butadiene. The polymerization was carried out at 50oC for 100 minutes and Then for soceoC, 12 hours, was added 20 ml of ethanol.

The polymer stabilized with 0.2 g BHT/100 g polymer and 0.4 h Polygard 100 hours and was separated by steam distillation, obtaining a white powder. Product Pb were analyzed according to ASTM D3536. The content of vinyl groups was determined by the method of IR-spectroscopy, described in ASTM D3677 (see tab. A).

TNAS the test is carried out in a thermostat with air circulation, equipped with an Electromechanical device that provides monitoring step temperature change. Inside thermostat on the side walls reinforced brackets that can be installed at an angle of 2osix aluminum shelves. These shelves are 6 metal or glass plates, on which is placed the sample tape. These plates are placed opposite narrow ledge, which cut six slots; free portion is covered with a film, on which hung the goods pass along these grooves.

One end of the tape center and partially glued to a glass plate; the other end of the tape have to avoid its contact with the plate and she would lie below. The tape pressed against the glass plate to squeeze out air bubbles. Sticky part of the tape is cut at a distance of 25,EC, the samples incubated for 24 hours.

Shelves with samples placed in a thermostat and to the free end of the tape attached loads 500 or 1000 g using clips "Humana". These goods are first mounted on the main plate, which can be raised or lowered using a laboratory lift. Directly before the test plate is lowered so that the cargo was hanging freely above the micro - or photoelectric switches. These switches are attached to the meter. The oven temperature register on the screen of the digital thermometer.

With the disengagement of the tape burden falls on the microswitch and stops the timer. At the time of separation determines the temperature at the time of separation, using a graph of temperature over time. Is TNAS defined as the average of the two temperatures and two samples.

Average values of p and q for polymers P1 - P4 are shown in table XI.

1. The copolymers suitable for radiation curing the molten adhesive composition, with the General formula

(AB)p(a1)q X,

where a represents polyvinylpyrolidine block;

In and1- represents the same or different Penta combination,

and full of apparent molecular mass of blockcopolymer according to the gel chromatography is in the range from 100000 to 500000, wherein the content of 1,2-vinyl units in the polybutadiene blocks is 25 to 70 wt.%, the maximum active centers (m) agent in a combination of X ranges from 3 to 6, where the values of p and q are in the range from 1.5 to m, provided that the average value of the sum of the values of p and q is less than m, and the effectiveness of the combination is less than 90%, and the average full content vinylaromatic links in the specified blockcopolymer is in the range from 10 to 50 wt.%.

2. The copolymers under item 1, wherein X is the remainder of the four or trivalent combining agent.

3. The copolymers under item 1 or 2, characterized in that the apparent molecular mass of blocks and1each is from 20000 to 100000.

4. The copolymers according to any one of paragraphs.1 to 3, characterized in that the apparent molecular mass of blocks And ranges from 7000 to 20000.

5. The copolymers according to any one of paragraphs.1 to 4, characterized in that the total apparent molecular weight is 150,000 to 350,000.

6. The copolymers according to any one of paragraphs.Asia, sealing or coating compositions comprising one or more copolymers, characterized in that as blockcopolymer use of copolymers according to any one of paragraphs.1 - 6.

8. Radiation-curable molten adhesive compositions comprising one or more copolymers and one or more fillers selected from the group including resin, increase stickiness, oil filling, plasticizers, petroleum waxes, antioxidants, photoinitiator and the modifying resin, characterized in that the copolymers are used, the copolymers according to any one of paragraphs.1 - 6.

9. UV radiation curable adhesive compositions comprising one or more copolymers of at least together with one photoinitiator, characterized in that the copolymers are used, the copolymers according to any one of paragraphs.1 - 6.

10. UV radiation curable adhesive compositions under item 9, characterized in that photoinitiator include in the amount of 1 - 5 wt.h. on 100 wt.h. blockcopolymer.

11. Sensitive to compression of the radiation-curable tape or labels, which includes a flexible band substrate and the layer of adhesive composition applied to the primary p is any one of paragraphs.7 - 10.

12. Radiation-curable adhesive, sealant or coating composition derived from a radiation cured composition, characterized in that the radiation cured compositions using the compounds according to any one of paragraphs.7 - 11 and radiation-curable adhesive, sealant or coating composition preferably receive on the air.

13. The method of obtaining sensitive to radiation block copolymers, characterized in that the copolymers according to any one of paragraphs. 1 - 6, and the method includes: (a) the polymerization of predominantly mobilisations monomer in the presence of an organolithium initiator RU and preferably alkylate containing 4 to 6 carbon atoms, to obtain a living polymer ALi; (b) the polymerization of predominantly butadiene to the living polymer ALi and add at some point organolithium initiator RLi with a mixture of living polymers A-B-Li and B1Li, where the segments IN the1can have the same or different molecular mass, [M], M[B] [B1] depending on the moment of addition of RLi; where the content of 1,2-vinyl units in the polybutadiene blocks is 25 to 70 wt. per cent; (C) SOH conditions, the effectiveness of a combination of less than 90%.

 

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