Hot melt pressure-sensitive adhesives for paper labels

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

 

The present invention relates to the composition of hot-melt pressure-sensitive adhesive (HMPSA), laminated to a system comprising an adhesive layer consisting of the specified HMPSA, and paper face material, and permanent self-adhesive labels obtained from the specified laminated system.

Pressure-sensitive adhesives (PSA) are adhesives that coating the surface of paper or film, make it permanently sticky at room temperature and give the specified surface is the ability to stick to the substrate under the action of light and momentary pressure. PSA are widely used in industrial production of labels, including labels based paper, which are secured on the products in order to provide information (such as a bar code, name, price) and/or simply for decorative purposes.

PSA is usually applied by a continuous coating process on a large surface of the material substrate (also called outer material), which consists of paper or plastic film. An adhesive layer which covers the substrate layer, protects anti-adhesive material, for example, consisting of paper coated with organosilicon compounds. The resulting laminated system usually produce thus the om, so it was wound on itself in the form of large rolls up to 2 m in width and 1 m in diameter, intended for storage and transport.

This system can later be turned into commercially used labels after further manufacturing operations, which include printing and cutting. These labels are usually referred to as pressure-sensitive or self-adhesive labels, or PSA labels. After removal of the antiadhesive material of the label can be affixed to a substrate, such as a product that must have a label, usually through automatic labeling equipment, for example, packaging of industrial sites for end users. PSA due to its high adhesiveness make possible the production of self-adhesive labels, which in a very short time are fixed on the substrates, thereby providing a high performance.

Hot-melt adhesives (HM) are insoluble and water-free adhesive, which is in a solid state at room temperature. They are applied in the molten state and harden when cooled, forming a bond that secures the two substrates assembled. Some HM prepare so that they gave the corresponding Pokrywa is the PTO substrate relative rigidity and the lack of adhesive properties. Other HM give the coated substrates relative flexibility and high adhesion: any HM represent the PSA, which find wide application in the production of PSA labels. Such adhesives indicate the name of the hot-melt pressure-sensitive adhesive (or HMPSA).

Some of these HMPSA designed for labels (in particular, paper labels) with a high bonding strength, which can be permanently fixed on designated products. After removal of anti-adhesive material and fixing on the substrate, these labels are resistant to any attempts to remove them. Such HMPSA is also designated as permanent HMPSA, unlike removed HMPSA, which are designed for the production of labels, which after fixing to the substrate must have the ability to remove them from the substrate after the time of retention and re-attach to it.

HMPSA usually include a thermoplastic polymer (in particular, elastomeric block copolymers) in combination with increasing the stickiness of resins and plasticizers.

When such HMPSA deposited on the substrate surface (or face cloth), made of paper for the production of labels, there often arises a problem in that the color of the surface of the paper face of the material opposite to the coated surface, varies with the course the eating time especially when stored at temperatures above room temperature. This discoloration may appear as spots or loss of whiteness. Although it is believed that this is a violation of the painting may be associated with some kind of migration is presented in HMPSA compounds with low molecular weight that is similar to some increase adhesion substances, it is highly undesirable from an aesthetic point of view.

Known overcoming this shortcoming by pre-treatment of the paper layer before applying the HMPSA, aimed at creating an intermediate oil barrier. However, this complicates processing General manufacturing process of the laminated system.

Patent document US 6214935 describes the HMPSA composition, characterized by a lower susceptibility to discoloration and floor spots. These HMPSA based on elastomeric components, such styrene block copolymers, and increases the stickiness of the resin with a softening temperature in the range from about 35 to about 65°C.

Patent document WO 99/20708 refers to HMPSA based block copolymer having a high content of diblock copolymer, which demonstrates minimal staining of the paper. However, this HMPSA belongs to the class removed HMPSA, whose adhesive abilities are insufficient for development of permanent PSA labels.

The objective of this is about of the invention is to create a HMPSA, which after application to the paper exhibits a reduced tendency to discoloration or staining of the specified paper after storage of the corresponding laminated system at temperatures considerably above room temperature, at the same time providing the specified coated paper of high adhesiveness and a high adhesive ability on various substrates.

In accordance with one aspect of the present invention features a composition of hot-melt pressure-sensitive adhesive (HMPSA)containing:

a) from 30 to 50% of a mixture of styrene block copolymers, consisting of:

- from 10 to 70% of at least one SX1S triblock-copolymer, and

- from 30 to 90% of at least one SX2the diblock copolymer; where:

- S indicates a polymerized segment of styrene monomer,

- X1and X2identical or different, each represent an elastomeric polymerized segment of one or two monomers selected from the group consisting of isoprene, butadiene, and their corresponding hydrogenated derivatives;

and where the total content of styrene monomer in the above-mentioned mixture between 14 and 40%;

b) from 40 to 55% of one or more enhancing the adhesiveness of the resin with a softening temperature between 70 and 150°C, containing increasing the stickiness of the resin (i)obtained by hydrogenative, polymeris the tion or copolymerization of mixtures of unsaturated aliphatic hydrocarbons, containing approximately 5, 9 or 10 carbon atoms;

c) from 4 to 20% of the hydrocarbon oil with a content of aromatics of less than 15%;

d) from 1 to 6% of a filler selected from calcium carbonate or homopolymer or copolymer of polyethylene with a low molecular weight.

Unless otherwise stated, the percentages used in this document to refer to the content of the various components, refer to the mass percent (mass component of the total mass).

The composition according to the present invention mainly provides the laminated system produced by coating the material of the substrate in a strong adhesive at room temperature, which makes the laminated system is especially suitable for use as a PSA labels. In addition, this high stickiness appears at low temperature is approximately 2°C, which makes it possible to apply labels on cold items like chilled foods packaged in plastic film, such as fruit, vegetables or meat. Moreover, the system also has a very good adhesive properties, which makes it possible permanent fastening end labels on various substrates products for marking. In conclusion, in the coating on glossy white paper composition is I of the present invention shows low staining or discoloration of the paper after storage of the laminate at a temperature of approximately 75°C and under pressure.

Styrene triblock and diblock copolymers included in the composition of the present invention have an average molecular mass Mwcontained between 60 and 420 kDa, and can be linear or radial. If not stated otherwise, the average molecular mass Mwthat given in the text of this document, specified in Daltons (Da) and determined by Gel Chromatography; the column was calibrated on polystyrene standard. These styrene block copolymers are well known to this art and commercially available.

The preferred mixture SX1S triblock and SX2diblock copolymers include from 10 to 30% triblock and from 70 to 90% of the diblock copolymers. In a more preferred mixtures SX1S triblock and SX2diblock copolymers polymerized elastomeric segments X1and X2consist of the same monomer. More preferably, the total content of styrene monomer, 15 to 30%.

The preferred composition of the present invention includes a mixture SX1S triblock and SX2diblock copolymers, where X1and X2denote polymerized segment of isoprene or polymerized segment of butadiene. Such copolymers are also referred to as SIS, SI, SBS or SB block copolymers. Examples might include:

- Europrene® Sol T6320, which is a mixture priblizitelen is 25% styrene-butadiene-styrene (or SBS) linear block copolymer (M wapproximately 170 kDa) and approximately 75% SB diblock (Mwapproximately 70 kDa). This mixture contains 30% styrene, commercially available from Polimeri Europa.

- DPX® 586, which is a mixture of approximately 20% styrene-isoprene-styrene (or SIS) radial block copolymer (Mwapproximately 420 kDa) and approximately 80% SI diblock (Mwapproximately 110 kDa). This mixture contains 30% styrene by weight and commercially available from Exxon.

- Solprene® 1205, which is a styrene-butadiene (or SB) diblock copolymer containing about 30% styrene and having Mwapproximately 100 kDa, commercially available from Dynasol.

- Kraton® D1113 BT, which is a mixture of approximately 44% linear SIS block copolymer (Mwapproximately 190 kDa) and approximately 56% of SI diblock (Mwapproximately 97 kDa). This mixture contains 15% styrene, commercially available from Kraton.

Other block copolymers, which can be used in HMPSA compositions of the present invention include derivatives of triblock copolymers SIS and SBS received by hydrogenative middle of the block. Such block copolymers are also known as styrene-ethylene-butylene-styrene (SEBS) or styrene-ethylene-propylene-styrene (SEPS). HMPSA compositions can also include block copolymers of the type SIBS, which are described, for example, in patent document US2005/0137312, published 23/06/2005.

HMPSA composition of the present invention includes one or more improve the adhesion of resins, each with a softening temperature that is between 70 and 150°C. the Total content of these increase the adhesiveness of the resin in the HMPSA composition between 40 and 55%.

These increase the adhesiveness of the resin include one or more enhancing the adhesiveness of the resin (i)obtained by hydrogenative, polymerization or copolymerization (aromatic hydrocarbon) mixtures of unsaturated aliphatic hydrocarbons containing approximately 5, 9 or 10 carbon atoms, the compounds produced by cracking of crude oil.

In HMPSA composition in one of the embodiments of the present invention improves the adhesion of the resin(s) (i) are used in a mixture with up to 50% (based on the total weight of this mixture) of one or more improve the adhesion of the resins selected from the group consisting of:

- increase the adhesiveness of the resin (ii), consisting of natural or chemically modified resins;

- increase the adhesiveness of the resin (iii), consisting of terpene resins, optionally modified under the action of phenols; and

- increase the adhesiveness of the resin (iv)consisting of copolymers based on natural terpenes.

Each of enhancing the adhesiveness of the resin (ii), (iii) and (iv)do not necessarily included in the mixture of resin (i) in the present HMPSA composition, has a softening temperature that is between 70 and 150°C. Preferably the mixture comprises about 50% resin (i) and approximately 50% resin (ii), (iii) and (iv).

As for increasing the adhesiveness of the resin (ii), as examples of natural rosin: gum rosin collected from living trees, extraction rosin, isolated from the roots of trees, of rosin tall oil produced as a by-product in the paper industry. Chemically modified rosin includes rosin, modified by such processes as hydrogencyanide, dehydrogenation, dimerization, polymerization, or the esterification of alcohols, including polyols of the type of pentaerythritol.

Relatively increase the adhesiveness of the resin (iii), terpene resin is usually obtained by polymerization of terpene hydrocarbons such, for example, monoterpene (or pinene) in the presence of a catalyst of the Friedel -.

As for increasing the adhesiveness of the resin (iv), as examples are copolymers based on natural terpenes, the copolymers of styren/terpene, alpha methylstyrene/terpene and vinylcolor/terpene.

Increase the adhesiveness of the resin (i), (ii), (iii) and (iv) generally have an average molecular mass Mwcontained between 300 and 5000 Da. They are commercially available, and in the case ol the lead following the collection of the following products:

(i) Wingtack® 86 from Cray Valley, which is aromaticheski modified C5 hydrocarbon resin with a softening point of 86°C and Mwapproximately 1670 Yes; Escorez® 5600 from Exxon Chemicals, which is a hydrogenated Dicyclopentadiene-modified aromatic compound having a softening temperature of 100°C and Mwapproximately 980 Yes; Escorez® 5690 from the same company, which is a hydrogenated Dicyclopentadiene-modified aromatic compound having a softening temperature of 90°C and Mwapproximately 800 Yes;

(ii) Sylvalite® RE 100 L from the company Arizona Chemical, which is a rosin, esterified pentaerythritol having a softening temperature of 100°C and Mwapproximately 1700 Yes;

(iii) Sylvalite® TP 95 from the same company, which is a resin with a softening temperature of 95°C and Mwapproximately 1120 Yes;

(iv) Sylvalite® ZT 105LT from the same company, which is a copolymer of styren/terpene with a softening temperature of 105°C.

The softening temperature of the resin is determined through a standardized ASTM E 28 analysis using the handset Rings and the Ball, the principle is the following. Bronze ring with a diameter of approximately 2 cm fill the studied resin in the molten with the being. After cooling to room temperature, the ring and the resin in the solid state is placed in a horizontal position in glycerol bath, the temperature of which can be improved with a uniform speed of 5°C per minute. Steel ball with a diameter of approximately 9.5 mm is placed in the center of the disk of solid resin. The softening temperature is a temperature at which the drive of the resin will decrease at a distance of 25.4 mm under the weight of the ball.

The preferred increase the adhesiveness of the resin have a softening temperature, which is contained between 80 and 140°C and more preferably between 85 and 110°C.

Hydrocarbon oil that can be used as component (C) in the composition of the present invention has a content of aromatics of less than 15%, preferably less than 7%.

The content of aromatics in the oil represents the percentage weight of aromatic hydrocarbons, divided by the total weight of paraffinic, aromatic and naphthenic hydrocarbons. The number of paraffinic, aromatic and naphthenic hydrocarbons can be determined by standard measurements, known qualified in this prior art experts and based on IR spectroscopy. Preferably used oil with essentially the same content of naphthenes and paraffins. Such mineral oil commercially available. The quality is TBE example Nyplast® 222B from Nynas, which contains 5% aromatic carbon, 47% paraffinic carbon, 48% naphthenic carbon.

Calcium carbonate, which can be used as filler (d) in HMPSA compositions of the present invention, preferably used in the form of fine powder particles with an average size of less than 10 microns, more preferably less than 5 μm and even more preferably about 2 microns.

Preferably the filler is a homopolymer or a copolymer of polyethylene with an average molecular weight that is between 1 and 5 kDa. Such products are commercially available, for example, AC8® from Honeywell is a Homo-polymer of polyethylene having an average molecular weight of 2800, and the index polydispersity 1,69, AC400 from the same company is a copolymer of polyethylene and vinyl acetate having an average molecular weight of between 1 and 3 kDa.

In a preferred embodiment, HMPSA composition of the present invention contains:

- from 32% to 40% of the component (a);

from 45 to 50% of component b);

from 10 to 20% of component c); and

- from 3 to 5% of component d).

Preferably HMPSA composition of the present invention contains one or more stabilizers or antioxidants in an amount of from 0.5 to 2%. These compounds are added to protect the adhesive from degradation caused by reaction with oxygen, to ora can be carried out under the action of heat, light or catalyst remaining from the original materials, such as increasing the adhesiveness of the resin. These compounds can include key antioxidants, which act as scavengers of radicals and usually contain phenols such Irganox® 1010 from CIBA. Key antioxidants can be used alone or in combination with other antioxidants, such as phosphites, such Irgafos® 168 from CIBA, or sulfites, such Irganox® from the same company.

Other components such as dyes, pigments or coloring agents may also be included in the HMPSA composition.

The viscosity of the HMPSA composition of the present invention, measured by a Brookfield viscometer® RVT, preferably lies between 4000 and 50,000 mPas at 163°C and more preferably between 8000 and 30000 mPas at 163°C.

HMPSA composition of the present invention receive by simple mixing of its components in the bath or polovine mixer at a temperature of between 130 and 200°C. methods of mixing are well known to a qualified specialist in this technology.

In accordance with another aspect of the present invention proposed system, including:

- adhesive layer consisting of HMPSA compositions of the present invention,

paper face material connected with the specified adhesive layer, and

- anti-adhesive m is a material predetermined, connected to the adhesive layer.

The paper used as a face material, typically has a basis weight between 60 and 100 g/m2and often represents a high-gloss paper or vellum paper, preferably white. Anti-adhesive material protects the adhesive prior to application to the substrate and can represent, for example, the layer coated with the organosilicon compounds Kraft paper.

For the industrial production of such laminated system HMPSA composition applied to the surface or used in any other way on a paper face material, or, more preferably, is applied to the surface of the anti-adhesive material and then laminated them with a paper face material. Surface application is achieved by methods well known to a qualified specialist in this prior art, such as oblivanie roll, cover the slot in the matrix or coating, applied irrigation at temperatures of from about 120 to 175°C. the coating Weight HMPSA may be concluded between 15 and 30 g/m2.

In accordance with another aspect of the present invention is an adhesive label obtained through the conversion laminated system of the present invention. Methods of conversion include longitudinal cutting, stamping and matrix separation.

The adhesive is haunted properties HMPSA compositions of the present invention evaluated by Peel 180° analysis on stainless steel, as described by way of analysis FINAT n°1, published in Manuel Technique FINAT 6th edition, 2001. FINAT is an international Federation of producers and processors of adhesives and hot melt glues for paper and other stakeholders. The principle of this analysis is the following. First of all HMPSA is applied with a thickness of 50 μm on the surface of a film of polyethylene terephthalate (PET) with a weight of 20 g/m2. The resulting laminate is cut into rectangular strips (25 mm × 175 mm), which is fixed on the substrate, consisting of a plate of stainless steel. This Assembly is left for 20 minutes at room temperature. Then it is placed in the apparatus for stretching, able to tear off strips at an angle of 180° with a speed of 300 mm per minute. Force required for effective Stripping, measured in these conditions. The results are expressed in N/a see Is Peel 180° on stainless steel suitable for the permanent PSA labels HMPSA usually more than 4 N/cm, preferably more than 7 N/a see

Tack at room temperature, achieved through HMPSA compositions of the present invention, determined through an analysis of stickiness loop, using the method of analysis described in FINAT n°9, also published in Manuel Technique FINAT 6th edition, 2001. First of all HMPSA is applied to the surface to obtain a rectangular strips (25 mm × 175 mm), as described wished the end of such strips connected in a loop (adhesive layer to the outside) and is fixed in the movable clamping device of the apparatus for stretching, able to move up and down with a speed of 300 mm per minute along the vertical axis. The lower part of the loop first move down to contact with the horizontal glass panel with a width of 25 mm and a length of 30 mm, with a surface area surface area of approximately 25 mm × 25 mm as soon As contact occurs, the direction of movement is changed to the opposite. The stickiness of the loop is the value of the force required for complete separation of the loop from the glass panel. Stickiness hinges at the PSA usually more than 1.3 N/cm2.

Stickiness at 2°C is determined through analysis of the stickiness of the probe. A cylindrical probe with a diameter of 5 mm stainless steel connected with a load cell equipped with a force sensor. The end of this probe is placed in and removed from contact with the layer HMPSA deposited on a PET film with a thickness of 50 μm, while registering a perfect move and the resultant force. The load cell and the probe are part of the texture analyzer; layer HMPSA and probe closed in a thermostatic chamber, maintaining temperature 2°C. the Adhesion of the probe represents the maximum force registered during the time of the release of the probe, and is expressed in N/cm2.

The propensity for staining paper HMPSA compositions of the present invention defined in the following analysis. HMPSA caused on the surface of the antiadhesive material p and a temperature of approximately 160°C and then was eliminirovali paper face material. Surface application implemented using the crevice tool on the mouthpiece. Paper face material is a 70 g/m2white high gloss paper. The weight of the coating adhesive is a 20 g/m2.

Laminated system cut by 21 × 29,7 cm strips, which were stored for 7 days at 75°C under pressure of 32 kg/m2.

Discoloration ΔE paper face material was measured by means of measurements carried out by measuring the color before and after storage of the strips. Based on a model of color, referred to as the CIE L*a*b, this device (Minolta Chromometer CR 200) determines whether the light source ratio (type D, i.e. D65corresponds to the color temperature of 6504 K) the three parameters for a specific color of its brightness (L*), its position between Magenta and green (a*) and its position between yellow and blue (b*).

Thus, the measurement is carried out to store, gives three parameters: L*0a*0that b*0; while the measurement is conducted after storage, gives the other three parameters: L*storagea*storagethat b*storage.

Discoloration ΔE is calculated by the formula:

ΔE = [(L*0-L*storage)2+ (a*0-a*storage)2+ (b*0-b*storage)2]1/2

The present invention will be further illustrated by the following non-limiting note the Rami.

The following HMPSA compositions were prepared by simple mixing of the ingredients at a temperature between 160 and 180°C.

All these compositions contain 0.5% Irganox® 1010 and 0.5% Irganox® PS800. The content of the remaining components shown in Table 1.

The viscosity of these compositions were measured using a Brookfield RVT viscometer at 163°C. the Obtained values, and the results of the analyses described above in the text of the present document are listed in the following Table 2.

Subjects HMPSA compositions provide acceptable discoloration ΔE paper face material in the harsh conditions of storage laminated system, thus demonstrating the advantages of adhesive and adhesive properties in the Peel test 180°. These properties make these compounds particularly suitable for the production of PSA labels.

In addition, labels, obtained by applying to the surface (weight 20 g/m2each of these compositions to paper weighing 80 g/m2first cemented into the glass, then peeled at an angle of 180°. During this stage Stripping all labels demonstrated some gap fibers. Subjects HMPSA, therefore, particularly suitable for the production of permanent PSA labels.

Table 2
Re ulitity
analysis
Example
1
Example
2
Example
3
Example
4
Example
5
Example
6
Example
7
Example
8
Example
9
Example
10
Example
11
Viscosity at 163°C (PA·s)830102415161615171818
Peeling
at 180°C
stainless steel (N/cm)
10897,57127,297,2810
The stickiness of the loop (N/cm2)3,7 453,64,25,6444,854,5
The adhesion of the probe at +2°C (N/cm2)1,240,61,090,470,551,20,550,780,480,30,3
ΔΕ2,51,42,31,91,61,61,71,91,72,52,3

1. The composition of hot-melt pressure-sensitive adhesive (HMPSA)containing:
a) from 30 to 50% of a mixture of styrene block copolymers, consisting of:
from 10 to 70% of at least one SX1S triblocaltara, and
from 30 to 90% of at least one SX2diplomaprimary;
where S denotes Ameritania segment styrene monomer,
X1and X2identical or different, each represent an elastomeric polymerized segment of one or two monomers selected from the group consisting of isoprene, butadiene, and their corresponding hydrogenated derivatives;
and where the total content of styrene monomer in the above-mentioned mixture is between 14 and 40%;
b) from 40 to 55% of one or more enhancing the adhesiveness of the resin with a softening temperature between 70 and 150°C, containing increasing the stickiness of the resin (i)obtained by hydrogenative, polymerization or copolymerization of mixtures of unsaturated aliphatic hydrocarbons containing approximately 5, 9 or 10 carbon atoms;
c) from 4 to 20% of the hydrocarbon oil with a content of aromatics of less than 15%;
d) from 1 to 6% of a filler selected from calcium carbonate, or homopolymer, or a copolymer of polyethylene with a low molecular weight.

2. HMPSA composition according to claim 1, where the mixture of styrene block copolymers contain from 10 to 30% SX1S tribocorrosion and from 70 to 90% SX2diamatapoulou.

3. HMPSA composition according to any one of claims 1 or 2, where the cured elastomeric segments X1and X2consist of the same monomer.

4. HMPSA composition according to claim 1, in which the total content of styrene monomer from 15 and 30%.

5. HMPSA composition according to claim 1, where X1and X2denote poly is harisovannyy segment of isoprene or polymerized segment of butadiene.

6. HMPSA composition according to claim 1, where increasing the stickiness of the resin(s) (i) is mixed up to 50% with one or more improve the adhesion of the resins selected from the group consisting of:
increasing the stickiness of the resin (ii), consisting of natural or chemically modified resins;
increasing the stickiness of the resin (iii), consisting of terpene resins, optionally modified under the action of phenols; and
increasing the stickiness of the resin (iv)consisting of copolymers based on natural terpenes.

7. HMPSA composition according to claim 6, where the mixture comprises about 50% resin (i) and approximately 50% resin (ii), (iii) and (iv).

8. HMPSA composition according to claim 1, where increasing the stickiness of the resin has a softening temperature between 80 and 140°C., preferably between 85 and 110°C.

9. HMPSA composition according to claim 1, where the hydrocarbon oil has a content of aromatics of less than 7%.

10. HMPSA composition according to claim 1, where the filler is a homopolymer or a copolymer of polyethylene with an average molecular weight between 1 and 5 kDa.

11. HMPSA composition according to claim 1, which contains:
from 32 to 40% of component (a);
from 45 to 50% of component b);
from 10 to 20% component (C); and
from 3 to 5% of component d).

12. HMPSA composition according to claim 1, which contains one or more stabilizers or antioxidants in an amount of from 0.5 to 2%.

13. Laminated system, including:
an adhesive layer comprising the C HMPSA composition according to any one of claims 1-12,
paper face material connected with the specified adhesive layer, and
anti-adhesive material connected to the adhesive layer.

14. Laminated system of item 13, where the paper is a white paper having a weight between 60 and 100 g/m2.

15. Self-adhesive label obtained through the conversion laminated system defined in any of PP or 14.



 

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The invention relates to a block copolymer composition, curable by ultraviolet radiation (hereinafter UV block copolymer composition)

FIELD: chemistry.

SUBSTANCE: invention relates to production of shrinkable polymer labels, particularly to preparation of a film composition. The composition contains (a) a high-impact polystyrene component (HIPS) with a block-copolymer grafted to the polystyrene, (b) 10-50 wt % general purpose polystyrene (GPPS) and (c) approximately 2-80 wt % styrene block-copolymer. Component (a) contains a grafted rubber component which is a styrene block-copolymer and a rubber-like diene with conjugated double bonds from 1 to 7 wt % of the weight of the HIPS; less than 10 wt % concentration of gel, defined by extraction of the methylethylketone/methanol mixture. The average particle size of the rubber is less than 1 mcm and 0.01 mcm or more. Approximately 40-90 vol % of the rubber particles have diametre approximately less than 0.4 mcm and approximately 10-60 vol % of the rubber particles have diametre of approximately 0.4-2.5 mcm. Most of the rubber particles have a nucleus-shell morphology and said particles are in concentration of 10-70 wt % of the total weight of the polymer composition, and 1-5 wt % of the rubber-like diene of the total weight of the polymer composition.

EFFECT: film made from said composition has ratio of directed length to non-directed length in the direction of the greatest drawing at least equal to 3:1 and enable increase in size by 20% in the direction of less stretching at 110°C.

10 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is a composition of bound high molecular weight block copolymers for making compounds, moulded articles and oil gels, containing: (a) a linear di-block copolymer (I) of general formula (A-B), having maximum apparent molecular weight between 230000 and 275000, (b) a linear double-beam block copolymer (II) of general formula (A-B)2X, (c) a three-beam block copolymer (III) of general formula (A-B)3X, (d) greater than the three-beam block copolymer (IV) of general formula (A-B)n>3X, (e) secondary polymer structures mainly based on monovinylaromatic hydrocarbons having maximum apparent molecular weight less than that of the linear di-block copolymer (I), where A is a block of mainly poly(monovinylaromatic hydrocarbons), and where content of poly(monovinylaromatic hydrocarbons) lies between 20 and 35 wt %; where B is a block of mainly poly(conjugated diene); where X is a residue of a trifunctional and/or tetrafunctional binding agent; where the composition of block copolymers has weight-average molecular weight Mw between 450000 and 800000, and where relative amounts of block copolymers are as follows: I between 5 and 15 wt %; II and III together between 70 and 90 wt %, where III is more than 10 wt %; IV ranges from more than 0 to less than 10 wt % and secondary polymer structures range from more than 0 to less than 10 wt %, respectively, relative the weight of the all the composition of block copolymers, in which the sum of the components is equal to 100%. The invention also describes a method of obtaining the composition of bound block copolymers. Described also are moulded articles and gels, obtained from the composition of bound block copolymers.

EFFECT: obtaining a composition of bound block copolymers with high molecular weight and low viscosity.

12 cl, 13 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a composition of an oil-containing gel, which contains a block copolymer with controlled link distribution and at least one non-aromatic ester oil. The block copolymer is formed from monoalkenyl and a conjugated diene. The block copolymer undergoes selective hydrogenation and contains block A from monoalkenylarene homopolymer and block B with controlled link distribution in form of a medial block formed from monoalkenylarene and a conjugated diene. The non-aromatic ester oil is natural oil, eicosyl erucate or C12-15 alkyloctanoate. Oil content is equal to 250-2000 pts. wt per 100 pts. wt of the hydrogenated block copolymer.

EFFECT: invention enables to obtain stable transparent gels with improved properties.

14 cl, 13 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyester compositions containing oxygen-absorbing polydienes and used in packing food products and drinks. The invention describes a composition which contains a combination or a reaction product (i) resins based on aromatic polyester and (ii) hydrogenated polydiene with terminal hydroxyl groups, where 30-70 mol % monomer links of said polydiene are vinyl links or their hydrogenated residues, and in which 60-80% of initial double bonds remain after hydrogenation. Described also is a method of preparing the composition, involving anionic polymerisation of conjugated diene monomer to form polydiene with terminal hydroxyl groups and mixing the aromatic polyester to obtain polydiene.

EFFECT: good oxygen-absorbing properties and prevention of colouring of polyester compositions during secondary processing.

21 cl, 2 ex

FIELD: physics; photography.

SUBSTANCE: invention relates to a photosensitive polymer composition, preferably used in a flexographic printing plate. A photosensitive polymer composition is proposed, which contains a thermoplastic elastomer (a), which contains at least a vinyl aromatic hydrocarbon link, a butadiene link and an alkylene link, where content the alkylene link is not less than 10 wt % and not more than 60 wt % of the total amount of butadiene and alkylene links; a photopolymerisable unsaturated monomer (b) and a photopolymerisation initiator (c).

EFFECT: photosensitive polymer composition provides for high reproducibility of thin lines, resistance to ether solvent and prevention of formation of cracks on the surface of the plate.

15 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: thermoplastic elastomer material contains: (a) from 10 to 100 wt % of at least one thermoplastic elastomer based on styrene; (b) from 0 to 90 wt % of at least one thermoplastic homopolymer or copolymer of α-olefin, different from (a); where amount of (a)+(b) equals 100; (c) from 2 to 90 pts. wt of vulcanised rubber in crushed state; (d) from 0.01 to 10 pts. wt of at least one coupling agent which contains at least one unsaturated ethylene; where amounts (c) and (d) are expressed in ratio to 100 pts. wt of (a)+(b).

EFFECT: improved mechanical properties, specifically breaking stress and breaking elongation, increased wear resistance.

60 cl, 6 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a thermoplastic elastomer composition with high melt strength, to a method of making moulded elastomer objects and to moulded elastomer objects, made from the said composition. The composition contains at least one linear crystalline polyolefin and at least one compatible thermoplastic elastomer or a mixture of one or more styrene block copolymers with a thermoplastic and/or plasticiser. The polyolefin has melting point of at least 100° C and polydispersity index (PI) greater than 20, determined through isothermal dynamic frequency sweep at 190°C and calculated from the equation PI = 100000/Gc, where Gc is expressed in pascals and is the modulus at the point of intersection (Gc=G'=G"), and the thermoplastic elastomer or mixture has compression set below 50%, determined at ambient temperature 24 hours after compression on ASTM D395-03.

EFFECT: obtaining a composition which can be used in processes which include a stage for unsupported stretching while the composition is molten, such as foaming, film blowing, fibre drawing, blow moulding, profile extrusion and hot moulding.

17 cl, 6 ex, 9 tbl

FIELD: chemistry.

SUBSTANCE: thermoplastic gel composition which can be cured under the action of radiation includes: (a) approximately from 5 to 40 wt % of cured block-copolymer selected from the group consisting from compounds of formula (II) or (III) or (IV), whereat A is vinyl aromatic hydrocarbon block with molecular mass from 4000 to 30000, HD is hydrogenated conjugated diene block with molecular mass from 10000 to 100000, Y is multifunctional binding agent, UD is conjugated diene block with molecular mass from 1000 to 80000 or conjugated diene block with molecular mass from 1000 to 80000 which is partially hydrogenated, x is integer number from 1 to 20, y is equal to 0 or 1, z is integer number from 1 to 20 and in the formulas (II) and (III) the sum (x+z) is in the range from 2 to 30; (b) from 60 to 90 wt % of the liquid component selected from the filling oils, plasticisers and solvents compatible with the curable copolymer; (c) from 1 to 20 wt % at least one curative agent selected from bifunctional or multifunctional acrylate or metaacrylate monomers or vinyl ethers; d) optionally from 0 to 10 wt % of the expanding microspheres; and (e) optionally from 0 to 3 wt % of the photoinitiator whereat total component amount is equal 100 wt %. The thermoreactive article containing the thermoplastic gel composition subjected to the action of radiation is described as well as the thermoplastic gel composition which can be cured under the action of radiation and includes: (a) from 5 to 40 % w/w of the mixture of curable block-copolymer with formula (I) whereat S is polystyrol block, B is polybutadiene polymer block having the content of 1,2-vinyl groups in the range from 10 to 80 mole %, Y is the radical of the binding agent, x is integer number from 1 to 20, preferably 2, y - integer number from 0 to 20, preferably 2, with sum (x+y) being in the range from 2 to 30; and block-copolymer of the (polystyrol -hydrogenated polybutadiene -polystyrol ) type with ratio (block-copolymer of formula (I): (block-copolymer of (polystyrol -hydrogenated polybutadiene -polystyrol ) type being in the range from 3:1 to 1:3; (b) from 60 to 90 wt % of the liquid component selected from the filling oils, plasticisers and solvents compatible with the curable copolymer; (c) from 1 to 20 wt % of at least one curative agent selected from bifunctional or multifunctional acrylate or metaacrylate monomers or vinyl ethers; (d) from 0.1 to 10 wt % of expanding microspheres; and (e) from 0 to 3 wt % of photoinitiator whereat total component amount is equal 100 wt %.

EFFECT: increase of high-temperature shrinkage resistance.

10 cl, 8 tbl, 30 ex

FIELD: chemistry.

SUBSTANCE: method for preparation of functionalised, bound or star-block copolymer used in sulphur-cured rubber composition containing carbon char and having in cured state decreased hysteresis with at least one of said blocks containing polyisoprene and at least one other block consisting of diene elastomer different from polyisopren with mole content of repeating units of one or more of conjugated dienes exceeding 15% includes: copolymerisation of one or more monomers containing at least one conjugated diene different from polyisoprene with catalitycal system containing hydrocarbon solvent halogenated or unhalogenated metal-organic compound A of the group IIIA metal, alkaline-earth metal compound B and polymer initiator C containing bound C-Li formed by unfunctionalised monolythium-containing polyisopren intended for formation of the said block or every polyisoprene block and (ii) adding to the product of the said polymerisation of the functionalising, binding or star-shape forming agent containing acetoxy group of formula Rn-Sn-(O-CO-R')4n> whereat n is integer natural number from 0 to 4 and R and R' each represents following groups: alkyl, cycloalkyl, aryl, aralkyl, same or different, for functionalisation or binding or forming of star-shape structure of the said block consisting of dien elastomer different from polyisopren. The said one or more polyisopren blocks have number average molecular mass Mn1 from 2500 to 20000 g/mole, the said one or more dien elastomer blocks have number average molecular mass Mn2 from 65000 to 350000 g/mole. Functionalised, bound or star-block copolymer, curable or cured rubber composition with lowered hysteresis in cured state, containing reinforcing filler completely or partially consisting of carbon char and containing aforementioned functionalised, bound or star-block copolymer are described also. Pneumatic tyre tread containing aforementioned rubber composition is described as well as pneumatic tyre containing described above tread.

EFFECT: hysteresis decrease of cured the rubber composition.

36 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to the method of producing functionalised, linked or star block copolymer, used in rubber compositions, cross-linked with sulphur and with low hysteresis in the cross-linked state. Described is a method of producing the said copolymer, containing soot and with low hysteresis in the cross-linked state. At least one or the above mentioned blocks consists of a diene elastomer, distinct from polyisoprene, the molar content of branches of one or several conjugate dienes of which exceeds 15%. The method is distinguished by that it involves: (i) copolymerisation of one or several monomers, containing at least one conjugated diene, distinct from isoprene, using a catalyst system, containing a hydrocarbon solvent, halogenation or non-halogenated organo-metal compound A of a group IIIA metal, compound B of an alkali-earth metal and a polymer initiator C, containing C-Li bond, which is formed from non-functionalised mono-lithium containing polyisoprene, meant for forming the said or each polyisoprene block; the said one or several polyisoprene blocks have average molecular mass Mn1 from 2500 to 20000 g/mol, in effect that, one or several blocks, containing diene elastomer, distinct from polyisoprene, contains 70% or more 1,4-trans-branches and has average molecular mass Mn2 from 65000 to 350000 g/mol, and (ii) addition into the copolymerisation product of a functionalised, linking or star structure forming agent, containing one, two or at least three epoxy groups, respectively, for functionalising, linking or forming a star structure of the given block, consisting of diene elastomer, distinct from polyisoprene. Description is also given a functionalised, linked or star block-copolymer, cross-linkable or cross-linked rubber composition, containing the said functionalised, linked or star block-copolymer, and description is also given of a pneumatic tyre tread and a pneumatic tyre.

EFFECT: obtaining a block-copolymer, which is used in compositions for pneumatic tyre treads, and which reduces hysteresis of the given composition in cross-linked state.

40 cl, 4 ex

FIELD: manufacture of materials changing physical, chemical and mechanical properties of road, bridge and airfield pavement components.

SUBSTANCE: proposed binder for road pavement contains mixture of bitumen, block copolymer of diene and styrene and additives in form of improved paving bitumen. Craton is used as block copolymer of diene and styrene and oil fraction obtained from direct refining of heavy low-paraffin naphthene base is used as additive; it is characterized by kinematic viscosity at +50°C from 65 to 85 cSt, solidifying temperature below -18°C; binder is characterized by tensibility more than 70 cm at +25°C, elasticity more than 70% at +25°C, softening temperature more than 65°C and viscous-flow state at 135°C.

EFFECT: improved physico-mechanical properties of bitumen pavement.

4 tbl

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