DE2417912A1 - SELF-ADHESIVE MELT ADHESIVE COMPOSITION - Google Patents

Description

PATENT ADVOCATE

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A 844-14 / 1YlB

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Rennerle 10 ■ P.O. Box 3160

April 9, 1974

Arakaiua Rinsan Kagaku Kogyo Kabushiki Kaisha 21,1-chome, Hiranomachi, Higashi-ku, Osaka-shi / 3apan

Self-adhesive melting jar composition

This invention relates to novel self-adhesive adhesives Aufschmslz adhesive composition, in particular an adhesive composition, ujBlche can be applied to a tape, a sheet or the like base material in the molten state and ujBlche has self-adhesive adhesive properties when cooled

- 2 -

4Ö3843 / 1057

With regard to the health of employees and pollution control is in the last few years the self-adhesive adhesives of the melt-on type, which are no Containing solvents, more and more attention is paid to them.

As already known, self-adhesive adhesives must be used in the three adhesive properties, adhesiveness, adhesion and cohesion will be excellent. Further must be with those the melting method, milk in the molten state on the Base material to be applied, the adhesives must be free of color when melted and must be excellent Have stability against aging, so that the adhesives after being applied to the base material in a molten state over time in any of the above cited three adhesive properties are not degraded.

However, these requirements are not met in the case of conventional self-adhesive adhesives of the melt type murder. For example, block copolymers are produced by the anionic copolymerization of diene polymers, such as polyisoprene, polybutadiene, etc., and polyvinyl arenes such as polystyrene are used has been suggested as the elastomer ingredient of pressure sensitive hot melt adhesives. Dgr proposal has Aroused interest as block copolymers are excellent

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Have cohesion and "U / arm deformability. The block copolymerB However, they are of poor compatibility with terpene resins, glycerine esters of rosin, glycerine esters of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, coumarone indene resins, petroleum resins and the like known tackifiers, with the result that the composition of the two ingredients of the above admonished block copolymer and tackifier extremely has poor adhesiveness and cannot be used in practice. It is therefore necessary to ensure compatibility of the block blend polymer with the tackifier and make the composition more sticky confer by using an extender oil, together with the block copolymer, which extender oil with the Polyvinylarene — incompatible component of the block copolymer, but is compatible with the diene polymer, as in that U.S. Patent No. 3,239,478, whereas the use such an extender oil reduces the cohesion that characteristic property of the block copolymer and the stability of the composition adversely affected, after it has been applied to the base material.

An object of this invention is to provide a self-adhesive To provide a hot melt adhesive composition which contains a block copolymer as its elastomer ingredient and in the three adhesive properties of tackiness, adhesion

409843/1057 _ ₄ _

and cohesion is excellent regardless of the composition The composition does not contain any diluent oil thus free from the above disadvantages as a result of the use where diluent is oil.

Another object of this invention is to provide a pressure sensitive hot melt adhesive, UJBlcher, uienn melted, the color is free.

Yet another object of this invention is to provide a pressure sensitive hot melt adhesive which which is free from aging after being applied to the base material.

The self-adhesive composition of the present invention includes:

a) A block copolymer: · with the general formula

A-B (I) or

A-B-A (II),

marine A is a vinylarene polymer lock having an average molecular weight of et'ja 5,000 to about 125,000, B is a conjugated diene polymer b.Lock having an average molecular weight of about 5,000 to 250,000, and the content of the ί polymer block represented by B is at least 20% by weight , and

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b) a hydrogenated aromatic petroleum resin, produced by polymerizing a crevice distilled petroleum fraction which boils between -10 and 280 C and contains polymerizable unsaturated hydrocarbons at at least 50 weight - / ^, of which are polymerizable aromatic hydrocarbons and hydrogenating the resulting aromatic hydrocarbon resin to one Degree of hydrogenation of the aromatic ring from 30 to 100 %.

The "degree of hydrogenation of the aromatic ring" or the "degree of hydrogenation" referred to herein is determined by the following equation in terms of the infrared absorbent at 700 cm " ¹ .

- 1

Absorbent at 700 cm

Degree of hydrogenation ' won petroleum resin

the aromatic * / 1 - the hydrogenation ,

Ringes {%) I absorbent at 700 cm-1 ' ^{x | UU}

\ of petroleum resin

\ the hydrogenation

Our research has revealed that the above-mentioned hydrogenated aromatic hydrocarbon resin has excellent compatibility with block copolymer, and that the composition prepared by mixing these two ingredients has excellent properties as a pressure-sensitive hot melt adhesive in that it has high tack, high cohesion and adhesion shows fxei of color despite the absence of an extender oil

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or changes in viscosity in the molten state and not after application to the base material Is subject to aging. Ufir have on different well-known tackifiers conducted studies to find that they are all unable to be satisfactory To give adhesion unless an extender oil is used uiird and that the above-mentioned specific, hydrogenated aromatic hydrocarbon resin such excellent Properties only without the extender oil.

The block copolymer to be used in this invention is represented by the general formula

A-B (I) or

A-B-A (II),

in which A and B are the same as above and in dBr Formal (il) polymer blocks A are the same or different Are uinylarenes. The polymer block A weighs in average molecular weight from 5000 to 125000, preferably 15,000 to 100,000 and a glass transition temperature of usually at least 20 C. The polymer block forming monomers are one or at least two of styrene, IKlBthylstyrol, chlorostyrene, vinyltoluene, vinylxylene, Vinyl naphthalene and the like vinyl arenes. Preferably the polymer block A is polystyrene. The ConventionalB diene polymer block B has an average molecular weight of 15,000 to 250,000, preferably 25,000 to 150,000.

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The glass transition temperature of the polymer block B is at least 50 ° C., preferably at least 100 ° C., lower than that of the polymer block A. The polymer block B is produced from one or at least two of the conjugated dienes, such as butadiene, isoprene, piperylene, etc. The polymer block B contained in the block copolymer must be at least 20 % by weight, and may preferably be in the range of 20 to 80% by weight. The block A and the block B are linked together directly or with a suitable connecting means, such as dipromobutane, divinylbenzene or the like.

The block copolymer is partially or fully hydrogenated. Usually the polymer block B is in the block- mixed polymer hydrogenated to ensure improved weather resistance.

Typical block copolymers are those having the formula (I) in which the P _o lymerblock A is polystyrene and the polymer block B is polybutadiene and those having the formula (Il) in which each polymer block A is polystyrene and polymer block B is polybutadiene , Polyisoprene, or hydrogenated polyisoprene, the latter block copolymer (II) being the most preferred. The block copolymers (i) are preferably, for example, polystyrene-polybutadiene block copolymers, and are preferably block copolymers

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(il) e.g. polystyrene-polybutadiene-polystyrene block copolymer, Polystyrene-polyisoprene-polystyrene block copolymer and polystyrene-hydrogenated polyisoprene-polystyrene block copolymer. These interpolymers are readily available under the trademarks of "Solprene 1205" (polystyrene-polybutadiene Block copolymer from Phillips Petroleum Company, USA), "Cariflax TR-1102" (polystyrene-polybutadiene-polystyrene Block blend polymer from Shell Chemical Company, USA), "Cariflex TR-1107" (polystyrene-polyisoprene-polystyrene Block copolymer from Shell Chemical Company, USA), "Kratom GX-6500" (polystyrene-hydrogenated polyisoprene-polystyrene Block copolymer from Shell Chemical Company, USA) etc.

The block copolymer can be prepared by known methods, preferably those known in the art active polymerization. E.g. uinylarenes will be in the presence polymerized by a lithium based initiator such as lithium metal, alkyllithium or Dilithium initiator to obtain a t / inyl arene polymer, which has a specified molecular weight and a conjugated diene then becomes the reaction system for polymerization added to a polyvinylarene-polydiene block copolymer with the formula (i) of the desired molecular weight to obtain. If a block copolymer having the formula (II) is to be obtained, a vinylarene is the

409843/1057

resulting reaction system further added to the
To effect polymerization and thereby obtain a vinylarene-diene-vinylarene block copolymer having the desired molecular weight. In general, the polymerization reaction is carried out in the presence of a polar or non-polar solvent. If desired, one
Mixed polymer with a diene polymer block of high cis-
To obtain structure, isoprene is used as the diene and the polymerization is carried out in a non-polar solvent. If a multi-branched structure is desired, a polar solvent can be used. If the polymerization system contains a suitable connecting means, the polymer blocks A and the polymer block B can be connected together with the aid of the connecting means
will.

D s _a block copolymer described is an elastomer,
which itself has rubber-like elasticity and thermoplasticity and is soluble in organic hydrocarbon solvents, such as cyclohexane, toluene, benzene, xylene, etc. It is also possible to produce a block iso-polymer of the desired molecular weight according to the reaction conditions. Thus this is obtained
Mixed polymer can be used as it is, not like natural rubber, which needs vulcanization and mastication.

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According to the present invention, it is essential to have a To use hydrogenated product of specified aromatic patrol resin. This makes it possible to have an excellent to obtain self-adhesive grease adhesive, which contains the above-mentioned block copolymer as its elastomer component without adding an extender oil use.

The aromatic patrol resin to be used in this invention is made from a petroleum fraction containing at least 50 % by weight of polymerizable aromatic hydrocarbons based on the total weight of the polymerizable unsaturated hydrocarbons contained therein. The polymerizable aromatic hydrocarbons include aromatic hydrocarbons having a polymerizable double bond either on the side chain ^v or in the condensed ring. Examples thereof are styrene, uinyltoluene, uinylxylene, propenylbenzene, indane, ethylindene, ethylindene, etc. Usually the above starting fraction is obtained by cracked distillation or reforming of petroleum ether and boiling in the range from -20 to 280 ° C, preferably -1G up to 260 C. Such petroleum fractions contain polymerizable unsaturated hydrocarbons other than polymerizable aromatic hydrocarbons. The other polymerizable unsaturated hydrocarbons than

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polymerizable aromatic hydrocarbons cyclic olefins and diolefins, such as, for example, cyclopentene, Cyclopentadiene, dicyclopentadiene, cyclohexene, Cyclooctene etc. and aliphatic olefins and diolefins, ujie for example butene, butadiene, isoprene, pentene, Pentadiene, octadiene etc .. The fraction may also contain Paraffins, alkylbenzenes and the like. Non-polymerizable substances.

The above fraction is polymerized by conventional methods. In one of the preferred processes, the polymerization in an organic solvent is carried out in the Presence of a radical catalyst or Friedel Crafts catalyst, generally at -50 to 100 C under atmospheric or elevated pressure for 2 to 8 Hours running. The resulting resin from which the catalyst and solvent are removed is in oily to bulk form, colorless or brown in color. Preferred resin is a liquid or solid with a softening point of up to 130 ° C, although the physical properties can be varied by the starting fraction used and the polymerization conditions can.

According to this invention, the aromatic petroleum resin then hydrogenated. The degree of hydrogenation plays an important role

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Effect on the compatibility with the block copolymer and the tackiness and adhesion of the resulting composition. In accordance with this invention, it is essential that the aromatic rings be hydrogenated to a degree of hydrogenation of from 3D to 100 % . Ulir have found that a marked improvement in the compatibility with the black copolymer is ensured at a degree of hydrogenation of between about 30 and 100 % . If the level is below 30 % , the resin will have greatly reduced compatibility with the block copolymer and poor adhesiveness and adhesion, possibly causing the resulting composition to suffer discoloration and changes in viscosity upon melting. Thus, only when the hydrogenation is carried out to a degree of hydrogenation of 30 to 100 % , the resulting resin exhibits excellent compatibility with the block copolymer and gives a pressure-sensitive hot melt adhesive composition excellent in adhesiveness, level adhesion and cohesion. The preferred degree of hydrogenation of the aromatic ring depends on the type of block copolymer used. For example, a degree of hydrogenation of 30 to 80 %, especially 50 to 80 % for polystyrene-polybutadiene-polystyrene block copolymer is preferred, 30 to 100 %, especially 50 to 100 %, for polystyrene-polyisoprene-polystyrene block copolymer and 80 to 100 % for hydrogenated Block copolymer of

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Polystyrene-polyisoprene-polystyrene.

The method of hydrogenation is not particularly limited, but conventionally known methods can be adopted. For example, the hydrogenation can be carried out at a temperature of 15G to 300 ° C and a pressure between 10 and 300 kp / cm in the presence of a known hydrogenation catalyst, such as nickel, palladium, cobalt, ruthenium, platinum, rhodium, with the conditions are such that they permit the production of resins with a degree of hydrogenation of from 30 to 100 % . The amount of the catalyst to be used is usually in the range of 0.05 to 20 parts by weight based on the weight of the resin used. The hydrogenation reaction is generally completed within 0.5 to 10 hours.

Preferred as the hydrogenated resins are those in the form of a liquid at room temperature which have boiling points not lower than 300 ° C and those in the form of a solid at room temperature and softening points not higher than 125 ° C. Particularly preferred are those having a softening point uon 20 to 70 ⁰ C, at beuorzugtesten 30 to 60 ° C. The liquid resin mixture is preferably in uerwendet 'with solid resin.

09843/1057 - 14 -

The hot melt pressure sensitive adhesive composition of this invention is made by wiping the block blend polymer and the hydrogenated aromatic petroleum resin with a rubber kneader or a (cliché roller and melting the resulting mixture / orzugujeise at one temperature from ettua 120 to 200 C. The relationship between these two ingredients is usually 30 to 300 parts by weight, preferably 50 to 250 parts by weight of the latter per 100 parts of the former. Synthetic rubbers, such as arbitrary SBR, polyisobutylene etc. and Ethylene vinyl acetate copolymer can be used together with dBm Block copolymer also used. With the hydrogenated Aromatic petroleum resins are also known tackifiers can be used with, for example, hydrogenated rosin, polyterpene resins, glycerol esters of hydrogenated rosin, Pentaerythritol ester of hydrogenated turpentine resin, IYIethy 1— aster of hydrogenated rosin, higher alcohol esters of hydrogenated rosin etc. These additional ingredients however, must be used in such amounts as to improve tack, adhesion, cohesion and Aging stability of the composition obtained will not degrade. The composition of this invention need not include extender oil therein, which has heretofore been used as an essential ingredient whereas, as in conventional practice, the composition may contain various additives such as

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for example antioxidants to prevent the Oxidizing the composition and a softener for Lowering the melt viscosity. These additives should too used in amounts such that they will not degrade the properties of the composition.

The self-adhesive adhesive composition of this invention is applied in the molten state on various base materials, which are in a sheet-like shape Shape such as film and foil. Examples of these sheet-like base materials are paper, Plastic film, plastic sheet, woven fabric, non-woven Fabric, wooden board, metal board, cast board, thin Rubber sheet, synthetic paper, tape, tile, laminate etc .. The preferred melting temperature of the Composition is usually about 120 to 200 C. Advantageous Compositions having melt viscosities of 10,000 to 230,000 cps are useful. Usually the molten composition is applied to the surface of the base material by an applicator, a roller device Od. The like. Layer arrangement applied and then cooled. The coating has ordinary one Thickness of about 10 to 500 microns. The base material can also be continuously melted through a composition running, whereby coatings are formed on the surfaces and then cooled. Likewise

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- 1 D -

'- 16 -

are various other known B order procedures applicable, For example, the present composition can be in melted State to be extruded to produce a film or sheet on either or both of them Surfaces of release paper stuck on.

For a better understanding of the invention, the following examples are given.

example 1

By steam crack distillation won petroleum ether was a Carbon dioxide fraction obtained, which has a boiling point from 130 to 240 ° C and 52% by weight styrene, indene and their polymerizable derivatives contained 39% by weight non-polymerizable aromatic substances, 3% by weight Olefin, less than 1% by weight diolefin and 5% by weight "paraffin and naphthene. To 1000 g of the hydrocarbon fraction was added consisting of 300 g of hydrocarbons from 58% by weight of olefin and 42% by weight of paraffin and obtained by removing diolefin from a hydrocarbon fraction, which boiled at -10 to 15 ° C. To the mixture was added 13 g of boron trifluoride phenate as a one Catalyst, and the mixture was then at a temperature polymerized at 30 C for 3 hours. To the reaction mixture obtained, 10% by weight of aqueous was added

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Sodium hydroxide solution and then the mixture was taking

ο atmospheric pressure to a temperature of 80 C heated.

The aqueous phase was then deposited, the reaction mixture was washed three times with hot water at 50.degree and was thereafter under a reduced pressure of 5 mmHg heated to 180 C to remove unreacted substances and low polymers. As a result were 480 g of a hydrocarbon resin with a ball and Ring equilibrium point of 55 C obtained. The resin is in hereinafter referred to as sample resin 1.

100 g of the aromatic petroleum resin thus obtained and 100 g of cyclohexane were dissolved in an autoclave to prepare a solution, which was then heated at 200 ° C. at a hydrogen pressure of 200 kgf / cm in the presence of 8 g of Raney nickel catalyst for 2 hours. After the reaction, the catalyst was removed by passing the resulting hydrogenated solution through a glass filter. Then cyclohexane was distilled off from the solution to 100 g to obtain a hydrogenated resin having a hydrogenation degree of 12% and a softening point of 55 ⁰ C. The resin is referred to as a sample resin 2 hereinafter.

403843/105?

- 18th

In the same way as above, hydrogenated resins were used various degrees of hydrogenation and softening points can be added to the sample resin 1 by varying the type and amount of the Catalyst, hydrogen pressure, reaction temperature and time made, taie in the table below listed, including each hydrogenated resin thus obtained in hereinafter referred to as sample resin 3, 4, 5, 6 or 7, luia given in Table 1.

4 0 S 8 4 3/1 0 5 7

- 19th

Prob
hfl v-7 Catalyst length (g) Reaction Table 1 LUasser- yield Expansion Hydrie lld X ί-
No. Art IfIe temperature Reaction material-
print ₂ (*) chungs
Point
(OC) guessing
Degree 1 ■ 8
1 time (h)
( 55 0 2
3 Ra neynickel
Nickel atom
Earth 1.5
2 200
200 5
50 100
97 55
53 12th
35 JN
O
ίΟ
CO
J- * 4th
5 stabilized
Nickel dia tomen-
Earth
stabilized
Nickel atom
Earth CJl 250
250 2
5 150
150 98
95 52
52 52
70 ►3 / 1057 6th stabilized
Nickel atom
Earth 10 250 5
5 150 95 50 80 7th stabilized
Nickel atom
Earth 250 CJl • 150 90 50 100 5

'- 20 -

100 g of commercially available polystyrene-polybutadiene-poly- styrene block copolymer (trademark: "Cariflex TR-1102", Product of Shell Chemical Company, USA) and 140 g of Sample Resin 4 were mixed together and 1 g of zinc di-n-butyldithiocarbamate (Antioxidant) was also added. The resulting mixture was heated to 120 ° C mixed and then heated to 180 C to form an adhesive composition with a melt viscosity of 40,000 to 60,000 cps. In the same way as above, similar ones became Compositions using the sample resins 3, 5 and 6 listed in Table 1 prepared. Likewise became sample resin 1 to 2 and glycerol ester of hydrogenated Rosin, pentaerythritol ester of hydrogenated rosin, Terpene resin and 2-methyl-2-butenepiperylene resin used, to make similar compositions for comparison.

Each of the compositions was at the same temperature applied to a polyester film as above (trademark: "Lumirror", a product of Toray Industries, Inc., Japan) applied to a thickness of 150 microns by an applicator, to make a self-adhesive tape. The tape was then cooled to 20 C for 12 hours left to stand and then at 20 ° C. for adhesion, adhesion and cohesion with the values given in Table 2 below the results given.

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Further, after the composition was applied, the adhesive tape was left to stand in an air oven at 7D C for 3 days and then held at 20 C for 12 hours. The tape was then similarly examined for degradation due to aging. The results are shown in the table 2 given in brackets.

The properties of the adhesive tape were as follows Procedure determined as determined by the Self-Adhesive Tape Committee (PSTC).

Adhesion:

A polyester film, 25 mm by 300 mm, was applied by an applicator coated with the adhesive composition, and the obtained tape was examined to measure the adhesiveness according to the method of PSTC-6. The polyester film was placed on a horizontal plate with the coated surface facing up and another plate became attached to one end of the polyester film, sloping upward at a 30 ° angle to the horizontal plate to extend. A steel ball 10 mm in diameter was placed on the inclined plate from a position 10 cm from the floor the plate rolled down, and the distance the steel ball rolled along the adhesive surface of dBs polyester film, was measured. The smaller the measured amount, the more

"409843/1057 - 22 -

the result is better.

Adhesion:

A polyester film of 15 mm in width was coated with adhesive composition by an applicator to form an adhesive tape to manufacture. As noted under PSTC-1, the tape was adhered to a stainless steel plate, and the plate was placed on a Tensilon Tester, Model UTHfI-III (manufactured by Toyo measuring Instruments Co., Ktd., Japan) and a detachment attempt at an angle of 180 30 mm / min subjected to that required for peeling Measure load.

Cohesion:

A polyester film 15 mm wide was coated with the adhesive composition coated to make an adhesive tape. The test piece was attached to a glass plate over an area of 15 5 mm glued, and the plate was attached to the same Tensilon tester as above and the shear tensile test When exposed at a constant rate of 5 mm / min, the glued-on test piece could be different from the original Position on the glass plate was moved, this became the case required load measured;

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ORIGINAL INSPECTED

table 2

Sample no.

Degree of hydrogenation {%)

Softening point of the hydrogenated product ( ⁰ C)

Adhesion
(cm)

adhesion
(p / 15 mm)

cohesion

2 (p / i5x5 mm)

CO

co

U)

at

1
2
3
4th
5
6th
A.

C.
D.

0 55

12 55

35 53

52 ■ 52

70 52

80 50

Glycerol ester won

hydrogenated turpentine- 70

resin

Pentaerythritol ester won

hydrogenated rosin 95

Terpene Resin '70

2-ethyl-2-butene- _g5 piperylene resin

no (no)
over 30 (none)

(25)
(14)

(10)
(10)

over 30 (none)

no (no)
no (no)

500 (-) 800 (-)

800 (300) 1000 (1500)

1300 (700) 1800 (2200)

1500 (900) 2000 (2300)

1400 (900) 2000 (2250)

over 30 (none) 2500

1500

• 1500

2000

no

Note: The symbol "-" indicates that the property cannot be determined, as in the following tables.

Example 2

For 100 g of a commercial polystyrene-polyisoprene-polystyrene block copolymer (Trademark: "Cariflex TR-1107" Product of Shell Chemical Company, USA) and are added 140 g of the hydrogenated resin prepared in Example 1, followed by the same procedure as in Example 1, to produce a Make self-adhesive tape, ll / ie in dBr the following Listed in Table 3, the adhesion and cohesion and seven types of tapes thus made are measured, along with their stability against aging (given in brackets). These properties were based on the same procedure was determined in Example 1.

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- 25 -

-ο-co

Hydrogenation
degree {%) Softening
point of
hydrogenated
Product ( ⁰ C) Table 3 r 30) 0) adhesion
(p / 15 mm) (") cohesion
(p / i5x5 mm) (") I. Sample-
No. 0 55 Detention
capital
(cm) 12.6. (26) 0) 1850 (-) 3200 (-) Oil 1 12th 55 8.0 (20, 4) 1790 (1850) 3000 (3000) \ 2 35 53 5.0 (15. 2) 1640 (1200) 2450 (2500) 3 52 52 over 30 (none) ' 5.4 (13. 1580 (1300) 2000 (1900) 4th 70 52 over 30 (ex 5.5 (10, 1550 (1320) 1950 (1940) 5 80 50 1510 (1410) 1920 (2000) 6th 100 50 1550 1900 7th

Example 3

100 g of commercially available polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (polystyrene-ethylene propylene copolymer-polystyrene block copolymer) (trademark: "Kratom GX-6500", product of Shell Chemical Company, USA) and 140 g of the hydrogenated resin obtained in Example 1 were mixed together and 1 g of zinc di-n-butyl-dithiocarbamate was added. The mixture was then mixed and melted at 180 ° C to prepare an adhesive composition. For comparison, similar compositions were prepared in the same manner as above using non-hydrogenated resin, resin having a degree of hydrogenation of 12 % and adhesiveness of glycerin ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, and rosin, respectively.

Using an applicator, each of the compositions was applied to a polyester film up to a thickness of 250 microns to obtain an adhesive surface, ujelche was left to stand overnight at 20 C and then was examined for tackiness, adhesion and cohesion.

Adhesion was measured on a Polyken Probe Tack Tester (Product of Kendal Company, USA) examined under the following conditions:

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Examination diameter 5 mm

Contact pressure 10 p / cm

Contact time 0.2 sbc

Tear resistance 5 cm / sec

The larger the measured amount, the worse it is Result.

The adhesion and cohesion were determined in the same way determined in example 1. The results are in the following Table 4 given.

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Table 4

Sample-
No. Degree of hydrogenation Eruj point of reference
of hydrogenated
Product (oc) Adhesion
(p / cm ² ) adhesion
(p / 15 mm) Cohesion
(p / i5x5mm) 1 D. 55 no - - 2 12th 55 no I. - • Ρ »
O 3 35 53 70 1600 4000 to
co
■!> ■ 4th 52 52 100
* 3000 3500 - **. 5 70 52 180 2800 2800 O 6th 8D 50 400 2400 2100 W. 7th 100 50 600 1800 1400

Glycerol esters of
hydrogenated rosin

PentaBrythritBster from
hydrogenated rosin

Terpene Ha rz

70

95 70

no

no no

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Example 4

With stirring and water bath cooling, 120 g of boron trifluoride etherate were obtained 12 kg of a fraction added dropwise, which in the range where 14G boils to 200 ° C, obtained by thermal Crack distillation won petroleum ether. The starting fraction consisted of 38% by weight of styrene, indene and theirs polymerizable derivatives, 47 weight / ?! not polymerizable aromatic compounds and 15% by weight non-polymerizable Substances. The mixture was continued for another 3 hours at about 25 C after the heat generation stopped touched. 1 liter of a 5% by weight aqueous Sodium hydroxide solution was then added to the mixture, followed by vigorous stirring for 1 hour. to decompose the catalyst. The resulting aqueous phase was separated. The product obtained was then washed three times with water and then distilled to give 5.1 kg of a mass of aromatic hydrocarbon resin brown in color as a residue. The resin had a ball and ring softening point of 124 ° C.

500 g of the aromatic petroleum resin thus obtained was obtained dissolved in the same amount of naphthane, and the solution was in an autoclave under a hydrogen pressure of 150 kgf / cm at a temperature of 300 C in the presence of 20 g IMickel diatomaceous earth catalyst heated for 8 hours to

409843/1057 - 30 -

- 3U - ■

To obtain 400 g of hydrogenated resin which had a softening point of 54 ° C. and a degree of hydrogenation of 100 % .

To 100 g of a commercially available polystyrene-hydrogenated polyisoprene-polystyrene Block copolymer (trademark: "Kratom GX-6500", the same as in Example 3) was 140 g of the above hydrogenated resin and 1 g of zinc di-n-butyldithiocarbamate was also added. The mixture was mixed and melted at 180 ° C to form a composition obtain a melt viscosity of 200 cps at 180C. The composition was applied by an applicator to a polyester film to a thickness of 250 microns applied at the same temperature to create an adhesive surface, which is then cooled to 20C and left to stand overnight. In the same way as in Example 3, the adhesiveness, adhesion and cohesion of the surface were measured with those given below Results.

Adhesion (p / cm) 580

Adhesion (p / 15mm) 1900 Cohesion (p / i5x5mm ² ) 1600

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Example 5

To 100 g of a commercial polystyrene-polybutadiene mixed polymer (trademark: "Solprene 1205", product of Phillips Petroleum Company, USA) were added 100 g of sample resin 5 with a degree of hydrogenation of 70 % and 1 g of zinc di-n-butyl carbamate was also added. The mixture was mixed at 120 ° C. and further at 180 ° C. to obtain a self-adhesive meltable composition having a melt viscosity at 180 ° C. of 60,000 cps.

Claims

4098 / + 3/105 7

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Claims (1)

b) Gin hydrogenated aromatic petroleum resin, produced by polymerizing a crack-distilled petroleum fraction which boils between -10 and 2SG ° C and contains polymerizable unsaturated hydrocarbons, of which at least 50 are polymerizable aromatic hydrocarbons and hydrogenate the resulting aromatic carbon dioxide to a degree of hydrogenation of the aromatic ring of 30 to 100 % 2. Self-adhesive adhesive composition according to claim 1, characterized in that 4098 Δ 3/1057 - 33 - that the block blend polymer Br has the general formula AWAY, ujorin A is a Winyla renpolymer block, the Am in between lYlolekulargeujicht has from about 50Q0 to about 125000, B is a conjugated diene polymer block having an average molecular weight of about 15,000 to 250000 and the content of the represented by B. Palymerblockes is at least 20% by weight. 3. Self-adhesive hot melt adhesive composition according to Claim 2, characterized in that A is a polymer block of polystyrene and B is a polymer block of polybutadiene. 4. Self-adhesive hot melt adhesive composition according to Claim 1, characterized in that that the block copolymer has the general formula A-B-A, wherein each A is a vinylarene polymer block that is an average Molecular weight from about 5000 to about 125000, B is a conjugated diene polymer block, which has an average molecular weight of about 15,000 to 250,000 and the content of that represented by B. Polymer block is at least 20% by weight. 409843/105 7 - 34 - - 54 - 5, self-adhesive hot melt adhesive composition according to Claim 4, characterized in that that A is a polymer block of polystyrene and B is a polymer block of polybutadiene, polyisoprene or hydrogenated Is polyisoprene. 6. Self-adhesive hot melt adhesive composition according to Claim 4, characterized in that the block copolymer is a polystyrene-polybutadiene-polystyrene block copolymer, Polystyrene-polyisoprene-polystyrene block copolymer or polystyrene-hydrogenated polyisoprano-polystyrene block copolymer is. Self-adhesive hot-melt adhesive composition according to claim 1, characterized in that the block copolymer is a polystyrene-polybutadiene-styrene block copolymer and the degree of hydrogenation of the hydrogenated aromatic petroleum resin is in the range from 30 to 80 % . S ₁ Self-adhesive hot-melt adhesive composition according to Claim 7, characterized in that the degree of hydrogenation is in the range from 50 to 80 % . 5c Self-adhesive melt-on glue composition according to Claim 1, characterized in that 4 0 9843/105 '' - v- - that the block copolymer is bin plystyrene-polyisoprene-polystyrene block copolymer Br and the degree of hydrogenation of the hydrogenated aromatic petroleum resin is in the range of 30 to 100 % . 10. Self-adhesive melting KlBbBzusammBnsBtzung according to claim 9, characterized in that the degree of hydrogenation in the range of 50 to 100 % i 11. Self-adhesive hot melt adhesive composition according to claim 1, characterized in that the block copolymer is a polystyrene-hydrisrtes P _o lyisoprene-polystyrene-block mixed polymer and the hydrogenation level of the hydrogenated aromatic petroleum resin is in the range from 80 to 100 % . 12. Self-adhesive hot melt adhesive composition according to Claim 1, characterized in that the hydrogenated aromatic petroleum resin in an amount of 30 to 300 parts, based on 100 parts of the block copolymer. 13. Self-adhesive hot-melt adhesive composition according to Claim 12, characterized in that that the amount of hydrogenated aromatic petroleum resin in the range of 50 to 250 parts, based on 4 0 9 8 L 3/1 0 K 7 - 36 - 100 parts by weight of the block blend polymer. 14. self-adhesive hot melt adhesive composition; characterized by a foil-like Base material with a coating of the in Claim 1 has the composition claimed. 409843/1057