JP2619868C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for preparing a novel terpolymer tackifier which is particularly adapted for use as a tackifier in an adhesive composition. European Patent Application 75,771 shows (1) the reaction of an alkylated phenol with a terpene or (2) the reaction of a phenol with a terpene and the process wherein the reaction product is alkylated with, for example, styrene. . The product is used as a polymer stabilizer. The general formula of the phenol used during the reaction is shown below. Wherein R can include a terpene group or an alkyl, cyclohexyl or cyclohexenyl group, or a group derived from divinylbenzene or diisopropenylbenzene, wherein R ¹ , R ² and R ³ are hydrogen, It is an alkyl, cycloalkyl or aralkyl, n is a number from 0 to 20.) In the process of the European patent application, if a vinyl-substituted aromatic component is present, at the same time no terpene component is present in the reaction mixture. Therefore, there is no structure having a combination of a terpene component and a vinyl-substituted aromatic component. A method of making a vinyl-substituted aromatic / terpene / phenolic terpolymer tackifier suitable for use as a stabilizer in an adhesive component, wherein the vinyl-substituted aromatic component and the terpene component bind to each other and also bind to the phenol component. It is desirable to invent. According to the present invention, a method for producing a tackifier for use in an adhesive composition from a phenol, a terpene and a vinyl-substituted aromatic component is represented by the following formula (1) Wherein R ′ is hydrogen or —CH ₃ , and R ″ is hydrogen, —CH ＝ CH ₂ or an alkyl group having 1 to 10 carbon atoms.
5% (2) about 5 to 75% of at least one monoterpene hydrocarbon; and (3) about 0.75 to 50% of at least one phenol. {Of components (1), (2) and (3) The sum of the percentages is 100%. The vinyl-substituted aromatic / terpene / phenol terpolymer having a ring and ball softening point of about 69-130 ° C. is obtained by simultaneously polymerizing the monomers in a mixture containing｝ in a solvent in the presence of a catalyst. All parts and percentages are characterized by weight unless otherwise noted. In the process of the present invention, all components are present simultaneously during the reaction mixture, thus
Terpolymers are formed by the polymerization of co-existing vinyl-substituted aromatic, monoterpene and phenolic components, the phenolic components being an integral part of the polymer chain. The combination of the three components will be random and no particular structure can be written. The positions on the phenol that affect the reaction of the vinyl-substituted aromatic component with the monoterpene component have -OH groups, and none of the carbon atoms in the ortho and para positions are replaced with -OH groups. For example, the phenol itself has four reaction sites where the other two component combinations of monomer loading occur. There are several suitable approaches to accomplish the method of the present invention. In one approach, the three monomer mixtures and catalyst are added to the solvent in the reaction vessel with vibration via separate inlets. Temperature is controlled by external cooling water. Sufficient catalyst in this approach is added at the start of the reaction. In another approach, the solvent and all monomers are initially present in the reaction vessel. The reaction is initiated by the intermittent addition of a small amount of catalyst until the amount of heat generated is controlled by external cooling water. The other approach may be used when the monomer charge has 20% or more by weight phenolic components. This approach is followed the slow addition of a solution of phenolic components and BF ₃ make the mixing of the catalyst a vinyl-substituted aromatic component and the monoterpene component in the solvent in BF ₃ / phenol mixture. The requirement that the weight ratio of the phenolics component in the monomer charge be at least 20% ensures that at least about 0.75% phenol is present in the mixture before the addition of the other two monomers is complete. . In either approach, after completion of the reaction, the catalyst is neutralized by the reaction of this approach using an aqueous caustic or lime. After removing the solvent and any volatiles, the product is separated. Reaction temperatures are from about -15 ° C to about + 65 ° C, but preferably from about 0 ° C to about + 50 ° C. Suitable catalysts include BF ₃ , BCl ₃ and are complexed with BF ₃ , for example, with water, ethyl alcohol, H ₃ PO ₄ , phenol or ether. Rather, BF ₃ is better. The solvents used are those which are inert under the conditions of the polymerization and are aliphatic or rather aromatic hydrocarbons, such as toluene or xylene, or Exxon Aromatic
It has a mixture of aromatic hydrocarbons such as 100. The vinyl-substituted aromatic hydrocarbon (1) used in the method of the present invention has a general formula Wherein R ′ is hydrogen or —CH ₃ and R ″ is hydrogen, —CH ＝ CH ₂ or an alkyl group having 1 to 10 carbon atoms. Suitable vinyl-substituted aromatic hydrocarbons are limited. But not limited to styrene, alpha methyl styrene, para methyl styrene, vinyl toluene, tertiary butyl styrene, alpha-P-dimethyl styrene and divinyl benzene, with styrene being preferred. Vinyl-substituted aromatic hydrocarbons may be used if desired as component (1), preferably from about 12% to about 95% by weight based on total monomer charge, preferably from about 12% to about 95%. Is used from about 21% to about 77% The monoterpene hydrocarbon used in the process of the present invention is not limited, but is not limited. It has alpha-pinene, beta-pinene, dipentene, limonene and confen.A mixture of two or more monoterpene hydrocarbons is used as the desired component (2). From about 5% to about 75% by weight, and more preferably about 19% by weight.
Used up to about 65%. The phenols (3) used in the process of the present invention include, but are not limited to, phenols that at least replace the C atom in the ortho or para position with an -OH group, but are not limited to para-nonylphenol, meta- -With phenols such as cresol, ortho-cresol and bisphenol A and alkali-substituted phenols. Phenol is preferred. If necessary, a mixture of two or more phenols can be used as the component (3). The phenols are used in a total amount of about 0.75% to about 50% by weight based on the total monomer feed, preferably
Used from about 3% to 40% by weight. Also, according to the present invention, a polymer product formed from phenols, terpenes, and vinyl-substituted aromatic compounds has a vinyl-substituted aromatic / terpene / phenol having a ring and ball softening point of about 69 ° C. to about 130 ° C. A terpolymer tackifier, suitable for use in adhesive compositions, where the polymerized product has the general formula (1) Wherein R ′ is hydrogen or —CH ₃ and R ″ is hydrogen, —CH ＝ CH ₂ or an alkyl group of 1 to 10 carbon atoms. (2) from about 5% to about 75% of monoterpene hydrocarbons (3) formed by simultaneous polymerization of about 0.75% to 50% of phenols. The terpolymer has a bright tint (Gardner 1-
5). The resistance to blackening of the color at elevated temperatures in air may be improved by the addition of small amounts of antioxidants such as dilauryl thiodipropionate or distearyl thiodipyrropionate. Terpolymers formed by the process of the present invention have a ring and ball softening point of about 69 ° C to 130 ° C and are particularly suitable for use as tackifiers in adhesive compositions. Smaller molecular weight products are preferred because, in general, smaller molecular weight products are more readily soluble in any given adhesive composition than higher molecular weight products.
The weight average molecular weight of the terpolymer is preferably between about 500 and about 2000. The compatibility between the terpolymer and the composition of the adhesive used in the composition of the adhesive can be controlled by adjusting the ratio of the three components of the monomer supply amount. For example, if the composition of the adhesive is primarily aromatic, it may be necessary to increase the proportion of the vinyl-substituted aromatic component. If the composition of the adhesive is primarily aliphatic in nature, it may be necessary to increase the proportion of the terpene component. Further, compatibility can also be controlled by changing processing conditions such as reaction time, reaction temperature or type of catalyst used. These processing conditions affect the molecular weight of the terpolymer product and its softening point. One type of adhesive composition in which the terpolymer can be used is a solvent-based pressure sensitive adhesive. Such an adhesive may be a tripolymer or a natural rubber, styrene-butadiene (SBR), styrene-isoprene-styrene (SIS), or a multi-block copolymer of styrene-butadiene produced by the method of the present invention. The adjustment may be made using a polymer of a high-molecular elastic substance. The terpolymer and elastomer (elastic polymer) are dissolved in a solvent such as toluene. If necessary, antioxidants and other stabilizers such as tetrakis [methylene- (3,5-dita tert-butyl 4-hydroxyhydrocinnamate)] methane (Irganox 1010, Ciba-Geigy) are included in the ingredients. May be. Another type of adhesive composition in which the terpolymer can be used is a hot melt pressure sensitive adhesive. Such adhesives may be prepared, for example, by dissolving the terpolymer at elevated temperatures, by an antioxidant in an elastomer as described above, or a plasticizer of the naphthine class. Another type of adhesive composition in which the terpolymer can be used is a non-pressure sensitive hot melt adhesive. The components of such adhesive compositions are formulated at elevated temperatures and may be, for example, terpolymers, waxes such as paraffin, elastomers such as ethylene / vinyl acetate copolymer. In all of these adhesive compositions, the weight ratio of terpolymer to elastomer is determined by the intended use of the composition. The terpolymer tackifier of the present invention may also be used as a viscosity modifier for the components to be applied or as a modifier for printing inks. Terpolymer tackifiers may also be effective as oxidation stabilizers for other polymers because they hinder phenolic substances. The following examples illustrate the invention. In any case, it is not limited to the scope of the embodiment. Example 1 A one-liter, three-necked reaction vessel was equipped with a mechanical stirrer thermometer well, an addition funnel, a tube for feeding the catalyst source below the liquid level, and a device for surrounding with dry nitrogen. The reaction vessel is supplied with 270 g of dry aromatic solvent and flushed with dry nitrogen, while cooling the contents to 0 ° C. with an external dry ice / isopropanol cooling bath. A mixture of 120 g dry styrene and 180 g dry alpha pinene is mixed with 30 g pure phenol dissolved in 30 g aromatic solvent forming a monomer solution. The monomer solution is added to the reaction vessel at 0 ° C. over a period of 36 minutes, while simultaneously adding 4.3 g of gaseous BF ₃ catalyst. 6.0g
The catalyst addition is continued for another 14 minutes until all of the BF ₃ has been added. The reaction mixture is heated to 40 ° C. and kept stirring for 1 hour. The catalyst is removed by neutralization with 110 ml of hot caustic solution and then three hot water washes. The aqueous phase is separated and eliminated.
The organic phase is heated under nitrogen while dispersing with ultra-high temperature steam at 225 ° C. to remove the solvent and finally isolate the terpolymer product. The resulting terpolymer has a ring and ball softening point of 108 ° C. and a Gardner color of 4+, with a yield of 92%. The aromatic solvent used in Examples 1-13 is a recycled mixture of various aromatic compounds. The main components are para- or meta-xylene (10.6%), para- or meta-ethyltoluene (13.8%), mesitylene (7.0%), pseudocumene (9.5%) and hemimelitene (7. 2%) and a high boiling component (13.6%). Example 2 A one-liter, three-necked reaction vessel was equipped with a mechanical stirrer, a thermometer well, a device for surrounding with dry nitrogen, and an adjustable tube for feeding the catalyst source below the liquid level. . The reaction vessel contains 180 g dry styrene, 120 g dry alpha-methylstyrene, 30 g dry alpha-pinene, 313 g dry aromatic mixture, 1
5 g of phenol are fed. Under nitrogen, the temperature is adjusted to 0 ° C. with an external dry ice / isopropanol bath. Then, gaseous BF ₃ (0.48 g) is introduced intermittently over 15 minutes. A large amount of heat is generated and the temperature is controlled from 0 ° C to 5 ° C. After the exotherm subsides, the addition of BF ₃ is continued until 0.86 g of total BF ₃ is added to the reaction vessel. The reaction mixture is then heated to 40C.
After one hour, excess lime is added to neutralize the catalyst. The temperature is raised to 100 ° C. and the lime and neutralized products are removed by filtration. The terpolymer is isolated by heating under nitriding and finally dispersed at 225 ° C. with ultra-high temperature steam. 11
A tripolymer with a ring and ball softening point of 9 ° C. and Gardner color 1+ is obtained in a yield of 91.4%. Example 3 The same reactor as described in Example 1 was used. 30 in the reaction vessel
0 g of dry aromatic solvent is supplied and flushed with dry nitrogen and the contents are cooled to 0 ° C. A solution of 30 g phenol in 120 g dry styrene and 180 g dry beta pinene is added dropwise to the reaction vessel at 0 ° C. over 35 minutes, while at the same time 4.2 g gaseous BF ₃ are added. The reaction mixture may be warmed to 20 ° C. for more than one hour, after which the catalyst is neutralized with excess lime. The temperature is raised to 100 ° C. After filtration, the organic phase is heated under a nitrogen atmosphere and finally dispersed with steam at 225 ° C. A terpolymer having a ring and ball softening point of 102 ° C. and a Gardner color of 5- was obtained in a yield of 89.4%. Example 4 The reactor is the same as in Example 1 described above. The reaction vessel is filled with 150 g of a dry aromatic solvent, flushed with dry nitrogen and the contents are cooled to 0 ° C. 1 g in 210 g dry styrene with 90 g dry dipentene and 150 g dry aromatic solvent
A solution of 5 g phenol is added dropwise to the reactor at 0 ° C. over 1 hour, at the same time 7.2 g of gaseous BF ₃ catalyst are added. While stirring for an additional hour, the reaction mixture may rise to + 15 ° C., after which the catalyst is neutralized with excess lime. The temperature can be raised up to 100 ° C. Lime and neutralized products are removed by filtration. The organic phase is heated in a nitrogen atmosphere and finally dispersed with steam at 250 ° C. 11
A terpolymer having a ring and ball softening point of 0 ° C. and a Gardner color of 3+ is obtained in a yield of 91.5%. Example 5 The reaction apparatus is the same as in Example 1 described above. 277 g of a dry aromatic solvent is placed in a reaction vessel. After washing with dry nitrogen, a solution of 15 g phenol in 210 g dry styrene and 90 g dry α-pinene is added over a period of 34 minutes, during which the contents of the vessel are stirred and cooled to 0 ° C. 4.1 g of gaseous B during monomer addition
F ₃ is also added continuously to the reaction medium. The mixture is warmed to 40 ° C. and kept at this temperature for 1 hour. Lime is used to neutralize the catalyst. The terpolymer product is separated by filtration, after which the solvent is distilled off under a nitrogen atmosphere and finally 260
Dispersed with steam at ℃. At a ring and ball softening point of 97 ° C., a terpolymer of Gardner color 1 is obtained in 92.0% yield. Example 6 The reactor is the same as in Example 2 described above. The reaction vessel was filled with 172.8 g dry styrene, 57.6 g dry α-pinene, 4.8 g divinylbenzene, 9.6 g phenol, and 360 g dry aromatic solvent. The contents are 0 ° C under nitrogen atmosphere
Cooled to, gaseous BF ₃ of 0.86g is intermittently added over 28 minutes. A subdued strong exotherm of 0 to 2 ° C. lasts for 20 minutes. After the exotherm decreases, the BF ₃ addition is continued until the total catalyst amount is 1.1 g. Continue stirring at 0 ° C. for 30 minutes. After neutralizing the catalyst with excess lime, it is filtered at 100 ° C. The organic phase is heated under a nitrogen atmosphere to remove the solvent and finally dispersed with steam at 245 ° C. A terpolymer having a ring and ball softening point of 116 ° C. and a Gardner color of 1 is obtained in a yield of 95.4%. Example 7 The reactor is the same as that described in Example 1. 300 g of dry aromatic solvent is charged into the reaction vessel and the contents are set at 0 ° C. under a nitrogen atmosphere. 21
A mixture of 15 g phenol in 0 g dry vinyl toluene and 90 g dry α-pinene is added with stirring at 0 ° C. over 30 minutes. During this time, 3.6
g of gaseous BF ₃ catalyst is also added continuously to the reactor. Over the next hour, the temperature rises to 20 ° C., after which the catalyst is neutralized with excess lime. After heating to 100 ° C. and filtration, the organic phase is removed under nitrogen and steam sparged at 250 ° C. 1
A turbolimer having a ring and ball softening point of 10 ° C. and a Gardner color of 1 is obtained in a yield of 91.7%. Example 8 The reactor and the general procedure are the same as described in Example 1. A reaction vessel containing 284.5 g of aromatic solvent maintained at 0 ° C. was charged with 192 g of styrene and 10
8 g of α-pinene, 18 g of phenol are added over 30 minutes,
. 8 g of BF ₃ are also added. After further reacting at 40 ° C. for 1 hour, the catalyst is neutralized. 97.6% of a terpolymer having a Gardner Color of 3 at a ring and ball softening point of 97 ° C.
In a yield of. Example 9 The reactor was the same as that described in Example 1. A solution consisting of 180 g of styrene, 120 g of α-pinene and 30 g of P-nonylphenol is added to a reaction vessel containing 300 g of dry aromatic solvent and kept at 25 ° C. for 1 hour. BF ₃ 8.
4 g are also introduced into the reaction mixture. After an additional hour at 25 ° C., the catalyst is neutralized. 85. A terpolymer having a ring and ball softening point of 80 ° C. and a Gardner color of 1+.
Separated in 6% yield. Example 10 The reactor was the same as that described in Example 1. The BF ₃ catalyst is led into a reaction vessel containing 300 g of dry aromatic solvent maintained at 25 ° C. A solution consisting of 180 g of styrene, 120 g of α-pinene and 30 g of O-cresol is added over one hour. After a further reaction time of 1 hour, the catalyst is neutralized. A terpolymer having a ring and ball softening point of 85 ° C. is obtained in a yield of 84.1%. Example 11 The reactor was the same as that described in Example 2. The reaction vessel is filled with 180 g of styrene, 120 g of α-pinene, 30 g of bisphenol A, and 400 g of an aromatic solvent, and these contents are set at 40 ° C. 2.6 g of BF ₃ are added over 2 hours, the time during which the bisphenol A gradually dissolves in the reaction medium. After an additional 20 minute induction period, a strong exotherm occurs. When the exotherm subsides, the reaction is continued at 40 ° C. for another 1.5 hours. Thereafter, the catalyst is neutralized. Terpolymer having a softening point of 90 ° C. and a curdner color of 3+ yields 84.1%.
Separated by Example 12 The reactor and the overall procedure are similar to those described in Example 1. In a reaction vessel containing 300 g of aromatic solvent kept at 0 ° C., 180 g of dry styrene and 1
A solution consisting of 20 g of α-methylstyrene, 15 g of α-pinene and 2.5 g of phenol is added over 1 hour, while at the same time 3.8 g BF ₃ are added. After an additional hour at 40 ° C., the catalyst is neutralized. At a ring and ball softening point of 69 ° C., a terpolymer having a Gardner color of 1 is separated with a yield of 93.8%. Example 13 The reactor was the same as that described in Example 1. The reaction vessel is filled with 63 g of phenol dissolved in 300 g of aromatic solvent. At 25 ° C., 1.5 g of BF ₃ are led to the reaction vessel to form a soluble complex with phenol. While maintaining the reaction temperature at 25 ° C., a solution consisting of 63 g of styrene and 174 g of α-pinene is added to the stirred reaction vessel over 3.3 hours. After a further 0.5 hours, the catalyst is neutralized. At a ring and ball softening point of 129 ° C., a terpolymer having a Gardner color of 4+ is isolated in a yield of 87.4%. Example 14 A pressure sensitive adhesive composition based on a solvent is made by the following procedure. Forty parts by weight of the terpolymer prepared according to Example 1 were mixed with 60 parts by weight of masticated natural rubber in 733 parts of toluene (pail crepe containing 1% by weight of P, P'-dioctyldiphenylamine and 0.5 parts by weight of antioxidant (
(Irganox 1010, Ciba Geigy) by mixing in a vial for 3-4 days. This procedure is repeated for two additional samples using turbo-limer to rubber weight ratios of 50:50 and 60:40. The adhesive is cast as a 1.0 mm film on a Mylar substraight, dried in air, and finally dried in a dryer at 60-70 ° C. for 5 minutes. Once cooled, the released paper is applied to the adhesive, which is at 22 ° C., 5% relative humidity.
Stored at 0%. The adhesion test is performed after storage for 24 hours. Pr used
The essure Sensitive Tape Council (PSTC) test and test results are shown below. Example 15 A solvent based pressure sensitive adhesive is prepared by the following procedure. 40 parts by weight of terpolymer, 60 parts by weight of styrene-butadiene elastomer (Ameripol SBR1011, BFGoodrich) prepared according to Example 5
Co.) and 0.3 parts by weight of an antioxidant (Irganox 1010, Ciba Geigy)
Dissolved in 900 parts of toluene by rolling for ~ 4 days. The adhesive is cast as a 1.0 mm film on Mylar's substraight,
It is dried in air and finally in a dryer at 60-70 ° C. for 5 minutes. The cooled and released paper is applied to the adhesive, which is stored at 20 ° C. and 50% relative humidity.
The adhesion test was performed after storage for 24 hours, and the following results were obtained. Peel Strength 61 oz / in Rapid Adhesion 32 oz / in Rolling Ball Adhesion 4.1 cm Shear Adhesion 2614 minutes Example 16 A hot melt pressure sensitive adhesive is prepared by the following procedure. 60 parts by weight of the terpolymer prepared according to Example 8 are mixed with 20 parts of a plastic oil (Shellflex 371) and 0.5 parts of an antioxidant (Irganox 1010, Ciba Geigy) in a nitrogen atmosphere and at 175 ° C. Heated until. Forty parts by weight of butadiene-styrene multiblock copolymer (Steron 840A, Firestone Co.) are added and mixing is continued until uniformity is obtained. The adhesive is cast as a 1 mm film on Mylar substraight at 350 ° F. Upon cooling, the released paper is applied to an adhesive film, which is stored at 22 ° C. and 50% relative humidity. The adhesion test was performed after storage for 24 hours, and the following results were obtained. Peel strength 73 oz / in Rapid bonding 55 oz / in Rolling ball tack 30 cm Example 17 The terpolymer of the present invention can also be used as a non-pressure sensitive hot melt adhesive composition. 70 parts by weight of paraffin wax (Chevron 155), 105 parts by weight of ethylene / vinyl acetate (Elvax 220, DuPont Co.), 175 parts by weight of the terpolymer and antioxidant shown in the table in nitrogen Heating becomes uniform,
Stir. The cloud point data and heat aging data for the hot melt adhesive composition are shown in the table. * Dilauryl thiodipropionate antioxidant ** About 200 g was aged in a 400 ml glass beaker without cover.

Claims (1)

[Claims] 1. By weight ratio (1) General formula Wherein R ′ is hydrogen or —CH ₃ , and R ″ is hydrogen, —CH ＝ CH ₂ or an alkyl group having 1 to 10 carbon atoms.
% (2) 5 to 75% of monoterpene hydrocarbons, and (3) 0.75 to 50% of phenols including {the sum of the percentages of components (1), (2) and (3) is 100%} Phenols, characterized in that the monomers in the mixture are simultaneously polymerized in the presence of a catalyst in a solvent to produce a vinyl-substituted aromatic / terpene / phenol terpolymer having a ring and ball softening point of 69-130 ° C. A method for producing a tackifier for use in an adhesive composition from a terpene and a vinyl-substituted aromatic component. 2. 2. The method according to claim 1, wherein the vinyl-substituted aromatic hydrocarbon (1) is styrene. 3. 3. The method according to claim 1, wherein the monoterpene hydrocarbon (2) is [alpha] -pinene. 4. 4. The method according to claim 1, wherein the phenol (3) is phenol. 5. Wherein the catalyst is BF _3, The method according to any one of Claims first to fourth terms. 6. The method according to any one of claims 1 to 5, wherein the reaction is carried out at -15C to 65C. 7. A tackifier for use in an adhesive composition, wherein said tackifier comprises 6
Has a ring and ball softening point of 9 ° C to 130 ° C, and (1) a vinyl-substituted aromatic hydrocarbon;
A vinyl-substituted aromatic / terpene / phenol terpolymer produced by simultaneous polymerization of monoterpene hydrocarbon and (3) phenols,
The above tackifier. 8. That the tackifier is produced by the simultaneous polymerization of (1) vinyl substituted aromatic hydrocarbons 12 to 95%, (2) monoterpene hydrocarbons 5 to 75% and (3) phenols 0.75 to 50%. 8. The tackifier according to claim 7, wherein the tackifier is characterized in that: 9. Vinyl-substituted aromatic hydrocarbon (1) has the general formula Wherein R ′ is hydrogen or —CH ₃ , and R ″ is hydrogen, —CH ＝ CH ₂ or an alkyl group having 1 to 10 carbon atoms. 7
Or the tackifier according to item 8. 10. The tackifier according to claim 7, wherein the vinyl-substituted aromatic hydrocarbon (1) is styrene. 11. The tackifier according to claim 7, wherein the monoterpene hydrocarbon (2) is α-pinene. 12. The tackifier according to claim 7, wherein the phenol (3) is phenol.