Hot-melt pressure-sensitive adhesive (hmpsa) composition for detachable self-adhesive labels

FIELD: chemistry.

SUBSTANCE: invention relates to a hot-melt pressure-sensitive adhesive (HMPSA) composition used for self-adhesive labels. The HMPSA composition contains a styrene block-copolymer which is compatible with a tackifying resin, as well as one or more carboxylic acids whose hydrocarbon chain contains 6-54 carbon atoms. The softening temperature of the tackifying resin ranges from 80 to 150°C and its acid number is less than 20. A multilayer system, having a layer of the HMPSA composition, contains a printable base layer and an adjoining protective layer. The self-adhesive label is obtained by converting the multilayer system. An article coated with the self-adhesive label is a storage container, a container made from glass or plastic, preferably a glass bottle. The article with the label is recycled by removing the label by immersing the article in hot aqueous alkaline solution.

EFFECT: high efficiency of the hot-melt pressure-sensitive adhesive composition.

17 cl, 2 tbl

 

The object of the present invention is a hot melt adhesive by pressing the composition, suitable for attaching self-adhesive labels that can be removed during the recycling process of the products to which they were attached (such as packing containers and/or containers, e.g. glass bottles). This invention also relates to a multilayer structure comprising a layer consisting of the above composition, adhesive label, to the appropriate product with adhesive label and method of disposal of the above items, which includes a step of detaching the labels.

Most items packaging and/or containers with stickers after extracting their contents are subjected to cleaning processes (or disposal) or reuse, or after their destruction in order of reuse of their constituent substances. In the event of such processes to facilitate the recycling process often requires that the label is completely separated from the product to which it is attached, not leaving residues of adhesive composition on the surface of the above items.

Such recycling processes, such as the process, which is used for the purification of used glass bottles, such as beer bottles,usually include a stage dive products, which is to be cleaned in an aqueous alkaline compositions, the temperature of which is supported from 60 to 100°C. the Purpose of this stage is to detach the label attached to the product, and separating labels from him.

Adhesive pressing adhesives or PSA are substances that give covered their substrate adhesiveness at room temperature, that causes its immediate adhesion to the substrate during short-term exposure to low pressure. The PSA compositions are widely used for the manufacture of self-adhesive labels that are attached to the products in order to provide information (such as a bar code, description, cost) and/or for decorative purposes.

The PSA compositions usually applied using a continuous coating processes on the entire surface suitable for printing layer basics large size of paper or film of polymeric material consisting of one or more layers. The layer of adhesive composition, which covers suitable for printing layer-based (usually the opposite is suitable for printing hand side), itself covered with a protective layer (often referred to as "coating layer")comprising, for example, siliconized film. The obtained multilayered structure, usually Packed, collapsing in the form of large rolls Shi is different to 2 m and diameter up to 1 m, you can store and transport.

Such a multilayer structure may then be converted into self-adhesive labels, which the end user can use, using transformation methods, which cover the printing of desirable decorative items and/or information useful to the printing side of the layer structure with a subsequent cutting to the desired shape and size. The protective layer can be easily removed without conducting modification of the adhesive layer, which remains attached to suitable for printing layer-based. After separation from protecting layer label at a temperature close to room temperature, is applied to the product to which it is to be applied, either manually or on automated packaging lines using a damaging label of the device.

The use of PSA compositions due to their high adhesiveness at room temperature leads to the ability to quickly attach the label to the product on which it is to be applied (e.g., bottle), suitable for achieving a high speed of industrial production.

In the patent US 3763117 described the PSA composition based on acrylate with good adhesive properties, which allows for easy separation at elevated temperature using aqueous alkaline solution.

The patent is US 5385965 also described the composition of the PSA, application which provides after application to the paper or film of polymeric material, the possibility of obtaining labels, which can be disconnected from the product of the substrate when exposed to a hot alkaline solution. Such a PSA composition is an aqueous emulsion of a copolymer based on acrylate or styrene-butadiene copolymer. The solids content of this emulsion does not exceed 70%, so that the application of similar composition PSA layer-based complicated by the need for a stage of drying the emulsion. In addition, such adhesives have the disadvantage associated with partial transition in solution or in suspension in water of the compounds used in recycling bottles with stickers, thereby imposing restrictions on industrial installations used for processing these compounds before discharge into the environment.

In the patent US 4680333 considered hot-melt adhesive by pressing the adhesive composition comprising a block copolymer of styrene/isoprene/styrene, aliphatic resin having a low softening temperature, and the metal-containing salt of a fatty acid. The use of such a composition allows after you put it on a paper basis, and this basis was attached to the product substrate, to separate at any time in this way is attached to the base dry and when anatoy temperature without performing any other processing, giving, therefore, covered by this part of the basis of the ability to re at another location.

Hot-melt adhesives or hot melt (HM) are substances, which at room temperature are solid and do not contain any water or solvent. They are applied in molten form and utverjdayut upon cooling, forming, thus, the area of connection for attaching products-substrates that need to stick together. Some glue is designed to provide the basis on which they are applied, the relative hardness and lack of stickiness. Other glue is attached to the base of the product relative softness and high adhesiveness. The PSA compositions are widely used for the manufacture of self-adhesive labels; the corresponding adhesive compositions designated as a hot-melt adhesive by pressing adhesive compositions or HMPSA.

The HMPSA composition described in patent US 4680333, not attached covered her label capacity for a long time to join the product substrate, since the aforementioned label, you can disconnect at any time to dry.

In patent application US 2004/0220308 described hot-melt adhesive composition that includes a styrene block copolymer, a solvent containing acid functional groups, such as fatty acid, and acid increases the stickiness of the resin with the PCI-e slot number more than 100.

The purpose of the present invention is to provide adhesive composition, which gives the label the ability to permanently join the product, such as product packaging and/or container (e.g. glass bottles), and also provides fast and complete separation of the labels during the immersion of the product with an affixed adhesive label located at high temperature aqueous alkaline solution, and the adhesive composition essentially remains on the label after its branches.

During this work it was found that this objective can be fully or partially achieved by using hot-melt adhesive by pressing the adhesive composition constituting the essence of the present invention.

In this regard, this invention relates to a hot melt adhesive by pressing the adhesive composition (HMPSA), including:

and from 25 to 50% of one or more styrene block copolymers selected from the group comprising SIS, SIBS, SEBS and SEPS block copolymers, mixed optionally with SBS styrene block copolymer, the amount of which is less than 50 of the total mass of styrene block copolymers;

b) from 35 to 75% of one or more compatible enhancing the adhesion of resins having a softening temperature of from 80 to 150 º C and an acid number of less than 20; and

- in) from 0.5 to 20% of one or more carboxylic acids, the hydrocarbon chain of which contains from 6 to 54 carbon atoms.

Unless stated otherwise, the percentage used in this text to Express quantities, refer to fractions of weight/mass.

The composition of this invention achieves after application on the basis of oriented polypropylene (OPP) strong adhesion of the above framework to the glass-substrate, which corresponds to the ability to adhesion (measured by testing the peel on glass at an angle of 180°) mainly from 1 to 15 N/cm, preferably from 2 to 10 N/a see the Stickiness of the foundations of the glass product substrate is maintained over time, including at high relative humidity. However, attached in this way to the glass-substrate OPP-base easily and completely detached when immersed in an aqueous alkaline medium, without leaving any trace of adhesive composition on the above-mentioned product substrate.

In contrast to the known from the previous prior art PSA compositions based on acrylate composition according to this invention is a HMPSA composition, solid form at room temperature allows to apply it in the form of a coating, mainly in the molten state, suitable for printing layer-based labels without having to use the best stage of drying. Before applying the coating composition of the HMPSA according to this invention may, without any prejudice be kept in the molten state in the tank (also called a melting apparatus) at a high temperature, varying in the range up to 160°C over a period of time of several hours to 1 or 2 days.

In addition, when immersing the adhesive composition remains essentially attached to the ORR-based after it was disconnected from the glass-substrate. Thus, the adhesive composition is not soluble (or is not dispersed or dissolved (or dispersed) only in very small amounts in the aqueous compositions used in the processes of recycling, avoiding thereby used for cleaning additional processing in the washer tub.

Block copolymers that can be used in the composition of the HMPSA according to this invention generally have srednevekovoi molecular mass Mwfrom 60 kDa to 400 kDa and consist of blocks of different undergone polymerization of the monomers. They have the structure of triblock-copolymer with the General formula:

A-b-A (I)

where:

Is elastomeri styrene block (or polystyrene)

- B is an elastomeric block, which can be represented as:

- polyisoprene: then the block copolymer has the structure Polist the rol/polyisoprene/polystyrene, and it is called SIS;

- polyisoprene-polybutadiene: then the block copolymer has the structure of the polystyrene/polyisoprene/polybutadiene/polystyrene, and it is called SIBS;

- fully or partially-hydrogenated polyisoprene: then the block copolymer has the structure polystyrene/polyethylenepropylene/polystyrene, and it is called SEPS;

- polybutadiene: then the block copolymer has the structure of a polystyrene/polybutadiene/polystyrene, and it is called SBS; and

- fully or partially hydrogenated polybutadiene: then the block copolymer has the structure polystyrene/polyethylenimine/polystyrene, and it is called SEBS. Such SEBS copolymer can optionally be chemically modified using maleic anhydride.

Such styrene triblock copolymers can be obtained using known methods and are commercially available. In most cases, the methods of obtaining these commercial products also lead to the formation of different amounts of diblock copolymer compounds with the formula A-C. Thus, within the meaning of the present text, the terms SIS, SEBS, SEPS and SBS means, in essence, a mixture of triblock and diblock copolymers. The amount of diblock copolymers may change without any damage from 0 to 90% by weight of the total styrene copolymers. In addition to the linear structure represented by formula (I), sterelny the triblock copolymers, you can use the HMPSA composition of this invention may also have a star structure.

Obviously, styrene(s) block copolymer or block copolymers included in the HMPSA according to this invention, which is selected from the group consisting of SIS, SIBS, SEBS and SEPS block copolymers, may only belong to one or more of these four families of copolymers.

The styrene content of the block may itself vary in a wide range, such as from 15% to 50% (by weight of the total block copolymers).

As examples of commercial products we can mention the following products:

- linear SIS: Vector® 4411 with the content of the diblock copolymer of 0% and a styrene content of 44%, offered by the company, ExxonMobil, Kraton® D1113 (56% diblock copolymer and 16% styrene), from the company Kraton, and Kraton® D1165 (25% of the diblock copolymer and 30% styrene);

- star SIS: Kraton® D1124 (29% diblock copolymer and 30% styrene), and Vector® DPX 586 (80% of the diblock copolymer and 18% styrene), offered by the company ExxonMobil;

- SIBS: Kraton® MD 6455 (35% of the diblock copolymer and 18% styrene);

SBS: Europrene® Sol T 166 (10% of the diblock copolymer and 30% styrene), offered by the company Polimeri Europa (Italy), Stereon® 840A, from the firm Firestone, and Kraton® D1120 (75% of the diblock copolymer and 30% styrene); and

- SEBS: Kraton® G1726 (70% diblock copolymer and 30% styrene) and Kraton® G1924 (30% diplomaprimary and 13% styrene), represents a modified 1% maleic anhydride (SEBS.

According to a preferred variant of the HMPSA composition according to this invention, the content of the styrene block copolymer may be in the range from 35 to 50%, and more preferably from 40%to 45%.

According to another of the same degree preferred option styrene(s) block copolymer or a block copolymer contained in the composition of the HMPSA according to this invention, are selected from the group consisting of SIS, SEBS and SEPS block copolymers, taken individually or as a mixture. More preferably, if the HMPSA composition includes one or more SIS block copolymers.

Increase(s) the stickiness of the resin or resin, which is(s) can be used in the HMPSA composition of this invention has(have) srednevekovoi(s) molecular(s) weight(mass) Mwusually from 200 to 5000, and, in particular, chosen from among:

(i) natural or chemically modified rosin resins, such as a natural resin extracted from pine resin, and wood resin, extracted from the roots of trees, as well as their hydrogenated, demonizovana or polymerized derivatives or esterified with monobasic alcohols or polybasic alcohols, such as glycerin, pentaerythritol or neopentylglycol;

(ii) resins obtained is by hydrogenation, the polymerization or copolymerization of (aromatic hydrocarbon) mixtures of unsaturated aliphatic hydrocarbons with carbon atoms 5, 9, or 10, obtained from petroleum fractions;

(iii) terpene resins, usually obtained by polymerization of terpene hydrocarbons, such as monoterpene (or pinene), in the presence of catalysts of the Friedel-modified, if desired, by interaction with phenols; and

(iv) copolymers based on natural terpenes, e.g. styrene/terpene, α-methylsterol/terpene and vinylcolor/terpenes.

For inclusion in the HMPSA composition according to this invention is chosen increases the adhesiveness of the resin, which have a softening temperature of 80 to 150°C. and an acid number equal to zero or less than 20.

The temperature (or point) softening determined according to standardized test ASTM E 28, the principle of which is as follows. Brass ring with a diameter of approximately 2 cm is filled with resin, which must be tested, in the molten state. After cooling to room temperature, the ring and the solid resin is placed horizontally in thermally glycerin bath, the temperature change of 5°C per minute. A steel ball with a diameter of about 9.5 mm is placed in the center of the disk of the solid resin. The softening temperature is Soboh is such a temperature when in the course of a stage at which the bath temperature increase of 5°C per minute, a plastic deformation of the disk from the resin under the weight of the ball is 25.4 mm

Acid number (or AN) represents a content of free acid and is expressed as determined by the method potentiometry amount of potassium hydroxide in milligrams that is required to neutralize contained in 1 gram of the resin acids. Acid number of the resins belonging to the families of resins (ii) and (iv), is zero.

Increase the adhesiveness of the resin are commercially available and among them those that have a softening temperature of from 80 to 150 º C and an acid number equal to zero or less than 20, which can be mentioned in the above collections represent, for example, the following products:

(i) Sylvalite® RE 100S offered by the company Arizona Chemical (ester of rosin and pentaerythritol with a softening temperature of about 100ºC and is AN less than 10), Dertoline® G2L (softening temperature 87º and is AN 20) and Dertopoline® CG (softening temperature 117º and is AN 7), proposed by the French company DRT; and

(ii) Escorez® 5600 offered by the company, ExxonMobil Chemical, which is gidrirovannoe Dicyclopentadiene resin, a modified aromatic compound (with Mwabout 980 and a softening temperature of 100°C), Escorez® 5615 the same structure (the softening temperature of 115°C) and Escorez® 5400 (softening point 100°C.) from the company Exxon Chemicals, Wingtack® 86, from the company Cray Valley, and Regalite® R5100, from company Eastman;

(iii) Dertophene® T offered by the company DRT, (with a softening temperature of 95°C m an acid number less than 1) and Sylvarez® TP95 offered by the company Arizona Chemical, which is a terpene phenolic resin with a softening temperature of 95°C and Mwapproximately 1120 Yes; and

(iv) Sylvarez® ZT105LT offered by the company Arizona Chemical, which is a copolymer of styrene/terpene with a softening temperature of 105°C.

The term "compatible enhancing the adhesiveness resin" is understood as meaning increasing the stickiness of the resin, which when mixed with the block copolymer selected from the group comprising SIS, SIBS, SEBS and SEPS block copolymers in the ratio of 50%/50% forms an essentially homogeneous mixture.

Increase the adhesiveness of the resin with a softening temperature of from 95 to 120°C. and an acid number less than 10, such as Escorez® 5600 or 5615, Sylvarez® ZT 105 LT or Sylvalite® RE 100S, are preferred.

According to another preferred variant of this invention, the acid number increases the adhesiveness of the resin is approximately equal to zero.

Content increases the viscosity of the resin composition of the HMPSA according to this invention is preferably from 40 to 55%.

Carboxylic acid in the composition according to this invention have a hydrocarbon chain comprising from 6 to 54 carbon atoms. Such carboxylic acids which you can choose from among:

(α) saturated or unsaturated monobasic carboxylic fatty acids either in pure form or as mixtures;

(β) mixtures of saturated or unsaturated polybasic carboxylic fatty acids, dimeric or trimeric type; and

(γ) mixtures of saturated or unsaturated polycyclic monobasic carboxylic acids.

Monobasic carboxylic fatty acids (α), as a rule, possess a linear or optionally branched chain hydrocarbon radical. In the case of use of pure acids, preferred are those hydrocarbon radicals which contain from 10 to 20 carbon atoms.

The use of mixtures of monobasic carboxylic fatty acids (α) is the predominant, because these compounds are derived from animal or vegetable fats and they are called "factions". Similar fractions enriched acids, hydrocarbon radicals which contain from 6 to 22 carbon atoms. Non-limiting examples of such fractions, which can be mentioned include:

- oleic fatty acids, such as RADIACID® 208, offered by the company Oleon;

fatty acids from sunflower fatty acids of copra (RADIACID® 600), fatty acids from canola seeds (RADIACID® 166), fatty acids from soy (RADIACID® 110 and RADIACID® 121), fatty acids from palm trees and fatty acids from coconut kernels of nuts or derivatives of tall oil;

- tall is the first fatty acid, such as RADIACID® 401 and RADIACID® 403; and

- hydrogenated tallow fatty acids, such as RADIACID® 408 and RADIACID® 409.

A mixture of (β) polybasic carboxylic fatty acids obtained by dimerization of fractions of unsaturated monobasic carboxylic fatty acids, hydrocarbon radicals which contain predominantly from 16 to 18 carbon atoms. The products are essentially dimers (such as RADIACID® 951 and RADIACID® 970) or a mixture of dimers and trimers (such as RADIACID® 980).

A mixture of polycyclic monobasic carboxylic acids (γ) is preferably produced from scraps of vegetable origin, enriched with compounds containing from 18 to 22 carbon atoms and 3 connected ring, each of which contains 6 carbon atoms. Examples of such compounds are abietic, levopimaric, neoabietic, dehydroabietyl, Polustrovo and pimaric acid. Usually a mixture of (γ) are commercially available in the form of:

- gum rosin, entregaremos from pine oleoresin, or

- resins, tall oil, extracted from black liquor, which are by-products of the paper industry.

As examples of such products we can mention the following products: FORAL® AX, offered by the company Hercules, which is gidrirovannoe resin metal is oil, Staybelite® E from company Eastman, which is a partially gidrirovannoe gum rosin, and Sylvatal® 20/25, from the company Arizona Chemical, which is a tall oil resin.

Products (α), (β) and (γ) have an acid number (AN) (as defined above) from 130 to 280 mg KOH/g iodine number (IN) from 0 to 140. Iodine number corresponds to the number of double bonds in the hydrocarbon radicals and represents the number of grams of iodine that connects with 100 grams of fatty acids.

Thus, in the case RADIACID® 208 is AN is in the range from 184 to 196, and the value is IN between 75 and 94. If RADIACID® 970 is AN is in the range from 188 to 198, and the value of IN is less than 94. If RADIACID® 980 is AN 180 and the value of IN is less than 94. If RADIACID® 403 is AN is in the range from 192 to 198, and the value IN ranges from 42 to 51. If RADIACID® 600 is AN is in the range from 250 to 264, and the value of IN is from 6 to 9. If FORAL® AX is AN is in the range from 130 to 160, and the value IN approximately 0. In the case of Staybelite® E is AN approximately 162. If Sylvatal® 20/25 is AN equal 188, and is IN approximately 0.

Preferably, the content of carboxylic acid in the composition of the HMPSA according to this invention ranged from 3 to 15%.

Carboxylic acids of type (α) and (β) ensure in the osobennosti favorable results, moreover, the products of type (β) are more preferred due to the increased adhesiveness of the HMPSA composition.

In addition, it is preferable that the composition of this invention was administered in an amount of from 0.1 to 2% of one or more stabilizers or antioxidants). Such compounds added to prevent degradation of the structure due to interaction with oxygen, which can be formed under the influence of heat, light or residual quantities of catalysts on some raw materials such as increasing the adhesiveness of the resin. Such compounds may include primary antioxidants that capture free radicals and, as a rule, represent a substituted phenols such as Irganox® 1010, from the company Ciba-Geigy. Primary antioxidants can be used alone or in combination with other antioxidants, such as phosphites such Irgafos® 168, also offered by the company Ciba-Geigy, or with UV-stabilizers, such as amines.

In addition, the composition of this invention can contain up to 20% plasticizer. Such a plasticizer may be a paraffinic or naphthenic oil, which may contain a fraction of aromatic compounds (such as Primol® 352 offered by the company Esso) or does not contain such a fraction (such as Nyflex 222B, from the company Nynas).

The composition in this image is the shadow may also include a polyethylene wax homopolymer (such as a-C® 617, from Honeywell) or waxy copolymer of polyethylene/vinyl acetate, or pigments, dyes or fillers.

Hot-melt adhesive composition according to this invention are made by simple mixing of its components at a temperature of from 130 to 200°C. to obtain a homogeneous compound. The required conditions of mixing are well known skilled in the art specialists.

The aim of the present invention is a multilayer system, including:

- adhesive layer consisting of a hot melt adhesive, pressing the composition according to this invention;

- suitable for printing layer-the base adjacent to the above-mentioned adhesive layer consisting of paper or a polymeric film having one or more layers; and

- protective layer adjacent to the above-mentioned adhesive layer.

As suitable for printing layer basis is preferable to use a two-layer film, OPP/PET, OPP layer which is adjacent to the adhesive layer.

To obtain the adhesive layer, the composition of the HMPSA according to this invention in the molten state at a temperature exceeding 130°C., is applied usually in an amount of from 15 to 30 g/m2suitable for printing layer basis. Application carried out by known methods of coating, such as coating covered with what I'm using nozzles with a nozzle (at a temperature of from about 160 to 180°C) or curtain coating (at a temperature of from about 120 to 180°C). The HMPSA composition typically is applied on the protective layer by using a nozzle with a spout, and then click system laminate with a layer-based (translated floor). The application of the HMPSA composition method of coating operations can be performed directly on a layer basis, depending on the temperature of the coating.

A multilayer system are in the form of a rectangle, with a very long and usually Packed, collapsing in the form of a large roll width up to 2 m and a diameter of up to 1 m

This invention also relates to self-adhesive label that can be obtained by converting the above-described multilayer system. Apply the conversion process typically includes:

- the stage of printing, for printing suitable for printing layer basis; then

- the stage of cutting, for cutting the multilayer system to reduce its width and as a consequence repackaging it on a roll of less width; and then

- stage (called "the work of improving") to obtain a multilayer system, Packed on the roll of the preceding stage, in which an unmodified protective layer attached only to the portion suitable for printing layer, which corresponds to the shape and sizes of self-adhesive labels, suitable for its end use. Therefore this stage is to select the main circumcision, followed by removal of unwanted portions of the layer-substrate and the adhesive layer, moreover, the above part is often called the "skeleton label.

The last-mentioned multilayer systems used on packing lines of products that you need to apply labels with the help of automated systems, separating self-adhesive labels from the protective layer and fixing them on the products that you want to apply labels.

The purpose of this invention is the product that caused the self-adhesive label, as described above.

Preferably, the product with the pasted label represented the product packaging or container made of glass or ordinary representing a plastic material selected from among PET (polyethylene terephthalate), PVC (polyvinyl chloride), PE (polyethylene) and PP (polypropylene). Particularly preferred is a glass bottle. The surface of glass bottles, referred to in the course of their manufacture can be processed, putting them on the cover in order to maintain their mechanical properties over time and prevent them from scratching or may not be subjected to such treatment. Such processing results, for example, applying a layer of metal oxide on the glass surface, and above the layer of metal oxide can, if desired, to apply an extra layer vosloorus the character.

Finally, this invention relates to a method of disposing of this product with pasted label, which includes a step of detaching the labels when diving products with pasted label in aqueous alkaline solution, the temperature of which is supported in the range from 60 to 100°C., characterized in that the product with the pasted label is one that is defined above.

Removing labels this process mainly leads to its complete separation from the products without any residues of adhesive composition on the surface of the above items and without contamination of the aqueous alkaline cleaning solution of the adhesive composition. In the context of the industrial implementation of this process the result is that the contamination of the used wash water is becoming less and disposal process is more economical, in particular, from the point of view of the quantity of water consumed. Labels separated in this way from the processed products can be collected and removed from the wash bath, using suitable mechanical means.

Preferably, the process according to this invention is conducted at a temperature of about 80°C.

The adhesive ability of the HMPSA composition according to this invention is determined by testing on peeling angle of 180° on a glass plate, as described in the test method FINT Test Method No. 1, which is published in the instructions FINAT Technical Manual, 6thedition, 2001. Organization FINAT is an international Federation of producers and processors of self-adhesive labels (International Federation for Self-adhesive Label Manufacturers and Converters). The principle of this test consists in the following. ORR-side layer consisting of PET film thickness of 19 μm, laminated with OPP film thickness of 50 μm using a two-component polyurethane adhesive composition, pre-coated with HMPSA composition in an amount of 20 g/m2. The sample in the form of rectangular strips (25 mm × 175 mm) cut from the thus obtained self-adhesive base. A similar pattern is attached to the substrate, which is a glass plate. The resulting structure is left for 20 minutes at room temperature, and then placed in a tensile machine, it is capable to remove or detach the strip at an angle of 180° and with a separation velocity of 300 mm / minute. The machine measures the force required to detach the strips under such conditions. The results are expressed in N/a see the Force required for peeling off the glass plate at an angle of 180° for the manufacture of self-adhesive labels adhesive compositions, typically greater than 2 N/cm, preferably, when it exceeds 4 N/a see

The stickiness of the composition of the HMPSA according to this invention is determined by the t using tests for adhesion at the bend in the loop, described in the test method FINAT Test Method No. 9. ORR-film thickness of 50 μm pre-coated with HMPSA composition in an amount of 20 g/m2to obtain a rectangular strips with dimensions of 25 mm × 175 mm Two ends of such strips connect together with the formation of loops, the adhesive layer which face outward. Two connected end is placed in able to move the clip breaking machine, able to create a shear rate of 300 mm/min along the vertical axis with the possibility of movement forward and backward. The lower part of the vertical loop is first brought into contact with a horizontal glass plate with dimensions of 25 mm by 30 mm square represents a square with a width of about 25 mm as soon As such contact occurs, the direction of offset of the clip is changed to the opposite. Adhesion represents the maximum amount of force required to fully detach the loop from the plate. Typically, the stickiness PSA is equal to 1 N/cm2or exceeds this value.

The ability pre-attached to the glass substrate of the label is covered by the HMPSA composition according to this invention, to detach in a hot aqueous alkaline medium is determined using the following test.

Use glass bottles with a diameter of 5 cm and a height of 20 cm, and RA is really into two groups depending on the nature of the constituent glass. This is done because the surface layer of the glass depending on the surface treatment coating during the manufacture of bottles can be of two types. Layer 1-th type, consists essentially of tin oxide. Layer 2nd type, essentially contains an emulsion of oxidized polyethylene wax deposited on the layer of tin oxide. Layer 2nd type is characteristic of new glass bottles. Layer 1 is characteristic for glass bottles, which were immersed in an aqueous alkaline solution, at least during one cleaning cycle. The 1st group of bottles marked here and later in this document using the abbreviation "SnO", and the 2nd is by using the abbreviation "RE".

On the same layer-based put the HMPSA composition, which must be tested, and the conditions of application of the composition are the same as the conditions of application of the composition for testing on peeling angle of 180°. From the self-adhesive base, obtained in this way, cut a rectangular label (7 cm × 5 cm) and with a simple press attach it to a glass bottle, and the system is left for 24 hours at room temperature.

Then a glass bottle with an affixed adhesive label immersed in a thermostatted at 80°C water bath with a pH of 12.

After immersing the bottle in 60 seconds the proportion of detached labels (here and further in this document is e called "share detach") for bottles of the type "SnO" and type "D" is determined visually.

The amount of the adhesive composition, is present in the aqueous alkaline solution after immersion of the bottle with adhesive label and branch labels, determined as described below. In previous tests determine the mass of P1 self-adhesive labels to its attachment to the glass bottle. After the dive bottles and labels for 20 minutes in an aqueous alkaline solution of a label, which is then disconnected from the bottle, remove the back and dried to constant weight P2. The mass difference P1-P2, expressed as a percentage with respect to P1, corresponds to the loss of the HMPSA composition self adhesive label.

The following examples are presented solely to illustrate the present invention, but should not be construed as limiting its scope.

The compositions listed in table 1 below were obtained by simple blending hot ingredients at a temperature of 180°C. in Addition to these ingredients, the above compositions also contained 0.5% of Irganox® 1010 and 0.5% Irgafos® 168. The content of the other ingredients listed in table 1.

The results of the tests are shown in table 2.

In all these examples during testing disconnecting in a hot aqueous alkaline medium after separation of the labels on the surface of the bottles were not observed traces of the adhesive composition. Loss of HMPSA composition of the label is left 0 %, pointing out that in all these examples, the aqueous alkaline solution wash did not contain HMPSA composition.

Table 1
Content %
Ingredient
Example 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8Example 9Example 10Example 11
Kraton® D11244040-3125404040---
Kraton® D1165------ ---4040
Vector® 4411--30--------
Vector® DPX 586--15-----44--
Kraton® G1726---12-------
Europrene® Sol T 166--- -15------
Sylvarez® ZT 105 LT22242124232022182122-
Escorez® 56002023232124------
Escorez® 5400----------22
Escorez® 5615-----202019202020
Sylvalite® RE 100S5----5--455
Radiacid® 9704-10-4--4---
Radiacid® 980-4------ ---
Radiacid® 600-----64----
Radiacid® 208---3-------
Sylvatal® 20/25--------444
Foral® AX----- -510---
Primol® 35288-38888688
A-C® 617---5-------

Table 2
Results
TestExample 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8 Example 9Example 10Example 11
Peel on glass at an angle of 180° (N/cm)68352223452
The stickiness of the loop (N/cm2)51424113432
PE % detach10090908010080908080100100
SnO % detach100 10080100100100100100100100100

1. Hot-melt adhesive by pressing the adhesive (HMPSA) composition used for self-adhesive labels, including:
and from 25 to 50% of one or more styrene block copolymers selected from the group including polystyrene/polyisoprene/polystyrene (SIS), polystyrene/polyisoprene/polybutadiene/polystyrene (SIBS), polystyrene/polyethylenimine/polystyrene (SEBS) and polystyrene/polyethylenepropylene/polystyrene (SEPS) block copolymers, optionally, mixed with polystyrene/polybutadiene/polystyrene (SBS) block copolymer in an amount of less than 50% by weight of the total styrene block copolymers;
b) from 35 to 75% of one or more compatible enhancing the adhesiveness of the resin with a softening temperature of 80 to 150°C. and an acid number of less than 20; and
- in) from 3.0 to 15% of one or more carboxylic acids, the hydrocarbon chain of which contains from 6 to 54 carbon atoms.

2. The HMPSA composition according to claim 1, characterized in that the content of the styrene block copolymer may be in the range from 35 to 50%, and preferably ranges from 40 to 45%.

3. The HMPSA composition on l is the Boma one of claims 1 and 2, characterized in that the styrene(s) block copolymer or a block copolymer selected from the group including SIS, SEBS and SEPS block copolymers.

4. The HMPSA composition according to claim 1, characterized in that the styrene(s) block copolymer or block copolymers represent a SIS block copolymers.

5. The HMPSA composition according to claim 1, characterized in that increases the stickiness of the resin is chosen from among:
(i) natural or chemically modified rosin resins and their hydrogenated, dehydrogenated, demonizovana or polymerized derivatives or esterified with monobasic alcohols or polyols;
(ii) resins obtained by hydrogenation, polymerization or copolymerization of mixtures of unsaturated aliphatic hydrocarbons containing approximately 5, 9 or 10 carbon atoms, obtained from petroleum fractions;
(iii) terpene resins, optionally modified by the interaction with phenols; and
(iv) copolymers based on natural terpenes.

6. The HMPSA composition according to claim 1, characterized in that the increase(s) the stickiness of the resin or resins have a softening temperature of from 95 to 120°C. and an acid number less than 10.

7. The HMPSA composition according to claim 1, characterized in that the acid number increases the adhesiveness of the resin, essentially, zero.

8. The HMPSA composition according to claim 1, characterized in that the content increases the adhesiveness of the resin is from 40 to 55%.

9. The HMPSA composition according to claim 1 characterized in, what fatty acids are chosen from the ranks;
(α) saturated or unsaturated monobasic carboxylic fatty acids either in pure form or as mixtures;
(β) mixtures of saturated or unsaturated polybasic carboxylic fatty acids, dimeric or trimeric type; and
(γ) mixtures of saturated or unsaturated polycyclic monobasic carboxylic acids.

10. The HMPSA composition according to claim 1, characterized in that the use of a mixture of monobasic carboxylic fatty acids (α) in the form of fractions obtained from animal or vegetable fats.

11. The HMPSA composition according to claim 1, characterized in that it additionally contains from 0.1 to 2% of one or more stabilizers, and up to 20% plasticizer.

12. Multilayer system for producing self-adhesive labels, which includes:
- adhesive layer consisting of a hot melt adhesive, pressing the composition as defined in any one of claims 1 to 11;
suitable for printing layer-the base adjacent to the above-mentioned adhesive layer consisting of paper or polymer film, with one or more layers; and
- protective layer adjacent to the above-mentioned adhesive layer.

13. The multilayer system according to item 12, wherein suitable for printing layer-the base is a two-layer OPP/PET film, OPP layer which is adjacent to the adhesive layer.

14. Camogliese the Xia label, you can get conversion multilayer system as defined in any of PP and 13.

15. The product covered with a self-adhesive label as defined in 14.

16. The product according to clause 15, which consists of product packaging or container made of glass or plastic, preferably glass bottle.

17. The way of disposing of this product with an affixed adhesive label comprising a stage of detaching the labels when diving products with pasted label in aqueous alkaline solution, the temperature of which is supported from 60 to 100°C., characterized in that the product with the pasted label is such as defined in any of PP and 16.



 

Same patents:

FIELD: packaging industry.

SUBSTANCE: film for the manufacture of a fused label contains the core layer and the hot-melt layer. The core layer has a first and a second surface, and the hot-melt layer has an inner surface and outer surface. The inner surface of the hot-melt layer is located above the first surface of the core layer. The hot-melt layer contains a very low-density polyethylene, high density polyethylene and alkene copolymer selected from the group containing a copolymer of alkene and vynilcarboxylate, a copolymer of alkene and a methacrylic acid, alkene copolymer and alkyl methacrylate, a copolymer based on the alkali metal salts or zinc of methacrylic acid and an alkene, and the mixture of at least two of the above alkene copolymers.

EFFECT: manufacture of film for improvement of methods to label products using fused labels, improving the quality of labeled products and improving the technological properties of the film for fused labels.

20 cl, 1 tbl, 2 dwg

Strapping tape // 2319651

FIELD: packing means, particularly strapping tape, namely combination of mechanical lock made as strapping tape with product code.

SUBSTANCE: strapping tape has the first face and the second face. The first strapping tape face is made of thermoplastic material shaped as strips with hooks having the first and the second sides. Hook-shaped extensions are made on the first strip side. The extensions at least partly define the first strapping tape side. The second strap side is made as film provided with UPC code printed thereon. The UPC code may be read through the first face of the strip.

EFFECT: increased usage convenience and simplified production.

17 cl, 11 dwg, 2 ex, 2 tbl

The invention relates to the statement and the payment of fines imposed by the police to monitor Parking in unauthorized locations or in breach of the rules of the road, and, in particular, to an automated system for the imposition and collection of fines

The invention relates to the products of the printing industry, namely the media and/or image, in which the components of the combined image removable items are attached to the surface of the substrate using an electrostatic field, and can be used in various fields related to the production of colorful printed products

FIELD: process engineering.

SUBSTANCE: set of inventions relates to metal cutting. Proposed method comprises gluing protective film 4, 9 with preset elongation at fracture on, at least, one surface 2 to be machined at preset adhesion force. Locating cutting tool 3 at preset position relative to said surface 2. Applying preset mechanical force to said tool 3 for preset time interval for cutting said workpiece 1. Lifting said tool 3 from said, at least, one machined surface 2 after said preset time interval. Protective film 9 features elongation of 80-120% while force of adhesion between said film 9 and machined surface 2 makes, in fact, 10 N/25 mm.

EFFECT: better protection.

11 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: self-adhesive tape has an adhesive layer protected on two sides by anti-adhesion paper. The adhesive layer is made from an adhesive composition containing perchlorovinyl resin, tricresyl phosphate plasticiser, pine rosin, baking soda and an acrylic elastomer and ethyl acetate. The acrylic elastomer is a carboxyl-containing copolymer of butyl acrylate and methacrylic acid.

EFFECT: self-adhesive tape is flame-proof, has high initial adhesion which is well retained for a long period of time, and high resistance to peeling and shearing.

1 tbl

FIELD: chemistry.

SUBSTANCE: composition contains perchlorovinyl chlorinated resin, pine rosin, tricresyl phosphate plasticiser, baking soda, ethyl acetate solvent and a solution of a butyl acrylate and methacrylic acid copolymer in ethyl acetate.

EFFECT: self-adhesive tape with an adhesive layer based on said composition is flame-proof, has high initial adhesion of the adhesive layer and high strength characteristics with respect to glass fibre.

1 tbl

FIELD: chemistry.

SUBSTANCE: acrylate dispersion adhesive contains at least one UV absorber selected from a group consisting of benzoate and benzoate derivatives, cinnamate and cinnamate derivatives, benzophenone and camphor derivatives. The laminate for transparent tags contains a film substrate or a paper substrate, a radiation-cured anti-adhesion separating coating, an adhesive layer and a transparent printed material. The separating coating contains epoxy siloxanes cured via a cationic mechanism or silicone acrylates cured via a radical mechanism. To obtain the laminate, the separating coating is applied on the film substrate or paper substrate. The adhesive layer is then deposited on the separating film or separating paper and cured if necessary. The transparent printed material is laminated onto the deposited adhesive layer.

EFFECT: invention reduces undesirable increase in peeling off when making transparent tags.

7 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: resin contains a main component and a modifier. The main component contains at least one colophony-based resinous substance, having circular and spherical softening temperature of about 85-125°C. The modifier contains at least one colophony-based resinous substance having low softening temperature. The resin is characterised by circular and spherical softening temperature, with mean softening temperature of about 35-60°C. The resin is part of the composition of the pressure-sensitive hot-melt adhesive, which has a first component which is at least one styrene-butadiene block-copolymer and a second component which is at least one styrene-isoprene-styrene block-copolymer or a mixture of styrene-isoprene-styrene and styrene-isoprene block-copolymers. The pressure-sensitive hot-melt adhesive composition is used for an adhesive article having a front surface made from paper and cardboard materials and materials made from polymer films.

EFFECT: pressure-sensitive hot-melt adhesive composition has good tackiness, high cohesion strength and good rheological properties.

10 cl

FIELD: process engineering.

SUBSTANCE: proposed invention relates to method of fabricating laminar material for labels. Proposed method comprises producing transparent polymer film 2a with first and second surfaces. Printing is made on second surface of said transparent polymer film. Method includes introducing substrate 6 including separation surface 6a and sole layer of dry adhesive 2c on said separation surface. Then, dry adhesive surface is activated to make it sticky. Thereafter, sticky adhesive on separation surface is attached to second surface of transparent polymer film.

EFFECT: simplified procedure, excluding one layer of transparent film and one layer of laminating adhesive.

5 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an adhesive film for road surface. The adhesive film contains a carrier substrate which is a polymer film, a surface layer on the substrate surface made from a polymer film and a layer of pressure-sensitive hot-melt adhesive. The polymer film is based on polyvinyl chloride, polyamide, acrylic resins, high-density polyethylene, polypropylene and polyethylene vinyl acetate. The surface layer contains resinous non-asphalt material or material which contains about 50% or more resinous non-asphalt component and about 50% or less asphalt component. The surface layer can form a bond with the adjoining layer of asphalt road material when the surface layer is heated to about 120°C or higher at pressure which is applied to the material of the adhesive film on the side of superimposed layer of asphalt road material. The layer of asphalt road material has thickness of about 3.8 cm or more. The surface layer is not adhesive at temperature of about 20°C and pressure of about 1 atm. The adhesive film for road surface can be used particularly for repairing old road surfaces without tack coat.

EFFECT: improved technical properties of the adhesive film for road surface.

2 tbl, 3 ex, 15 dwg

FIELD: chemistry.

SUBSTANCE: self-adhesive material has a base - aluminium foil and an adhesive composition applied on said base, having permanent stickiness, containing the following in pts.wt: isoprene-styrene thermoplastic elastomer with 5-7% styrene content 100, an adhesive agent - terpene phenol resin, terpene styrene resin or mixture thereof with perchlorovinyl resin 10-15, plasticiser - epoxidated vegetable oil 7-10 and an organic solvent - ethyl acetate or mixture thereof with benzine and methylene chloride 250-550. The adhesive composition can additionally contain chlorinated polyisoprene rubber in amount of 2-5 pts.wt. The ratio of the thickness of layers the base: adhesive composition is equal to 1:(0.25-1). The self-adhesive material is meant for repair and use at temperatures ranging from -60 to +80°C in aviation, in motorcar and shipbuilding and other engineering fields.

EFFECT: high adhesion strength, cohesive strength of the self-adhesive material, high resistance to static shearing at high temperatures, low labour input and power consumption when carrying out repair works on the surface of aircraft frames and other structures.

3 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing a coated adhesive layer with improved optical characteristics, in which a curable composition containing curable organopolysiloxane is applied onto the surface of a substrate, and improved optical purity is achieved owing to that the composition contains a group of silicon dioxide particles having average size ranging from approximately 1 to approximately 7 micrometres. The invention also discloses a method of producing a multilayer article with improved inter-layer adhesion characteristics owing to reduction of the air space between layers, where the adhesive layer is obtained using the disclosed method, and the corresponding multilayer article.

EFFECT: higher optical purity of the coating adhesive layer and adhesion between layers in multilayer articles owing to virtually no air trapping when applying the adhesive layer.

20 cl, 6 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention discloses versions of water resistant, pressure sensitive adhesive acrylic polymers having volume-average particle size of at least 250 nm, formed during polymerisation in the presence of a surfactant in an emulsion of a mixture of monomers. Disclosed also are versions of labels having a frontal base and a pressure sensitive adhesive, which is one of the versions of the disclosed water resistant acrylic polymers.

EFFECT: disclosed polymers enable to obtain pressure sensitive acrylic based adhesives, which during coating and drying in form of a film become transparent and resistance to whitening when exposed to water.

44 cl, 1 dwg, 2 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: hot-melt pressure-sensitive adhesive composition contains a solid rubber component, a liquid rubber component and an agent which increases adhesive capacity, with the following content in mass units: solid rubber component 100, liquid rubber component 5-24, agent which increases adhesive capacity 100-170, wherein the solid rubber component contains a first polymer selected from a group comprising styrene-butadiene-styrene copolymer, styrene-butadiene copolymer or mixture thereof, and a second polymer selected from a group comprising styrene-isoprene-styrene copolymer, styrene-isoprene copolymer or mixture thereof, with mass ratio of the first polymer to the second polymer ranging from about 0.3:1 to about 1:1. The composition additionally contains plasticising oil. Also disclosed is an adhesive article having a front layer and a layer containing the hot-melt pressure-sensitive adhesive composition.

EFFECT: disclosed pressure-sensitive adhesives can be used to make reeled sticky tape or sticker and can also be used as part of label paste or front surface.

11 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: adhesive composition contains a combination of butadiene-styrene thermoplastic elastomers with a linear or radial structure, glycerine rosin ester, petroleum resin, dibutylphthalate, quinol ether and an organic solvent.

EFFECT: composition increases adhesion strength of different flexible substrates, for example rubber, leather, textile materials, artificial leather and other materials.

3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: resin contains a main component and a modifier. The main component contains at least one colophony-based resinous substance, having circular and spherical softening temperature of about 85-125°C. The modifier contains at least one colophony-based resinous substance having low softening temperature. The resin is characterised by circular and spherical softening temperature, with mean softening temperature of about 35-60°C. The resin is part of the composition of the pressure-sensitive hot-melt adhesive, which has a first component which is at least one styrene-butadiene block-copolymer and a second component which is at least one styrene-isoprene-styrene block-copolymer or a mixture of styrene-isoprene-styrene and styrene-isoprene block-copolymers. The pressure-sensitive hot-melt adhesive composition is used for an adhesive article having a front surface made from paper and cardboard materials and materials made from polymer films.

EFFECT: pressure-sensitive hot-melt adhesive composition has good tackiness, high cohesion strength and good rheological properties.

10 cl

FIELD: chemistry.

SUBSTANCE: protective film includes a substrate layer and a pressure-sensitive adhesive composition. The substrate layer is preferably an extrudable substrate layer. The adhesive composition contains a block-copolymer, tackifying resin and, optionally, polyolefin, plasticiser and antioxidant. The block-copolymer contains at least two poly- or mono-vinylaromatic hydrocarbon blocks and at least one hydrogenated block of poly- or conjugated diene. The adhesive composition is obtained through dry mixture of components. The dry mixture is extruded and granulated in an underwater granulator to obtain wet granules. The wet granules are dried. The wet or dry granules can be treated with a powdering agent.

EFFECT: adhesive composition combines high adhesion during peeling and high melt flow rate.

13 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a composition of a hot melt pressure-sensitive adhesive (HMSPA), a laminated system and a pressure sensitive label containing said adhesive. The HMSPA composition contains: a) 30-50% mixture of styrene diblock- and triblock-copolymers, total content of the styrene monomer in the said mixture between 14 and 40%; b) 40-55% tackifying resin with melting point between 70 and 150°C, obtained through hydrogenation, polymerisation or copolymerisation of mixtures of aliphatic unsaturated hydrocarbons containing approximately 5, 9 or 10 carbon atoms; c) 4-20% hydrocarbon coil containing less than 15% aromatic compounds; d) 1-6% filler selected from calcium carbonate or a homopolymer or a copolymer polyethylene with low molecular weight. The laminated system includes an adhesive layer consisting of HMPSA and a paper front material. The pressure sensitive label is made from the laminated system.

EFFECT: HMPSA composition provides low susceptibility to decolouration during storage of articles.

15 cl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions of hot-melt adhesive for non-woven materials and block-copolymers used therein. The invention discloses a hot-melt adhesive composition for use in non-woven articles, containing: (a) 100 pts. wt block-copolymer of formula [S-(I/B)]n-X, where S is mainly a polystyrene block, and (I/B) is a polymer block obtained through arbitrary copolymerisation of a mixture of mainly isoprene and butadiene in weight ratio between 70:30 and 30:70, n is an integer between 3 and 5, and X is a residue to an alkoxy silane binding agent, where the block-copolymer has melt flow index measured at 200°C/5 kg between 0.1 and 12 g/10 min, content of polystyrene between 28 and 50 wt %, binding efficiency between 50 and 100%, (b) 250-300 pts. wt resin which increases adhesiveness, (c) 50-150 pts. wt plasticiser and (d) 0-3 pts. wt stabiliser and/or antioxidant. The invention also discloses a block-copolymer for preparing said composition.

EFFECT: composition has high cohesion and higher spraying capacity, which improves the technology of manufacturing non-woven articles.

18 cl, 5 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to process engineering. Proposed tape is made from flexible self-adhesive bearing inner layer that features thermoplastic properties and is furnished with two-side coat. The latter is made from foamed adhesive tape with foam-like structure built on water dispersion of adhesive material (pure dispersion acrylate, adhesive material based on isobutyl vinyl ether or isobutene) with a filler representing minor thermoplastic gaseous-hydrocarbon-filled hollow spheres made from plastic that expand at temperature varying from 70°C to 140°C.

EFFECT: higher reliability of sealing, elasticity preserving, deformations compensation fast adhesion, and no harm to environments.

11 cl

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