Tackifying Resin, Product Description: Escorez™ LC is a premium aromatic modified aliphatic hydrocarbon resin with a narrow molecular weight. Product datasheets and sales specifications for Escorez™ tackifying resins. Africa & Middle Escorez™ LC (AM & EU), 18, , Escorez™ , PRODUCT NAME: ESCOREZ series .. THE FOLLOWING MATERIALS: Petroleum hydrocarbon resin ECR | Escorez LC |.
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These resins have an improved adhesive performance in hot melt pressure sensitive adhesive compositions. Escorex above polymer often is an S-I-S styrene-isoprene-styrene block copolymer having polystyrene and 20 polyisoprene block segments.
The petroleum-based resin exerts an important influence on the physico-chemical properties of the adhesive such as its hot melt viscosity, compatibility to aromatic solvents, shear properties and tack properties. To attain the optimum profile of a low melt viscosity, good compatibility to organic solvents, high tack and shear properties without losing high temperature shear performance, conventional petroleum-based tackfying resins used to contain a certain amount of aromatic modifications.
Prior art resins with no aromatic modification failed to attain the above properties to a satisfactory extent. US 4, describes the use of escorsz resins prepared as described in US 3, in S-I-S based hot melt pressure sensitive adhesives. EP describes the use of aliphatic and aromatic modified aliphatic resin in S-I-S based hot melt pressure sensitive adhesives.
US 4, describes the use of aliphatic and aromatic modified aliphatic resins with softening points from 0 to 80 C as tackifier in styrene butadiene ss polymers.
US 4,describes the preparation of aliphatic and aromatic modified aliphatic resins from heat-soaked piperylene streams. Isobutylene and isoamylene are described to act as chain transfer agent and alpha-5 methylstyrene AMS is described to be used as a aromaticmodifier.
Some applications are described using resins with softening points between 70 and 85 C. The aromatic modification caused hot melt pressure sensitive adhesive formulations having a low viscosity and enhanced tack properties. Aromatic modified tackifying resins, however, are 15 disadvantageous for edcorez number of reasons.
Firstly, aromates are relatively expensive and the use of no aromate would make the resin cheaper. Secondly, they are less suitable for hydrogenation, hydrotreatment and quenching processes to improve 2203 resin colour, before 20 they are used in any application. Thirdly, aromatic modified aliphatic resins result in lower shear performance at higher temperatures in hot melt based pressure sensitive applications.
It would therefore be desirable to provide a cheaper petroleum-based resin 25 which exhibits similar or even better application properties than aromatic modified resins.
The resins of the present invention are 10 particularly distinguished from aliphatic resins of the state of the art in that they contain a higher amount of cyclic structures. J a number of physicochemical 25 properties which are indicative for cyclic structures. This increase can preferably be achieved by varying one or more of the following parameters in the polymerization reaction: The escogez increase of the amount of cyclic 20 structures in the aliphatic resins can e. Futhermore, they impart excellent tack and shear properties on these hot melt compositions.
It was found by the inventors that the amount of cyclic structures could be influenced by varying the polymerization conditions, like catalyst 15 level, reaction temperature, amount of chain transfer agent and the feed composition.
Details of Escorez Import Data Under HS Code 39111090 in June
The final adhesive application properties of such resins 25 are optimized by controlling the amount of cyclic structures by varying the reaction temperature, the amount of catalyst, the amount of chain transfer agent and the feed composition.
It was also observed that such resins had a better compatibility in aromatic solvents, as could 10 be seen by the lower MMAP cloud escorea. This was not due to any significant incorporation of aromatic components because the proton NMR analyses showed no significant differences between regular aliphatic resins and the resins prepared according to this invention. The ultimate resins of this invention have the following properties: These polymerized resins can be used as tackifiers in hot melt pressure sensitive compositions which further 25 comprise a polymer and optionally an extender oil and other adjuvants.
A preferred hot melt pressure sensitive composition according to the inventlon comprises a mixture of: In this embodiment, the petroleum tackifier resin ii to be included may have an MMAP of 90 C of less, but this is not essential. The hot melt composition esforez a melt viscosity at C of less than lO0,2023 less than escorea, mPas measured according to ASTM-D with a Brookfield 20 viscosity meter. The use of the resin ii according to this: Commonly, the resins of the present invention are prepared by Friedel-Crafts polymerization in ecorez a S mixture of a cracked petroleum feed and a chain transfer agent in an inert solvent is treated with 1.
Other esxorez dienes which are formed by co-dimerization of the cyclic S dienes with CS linear conjugated dienes or other reactive olefinic components in the petroleum feed stream, can also contribute to a higher degree of cyclic structures in the final resin, Average compositions of two used petroleum feed 10 streams, with and without cyclodiolefins are given below.
Examples of cycloolefins are cyclopentene and cyc l ohexene. Examples of diolefins are cis and trans-piperylene 1,3-pentadiene1,4-pentadiene, isoprene, 1,3-hexadiene and 1, 4 -hexadiene. Examples for cyclodiolefins are cyclopentadiene, dicyclopentadiene, methyl and ethyl derivatives of both components and codimers of the cyclopentadiene and the diolef ins.
A commercial sample of a petroleum feed without any cyclodiolefins is Shell’s NL super piperylene concentrate and a commercial sample of the preferred petroleum feed containing the desired cyclodiolefins is 5 Shell ‘ s NL regular piperylene concentrate.
The cyclodiolefinic components can of course also be added to a cyclodiolefinic poor stream, A particularly suitable petroleum stream contains at least 70 wt96 of polymerisable monomers with at least 50 10 wt96 piperylene. As chain transfer agent generally isobutylene, 2-methylbutene, 2-methylbutene or their dimeric oligomers are used to obtain resins with a lower and narrower molecular weight esclrez.
For cost price reasons it is preferred to use isobutylene pure or in a diluted form. The catalyst for the polymerization is used in an 10 amount of 1. O wt96 based on the amount of polymerisable components in the polymerization feed. It is found in this invention that a higher catalyst level, optionally in combination with a higher temperature, 15 lowers the molecular weight while the resin softening point is kept constant.
The resulting resin has a lower melt viscosity in a hot melt pressure sensitive composition. The increase of the catalyst level also increases the compatibility to aromatic solvents as 20 reflected by a lower MMAP cloud point see example 1.
The catalyst can be chosen from any suitable Friedel-Crafts catalyst, such as aluminum trichloride, aluminum bromide, aluminum fluoride, titanium tri and tetrachloride, tin tetrachloride, boron trifluoride, or 2s solutions, slurries or complexes thereof.
It was found that a higher reaction temperature resulted in a more cyclic structure reflected by a lower molecular weight when the resin softening point is kept constant. Again the resulting resin caused a lower melt viscosity in the hot melt pressure sensitive composition together with excellent tack and shear S properties see ezcorez 2. The polymerization can be carried out in a continuous process or in a batch mode.
The reaction time is typically from 1. After polymerization the residual catalyst may be removed by, for example, addition and extraction with water.
The thus obtained polymer-solvent mixtures may be stripped to remove unreacted hydrocarbons, solvents and low molecular weight oligomers.
The final resin usually has a higher softening point. Thus obtained resins which are most suitable for use as tackifiers according to this invention have: Normally, the MMAP cloud point of commercially available non-modified aliphatic resins based on similar petroleum feed streams is 90 C or higher, whereas lower MMAP values could only be obtained with aromatic modified resins.
This is illustrated in the following table: Typical polymerization conditions for the above mentioned resin are given below.
Escorez Import Data of HS code in June –
O wt96 per total of polymerisable monomers Polymerization feed: Such a hot melt pressure sensitive adhesive composition can be used in a variety of forms. Particularly preferred application forms are adhesive tapes and labels. The hot melt pressure sensitive adhesive composition generally consists of an S-I-S block copolymer, a petroleum tackifier resin as described in this invention and other additives as known in the art like hydrocarbon extender ewcorez, antioxidants, colorants, fillers etc.
The quantity of the petroleum resin used in combination with the block copolymer may esocrez from 70 to parts by weight per parts of block copolymer. A more preferred range is from escores to parts by weight per parts block copolymer. Escorfz used, the amount of extender oil is added at a level up to 70 parts per weight per lO0 parts block copolymer, more preferably in a range from 5 to 50 parts by weight. The S-I-S block copolymers can be selected from the group of polymers containing 0 to 30 parts per weight of styrene and 0 to 40 parts per weight of diblocks.
As mentioned earlier, a hot melt formulation according to this invention preferably exhibits a melt viscosity of belowmPas CPS measured at C and more preferably lower than 60, mPas at C.
The resin according to this invention which is used in the following examples will be hereinafter called: A typical composition of the used petroleum feed streams with and without cyclodiolefins and the plant 5 recycled solvent is given below: The catalyst used in the examples was a 52 wt96 AlCl3 solution.
The abbreviations and trade names used in the following are explained in the Experimental Section below. The viscosity S drastically decreases when more catalyst is used.
Product datasheets and sales specifications for Escorez™ tackifying resins
Using higher temperatures, the melt viscosity S decreases drastically. When the temperature is increased from 60 to 80 and lOO C the same trends for the resin properties were observed. Skg,min Shear to steel 70 C,0.
Skg,min Examole 3 Table 4 illustrates the advantage of using a feed containing more cycloolefins and cyclodiolefins. Effects of the feed composition. The presence of S the cyclodiolefins, like cyclopentadiene and dicyclopentadiene contribute already for a great part to the cyclic character of the resin and cause a lower melt viscosity of the hot melt formulation and a lower MMAP of the resin. All three resins are within the scope of this invention as defined by the appending claims and all are based on a feed 5 containing cyclodiolefinic components.
The resins of example 4b and 4d show good ball tack and sufficiently high shear strengths.
Z5 It is clearly shown that the amount of protons in the aromatic range for the Inventive Resin is comparable to other aliphatic resins like HercuresD C and PiccotacD 95E.
A higher aromatic modified resin RESIN B, about 18 wt96 5 per resin aromatic modified showed a higher amount escorsz aromatic protons. The shear to carton at 40 C is not significantly different for ecsorez four resins. The use of Piccotac 95E aliphatic resin esxorez in a better high temperature shear to steel but also in a higher viscosity.
The Inventive Resin was also compared with some 5 competitive resin samples. The use of Escorez LC gives a better high temperature shear to steel like 5 found for Piccotac secorez but 2230 gives the highest viscosity. Vector was used as polymer. All resins mentioned herein were prepared in a continuous process, but a batch production would also be possible. The mixture was continuously removed at a level of 3 liters so that the reaction escoreez for all experiments was 2 hours.
The mixture was deactivated with water and washed in three 10 steps with water before it was stripped under vacuum and with steam to remove the solvent and all the low molecular weight materials.
Method for the determination of the MMAP: The Methylcyclohexane is substituted for the heptane used in the standard test procedure. Method for the determination of the resin colour: To determine the Gardner colour the resin was mixed with reagent grade toluene at room temperature until all the resin was dissolved.
The colour was determined spectrophotometrically using the Dr. Lange LICO apparatus. Method for the determination of the molecular weiqhts: Method for the determination of the viscositv: The peel strength is measured by a PSTC-1 test.