RESIDUAL MONOMER CONTENT

The present invention is on processes for reducing residual monomers in final polymeric emulsion containing copolymerized amounts of at least one vinyl ester and a multi-functional monomer and providing improved adhesive properties.

Inherently tacky pressure sensitive adhesive (PSA) acrylic polymers formed by emulsion polymerization are well known the art as replacements for solution adhesive polymers.

The water borne pressure-sensitive adhesives utilize acrylic monomers to provide low glass transition temperatures (Tg) to the inherently tacky copolymer, unsaturated carboxylic acid monomers to enhance adhesion to polar surfaces and

multifunctional monomers to improve cohesive strength with minimal loss of loop tack and other properties. Recently (EP2524950) it has been teach that compositions based on vinyl ester of alkyl with 2 to 17 carbon atoms lead to excellent adhesive properties and particularly providing adhesion and tack while maintaining cohesion at high level. However, the copolymerization of such hydrophobic monomers by emulsion polymerization route results in high residual content of those vinyl esters. It is ecologically desirable to reduce residual monomer content in the emulsion and still to provide enhanced adhesive properties. This is the subject of the present invention.

Several technics have been proposed to avoid high level of residual monomer in the final emulsion. Attempts to make homopolymers of very hydrophobic monomers, such as those of vinyl branched esters, have failed because of very low conversions even if the polymerization is conducted for a long time, e.g. in excess of 48 hours . (Balic, R., deBruyn, H., Gilbert, R.G., Miller, CM. and Bassett, D.R., " Inhibition and Retardation in Emulsion Polymerization," Proc. 74th Colloid and Surf. Sci. Symp., Lehigh University, June, p.19 (2000).

Many attempts to polymerize said monomers resort to costly techniques such as: use of organic solvents or other monomers to act as solvents for the hydrophobic monomer; use of

macromolecular organic compounds having a hydrophobic cavity; and use of high levels of surfactants.

For example, US5521266 describes an aqueous polymerization method for forming polymers including the step of complexing at least one monomer having low water solubility with a

macromolecular organic compounds with a hydrophobic cavity used such as cyclodextrins and cyclodextrin derivatives.

The aforementioned methods use polar monomers to impart functionality to the latex particles. These polar monomers are usually carboxylic acids and hydroxy- and amide- containing monomers. It is well known to those skilled in the art that acid monomers are used in emulsion polymerization for various reasons, one being to improve latex stability. However, the presence of polymerized acid in the polymer is undesirable for coating applications and moisture sensitive applications, such as corrosion control, as it increases the affinity of the polymer for water, i.e., decreases the hydrophobicity of the polymer .

US56865T8 discloses a polymerization process, referred to as miniemulsion polymerization, for polymerizing monomers and monomer mixtures which are said to be essentially insoluble in water, i.e., which have water solubility ranging from 0 to about 5 weight percent.

US6160049 discloses an emulsion polymerization process that combines macroemulsion and miniemulsion feed streams for preparing an aqueous polymer dispersion from free-radically polymerizable compounds. The process requires feeding in separate streams a monomer with a solubility of at least 0.001 wt% and a monomer with a solubility of less than 0.001 wt%, and requires emulsification of both monomer streams. The

emulsification of the monomer streams is done using high pressure homogenizers at pressures of up to 1200 bar. However, this peripheral equipment is not commonly found in conventional emulsion polymerization practice.

Another example, W02006/044401 , is the use of specific

surfactants, which are characterized by a critical micelle concentration of less than 0.005WT%.

All those techniques are not providing a method leading to a total residual monomer level below 600 ppm.

In view of the disadvantages of known processes, an improvement to polymerize hydrophobic monomers by a radical initiation in an aqueous medium is requested by the industry. After an extensive research on the process conditions to be applied for the emulsion polymerization, we found that by adding an alkyl acrylate or methacrylate at the end of the polymerization reaction we could reduce the residual monomer level below the 500ppm. We found also that by adjusting the addition time of the pre-emulsions and the "cooking" period the residual monomer level was reduced. The ability to offer PSA showing an excellent Health Safety and Environmental (HSE) profile (Low Volatile Organic Content (VOC) and odor) is becoming critical- for more- and more PSA binder producers. In this respect, lattices with low- residual monomers play an important role to meet such requirements. As free monomers present in the final latex may contribute to VOC level and odor, those need to be reduced to very low levels.

Although, from the regulatory standpoint, in contrast to paints and coatings, there is no industry standard that specifies a particular residual monomer level for PSA.

The systems have been designed in such a way that 20% of VeoVa- 10 are combined with a blend of acrylic monomers to achieve a low Tg material (-40°C) .

Whereas a judicious choice of process conditions has led us to the development of robust systems, analysis of residual monomers by means of Gas Chromatography has revealed low amounts of unreacted VeoVa-10 (~350 ppm) by use of the

optimized booster system. This invention describes the approach we have followed to reach the target of < 500 ppm of residual VeoVa-10 or other alkyl (CI to C18) vinyl esters specially design for low Tg PSA applications.

The process of the present invention is set as follows: by using 3 sequential polymerization steps:

first step consists in

a) adding an emulsion, of vinyl ester of alkyl of CI to C18 carboxylic acids, to water containing a radical initiator, second step consists in

b) adding to a) an emulsion of alkyl acrylate and/or

methacrylate ,

third step consists in

c) adding to polymeric emulsion, resulting of the steps a) and b) , pure liquid acrylate or methacrylate with alkyl chain of Ci to Ci2.

An alternative process is set as follows: by using 3 sequential steps:

first step consists in

a) adding an emulsion, of vinyl ester of alkyl of CI to C18 carboxylic acids, to water containing a radical initiator, second step consists in

b) maintain the reaction for 30 to 60 minutes at the same temperature ,

third step consists in

c) adding to a) an emulsion of alkyl acrylate and/or

methacrylate . The vinyl ester of alkyl of CI to C18 carboxylic acids in the first step consists in a linear alkyl chain or from 3 carbon atoms is a branched alkyl chain or from 5 carbon atoms consists in branched tertiary alkyl chain or a mixture thereof. Examples are: vinyl propionate, vinyl n-butyrate, vinyl laurate, vinyl ester of 2-ethyl hexanoic acid (VEHA) , vinyl caprate (n- decanoate) , and vinyl stearate (n-octadecanoate) , vinyl esters of the so called versatic acids or vinyl neodecanoates (VeoVa 9, VeoVa 10), vinyl pivalate.

The acrylate monomers used are including the acrylate and the methacrylate ester are reaction products of ethylenically unsaturated carboxylic acids and CI to C20 alcohols. Examples of the acrylate monomers used in the second step are including the. acrylate and the methacrylate ester are: methyl

(meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- butyl (meth) acrylate, isobutyl (meth) acrylate , t-butyl

(meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate , 2-ethylhexyl

(meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, nonyl (meth) acrylate , decyl

(meth) acrylate, 2-propyl heptyl (meth) acrylate , undecyl

(meth) acrylate, dodecyl (meth) acrylate, tridecyl

(meth) acrylate, lauryl (meth) acrylate , stearyl (meth ) acrylate , isobornyl (meth) acrylate, norbornyl (meth) acrylate, 4- tertbutylcyclohexyl (meth) acrylate, 3 , 3 , 5-trimethylcyclohexyl

(meth) acrylate or a mixture thereof.

The liquid acrylate or methacrylate used could be with alkyl chain of 1 to 16 carbon atoms or preferably from 1 to 12 carbon atoms or more preferably from 1 to 8 carbon atoms. Examples are :

methyl (meth) acrylate , ethyl (meth) acrylate, propyl

(meth) acrylate, n-butyl (meth) acrylate , isobutyl

(meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate , benzyl

(meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl

(meth) acrylate, n-octyl (meth) acrylate, iso-octyl

(meth) acrylate or a mixture thereof.

Methods

Gas Chromatography analysis

A Gas Chromatography -FID method is used for the evaluation of the residual monomer. Approximately 50 ml of THF is added to a closed flask. Additionally, 2.5 g of latex is injected in the flask, and the mixture shaken until complete dissolution occurs. The samples are filtered with a 0.45mm filter, and 1 ml is injected in the GC . The concentration is calculated with the help of an external standard. First a high standard is analyzed to see what concentration level is present. Then a standard with a lower concentration is analyzed and the sample is calculated. When the samples are calculated with the two standards the difference is less than 5%. The result calculated with the lowest concentration is reported.

Column

Type Wax 52

Length 25m

Diameter 0.32 mm

Film Thickness 1 .2 μιη

GC settings

Auxiliary He flow to FID 30 ml/min

Carrier gas He

Flow 2 ml/min

Split ratio 1 /12.5

Sensitivity range 0

Attenuation 0

Equilibrium time 0 min

Air flow rate 300 ml/min

Hydrogen flow rate 30 ml/min

Temperature

Maximum oven temperature 300° C

Initial temperature 35° C

Initial time 15 min

Time length 74.17 min

Final temperature 250° C

Rate 6° C/min

Injection port temperature 250° C

FID temperature 250° C

Injection volume

Sample size 1 μΐ

Test methods: - Adhesion-180° Peel test according to the FINAT TEST METHOD No .1 (FTM-l)was done on samples after 24h storage at 25°C, RH:50%; the substrate is stainless steel (SS), glass or high densitypolyethylene (PE) .

- Loop-Tack test according to the FTM-9 method was done on a sample of lxl x 25 mm on SS after 24h storage at 25°C.

- Cohesion-static shear test according to FTM-8 method was done on a sample of 1x0.5 25 mm-1 kg on SS after 24h storage at 25°C.

Examples

Latex preparation see table 1 for the intake of composition of example 2.

The reactor is charged with water and potassium per-sulfate and heated to 85°C. A 10% seed from the pre-emulsion 1(PE 1)

(containing all of the VeoVa-10) is added and reacted for 10 minutes before the remainder of the PE 1 is fed for Ih. At the end of the addition, the PE 2 containing the acrylic monomers is added for 2 hours. At the end of this addition, a shot of pure monomer (acrylate or a vinyl ester) is added and reacted for 0.5h whereas the initiator solution is fed in parallel for a total of 3.5h. After a lh cooking period, the latex is cooled down to 60 °C. The agitation is slowed down to about 100 rpm, to avoid any "funnel" into the latex. A 10% solution of sodium carbonate and sodium hydrogenocarbonate (1/1) is added to adjust the pH to±4. A first addition of Bruggolite®FF6 M solution is added in one shot. After 5 minutes, the remainder of Bruggolite®FF6 M and the tBHP are added via two separate lines during 90 minutes.

Finally, the reactor is cooled down to room temperature and a biocide is added. The product is finally filtered over a 130μ filter. The final latex has a solid content of ~ 53%. A way to determine the residual level of VeoVa-10 and other residual monomers, is to perform a Gas Chromatography (GC) analysis. The GC method and sampling procedure is described in above section. The level of residual monomer was followed with time. A small amount (H—lOg) of latex is taken out from the reactor each 30 minutes, mixed with lOmg of hydroquinone and immediately place in the ice. The samples are then analyzed by GC.

Latex preparation of composition of example 3.

The reactor is charged with water and potassium per-sulfate and heated to 85°C. A 10% seed from the pre-emulsion 1(PE 1)

(containing all of the VeoVa-10) is added and reacted for 10 minutes before the remainder of the PE 1 is fed for lh 30 minutes. At the end of the addition, the reaction mixture is kept at 85 °C for 30 minutes after that period the PE 2 containing the acrylic monomers is added for 2 hours 30 minutes. At the end of this addition, the reaction medium was kept at 85°C for 30 minutes, then the latex is cooled down to 60 °C. The agitation is slowed down to about 100 rpm, to avoid any "funnel" into the latex. A 10% solution of sodium carbonate and sodium hydrogenocarbonate (1/1) is added to adjust the pH to±4. A first addition of Bruggolite®FF6 M solution is added in one shot. After 5 minutes, the remainder of Bruggolite®FF6 M and the tBHP are added via two separate lines during 60 minutes .

Finally, the reactor is cooled down to room temperature and a biocide is added. The product is finally filtered over a 130μ filter. The final latex has a solid content of ~ 60%. Table 1: intake for Ex 2

Product : Example 2 Intake (g)

Initial reactor content

Demineralised Water 380.25

Potassium persulfate 1.05

Na2C03 1.98

Monomer pre-emulsion 1 (lh addition)

Demineralised Water 79.81

DisponilA3065 (65%) 7.77

Rhodacal DS10 1.51

VeoVa-10 200

AA 3.09

MAA 10.1 nDDCM 2.02

Initiator solution (3h30 addition)

Demi Water 115.82

Potassium persulfate 4.76

Monomer pre-emulsion 2 (2h addition)

Demineralised Water 270.26

REASOAP 30.86

Rhodacal DS10 16.24

BA 639.79

EA 50.04

MA 50.46 Table 1 continued

AA 7.13

MAA 20.8

MMA 10.22

BA Shot (30 ' ) 25.36

Post cooking 60 '

Iron shot

Iron II - Fe(S0 ₄ ) 0.02 water 5.12

Conversion booster

Shot

Demineralised water 12.49

Bruggolite FF6 0.78

Addition in parallel with Shot

Demineralised water 33.42

Bruggolite FF6 2.86

Demineralised water 33.71 tBHP (70%) 4.07

Table 2: residual monomer levels

From the table 2 above, it appears that the new sequential process where all of the VeoVa is placed in the first pre- emulsion 1 and kept separated from the acrylic monomers has a profound effect on the total monomer conversion. Shots of various monomers were tested at the end of the addition of the second pre-emulsion . It is clearly demonstrate that the monomer conversion is higher, as the total residual level of below 500 ppm is reached. However a similar effect on the residual monomer can be reach by changing the sequence and the reaction time period (as for example 3) .

PSA properties

Upon applications and drying, the lattices prepared with the new core/shell approach, are defect free and show good clarity. PSA films were prepared by direct coating on 23 micron Polyester Facestock at 20 gsm coat-weight.

The basic PSA properties were evaluated and various substrates (Stainless Steel and High Density Polyethylene) after different dwell times .

The results given in Table 3 below shows slightly lower adhesion level, slightly higher loop tack and equal shear resistance. Overall it can be stated that the new process used to obtain residual monomer levels below 500 ppm does not affect significantly the PSA properties of the polymers.

Table 3

The dry films based on the composition of the present invention provide enhanced water whitening resistance. Moreover these polymer compositions could also formulated with nonpolar tackifiers and other additives without compatibility issues.