DE2555836A1 - PRESSURE SENSITIVE ADHESIVE - Google Patents

Description

The invention relates to a pressure-sensitive adhesive which is used for the production of pressure-sensitive adhesive tapes, sheets or labels or the like can be used and which is no or practically no organic Contains solvent. In particular, the invention relates to a pressure sensitive adhesive that is a liquid polymer based on diene with functional groups in the molecule, preferably at both ends, an isocyanate compound, which reacts with the liquid diene-based polymer in a polymerization reaction, and a tackifier, in order to achieve adhesive strength and tackiness, which contains an anionic surface active agent in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the total weight of the liquid diene-based polymer and the isocyanate compound has been added to avoid unevenness (voids created by heterogeneous Parts or stains of the mixture on the carrier have been caused) to avoid an adhesive layer that occurs during the The heating stage is formed, which is carried out to effect the polymerization reaction after the coating to accelerate the mixture on a carrier and to make a

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- To get 2 uniform smooth adhesive layers.

A method is already known in which a mixture is produced by adding appropriate agents, for example a tackifier, an emollient, a plasticizer, a pigment, etc. to a rubber-based polymer or acrylic-based polymer in an organic solvent is dissolved, the resulting pressure-sensitive solution, containing about 30 wt .-% solids on a support, for example a plastic sheet, a metal foil, etc. is coated with a defined thickness and then the organic solvent in a heating-drying stage is evaporated, as a result of which an adhesive from the above mixture is formed again on the carrier in layer form. This procedure is very often used to get pressure sensitive To produce adhesive tapes, etc.

In such a process, however, the amount of solvent is twice or more than that of the solids required to dissolve the solids of the adhesive and form an adhesive layer. The organic one used However, solvent does not play a role in increasing the pressure sensitive adhesive properties of the adhesive tape the slightest role. This method therefore has the disadvantage that the use of a large amount of the organic Solvent, the use of a heat source and a device to evaporate the organic solvent as well as the use of an apparatus for recovering the organic solvent, whereby the manufacturing cost of the product can be increased.

It has become the manufacture of pressure-sensitive adhesive tapes and the like without using any Solvents investigated and found a pressure-sensitive adhesive mixture that is able to uniform, high-quality, pressure-sensitive

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To give an adhesive layer in which a liquid polymer based on diene, which is flowable at room temperature, by reaction with an isocyanate compound on a Carrier has been polymerized with heating.

One of the features of the present invention is the addition of an anionic surfactant to one such an adhesive mixture containing a liquid polymer Diene base with a relatively low molecular weight, for example an average molecular weight of 1000 to 50,000, which makes it possible to reduce the non-uniformity of the adhesive layer in the manufacture of pressure sensitive tapes and the like. Avoid, so that uniform pressure sensitive adhesive tapes with smoother Surface and excellent properties, for example in terms of adhesive strength and holding power, etc., can be obtained.

When conventional pressure-sensitive adhesive mixtures des Solution type are applied to a support and then dried by heating, then the viscosity increases the coating layer by evaporation of the organic Solvent to so that voids are obtained in the coating layer, which are due to the Carrier repels heterogeneous parts or stains. It is therefore not possible to use pressure-sensitive adhesive tapes with smoother Surface can be obtained.

The liquid poljonere based on diene, which at ambient temperature Flowable has the disadvantage that when heated to a temperature not lower than 80 ° C is, the viscosity of a coating layer therefrom is markedly reduced (for example, to 20 cP at 120 ° C), so that the mixture can flow and voids can be formed in the adhesive layer on the carrier, whereby a

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Adhesive tape, with a uniform and smooth adhesive surface cannot be obtained.

This marked reduction in viscosity due to heating is an inherent property of the liquid diene-based polymer, which deteriorates the performance of an adhesive tape and a reduction the area of contact between the adhesive layer and the surface to which the tape is adhered is due to the unevenness of the adhesive layer. In this way they become important properties; for example, the adhesive strength, the retention force, etc., decreased.

Attempts have already been made to develop such Cavities by adding a thickener or a high molecular weight polymer or by selecting special ones Avoid reaction systems or process steps, but this has not yet given good results will.

As a result of appropriate studies on tolerability the mixture and the chemical processes taking place on the surface it has now been established that the addition of an anionic surfactant can solve this problem and it is possible to use a pressure-sensitive Manufacture adhesive tape that has a uniform and smooth adhesive surface as well as good adhesive has properties. Other surfactants do not produce this effect.

It is thus possible to produce adhesive mixtures from a wide variety of liquid diene-based polymers, isocyanate compounds and tackifiers to form what both dated

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Is very valuable from the standpoint of adhesive properties as well as technical cost.

Liquid diene-based polymers used herein contain an average of about 2.0 to in the molecule about 2.5 functional groups capable of reacting with an isocyanate group (preferably at least at both ends) and they are polymers that have a relatively low molecular weight of about 1,000 to about 50,000 and which are liquid at room temperature.

These liquid diene polymers are homopolymers of diene monomers such as butadiene, isoprene, chloroprene, etc. or copolymers of the above-mentioned diene monomers and vinyl monomers copolymerizable therewith such as styrene, acrylonitrile, etc., which are attached to both ends of the polymer or in some cases in of the polymer chain contain functional groups which are capable of reacting with an isocyanate group, for example -OH-, -CH ₂ OH-, -COOH-, -NHp-, -SH groups and the like. Many suitable liquid diene-based polymers are commercially available, for example the products Poly BD R-45 M, CS-15 and CN-15 manufactured by Arco Chemical Co., Hycar HTB, MTB, CHB and CTB-X manufactured by BF Goodrich Chemical Co., Nisso PB-G and PB-C made by Nippon Soda Co., Ltd., Telagen HT, Prim and CT made by General Tire & Rubber Co., Butarez HT and CTL made by Phillips Petroleum Co., etc. These diene-based liquid polymers can be used either alone or in combination with each other depending on the required properties of the pressure-sensitive adhesive.

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As used herein are isocyanate compounds Compounds that react with functional groups of the above-mentioned liquid diene-based polymers, whereby polymerization and crosslinking are effected. While the type of isocyanate compound the properties the adhesive layer is greatly changed, are polyisocyanates with two or more isocyanate groups in the molecule are used to initiate polymerization and crosslinking to effect.

Examples of suitable isocyanate compounds are diisocyanates wis p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethandii socyanat, 4,4 * -diphenyl ether diisocyanate, hexamethylene diisocyanate, Cyclohexane-1,4-diisocyanate and the like, Tri- or Diisocyane.tverbindungen, made from the above-mentioned diisocyanate compounds, and polyhydroxy compounds such as glycerine, Trimethylolpropane, polyether glycols, polyester glycols and the like with an intervening urethane bond such as Coronate 4099 and 4095 manufactured by Nippon Polyurethane Industry Co., Ltd., Takenate C-1150 by Takeda Chemical Industries Ltd .; Polyisocyanates such as triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate and the like; and additionally blocked polyisocyanates, produced by reacting the isocyanate groups of such isocyanate compounds with ROH compounds (where R is an aromatic, alicyclic or aliphatic means monovalent group).

The amount of the isocyanate compound added is varied depending on the properties required for the pressure sensitive Glue are required. In general, the amount of the isocyanate compound added corresponds to about 0.75 to about 1.2 equivalents of the isocyanate group per equivalent of the functional group of the liquid polymer on diene

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basis, which gives good results. The polymerization proceeds below about 0.75 equivalents Manufacture of the pressure sensitive adhesive does not proceed sufficiently and unreacted liquid polymers on it Diene bases remain, thereby causing some of the adhesive to remain on the article that the tape was adhered after the tape was peeled off. On the other hand, with sets of more than about 1.2 equivalents the crosslinking reaction proceeds too strongly, so that a reduction in tackiness and. Adhesive strength is caused and no satisfactory properties can be obtained.

Tackifiers, as used herein, are those compounds that are present in the pressure sensitive adhesive impart tack and which play a role in increasing the adhesive strength. For the purposes of the invention can with success conventional tackifiers, such as those generally used in the manufacture of pressure-sensitive Adhesives are used.

Representative examples of such tackifiers are alkylphenol resins, terpene resins, terpene phenol resins, xylene-formaldehyde resins, Rosin, coumarone resins, and in addition Mixtures of aliphatic and aromatic petroleum resins etc.

The addition of the anionic surfactant, which is one of the main features of the invention, enables the tackifier to be selected from a wide variety of tackifiers, including the tackifiers described above, depending on the desired properties of the pressure-sensitive adhesive tapes and the amount of tackifier to be added in the range of about / 10 to about 150 parts by weight per 100 parts by weight of the total weight of the liquid diene-based polymer and the isocyanate compound

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place.

If, as described above, a mixture that mainly of one or more liquid diene-based polymers and one or more isocyanate compounds and one or more tackifiers, on a support in the form of a thin layer (about 30 to about 50 / u thick) is applied and heated to obtain polymerization and crosslinking, then become particulate Voids are formed on the coating layer, thereby causing unevenness, i.e., unevenness. H. thick spots and spots that come in handy have no thickness on which supports are generated.

The anionic surfactants are used herein to overcome the disadvantages described above and conventional surfactants which are commercially available can be used as anionic surfactants Funds are used.

The anionic surfactant is preferably used in an amount of about 0.2 to about 10 parts by weight per 100 parts by weight of the total weight of the liquid diene-based polymer and the isocyanate compound. kernel the amount is below about 0.2 parts by weight, then the effect of preventing cavitation is poor, while at amounts above about 10 parts by weight, cavitation can be prevented, but the adhesive strength is undesirably reduced will.

The following are representative examples of suitable ones anionic surfactants indicated.

In the following formulas, R, R ¹ and R ″ denote branched or straight-chain hydrocarbon radicals having 1 to 18 carbon atoms.

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Carboxylates of the general formulas RCHp-COONa and CH ₃

RCON-CH ₂ -COONa, for example the sodium salt of an aliphatic acid (trademark: Nonsal TN-1 for a product of Nippon Oils and Fats Co., Ltd., trademark Oleoilsalcosine 21 P for a product of Nippon Oils and Fats Co., Ltd.), sulfonates of the formulas R- <

30, .Na, RCH-COOH etc., for example sodium dioctyl

SO ₃ Na

sulfosuccinate (trademark Lapisol B-80 for a product from Nippon Oils and Fats Co., Ltd.), sodium dodecylbenzenesulfonate (trademark: Newlex R for a product of Nippon Oils and Fats Co., Ltd., trademark: Lipon P-105 for a Product of Lion Fat & Oil Co., Ltd.), Sodium Naphthalenesulfona L (Trademark: Lunox S-100 for a product of Toho Chemical Industrial Co., Ltd.) etc., sulfate salts of

R "formulas RR ¹¹ CHOSO ₅ Na, RCOOR, etc., for example

OSO ₃ Na R'C

OSO ₃ Na

Sodium sulfates of lauryl alcohol (Trademark: Liponol NES and Liponol LL-103 for a product of Lion Fat & Oil Co., Ltd., trademark: Alscope 20413 for a product of Toho Chemical Industrial Co., Ltd.) etc.

Phosphoric acid ester salts, for example alkyl phosphoric acid esters, can also be used with 1 to 18 carbon atoms in the alkyl part (trademark: Elektol 201 for a product of Nippon Fats and Oils Co., Ltd.), trademark: Gaffac BS-410 for a product of Toho Chemical Industrial Co., Ltd.), phosphoric acid ester of the alkylphenyl type having 1 to 18 carbon atoms in the alkyl part (trademark: Gaffac RE-610 for a product of Toho Chemical Industrial Co., Ltd.) etc. may be used, although the invention is not limited to the use these connections is limited.

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According to the invention, a catalyst can be used to accelerate the reaction between the liquid diene-based polymer and the isocyanate compound. Suitable catalysts are organic metal salts, for example dibutyltin dilaurate, dioctyltin dilaurate, tin octenate, cobalt naphthenate and the like; Amino such as Ν, Ν, Ν ¹ , N'-tetraethylmethanediamine, 1,4-aza (2,2,2) bicyclooctane and the like; and organic acids such as p "-toluenesulfonic acid and the like.

The catalyst is used in amounts of from about 0.01 to about 5.0 parts by weight per 100 parts by weight of the liquid polymer Diene base added. At amounts below about 0.01 parts by weight, the catalytic effect is poor, while at amounts above about 5.0 parts by weight, the reaction takes place at room temperature and the viscosity of the Mixture mass increases sharply, so that a uniform coating of the carrier with the adhesive becomes difficult.

The adhesives of the invention may optionally further plasticizers or softeners such Dioctylphthal, dibutyl phthalate, polypropylene glycol, polyisobutylene, lanolin and the like. Or additives, such as antioxidants, as i herköramlicherweise ⁿ pressure-sensitive adhesives are used that contain an absorbent for ultraviolet rays, pigments, fillers and the like.. In the case that these additives and the raw materials are solid, they may be previously dissolved in a small amount of an organic solvent such as toluene, xylene, n-hexane to obtain a uniform layer.

The following is a method of making an adhesive tape described in more detail using the adhesive according to the invention.

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In the beginning, the predetermined tackifier, anionic surfactant, catalyst and others become optional additives are added to the liquid diene-based polymer and the resulting mixture is added Using a conventional rubber dissolving mixer such as a Banbury mixer, a kneader and the like., mixed uniformly. It is preferred that the isocyanate compound be applied immediately prior to coating the resulting Mass is added to the carrier. In the case of small amounts of the mixture, the components can be mixed in batches will. However, with large amounts of the mixture, it is preferred to use a continuous multi-liquid mixer as used in deforming urethane foams is used. This is due to the fact that when large amounts of ingredients are mixed at the same time the viscosity of the blended mass increases during the coating process and that the This makes coating difficult.

The mixed mass is then on a carrier, for example made of paper, cellophane, plastic sheets and the like, directly or with an intermediate layer by conventional coating measures, for Example using a reverse coater, a pad coater, a rake coater, or a Stacked extruders. The assembly obtained is placed in a heating furnace. Generally after implementation the coating layer at about 100 to about 180 ° C for a period of 40 seconds to 5 minutes Coating layer on the support essentially completely reacted, so that a pressure-sensitive adhesive layer obtained from flowability, threading and transfer of the adhesive to the Roller is free.

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The product obtained in this way is then wound up in the form of a roll, which is cut either as it is or after being stored overnight at a temperature of at most 60 ^° C. in order to accelerate the reaction if the reaction is not complete will. In this way, a pressure-sensitive adhesive tape can be obtained.

The fact that the type of anionic surfactant plays an important role in the manufacture of a pressure-sensitive Adhesive which is able to give a uniform and smooth adhesive layer, is explained in more detail using the following examples. All parts therein are based on weight, if nothing other is indicated.

example 1

100 parts of a liquid diene-based polymer, namely a polybutadiene containing a -COOH group at both ends thereof and having an average molecular weight of 1,500 (manufactured by Nippon Soda So., Ltd. under the trademark Nisso PB-C) and Seventy parts of a terpene resin (manufactured by Pennsylvania Industrial Chemical Corp. under the trademark Piccolyte A-115) was mixed in a kneader. To this, 11.5 parts of diphenylmethane diisocyanate, 0.05 part of cobalt naphthenate and 0.5 part of each of an anionic, cationic, nonionic and amphoteric surfactant shown in Table 1 were added, whereby various samples were obtained. These various samples were applied to a 150 / U thick sheet of plasticized polyvinyl chloride (manufactured by Mitsubishi Monsanto Co., Ltd.) coated at a thickness of about 30 / U (dry basis) and d.as product obtained was dried at 120 ⁰ C for 2 minutes heated for a long time and wound up in the form of a roll.

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The properties of these samples as pressure sensitive adhesive tapes were determined according to the following evaluation methods. The results obtained are in the table compiled.

Assessment of compatibility

A certain amount of the mixture (1 g) was placed on a clean transparent glass plate and kept at a constant rate Allowed to stand at a temperature of 40 ° C for 12 hours. Then it was done with the naked eye and a microscope (with 20x Magnification) observed from below with light shining on the glass plate. With regard to compatibility or Miscibility the following grades were used:

O completely transparent uniform layer;

Δ Spotting with spots of one diameter of 0.2 mm or less

X Spots with a diameter of 0.2 mm or less are present on the entire surface or there are spots 0.2 mm or more in diameter.

Progress of the polymerisation reaction

This test was conducted to determine to what extent the coating layer coated on the support undergoes polymerization and whether the coating layer is satisfactory in a pressure-sensitive adhesive layer has been converted. The adhesive was first squeezed with a finger to see if it stuck to the Finger stuck. A sample was then stuck to a stainless steel plate and peeled off to see if there was any residue Adhesive was left on the stainless steel plate. The following evaluations were made:

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O the polymerization proceeds enough so that on the finger or the stainless steel plate no glue left;

Δ some glue remains on the pinger or the Stainless steel back plate;

X the polymerization does not proceed sufficiently so that the adhesive on the finger or the stainless steel plate remains or that threading of the adhesive layer is caused.

Condition of the adhesive layer

The adhesive layer was visible to the naked eye observed whether it was formed on the support with a uniform thickness or uniformly, or whether: »particulate Irregularities or voids caused by the repulsion of heterogeneous parts are layered on the adhesive had formed.

O is the total surface area of the adhesive layer smooth and of uniform thickness;

Δ 10 or less voids with a diameter

ρ of 2 mm or less are present per m;

X more than 10 cavities with a diameter of

ρ 2 mm or less are present per m or

There are cavities with a diameter of more than 2 mm.

Adhesive strength

The sample was cut to a width of 20 mm and glued to a stainless steel plate with a mirror surface by using a roller and a load of 2 kg was pressed on. Then it was at a peeling speed of 300 mm / min. using one of the noble

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steel plate peeled off parallel force. The peeling force at 180 ° at this point was at room temperature of 20 ° C was measured with a tension meter manufactured by Toyo Measuring Instrument Co., Ltd..

Cohesive force

This term describes the holding force of the pressure-sensitive tape. The sample was cut into a defined area (1 × 2 cm) and glued to a carrier (a Bakelite plate). While pressing by applying a load of 1 kg with a roller, a defined load (in this case 300 g) was applied parallel to the carrier at 20 ^° C. for 1 hour and then the distance by which the sample was along the surface was measured to which the tape had been attached moved down. If the distance is small, then naturally the sample has a high holding force and it is considered to be a very good pressure-sensitive adhesive tape.

ORIGINAL INSPECTED

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Table 1

Try Surfactant
No. Type of trade mark

chen

«As g
10

12th

13th
14th

Lie progress fed. Pol3nneris, rant

Condition d. Bonding layer (g / 20mm force width) (mm / h)

anionic

Nonsal DK (1) sodium salt of a fatty acid

Sodium Sulpho- Newlex R (1) nat

»Neocol P (2)

Alcohol sulfate Liponol LL-103 (3) Phosphate Gaffac RS-410 (4)

O (4th

cationic amines (main Nimine S-204 (1) component;

non-ionic

ti

amphoteric

quaternary
Ammonium salt
Ether (skin component)
Alky! Phenol

Catinol HB Nonion E-220 (1) Nonion NS-210 (1) (D.

no encore

Ester (main nonion P-10

component)

Imidazoline- Quasoline 4OA (4)

derivatives

Amine and ali- anon BF (1)

phatic acid

Main comp.)

Alanine (Main Lipomin LA (3)

component)

O O O

X Δ

O O

χ
χ
χ
χ
χ
χ

480

420

390 450 450 230

280 120 250 300 290 110

210 290

O,:

0.45

0.52

0.64 ι 0.45

2.5 <* ι

3.6

fell off after 2 minutes fell off after 5 minutes fell off after 25 min. From 150

fell off after 7 minutes

fell about 7.5 after 5 minutes

Cn CO CO

2 £ 55ü 3

Suppliers of tackifiers

(1) Nippon Oils & Fats Co., Ltd.

(2) Dai-ichi Kogyo Seiyaku Co., Ltd.

(3) Lion Fat & Oil Co., Ltd.

(4) Toho Chemical Industrial Co., Ltd.

In experiments 1, 2, 3, 4 and 5, anionic surfactants were used Means based on sodium salts of fatty acids, sodium sulfonates, alcohol sulfonates and Phosphates used. The samples obtained with these anionic surfactants were as to the progress of the polymerization reaction and the condition of the adhesive layer were good, and they provided pressure-sensitive ones Adhesive tapes with similarly good adhesive strength and cohesive strength than those currently on the market plasticized polyvinyl chloride adhesive tapes available.

In the samples where cationic, non-ionic or amphoteric surfactants (i.e. not anionic surfactants) had been used, Circular voids 1 to 5 mm in diameter were formed on the entire surface. That The interior of the cavities was designed so that the adhesive would not adhere and there were places where the Product appearance was poor and where the polymerization reaction had not progressed sufficiently.

Example 2

To 50 parts of a liquid diene-based polymer (i.e., a styrene-butadiene copolymer having -OH groups at both ends and which contained an average molecular weight

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of 3600 (trademark: Poly BD CS-15, manufactured by Arco Chemical Co.) and 50 parts of a liquid diene-based polymer (a polybutadiene having -OH groups at both ends and an average molecular weight of 3000, trademark: Poly BD R-45 M from Arco Chemical Co.), 75 parts of 90 % toluene solutions of the various tackifiers shown in Table 2, 0.5 part of dibutyltin laurate as a catalyst, 1.0 part of antioxidant (manufactured by Allied Chemical Co .) as an anti-aging agent and 45 parts of a polyether diisocyanate (trademark: Coronate 4095 for a product by Nippon Polyurethane Industry Co., Ltd.). To one part of the resulting mixture was added 0.5 part of an anionic surfactant (trademark: Newlex R for a product of Nippon Oils and Fats Co., Ltd.), while in a second part of the mixture, the addition of the anionic surfactant was omitted became. The resulting compositions were applied to a 150 / U thick sheet of plasticized polyvinyl chloride having a thickness of about 30 / U (dry basis) using a reverse coater, and the resulting assembly was heated at 140 ° C. for 1.5 minutes, thereby producing the values shown in Table 2 Samples 1 a to 6 b shown were obtained.

In these samples, as in Example 1, progress was made the polymerization, the state of the adhesive layer, the adhesive strength and the cohesive force as pressure sensitive Adhesive tape measured. The results obtained are shown in Table 2.

As a result, it was confirmed that using Samples 1b to 6b containing an anionic surfactant, a smooth, void-free adhesive layer is formed and that the properties of the pressure-sensitive adhesive tape obtained were good.

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Table 2

Try tackifier 4 b Art ¥ z Lie BM (2) surfaces Away State Glue Cohesion ι No. 5 a fe active step d.Kleb sturdiness sion I. rant Means before d.PoIy- material (g / 20mm) force VO 5 b Xylene formaldehyde
resin act meris. layer (mm / h) I. 1a 6 a Nikonol H (1) 30 (3) no Δ Δ 300 4.02 1 b 6 b Coumarone resin there O O 480 0.53 2 a 0) Coumarones no X X 280 fell after Il 115 (4) 25 min. From o2 b Aromatic petrol there O O 450 1.27 CD _
oo3 a umharz NJ
η
C η no Hiresin i (4) no X X 220 fell after V- / Ί
cn en 25 min. From co o3 b Terpene resin there O O 470 1.07 Jj4 a YS resin PR 10603
(5) no X X 200 fell after «A 10 min. From Terpene phenol Industries Ltd. there O O 560 0.44 resin T-115 T + rl no Δ Δ 350 0.92 as above there O O 520 0.55 Sumilite no Δ Δ 310 0.62 Mitsubishi Gas Chemical: there O O • 450 0.58 Nippon Steel Corp.
ΦλΤλλ üa + νΐΛΐ oil in the Doei η f / Λ

(4) Yasuhara Yushi Kogyo Co., Ltd.

(5) Sumitomo Durez Co., Ltd.

2S55

Example 3

To 100 parts of a liquid diene-based polymer (a styrene-butadiene copolymer with OH groups on both of its Ends and with an average molecular weight of 3,600, trade mark: Poly B-D CS-15) and 9.8 parts of ethylene diisocyanate 50 parts of a terpene phenol resin (trademark: T-115 for a product of Yasuhara Yushi Kogyo Co., Ltd.) and a 90% toluene solution of 50 parts an aromatic petroleum resin (trademark: Hiresin 60 for a product by Toho Petroleum Resin Co., Ltd.) given. After this mixture was uniformly blended, 0.5 part of tin octylate was added and it became at Room temperature further stirred.

The resulting mixture was divided into several parts. An anionic surfactant was added to each part based on sodium sulfonate (trademark: Neocol P for a Product of Daiichi Kogyo Seiyaku Co., Ltd.), whereby adhesive compositions were obtained which the anionic surfactants in amounts of 0, 0.1, 0.2, 0.5, 1.0, 5, 10 or 15 parts per 100 parts of total weight of the liquid polymer of the isocyanate compound. These mixtures were then adjusted to a 150 / U thick sheet of plasticized polyvinyl chloride (manufactured by Mitsubishi Monsanto Co., Ltd.) using a conventional applicator applied. The product obtained was heated to 120 ° C for 5 minutes, whereby Samples 15 to 22 were obtained. In these samples, the progress of polymerization became the state of the adhesive layer and the properties of the pressure-sensitive adhesive layer according to Example 1 were evaluated. The results obtained are shown in Table 3. From these results it can be seen that samples without the addition of the surface-active agent, no smooth

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te adhesive layer revealed and that the properties of the adhesive tape, for example in terms of adhesive strength etc., were bad. On the other hand, samples containing the surfactant in an amount of more than 0.2 parts of smooth adhesive layers and the obtained Adhesive tapes showed good properties.

However, the addition of the surfactant in an amount of more than 10 parts leads to a decrease in adhesive strength and gives unsatisfactory pressure-sensitive adhesive tapes.

Table 3

Attempt Granted parts d. surface progress d. Condition d. Adhesive Cohesion

No. of active agents Polymerization Adhesiveness (g / 20mm force layer width) (mm / h)

15th

16 17 18 19 20 21 22

0 (without addition)

0.1

0.2

0.5

1.0

5.0

10.0

15th

Δ - ~ X X 130 fell after
15 min. From ι
IVJ
(V)
I. Δ Δ 250 10.8 I. O O 480 0.64 O O 490 0.24 O
O O
O 480
420 0.21
0.32 O O 350 0.51 O O 300 0.74

cn cn OO

Claims (7)

Claims 1. Pressure-sensitive adhesive, characterized in that it is a liquid diene-based polymer with an average of 2.0 to 2.5 functional groups in the molecule that can react with an isocyanate, an isocyanate compound having 2 or more isocyanate groups in the molecule and a tackifier, and an anionic one surfactant in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the total weight of the liquid diene-based polymers and the isocyanate compound. 2. Adhesive according to claim 1, characterized in that the liquid diene-based polymer is liquid at room temperature and has a molecular weight of 1,000 to 50,000. 3. Adhesive according to claim 1, characterized in that the liquid diene-based polymer has functional groups from the group -OH-, -CH ₂ OH-, -COOH-, "Contains ~ SH- or the like. 4. Adhesive according to claim 1, characterized in that the isocyanate compound from the Group of diisocyanates, diisocyanate compounds or triisocyanate compounds, made from diisocyanates and polyhydroxy compounds, polyisocyanates and blocked ones Polyisocyanates, prepared from these isocyanates and a compound ROH, where R is an aromatic, alicyclic or aliphatic monovalent group is selected. . ORIGINAL INSPECTED 609825 / 089S 2 ^ 55836 5 * adhesive according to claim 4, characterized in that it contains the isocyanate compound in one Amount of 0.75 to 1.2 equivalents of the isocyanate group per equivalent of the functional group of the polymer Includes diene base. 6. Adhesive according to Anaruch 1, characterized in that the tackifier from the group Alkylphenol resins, terpene phenol resins, xylene-formaldehyde resins, Rosin and hydrogenated rosin is selected. 7. An adhesive according to claim 1, characterized in that the adhesive further comprises a catalyst in an amount of 0.01 to 5.0 parts by weight per 100 parts by weight of the liquid diene-based polymer contains. 609825/0838