Low-viscosity hot melt adhesive compositions

FIELD: adhesives.

SUBSTANCE: invention relates to stable low-viscosity hot melt adhesive compositions, to special block copolymers used therein, and also to tapes and labels including said compositions. Objective of invention is to provide hot melt adhesive compositions having viscosity by 5% lower or higher than initial value when heated for 24 h at 177°C and having melt viscosity = 80 Pa·s at 177°C. Composition comprises: (a) at least one block copolymer containing at least two terminal polyvinyl-aromatic blocks and at least one core block composed of copolymerized isoprene/butadiene mixtures at weight ratio between 45:55 and 55:45 and having polyvinyl-aromatic content 17-20%, apparent common molecular mass 180000-190000, content of 1,2-vinyl bonds and/or 3,4-vinyl bonds not more than 15 wt% in conjugated diene blocks while bonding efficiency 63 to 80% at weight ratio 40-45% of the total mass of composition; (b) aliphatic/aromatic hydrocarbon resin increasing adhesiveness, containing less than 16 wt % of aromatic structure as measured by H-NMR method, having glass transition temperature (Tg) 30 to 55°C as measured by differential scanning calometry technique, and softening point (Ring & Ball) between 85 and 95°C at weight ratio 45-55% of the total mass of composition; and (c) plasticizer in amount 5-15% of the total mass of composition.

EFFECT: optimized physicochemical characteristics.

3 cl, 4 tbl, 2 ex

 

The technical field

The present invention relates to stable compositions of hot-melt adhesive having a low viscosity, to a particular block copolymers used in them, as well as tapes and labels, comprising the above composition.

Prior art

Low viscosity, hot-melt stable adhesive compositions were the target of development for a long time.

A serious disadvantage of the hot-melt adhesive compositions known from the prior art, comprising a block copolymer of the formula (S-I)nX, S-I-S, (SB)nX or S-B-S, where S represents a polystyrene block, I represents mainly the block of polyisoprene, and represents mainly the block polybutadiene, is that the melt viscosity is unstable and vary significantly in the process at the temperature of melting.

In particular, it is known that the viscosity of the hot melt adhesive compositions comprising block copolymers containing at least one polybutadiene block, increases during the processing of the melt due to the formation of cross-links, whereas the viscosity of the hot melt adhesive compositions comprising block copolymers containing at least one branch, Rubezhnoe, Ukraine mainly block, decreases during melt processing at the expense of breaking the circuit.

For example, the Pat is the EP 0659787 A (SHELL) from 28.06.1995 known adhesive under pressure (self-adhesive) hot melt compositions provides high shear strength, comprising (a) one or more than one linear block copolymer containing two terminal block mainly monovinyl aromatic compounds and one block mainly of a conjugated diene, where the content monovinyl aromatic compound is from 15 to 25%, the apparent total molecular weight is 130,000 to 180,000, and the actual total molecular weight is from 10000 to 14000, optionally mixed with a small amount of diblock copolymer comprising blocks similar to the blocks of the triblock-copolymer of the component (b) is compatible of the primary resin improves adhesion, (C) a plasticizing oil and/or secondary resin that increases the stickiness, and (d) a stabilizer.

Preferred resins that improve the adhesiveness used in these compositions were selected from a mixed aromatic and aliphatic petroleum hydrocarbon resins, where aliphatic hydrocarbons accounted for more than 50 wt.% of the total tar.

It was said that these compositions are preferably used for packaging tapes.

However, it was found that these compositions have a low stability of the melt, that is, their viscosity decreases with prolonged heating during processing.

From the application WO 9516755 A (EXXON) from 22.06.1995 known low is ASCII in the melt hot-melt adhesive of the adhesive composition, having increased adhesiveness.

The basis of these compositions is S-I-S block copolymer having a polystyrene segments and branch, Rubezhnoe, Ukraine blocks, mixed with oil resin, increase stickiness, which is the product of polymerization by Friedel-Crafts (i) recerving oil feedstock containing C5-olefins and diolefin or a mixture of C5- and6-olefins and diolefins, copolymerizing with (i, i) from about 5 to 15 wt.% monovinyl aromatic monomer containing 8 or 9 carbon atoms, such as styrene.

These compositions also include polystyrene-branch, Rubezhnoe, Ukraine diblock copolymer and recycled oil.

However, it was found that these compositions have a low stability of the melt, i.e. the viscosity decreases with prolonged heating during processing.

From the application DE 2942128 (BASF) from 30.01.1981 known about the use of block copolymers S(IB)S adhesives. These block copolymers are apparent total molecular weight in the range from 30000 to 300000, contain polystyrene blocks with the actual molecular weight in the range from 5000 to 50000, preferably from 15,000 to 25,000, where the polystyrene content is from 10 to 50 wt.%. The preferred molecular weight of the conjugated block preferably ranges from 60000 to 100000.

In this application atent does not contain any information, lets get hot-melt adhesive composition having improved acceptable stability of the melt in combination with an acceptable adhesive properties of the final products, such as tapes and labels that currently required in today's industry.

From the publication WO 02057386 A (KRATON) 25.07.2002 known adhesive compositions comprising (i) one or more than one styrene block copolymer, (i, i) enhancing the adhesiveness of the resin and (i, i, i) one or more than one plasticizer, in which the block copolymers have the General formula a-C-A (1) or (a-C)nX (2), where each And independently represents a polymer block of an aromatic vinyl compound, and a mixed polymer block (I) butadiene (b) and isoprene (I) in a mass ratio of In:I in the range from 30:70 to 70:30, with specified polymer block has a glass transition temperature (Tg) not higher than -50°S (determined according to ASTM-E-1356-98), where n is an integer greater than or equal to 2, and X is the remainder of the binder agent, and where increasing the stickiness of the resin has aromaticity (the relative percentage of aromatic protons, as determined by the method H-NMR) in the range from 3 to 18%.

However, in the specified publication no information that allows you to get a hot-melt adhesive composition having improved acceptable stability of the melt in combination with the pickup is acceptable adhesive properties of the final products, for example, tapes and labels, and in particular packaging tapes, as currently required in today's industry.

From the document JP 05345885 A known adhesive compositions containing styrene-isoprene/butadiene-styrene block copolymer having a content of isoprene in the isoprene/butadiene, from 10 to 90%, the content of polystyrene in the range from 5000 to 30000. However, in this document does not contain information that allows to obtain low viscosity, hot-melt stable adhesive composition, which is the aim of the present invention. Not provided no description of the other ingredients used in adhesive compositions, and in particular, no information about the use of resins that improve the adhesiveness.

It should be noted that the objective of the present invention to provide a hot-melt adhesive compositions having acceptable stability of the melt, i.e. a viscosity less than 5% below or above the initial viscosity after 24 hours at a temperature of 177°and having a melt viscosity ≤80 PA·at a temperature of 177°With, in combination with an acceptable adhesive properties of the final products.

Another object of the present invention to provide block copolymers having a specific fine-tuned microstructure, providing the above required properties is as hot melt adhesive compositions, in the composition of which they are members.

And another object of the present invention is to obtain tapes and labels are manufactured using the hot-melt compositions, in particular of packaging tapes.

As a result of extensive research and experimental work were unexpectedly obtained the specified target block copolymers and hot-melt adhesive compositions.

Disclosure of inventions

Thus, the invention relates to stable compositions of hot-melt adhesive having a low viscosity, including:

a) at least one block copolymer containing at least two end polivinilatsetatnyh block and at least one secondary unit of arbitrarily copolymerizing mixtures of isoprene and butadiene in a weight ratio of isoprene/butadiene comprising from 45:55 to 55:45, with the content polyvinylimidazole component in the range of 17 to 20%, apparent total molecular weight in the range of 180,000 to 190000, the content of 1,2-vinyl bonds and/or 3,4-vinyl bonds is not more than 15 wt.% in conjugated diene units and the effectiveness of binding in the range from 63 to 80% in mass ratio from 40 to 45 wt.% by weight of the entire composition,

b) aliphatic/aromatic hydrocarbon resin, increase stickiness, containing less than 16 wt.% aromatic structures, as determined met the house H-NMR, having a glass transition temperature (Tg)determined by the method of differential scanning calorimetry (DSC)in the range from 30 to 55°and a softening point (Ring &Ball) in the range of 85 to 95°in a mass ratio of from 45 to 55 wt.% by weight of the entire composition,

(C) a plasticizer in a mass ratio of from 5 to 15 wt.% by weight of the entire composition,

and having a stable melt viscosity that is less than 5% below or above the initial viscosity after 24 hours at a temperature of 177°and having a melt viscosity ≤80 PA·at a temperature of 177°C.

The invention also relates to tapes and labels containing the above-mentioned stable low-viscosity hot-melt adhesive composition on the carrier, and the block copolymers within the specified composition as the component (a).

Information confirming the possibility of carrying out the invention

Component (a)

Basic block copolymer component used in the adhesive composition is a block copolymer having a structure represented by the General formula S-(I/B)-S (1) or [S-(I/B)]nX (2), optionally mixed with a diblock copolymer S-(I/B) and with a small amount of one or more than one block copolymer selected from the group comprising S-B, S-B-S, S-I and S-I-S, where S is polyvinylpyrolidine block (I/C) is a block of about svalina copolymerizable mixture of isoprene and butadiene, where the mass ratio between isoprene and butadiene is in the range from 45:55 to 55:45, or in a molar ratio (mol/mol) from 0.66:1,01 to 0.80:0,83, where In represents a polybutadiene block, I represents the branch, Rubezhnoe, Ukraine block, n is an integer greater than or equal to 2, and X is the residue of a coupling agent.

As examples of aromatic vinyl compounds used in the implementation of the present invention, can be mentioned styrene, α-methylsterol, p-methylsterol, o-methylsterol, p-tert-butalbiral, dimethylstyrene and vinylnaphthalene or a mixture thereof. Here styrene is particularly preferred from the viewpoint of easy availability, reactivity, physical properties of the resulting block copolymers. The polymer block a may contain minor amounts of comonomers other than the aromatic vinyl compounds, for example up to 5 wt.% copolymerizable monomer, such as butadiene and/or isoprene (by weight of the overall unit). The most preferred units And obtained essentially pure styrene.

Preferably, the polymer blocks And had the actual molecular weight in the range from 10000 to 11000.

Mixed average polymer block (I/B) is derived from butadiene and isoprene as the monomer copolymerization, although it can also contain nez is acetelyne amounts of other comonomers, for example, up to 5 wt.% copolymerizable monomer, such as styrene (by weight of the overall unit), however, preferred are a mixture of essentially pure butadiene and isoprene.

The block copolymers according to the present invention, the content of the bound aromatic vinyl compound is in the range from 17 to 20 wt.% from the mass of the block copolymer. It is preferable that the content of the bound butadiene and the bound isoprene were in the range from 32 to 42 wt.%, and more preferably in the range from 38 to 42 wt.%. These quantities are related monomers (plus copolymerizate monomers, if any) add up to 100 wt.%.

Preferred block copolymers have the efficiency of binding from 64 to 80%.

Each of the block copolymers used in the adhesive compositions according to the present invention has an average molecular weight (apparent molecular mass Mw, i.e. expressed in terms of polystyrene) in the range of 180,000 to 190000, as determined by gel permeation chromatography (GPC, with calibration standards polystyrene, ASTM 3536).

The block copolymers used in the adhesive compositions according to the present invention preferably contain a 1,2-vinyl communications and/or 3,4-vinyl communications, each in an amount of 5 to 15 wt.% by weight of a conjugated diene or from 0.08 to 0.70 mol.%, and is more preferably in quantities of from 5 to 10 wt.% by weight of a conjugated diene or from 0.08 to 0.35 mol.%. Each of the block copolymers according to the present invention preferably has a dynamic elastic modulus (G′) from 1 to 300 MPa in the measurement of viscoelastic properties in the temperature range from 0 to 50°and With only one peak in the loss tangent (tan d), which can be attributed to the mixed butadiene/isoprene polymer block at a temperature of -50°With or below. If as a main polymer for adhesive bonding with pressure (SPES), use the block-copolymer with a dynamic elastic modulus (G′) below 1 MPa, the adhesive strength of adhesive bonding under pressure, is reduced. On the other hand, any dynamic modules of elasticity higher than 300 MPa yield adhesive with reduced stickiness.

These block copolymers used as the main component (a) in the adhesive composition, have arbitrarily copolymerizing block (I/C), which means that in a mixed middle box there is no significant formation of the homopolymer block. They can be obtained, as described in the publication WO 02057386 (KRATON) 25.07.2002 included in this description by reference.

In particular, polymers with mixed medium blocks can have the average length of the homopolymer block of less than 100 Monomeric units, preferably less than 50 Monomeric units, more preferably less than 20 monomer is x units. The average length of the homopolymer block may be determined by the method13C-NMR, as described in detail in the application WO 02057386 (KRATON) 25.07.2002.

The block copolymers according to the present invention can be obtained by any known means, including a well-known method full sequential polymerization, optionally in combination with re-initiation, and method combination, as described, for example, in patents US 3231635 (SHELL) from 25.01.1966, US 3251905 (PHILIPS PETROLEUM) from 17.05.1966, US 3390207 (SHELL) from 25.06.1968, US 3598887 (POLYMER CORP) from 10.08.1971, US 4219627 (FIRESTONE) from 26.08.1980 and EP 0413294 A (DOW) from 20.02.1991, EP 038761 A (DOW) from 19.09.1990, EP 0636654 A (SHELL) from 01.02.1995 and WO 9422931 (SHELL) from 11.04.1995.

Preferred block copolymers according to the present invention receives the connection "alive" diblock copolymer obtained by anionic polymerization, using a bonding agent.

Preferred binding agents are EPTON™ 825 or 826 (diglycidyl esters), debrabant, tetramethoxysilane or other tetraalkoxysilane.

The main block-copolymer in component (a) may, therefore, include a mixture linked polymer of formula (1) or (2) and intermediate dibelka, for example, in a molar ratio of from 60:40 to 75:25, preferably from 65:35 to 75:25.

It should be noted that the basic block copolymer component (a) can also be obtained by sequential polymerization according to stuudy monomers (styrene and a mixture of butadiene/isoprene) in combination with the re-initiation.

Block copolymers of formulas (1) and (2) can be obtained by a simple adaptation of the conventional methods used to produce the block copolymers of the type S-B-S and/or block copolymers of type S-I-S, instead of using a mixture of butadiene/isoprene. In the preparation of the block copolymers according to the present invention, it is important to avoid the formation of homopolymer block, to ensure an appropriate ratio of B/I and to obtain a polymer block in which arbitrary average unit has a temperature Tg -60°or less. As a rule, no randomization not used.

As indicated above, the basic block copolymer of formula (1) and (2) typically will include appropriate diblock in a molar ratio of from 20 to 40% and preferably from 25 to 35%.

Component (b)

It is established that an acceptable resin or mixture of resins that increase stickiness, are according to H-NMR, the content of aromatic protons less than 16%, preferably from 4 to 10%, the glass transition temperature (Tg)determined by the method of differential scanning calorimetry (DSC)in the range from 30 to 55°C, preferably from 35 to 50°and a softening point (Ring &Ball) of from 85 to 95°C.

They can be selected from modified aliphatic hydrocarbon resins, such as modified C5 hydrocarbon resin C5/C9 resin), strazdeliai terpene resins, partially hydrogenated C9-uglevodorov the different resins, as well as their mixtures. The aromatic component can be used in the form of a stream of material comprising one or more chemical compounds, such as polystyrene, α-methylsterol, vinyltoluene, alkyl substituted indene and the corresponding homologues.

Preferred examples of resins that can be used as component (b), are WINGTACK™ ET, modified aliphatic hydrocarbon resin with a content of aromatic protons according to H-NMR of 4.2%, a softening point (Ring &Ball) 94°C, QUINTONE™ S-100, modified aliphatic hydrocarbon resin with a content of aromatic protons according to H-NMR of 6.3% and a softening point (Ring &Ball) 94°C, PICCOTAC™ 8095, aliphatic hydrocarbon resin with a content of aromatic protons according to H-NMR 5.4% and a softening point (Ring &Ball) 93°C, WINGTACK™ 86, a modified aliphatic hydrocarbon resin with a content of aromatic protons according to H-NMR of 9.6% and a softening point (Ring &Ball) 86°C.

Preferred solid resin that increases the stickiness will have a softening point (Ring &Ball) in the range of 85 to 95°C.

Such resins are produced by firms GOODYEAR CHEMICALS, ZEON and EASTMAN CHEMICALS.

Adhesive compositions according to the present invention preferably include from 50 to 300 mass parts, and more prepact the tion, from 100 to 200 mass parts of the resin improves adhesion, per 100 mass parts component (a).

In the preferred adhesive compositions containing component (b) ranges from 48 to 55 wt.% by weight of the composition.

Component (C)

Acceptable plasticizers include mainly plasticizing oils, which are by nature paraffins or naphthenes (the proportion of aromatic carbon ≤5%, preferably ≤2%, more preferably 0%, as determined according to DIN 51378) and have a glass transition temperature below -55°S, as determined by the method of differential scanning calorimetry. These products are commercially available from companies Royal Dutch/Shell Group, such as SHELLFLEX oil™, CATENEX™ and ONDINA™. Other oils include oil KAYDOL™ from Witco or oil TUFFLO™ from Arco or NYPLAST™ from NYNAS. Other plasticizers include similar liquid resin that increases the stickiness, such as REGALREZ™ R-1018 or WINGTACK™ 10.

Can also be added other plasticizers, such as olefin oligomers; low molecular weight polymers (≤30000 g/mol), such as liquid polybutene, liquid copolymers of polyisoprene, liquid copolymers of styrene/isoprene or liquid hydrogenated copolymers of styrene/conjugated diene; vegetable oils and their derivatives; or paraffin and microcrystalline waxes.

Preferably, h is ordinary composition according to the present invention include a plasticizer in a mass ratio of from 5 to 15 wt.% by weight of the entire composition and from 10 to 85 mass parts of plasticizer per 100 mass parts of the block copolymer, part (a). In addition, each block copolymer of the component (a) may be previously mixed with a small amount of plasticizer manufacturer of the specified copolymer.

Other components (limitiruyuschie)

In the adhesive compositions according to the present invention can be introduced other elastomeric components. It is also known that some other components can be added to change the sticky, odor, color adhesives. In addition, can be added antioxidants and other stabilizing ingredients to protect the adhesive from degradation due to exposure to heat, light or during storage.

Can be used with different types of antioxidants, primary antioxidants, such as phenols or secondary antioxidants, such as derivatives, phosphites, or mixtures thereof. Examples of commercially available antioxidants are IRGANOX™ 565 from Ciba-Geigy (2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine), IRGANOX™ 1010 from Ciba-Geigy (tetracosactrin-93,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane) and POLYGARD™ HR from Yniroyal (Tris-(2,4-ditertbutyl)FOSFA). Can also be used with other antioxidants to protect against gelation polybutadiene segments, such as SUMILIZER™ GS from Sumitomo (2-[1-(2-hydroxy-3,5-directteller)ethyl)]-4,6-di-tert-interfamilial); SUMILIZR™ T-PD from Sumitomo (pentaerythritoltetranitrate-(3-dodecylthiophene)); or a mixture thereof.

Preparation of a composition

On the method of preparation of the adhesive compositions not imposed any particular restrictions. So it can be used any way, such as mechanical mixing is performed using a roll, Banbury mixer or clearesult Dalton, the method of the melt, characterized in that the heating and mixing is carried out with the use of the boiler for republicana, equipped with a stirrer, such as high-speed Z-blade mixer or a single - or twin-screw extruder, or a method of dissolving, in which component parts are poured into a suitable solvent and stirred, thereby obtaining thoroughly mixed mortar composition of the adhesive, bonding with pressure.

The use of a composition

The composition of the adhesive, bonding with pressure (KCH), according to the present invention can be applied in the form of a melt deposited on the base material, such as paper or plastic film, using a suitable machine for coating to obtain various kinds of adhesive tapes, in particular packaging tapes and labels.

KCH composition according to the present invention are suitable in particular for packaging tapes, such as tapes for closing cartons for industrial BYTOVOGO application, masking tape and stationery tape.

When producing labels multilayer material consisting of a face material, adhesive layer and the cover film passes through the machine, which turns the multilayer material into useful commercially labels and material for labels. The method includes, among other things, cutting and separating matrix for applying labels on the coating film.

Unexpectedly, it was found that in the manufacture of tapes, labels and dressing material according to the present invention, clogging of the cutter device used for cutting and trimming, rolled products and plates, is significantly reduced.

It should be noted that another aspect of the present invention is the use of tapes, labels or bandages.

Hereinafter the present invention will be further illustrated by the following examples of specific embodiments of the invention, which, however, do not limit the scope of the invention.

Testing methods

Standard definition adhesiveness, adhesion forces and viscosity of these compositions were performed according to the Manual test method self-adhesive tapes Council for self-adhesive tapes (PSTC), standard method of test for the Association FINAT for self-adhesive materials, methods test the Oia AFERA for self-adhesive tapes and related methods ASTM (American society for testing and materials (American Society for Testing Materials). Depending on the application used a different test surfaces: stainless steel sheets (No.304) ("ss"), as recommended by FINAT, and Kraft paper.

- Stick rolling ball (PCS) - the distance measured in cm; a steel ball rolls on the adhesive film with a standard initial viscosity (Pressure Sensitive Tape Council Test No. 6; ASTM D3121-73). Small values indicate strong adhesiveness.

- The strength of coupling (HP) Kraft paper - the time required for tightening the standard area of tape (2,5×1.3 cm) from Kraft paper with a standard load of 1 kg with a shift of 2° (Pressure Sensitive Tape Council Method No. 7; ASTMD-3654-82). For a long time indicates a high adhesion force. The results are expressed in hours (h) or minutes (min). Type of failure is expressed as the destruction of the adhesive bonding (adhesive fracture, AR) or destruction were in contact surfaces (cohesive failure, KR). This test is carried out at a temperature of 40°C.

A shot on Kraft paper defines the time in minutes required for the loss of grip tape Kraft paper. The test is carried out on the equipment, developed by ETS Holland, and simulate the pushing force of the cardboard flaps. Use the mass of 0.5 kg and 1 kg

The glass transition temperature Tg is determined by the method of differential scanning calorimetry in increments of temperature 40°C/min Tg seraut the beginning of the transition state.

- The content of polystyrene determined by the method of 1H-NMR.

- The average length of the homopolymer block is determined by the method of13C-NMR, using the above method. Spectra13C-NMR samples of the polymers are removed on a spectrometer Bruker AMX-500 FT at 125 MHz. Quantitative spectra of proton decoupling was recorded at 90° when the pulse excitation13And the repetition rate of 10 C. Used 10 wt.% the polymer solutions in CDCl3. To improve the relaxation time was added 0.1 mol/l acetylacetone chromium. Used the broadening of spectral lines was 2 Hz. The spectra were correlated so that the aliphatic carbon atoms of transpoliation corresponded to 31.9 ppm

- Quantitative percentage of aromatic protons in the aromatic modified hydrocarbon resin was determined in a liquid by the method of 1H-NMR after dissolution of the samples in deuterated chloroform and measurement instrument Bruker DPX-500.

The softening point (Ring &Ball) represents the temperature at which the resin softens according to test method ASTM E-28.

The viscosity and stability of the melt: melt viscosity of the adhesives was determined on a Brookfield viscometer DVII+ programmable thermoacetica. The measurements were carried out at a temperature of 177°continuously for 24 hours in accordance with ASTM D-3236-78.

Synthesis of copolymers (block copolymers b and C and block copolymers compare b and C)

Cyclohexane, styrene, butadiene and isoprene was purified with activated alumina and kept at a temperature of 4°C in nitrogen atmosphere. As a binder agent used EPON™ 826 (diglycidyl ether) and dibromide (the RHEED). Before synthesis was preparing a mixture of monomers of butadiene and isoprene and kept her at a temperature of 4°C in nitrogen atmosphere. This mixture was used as such.

In an autoclave equipped with a helical stirrer, were placed cyclohexane, and then the contents were heated to a temperature of 50-60°C. Immediately after the styrene monomer as an initiator was added sec-BuLi, which contributed to the complete course of polymerization. The reaction temperature was raised to 70°Since, at this temperature was added a mixture of monomers of butadiene/isoprene (B/I) and carried out the reaction. Resulting from diblock associated with excess EPON™ 825 or 826 (dipicolylamine esters) or, alternatively, the excess of the RHEED. This optional excess was removed with sec-BuLi followed by the addition of ethanol as an agent for breaking a chain. The reaction mixture was cooled to a temperature of 40°With, was transferred to a mixer and added stabilizing the complex (including IRGANOX™ 565 and Tris(Nonylphenol)postit 0,08/0,35 parts by weight per 100 parts of elastomer in the form of a solution in cyclohexane) and stirred at room temperature is re. Dry rubber compound was obtained steam coagulation, followed by drying in an oven.

The polymers were analyzed by GPC method (gel permeation chromatography). The results of the GPC analysis are presented in Table 1.

Synthesis of polymer with serial/re-initiation (block copolymer a and the block copolymer comparison (A)

Cyclohexane, styrene, butadiene and isoprene was purified with activated alumina and kept at a temperature of 4°C in nitrogen atmosphere. Before synthesis was preparing a mixture of monomers of butadiene and isoprene (in the required mass ratio) and kept it at a temperature of 4°C in nitrogen atmosphere. This mixture was used as such. In an autoclave equipped with a helical stirrer, were placed cyclohexane, and then the contents were heated to a temperature of 50°C. Immediately after the styrene monomer as an initiator was added sec-BuLi, which contributed to the complete course of polymerization. The reaction temperature was raised to 60°C, after which was added a mixture of monomers of butadiene/isoprene (I) and was completed the reaction. Immediately after the addition and completion of the reaction mixtures of the monomers butadiene/isoprene (I) was added to the second portion of sec-BuLi. Added the second portion of the styrene monomer and the reaction was carried out to completion. The reaction mixture was extinguished stoichiometric amounts of alcohol, cooled to pace the atmospheric temperature 40° C, transferred into a mixer, adding a stabilizing complex and stirred at room temperature. The white polymer was obtained by processing a steam coagulation, followed by drying in an oven. The results of the GPC analysis are presented in Table 1.

Additional components used in the examples presented in Table 2.

All the compositions in the examples were mixed using a WERNER and PFLEIDERER LUK 025 Z-blade mixer at a temperature of 165°With under nitrogen to exclude oxygen of the air. The samples used for the study of the viscosity of the melt.

In addition, all of the compositions in the examples is prepared without solvent. Different ingredients poured into toluene and stirred for 24 hours to dissolve. Subsequently, the solutions are applied on a polyester film (MYLAR, a thickness of 36 microns) using an automatic machine for coating BRAIVE Bar Coater to obtain adhesive coating weight of 22 g/m2dry matter. After that, the samples for the protection of laminated silicone paper. Before testing the samples kept in a ventilated room at a temperature of 21°C and a relative humidity of 50%.

Example 1

All compositions comprise 100 parts by weight of polymer (43,9%)/110 parts by weight of WINGTACK™ ET(48,2%)/15 parts by weight of EDELEX™ N956 (6,6%)/3 parts by weight of IRGANOX™ 1010 (1.3 percent). The reference sample D are KRATON® D-1160.

The results presented is in Table 4, show that the polymers a, b and C provide compositions noticeable and unexpectedly low and stable melt viscosity at a temperature of 177°With less than 5% change 24 hours after the study period. Other polymers which give the songs or significant viscosity increase or a significant decrease.

The increase in viscosity means that is blended polymer, and the decrease in viscosity indicates that the polymer undergoes breaking the circuit. In both cases, as is well known, these processes affect the adhesive characteristics such as tackiness, adhesion and cohesion.

Example 2

The results presented in Table 4 show that the adhesive properties of the composition based on a polymer of the invention give a packing tape quality, similar to those obtained for the composition of comparison D, but more stable melt viscosity, as shown in Example 1.

189
Table 1
PolymerComp. AndComp. InAndInComp.
Mw polystyrene*10312,11110,910,611,510,9
Total Mw*103206195184183174
The efficiency of binding (%)69876872,67464,4
The polystyrene content (%)1917,618,918,82020
The ratio of butadiene/isoprene (wt./wt.)50/5050/5050/5050/5045/5545/55
BindernoThe RHEEDnoEPON® 826EPON® 826EPON® 825
The vinyl content of butadiene (B), wt.%888888
The content of vinyl isoprene (I), wt.%555555

Additional components used in the tested adhesive compositions shown in the list below (table 2).

KRATON® B-1160linear block-copolymer-type styrene-isoprene-styrene, containing 19% of polystyrene, with a total molecular weight 178000 g/mol and the ratio with which Azania 100%. This polymer is used as a comparative D.
WINGTACK™ 86aliphatic/aromatic hydrocarbon resin with a softening temperature 86°C, aromaticity according to H-NMR of 9.6%, the glass transition temperature Tg 37°; developed by GOODYEAR CHEMICALS.
QUINTONE™ S-100aliphatic/aromatic hydrocarbon resin with a softening temperature 94°C, aromaticity according to H-NMR of 6.3%, a glass transition temperature Tg 49°; developed by ZEON.
WINGTACK™ ETaliphatic/aromatic hydrocarbon resin with a softening temperature 94°C, aromaticity according to H-NMR of 4.2%, a glass transition temperature Tg 44°; developed by GOODYEAR CHEMICALS.
PICCOTAC™ 8095aliphatic/aromatic hydrocarbon resin with a softening point 93°C, aromaticity according to H-NMR of 5.4%, a glass transition temperature Tg 36°developed by the company EASTMAN Chemical.
EDELEX™ N956naphthenic oil from DEUTSCHE SHELL AG.
IRGANOX™the antioxidant from the company CIBA.

Table 3
PropertiesComp. AndComp. InPolymer And The polymer InThe polymerComp. Comp. D
BP at 177°C (0 h), PA·1801158046734352
BP at 177°

(6 h), PA·
200127784672,54249
BP at 177°

(24 h), PA·
8044733545
change+11%*+10%*0%°-4,5%°0%°-23%-17%
*measured after 6 hours°measured after 24 hours

Table 4
Ingredients/propertiesEd.F-1F-2F-3F-4F-5
The reference sample D100
The polymer100 (43,9%) 100 (43,9%)100 (43,9%)100 (43,9%)
Wingtack™ ETparts by weight110 (48,2%)110 (48,2%)
Quintone™ S-100parts by weight110 (48,2%)
Piccotac™ 8095parts by weight110 (48,2%)
Wingtack™ 86parts by weight110 (48,2%)
Irganox™ 1010parts by weight3 (1,3%)3 (1,3%)3 (1,3%)3 (1,3%)3 (1,3%)
PCScm10,517129a 3.9
The impact on Kraft paper 0.5 kgmin43007100540047002000
The impact on Kraft paper 1 kgmin560390900730530
The impact on Kraft paper 1 kgmin2290533659
BP at 177°PA·5274676653

From the data presented in Tables 1 and 3, it is seen that the block copolymer of the component In the corresponding block-copolymer E in Table 1, p.19 application WO 02/A has the worst melt viscosity (BP) in comparison with the block copolymers used in hot-melt stable adhesive compositions of the present invention.

1. The hot-melt adhesive composition having a low viscosity, comprising a) at least one block copolymer containing at least two end polivinilatsetatnyh block and at least one secondary unit of arbitrarily copolymerizing mixtures of isoprene and butadiene in a weight ratio of isoprene/butadiene comprising from 45:55 to 55:45, with the content polyvinylimidazole component in the range of 17 to 20%, apparent total molecular weight in the range of 180,000 to 190000, the content of 1,2-vinyl bonds and/or 3,4-vinyl bonds is not more than 15 wt.% in the conjugated diene units, and the effectiveness of binding in the range from 63%to 80%, in a mass ratio of from 40 to 45 wt.% by weight of the entire composition,

b) aliphatic/aromatic hydrocarbon resin, increase stickiness, containing less than 16 wt.% aromatic structures, as determined by the method of H-NMR, having a glass transition temperature (Tg)determined by the method of differential scanning calorimetry (DSC)in the range from 30 to 55°and a softening point (Ring&Ball) in the range of 85 to 95°in a mass ratio of from 45 to 55 wt.% by weight of the entire composition,

c) a plasticizer in a weight ratio of from 5 to 15 wt.% by weight of the entire composition,

and having a stable melt viscosity that is less than 5% below or above the initial viscosity after 24 h at a temperature of 177°and having a melt viscosity ≤80 PA·at a temperature of 177°C.

2. The composition according to claim 1, characterized in that the block copolymer component (a) is a block copolymer of the formula S-(I/B)-S, where S is a block of polymerized essentially pure styrene and (I/B) represents a randomly copolymerizing isoprene/butadiene block, and where the polystyrene content is from 17 to 20 wt.%.

3. The composition according to claim 2, characterized in that the block copolymer component (a) has an apparent total molecular weight in the range of 180,000 to 185,000, the mass ratio of the isoprene/butadiene from 45:55 to 55:45 and the content of 1,2-vinyl bonds and/or 3,4-vinyl bonds from 5 to 10 wt.% in the conjugated diene blocks.

4. The composition according to claim 1, characterized in that the component (b) contains from 4 to 10 wt.% aromatic structure according to H-NMR.

5. The composition according to claim 1, characterized in that the component (C) is a mineral oil.

6. Adhesive tape containing the composition according to any one of claims 1 to 5, on the media.

7. Packing tape containing the composition according to any one of claims 1 to 5, on the media.

8. The block copolymer for use in the composition according to any one of claims 1 to 5, characterized in that it contains at least two end polivinilatsetatnyh block and at least one secondary unit of arbitrarily copolymerizing isoprene/butadiene mixtures with a mass ratio of isoprene/butadiene from 45:55 to 55:45, with the content polyvinylimidazole component in the range of 17 to 20%, apparent total molecular weight in the range of 180,000 to 190000, the content of 1,2-vinyl bonds and/or 3,4-vinyl bonds, each in an amount of not more than 15 wt.% in the conjugated diene units, and the effectiveness of binding in the range from 63 to 87%.

9. The block copolymer of claim 8, characterized in that it has the structure of formula S-(I/B), where S is a block of polymerized essentially pure styrene, a (I/B) represents a randomly copolymerizing isoprene/butadiene block.

10. The block copolymer of claim 8 or 9, characterized in that it has an apparent total molecular weight in the range of 180,000 to 185,000, the mass ratio of the isoprene/butadiene from 45:55 to 55:45 and the content of 1,2-vinyl bonds and/ili,4-vinyl bonds, each in an amount of from 5 to 10 wt.% in the conjugated diene blocks.

11. Adhesive label containing the composition according to any one of claims 1 to 5, on the media.



 

Same patents:

FIELD: manufacture of self-adhesing films for laying floor coats.

SUBSTANCE: proposed self-adhesing film has carrier layer which is coated with contact adhesive on upper surface facing the floor coat and on lower surface facing the floor. Layer of contact adhesive on upper surface is covered with removable covering anti-skid layer. Carrier layer is made from polymer film.

EFFECT: enhanced reliability in treatment and laying of film; low expenses.

20 cl, 5 dwg

FIELD: chemistry of polymers, chemical technology.

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11 cl, 15 tbl, 81 ex

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4 cl, 5 ex

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2 tbl, 7 ex

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2 cl, 1 tbl, 7 ex

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19 cl, 1 tbl, 12 dwg, 1 ex

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Glue melt // 2112005
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EFFECT: optimized physicochemical characteristics.

3 cl, 4 tbl, 2 ex

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