TWI542615B - The tackifier resin emulsion and the preparation thereof - Google Patents

Description

Viscosity-reducing resin aqueous emulsion and preparation method thereof

In order to improve the disadvantages of the foregoing prior art, the present invention relates to an aqueous emulsion of a tackifying resin and a process for the preparation thereof, which have the characteristics of not adding an organic solvent, and having a low emulsification temperature and a short reaction time in the process. The product of the invention can be used as a tackifying resin for rubber latex pressure sensitive adhesive.

The use of solid petroleum resins in the industry has been a long time as a tackifying resin for solvent-based pressure sensitive adhesives. In recent years, with the increasing awareness of environmental protection, solvent-based pressure-sensitive adhesives have gradually been replaced by water-based pressure-sensitive adhesives, and the added solid-state viscosity-increasing trees have gradually developed toward the development of tackifying resin aqueous emulsions.

In Chinese patent CN1448436A, an emulsification technique for solid petroleum resin is disclosed, and a preparation method of a petroleum resin emulsion is described, wherein the petroleum resin is carbon five (C5) or carbon nine (C9), and the softening point of the product is 60-120 ° C, heating After the melting, oleic acid is added and then ethanolamine is added for emulsification, the emulsification temperature is 85-100 ° C, the emulsification time is 30-180 minutes, and after cooling, the petroleum resin emulsion is obtained by filtration. However, the method has a high emulsification temperature and a reaction Long time, 98 ° C water is required for dispersion, which causes trouble to the operator in the process.

The Chinese patent CN101121808A discloses a petroleum resin emulsion and its preparation, and the application of the product in exterior wall coating, but using petroleum ether as a solvent, the solvent is irritating to eyes, mucous membranes and respiratory tract, and has strong irritation to the skin. Health hazard and the danger of burning and explosion.

The present invention has been completed in order to improve the disadvantages of the aforementioned prior art. The invention relates to an aqueous emulsion of a tackifying resin and a preparation method thereof, which have the characteristics that no organic solvent is added, and the emulsification temperature is low and the reaction time is short in the process. The product of the invention can be used as a tackifying resin for water-based rubber pressure sensitive adhesive.

The invention relates to an aqueous emulsion of a tackifying resin and a preparation method thereof, which can be used as a tackifying resin for an aqueous rubber pressure sensitive adhesive.

The invention relates to an aqueous emulsion of a tackifying resin and a preparation method thereof, the steps thereof comprising:

(1) Firstly, the petroleum resin with softening point of 80-130 ° C and environmentally friendly plasticizer are placed in a reaction tank to be heated at a temperature of 100-160 ° C, rapidly stirred, for example, 1000 rpm, and stirred until completely dissolved, and the temperature of the reaction tank is lowered to 90. -95 ° C.

(2) Take another container of deionized water and environmentally friendly emulsifier, stir until completely dissolved, and slowly put it into the reaction tank for emulsification, the emulsification time is 50-60 minutes.

(3) Finally, after the temperature of the reaction tank is lowered to room temperature, an appropriate amount of dispersant, defoaming agent and ammonia water are added to the reaction tank; and then filtered by a 120 mesh filter bag to form an aqueous emulsion of a tackifying resin, and the solid content thereof is formed. It is 55-65% and has a viscosity of 250-600 cps. The product of the invention can be used as a tackifying resin for water-based rubber pressure sensitive adhesive.

The composition of the aqueous emulsion of the tackifying resin of the present invention comprises: (a) 100 phr of petroleum resin having a softening point of 80 to 130 ° C (part per hundred); (b) 5-15 phr of environmentally friendly plasticizer; (c) environmental protection The emulsifier is 3-10 phr; wherein (b) the amount of the environmentally-friendly plasticizer used and (c) the amount of the environmentally-friendly emulsifier are calculated by (a) the total amount of 100 phr. And add appropriate amount of dispersant, defoamer and ammonia.

(a) A petroleum resin having a softening point of 80 to 130 ° C used in the present invention, including C5, C9, C5/C9, hydrogenated C5, hydrogenated C9 or hydrogenated C5/C9 petroleum resin, which is used in an amount of 100 phr.

(b) an environmentally friendly plasticizer used in the present invention, which comprises diisononyl phthalate (DINP), dioctyl terephthalate (DOTP), diisoindole cyclohexane- Diisononyl cyclohexane-1,2-dicarboxylate (DINCH), trioctyl trimellitate (TOTM) or acetyl tributyl citrate (ATBC) . The environmentally friendly plasticizer is used in an amount of 5-15 phr, calculated as (a) a total of 100 phr.

(c) environmentally friendly emulsifier used in the present invention, which comprises fatty alcohol polyoxyethylene ether, polyoxyethylene fatty acid ester, polyoxyethylene dehydrated sorbent Polyoxyethylene sorbitan oleate or lauryl alcohol polyoxyethylene ether sodium sulfate. The environmentally-friendly emulsifier is used in an amount of 3 to 10 phr, calculated as (a) a total of 100 phr.

The following examples are illustrative of an aqueous emulsion of a tackifying resin and a method for preparing the same according to the present invention, and are not intended to limit the scope of protection of the present invention.

[Example 1]

First, 100 g (g) C5 petroleum resin with a softening point of 80 ° C and 8 g of diisononyl phthalate (DINP) environmentally friendly plasticizer were placed in a reaction tank and heated at a temperature of 110 ° C. The stirring speed was maintained. After stirring at 1000 rpm until completely dissolved, the temperature of the reaction vessel was lowered to 90 °C.

70 g of deionized water and 3.0 g of fatty alcohol polyethylene oxide ether were taken, stirred until completely dissolved, and then slowly placed in a reaction tank for emulsification, and the emulsification time was 60 minutes.

After the reaction bath temperature was lowered to room temperature, 2.0 g of dispersant DP-24 (German Qian Company), 0.3g defoamer DC-65AD (Deqian Company) and 5g of 25% ammonia water were added to the reaction tank; then filtered with a 120 mesh filter bag to form a tackifying resin aqueous emulsion product with a solid content of 60 %, viscosity is 450cps.

[Example 2]

First, 100g of C5 petroleum resin with a softening point of 100 ° C and 12 g of dioctyl terephthalate (DOTP) environmentally friendly plasticizer were placed in a reaction tank and heated at a temperature of 130 ° C. The stirring speed was maintained at 1000 rpm and stirred until completely. After dissolution, the temperature of the reaction vessel was lowered to 90 °C.

72 g of deionized water and 5.0 g of fatty acid polyethylene oxide were taken, stirred until completely dissolved, and then slowly placed in a reaction tank for emulsification, and the emulsification time was 60 minutes.

After the reaction vessel temperature was lowered to room temperature, 2.0 g of dispersant DP-24 (Deqian Company), 0.3 g of defoamer DC-65AD (Deqian Company) and 5 g of 25% ammonia water were added to the reaction tank; The filter bag is filtered to form a tackifying resin aqueous emulsion product having a solid content of 58.5% and a viscosity of 400 cps.

[Example 3]

First, 100g of C5/C9 petroleum resin with a softening point of 110 ° C and 12 g of trioctyl trimellitate (TOTM) environmentally friendly plasticizer were placed in a reaction tank and heated at a temperature of 130 ° C. The stirring speed was maintained at 1000 rpm. After stirring until completely dissolved, the temperature of the reaction vessel was lowered to 90 °C.

70 g of deionized water and 6.0 g of polyoxyethylene sorbitan oleate were taken, stirred until completely dissolved, and slowly placed in a reaction tank for emulsification, and the emulsification time was 60 minutes.

After the reaction vessel temperature was lowered to room temperature, 2.0 g of dispersant DP-24 (Deqian Company), 0.3 g of defoamer DC-65AD (Deqian Company) and 5 g of 25% ammonia water were added to the reaction tank; The filter bag is filtered to form a thickened water-based lipid emulsion product having a solid content of 59.2% and a viscosity of 520 cps.

[Embodiment 4]

First, 100 g of C9 petroleum resin with a softening point of 130 ° C and 10 g of diisononyl cyclohexane-1, 2-dicarboxylate (DINCH) environmentally friendly plasticizer were placed in the reaction tank. The temperature was 150 ° C, the stirring speed was maintained at 1000 rpm, and the tank was stirred until completely dissolved, and the temperature was lowered to 90 ° C.

68 g of deionized water and 8.0 g of sodium lauryl alcohol polyoxyethylene ether sulfate were added, stirred until completely dissolved, and then slowly placed in a reaction tank for emulsification, and the emulsification time was 60 minutes.

After the reaction vessel temperature was lowered to room temperature, 2.0 g of dispersant DP-24 (Deqian Company), 0.3 g of defoamer DC-65AD (Deqian Company) and 5 g of 25% ammonia water were added to the reaction tank; The filter bag is filtered to form a thickened water-based lipid emulsion product having a solid content of 60.5% and a viscosity of 550 cps.

[Comparative Example 1]

First, 100g of C5 petroleum resin with a softening point of 80 ° C and 50 g of toluene (organic solvent) were placed in a reaction tank to heat, the temperature was 120 ° C, the stirring speed was maintained at 1000 rpm, and after stirring until completely dissolved, the temperature of the reaction tank was lowered to 90 ° C. .

40 g of deionized water and 6.0 g of sodium lauryl alcohol polyoxyethylene ether sulfate were taken, stirred until completely dissolved, and then slowly placed in a reaction tank for emulsification, and the emulsification time was 100 minutes.

After the reaction vessel temperature was lowered to room temperature, 2.0 g of dispersant DP-24 (Deqian Company), 0.3 g of defoamer DC-65AD (Deqian Company) and 5 g of 25% ammonia water were added to the reaction tank; The mesh filter bag is formed by filtration. The product has a solids content of 52.6% and a viscosity of 250 cps.

[Comparative Example 2]

First, 100 g of C5 petroleum resin with a softening point of 100 ° C and 30 g of toluene (organic solvent) were placed in a reaction tank to heat, the temperature was 120 ° C, the stirring speed was maintained at 1000 rpm, and after stirring until completely dissolved, the temperature of the reaction tank was lowered to 90 ° C. .

40 g of deionized water and 6.0 g of sodium lauryl alcohol polyoxyethylene ether sulfate were taken, stirred until completely dissolved, and then slowly placed in a reaction tank for emulsification, and the emulsification time was 100 minutes.

After the reaction bath temperature was lowered to room temperature, 2.0 g of dispersant DP-24 (German Zhike Company), 0.3g defoamer DC-65AD (Deqian Company) and 5g of 25% ammonia water were added to the reaction tank; and then formed by filtration through a 120 mesh filter bag. The product has a solid content of 58.0% and a viscosity of 700 cps.

[Comparative Example 3]

It is a commercially available tackifying resin emulsion product.

The main component contents (a) to (c) of the inventive examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1 below.

The environmentally friendly plasticizer used in the present invention has a list of abbreviations, English names and Chinese names as shown in Table 2:

The performance of the products of Examples 1 to 4 and Comparative Examples 1 to 3 of the present invention was tested according to the following method.

【testing method】

Solid amount (%): A small amount of the emulsion was placed in an aluminum pan, placed in an oven at 120 ° C / 1 hour, and taken out and placed at a constant temperature. Solid form calculation formula: (weight after drying / weight before drying) × 100%.

Viscosity: The viscosity of the emulsion was tested using a Brookfield VLE Rotary Viscator and the needle/speed was 63#/30 rpm at room temperature in units of cps.

Emulsion stability: After the emulsion was placed at 65 ° C / 7 days, it was placed at 5 ° C / 7 days to observe whether the emulsion was delaminated.

Toluene residue: determined by gas chromatography (Head-space GC) method, expressed in ppm (per million); ND means not detected. The minimum detection value of this detection method is 0.01 ppm.

The physical property comparison tables of the first to third embodiments of the present invention and the comparative examples 1 to 3.

As can be seen from the above table, in the first to fourth embodiments of the present invention, the obtained tackifying resin aqueous emulsion product has the effects of good emulsion stability and no residual amount of toluene, and in the process, the emulsification time is only 1 hour and Easy to operate features. On the other hand, Comparative Examples 1 and 2 and Comparative Example 3 (commercially available products) all have the disadvantage of containing a residual amount of toluene, which is harmful to the human body.

The present invention has the industrial patentability, the novelty and the progressability, and the like, and the above embodiments are only used to exemplify the object, technical content, features and effects of the present invention, and are not intended to limit the scope of the present invention.

Claims (7)

A thickening resin aqueous emulsion, the main components of which include: (b) the amount of environmentally friendly plasticizer used, and (c) the amount of environmentally friendly emulsifier used, respectively, relative to (a) = 100 phr; additional amount of dispersant, defoamer, ammonia, and deionized Water (c) environmentally friendly emulsifier is fatty alcohol polyoxyethylene ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan oil Polyoxyethylene sorbitan oleate or lauryl alcohol polyoxyethylene ethersodium sulfate. The tackifying resin aqueous emulsion according to claim 1, wherein (a) the petroleum resin having a softening point of 80 to 130 ° C is C5, C9, C5/C9, hydrogenated C5, hydrogenated C9 or hydrogenated C5/C9 petroleum resin. The aqueous thickening resin emulsion according to claim 1, wherein (b) the environmentally friendly plasticizer is diisononyl phthalate (DINP), dioctyl terephthalate (DOTP), Diisononyl cyclohexane-1,2-dicarboxylate (DINCH), trioctyl trimellitate (TOTM) or tributyl citrate (acetyl tributyl citrate, ATBC). A method for preparing an aqueous emulsion of a tackifying resin, the steps comprising: (1) First, (a) petroleum resin with softening point of 80-130 ° C and (b) environmentally friendly plasticizer are placed in a reaction tank for heating at a temperature of 100-160 ° C. After rapid stirring until complete dissolution, the temperature of the reaction tank is adjusted. Drop to 90-95 ° C; (2) Then, deionized water and (c) environmentally friendly emulsifier placed in a container, stirred until completely dissolved, slowly placed in the reaction tank for emulsification; emulsification time is 50-60 minutes And (3) Finally, after the reaction tank temperature is lowered to room temperature, an appropriate amount of dispersant, defoaming agent and ammonia water are added to the reaction tank; and then filtered by a 120 mesh filter bag to form a tackifying resin aqueous emulsion product. The solid amount is 55-65%, and the viscosity is 250-600 cps; wherein (c) the environmentally friendly emulsifier used in the step (2) is a fatty alcohol polyoxyethylene ether, a fatty acid polyepoxy Polyoxyethylene fatty acid ester, polyoxyethylene sorbitan oleate or lauryl alcohol polyoxyethylene ether sodium sulfate. The method for preparing an aqueous emulsion of a tackifying resin according to claim 4, wherein (a) the petroleum resin having a softening point of 80 to 130 ° C is C5, C9, C5/C9, hydrogenated C5, hydrogenated C9 or hydrogenated C5/C9 petroleum resin. . The method for preparing an aqueous emulsion of a tackifying resin according to claim 4, wherein (b) the environmentally friendly plasticizer is diisononyl phthalate (DINP) or dioctyl terephthalate (dioctyl terephthalate). DOTP), diisononyl cyclohexane-1,2-dicarboxylate (DINCH), trioctyl trimellitate (trioctyl trimellitate, TOTM) or acetyl tributyl citrate (ATBC). An aqueous emulsion of a tackifying resin according to any one of claims 1 to 3, which is used as an aqueous rubber pressure sensitive adhesive.