KR940010969B1 - Resin emulsions - Google Patents

Abstract

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Description

Process for preparing resin emulsion and product thereof

The present invention relates to a process for producing resin emulsions and to their products, in particular emulsions with improved mechanical stability. This is particularly useful when a mechanically stable emulsion is to be used for the coating line, especially for an adhesive coating line where the line has to be stopped frequently to clean the coating line as the emulsion breaks and deposits in the apparatus.

Modification of the polarity of the hydrocarbon adhesive resin improves compatibility with polar polymers, easily emulsifies, and can modify the properties of the resin, such as emulsion stability and adhesion to polar surfaces.

Grafting of unsaturated anhydrides, acids and the like to resins via thermal condensation processes has been described in US Pat. Nos. 3,379,663 and 3,953,407. This process requires long heating at high temperatures before emulsification. Grafting of free radicals, although not producing wood, is described in US Pat. Nos. 3,279,925, 3,005,800 and 3,161,620. The inventors have invented a process for the preparation of modified resin emulsions which are stable and compatible with polar polymers.

According to the present invention, the resin emulsion forms an emulsion of an aqueous solution of an unsaturated substance that reacts with the resin in the liquid resin, and reacts the resin with the unsaturated substance to a degree sufficient to convert the emulsion in which the emulsion is emulsified in water. It is prepared by a method consisting of adding water.

Although various other resins may be used in the present invention, hydrocarbon resins are preferred, and some commercially available resins are preferred to some degree of unsaturation. Examples of suitable resins include petroleum resins (aliphatic, aromatic or aliphatic / aromatic), pure aromatics. Resins, rosin derivatives, polyterpenes or derivatives thereof or coumarone-indene resins made by copolymerizing monomers (for example styrene, methylstyrene or vinyltoluene) with olefins and / or diolefins and derivatives thereof.

The petroleum resin can be prepared by polymerizing a fraction having a boiling point of -15 to 410 ° C. under atmospheric pressure, which is made by pyrolyzing petroleum raw materials. This fraction can be polymerized by heat or in the presence of a catalyst which is a friedel-Crafts catalyst such as AlCl.

Petroleum raw materials such as light naphtha, heavy naphtha, kerosene, gas oil, vacuum gas oil and C ₅ olefins and diolefins, C ₆ olefins and diolefins or mixtures of C ₅ -C ₆ olefins and diolefins in the presence of steam Usually degraded, the preferred temperature is 600-900 ° C.

The degraded product usually has a boiling point of −15 to 280 ° C. and may consist of about 30 to 60% olefins, 10 to 30% diolefins, 20 to 50% aromatics and 5 to 20% paraffins and naphthalenes.

It is desirable to fractionate the product to remove light C _2-4 material, heat soak and distill to remove hydrocarbons such as cyclic diolefins including the dimers methyl cyclopentadiene and cyclopentadiene.

After heat soaking and distilling, a naphtha is obtained, which is usually a columnar product that boils at 30 to 110 ° C, for example 30 to 80 ° C. This columnar naphtha mainly consists of isoprene and aromatics such as C ₅ diolefins, C _5-6 monoolefins and benzene, such as 1.3 cis- and transpentadiene. Tower naphtha generally has the following composition, but the exact composition depends on the nature of the petroleum material being steam cracked.

weight%

Total paraffin 1.0 to 41.4

Total diolefin 35.5 to 14.5

Total Olefin 33.5-13.0

Total aromatics 30.0 to 31.0

Isoprene 16.5 to 6.5

Pentadiene 1.3 14.5 to 4.5

Cyclopentadiene 1.0 to 2.5

The crude oil can also be a C ₉ crude oil which is a mixture of olefinic aromatics such as styrene, vinyl toluene, α-methyl styrene and indene or a mixture of C ₅ and C ₉ crude oils which can be polymerized. It is also possible to polymerize mixtures of C ₅ feeds with the pure aromatic monomers and / or terpenes described above. Particularly suitable resins are aliphatic-aromatic resins obtained by polymerizing a mixture of olefins (C _5-6 olefins and diolefins) with aromatic monomers such as styrene, α-methyl styrene and vinyl toluene.

If thermal polymerization takes place, fractions of naphtha, such as the columnar, are usually polymerized at 200 to 280 ° C. for 1-8 hours. If polymerized in the presence of a Friedel-Graft catalyst, it is polymerized in 1 / 4-2 hours at a polymerization temperature between -80 and 120 ° C, preferably between -10 and 80 ° C.

Aluminum trichloride, complexes of aluminum trichloride and aromatic hydrocarbons, aluminum tribromide, boron trifluoride, complexes of borontrifluoride and phenol, Friedel-Craft catalysts such as titanium chloride, ethyl aluminum chloride and ferric chloride can be used. Can be.

These catalysts can be used in the solid, liquid or gaseous state. Generally the amount of catalyst used is from 0.05 to 3.0% by weight, preferably from 0.1 to 1.5% by weight of the weight of the material to be polymerized.

The catalyst remaining after polymerization can be removed by washing with an aqueous solution of alkali, ammonia or sodium carbonate or by filtration immediately after the addition of an alcohol such as methanol.

This final resin can be steam stringed or distilled under reduced pressure to remove unreacted hydrocarbon "rapinates" (unreacted olefins) with high benzene and / or paraffins and oligomers such as low molecular weight oils. The products thus treated usually have a softening point of 0 to 250 ° C, in particular 30 to 140 ° C.

If desired, hydrogenated products of these resins can also be used. Hydrogenation is carried out at reaction temperatures of 150 to 250 ° C., preferably from 200 to 250 ° C. to 250 bar, preferably from 50 to 100 bar, for example diatomaceous earth, alumina, silica gel in a solvent such as aliphatic saturated hydrocarbons such as hexane or heptane. Or a catalyst such as nickel or Raney nickel supported on a pumice carrier.

Generally preferred resins are aliphatic petroleum resins obtained by polymerizing an oil having a boiling point of -15 to 60 ° C. at atmospheric pressure using a Friedel-Craft catalyst.

Hydrocarbon resins are usually solid at ambient temperatures and have an average molecular weight of 500 to 3000, preferably 700 to 2000. However, liquid or semi-liquid resins may also be used.

In the process of the present invention, if the resin is not a liquid, it must be made liquid, for example, by dissolving or dissolving the resin in a solvent. If the resin is dissolved, it is only necessary to heat the resin to a temperature slightly above the melting point of the resin, but it is not desirable to overheat the resin. The melting point of petroleum resins is usually between 0 ° C and 250 ° C. Otherwise, the resin may be paraffin such as a suitable solvent such as hexane, heptane, nonane, octane or mixtures thereof; It can be dissolved in aromatic hydrocarbons such as benzene, toluene, xylene, or aromatic hydrocarbons such as olefins such as heptene or nonene.

The unsaturated substance that reacts with the resin is preferably a substance that provides a polar group to the resin following the reaction to improve the stability of the emulsion. Examples of suitable materials are unsaturated acids, anhydrides and amines and salts thereof.

Preferred materials are unsaturated organic carboxylate eutectics and suitable unsaturated organic carboxylates include group I or group II metal salts or ammonium salts of unsaturated carboxylic acids or sulfonic acids, such as sodium or potassium salts. Suitable unsaturated carboxylic acids are acrylic acid, methacrylic acid, acrylic or methacrylic acid dimers, oleic acid, cis- and trans-crotonic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid citraconic acid and their hemi esters . Suitable unsaturated sulfonic acids are vinyl sulfonic acid, allyl sulfonic acid and styrene sulfonic acid.

The unsaturated material is dissolved in water to make an aqueous solution that is a solution that is thick enough so that the amount of water present in the resin / salt mixture forms a water emulsion in the oil. It is preferable that an amount of water is present in an amount of less than 20%, more preferably not more than 16% by weight of the resin.

The aqueous solution is effectively dispersed throughout the liquid resin so that the aqueous solution is added to the liquid resin, preferably with vigorous stirring, to make the water (w / o) emulsion in the oil. The amount of the unsaturated substance added is equivalent to 0.1 to 10, preferably 0.53% by weight of the resin weight. Preferably the emulsifier is added to the liquid resin together with an aqueous solution of for example carboxylate or sulfonate used to make the water emulsion in the oil. Emulsifiers are anionic or nonionic surfactants or mixtures thereof. Suitable anionic surfactants include, but are not limited to, alkali sulfonates such as sodium or calcium, alkyl benzene sulfonates; Fatty alcohol sulfates such as sodium lauryl sulfate; Phosphate esters such as the sodium salts of mono- and di-esters of orthophosphoric acid; Ester of sulfosuccinic acid; Sodium salts of sulfated monoglycerides; And sulfonates or sulfosuccinates of alkyl polyoxy alkylene oxide condensates or alkyl phenone polyalkylene oxide condensates, for example ammonium salts of nonylphenol polyethylene oxide sulfonic acid.

Suitable nonionic surfactants include fatty alcohols or alkyl phenols reacted with ethylene oxide, such as oleyl alcohol reacted with polyethylene oxide, for example 15 moles of ethylene oxide; Polyalkylene oxide block copolymers wherein the alkylene oxy block is, for example, a block of ethylene oxide and propylene oxide; Condensation products of carboxyamides, ie fatty acids and hydroxyalkyl amines, for example diethanol amine condensates and polyoxyethylene fatty acid amides, and ethoxylation of carboxylic acid esters such as glycerol esters, polyoxyethylene esters and fatty acids Esters and glycol esters are included.

If an emulsifier is used, the amount of emulsifier is preferably between 0.1 and 10% by weight of the resin weight, for example between 0.5 and 5% by weight.

As the water emulsion in the oil is made, the unsaturated material reacts with the resin. It is preferred that the glass inject the initiator into the emulsion to cause the reaction. Suitable free group initiators include organic peroxy compounds such as t-butyl peroxy-2-ethyl hexanoate, benzoyl peroxide, dicumyl peroxide and azo compounds such as 2,2'-ethyl hexanoate, Symmetrical azo such as benzoyl peroxide, dicumyl peroxide and azo compounds, for example 2,2 'azobis (2-methylpropionitrile), 2,2'-azo-bis (2,4 dimethyl valeronitrile) Symmetric azonitriles such as nitrile and 2- (tertiary butylazo) -2-methylpropionitrile and asymmetric anitriles such as 2- (tertiary butylazo) 2-methylpropionitrile, water soluble initiators, such as Ammonium antioxidant, sodium persulfate or potassium or a redox system, ie hydrogen peroxide or peracid salt with sodium bisulfite or sodium formaldehyde sulfoxylate.

The amount of the free group initiator to be added is not critical, but 0.0001 to 0.05% by weight of the resin weight, for example, 0.001 to 0.01% by weight is sufficient.

On the other hand, radiation can be used to initiate the reaction.

Although the nature of the reaction is not clear, it is believed that it can be grafted due to the initiating action of free radicals. However, it has been found that heating the reaction mixture, for example, to a temperature of about 70 to 100 ° C., is preferred when the reaction is carried out by free radical initiation so that the reaction occurs at the desired rate. However, the temperature varies to some extent depending on the softening point of the resin (if dissolved) and the half life of any free radical initiator used. When using a redox system, it does not have to be heated. The time it takes for the reaction to complete may vary but usually after 2 hours and after about 1 hour.

Before adding water or an aqueous solution, the reaction mixture may be cooled to a temperature of, for example, about 50 ° C to 95 ° C. Thereafter, water or an aqueous solution is added to the oil emulsion in the oil until it is converted into the oil emulsion in water, the amount being such that the water does not exceed 50% by weight of the resin weight, preferably not more than 15% by weight. When the substance reacting with the resin is an acid or anhydride, an aqueous solution of a neutralizing base can be conveniently used.

If the solvent is used to make the resin liquid, it is only after the conversion of the emulsion that the solvent is removed. This can be done by distillation, but another method that can be used is steam stripping.

In a preferred embodiment, the method comprises the steps of: i) adding an aqueous solution of unsaturated organic carboxylate or unsaturated organic sulfonate to the liquid unsaturated resin such that the amount of water does not exceed 16% by weight of the resin; Ii) injecting a free radical initiator to graf the unsaturated salt to the backbone of the resin in the water emulsion of the oil thus formed and raising the temperature of the reaction mixture to cause grafting if necessary; Iii) adding a sufficient amount of water or an aqueous solution to the oil to convert the water emulsion in oil into a stable oil emulsion in water.

In another embodiment, the resin emulsion comprises: i) injecting 0.1 to 10% by weight of an unsaturated substance reacting with the resin into the liquid resin; Ii) inject a free radical initiator to allow the resin and the unsaturated material to react and raise the temperature of the reaction mixture to allow the reaction to occur if necessary; Iii) adding water and neutralizing agent in an amount such that the amount of water is preferably not more than 20% by weight based on the weight of the resin so that a water emulsion in the oil is formed; Iii) Water Emulsion in oil is produced by adding more water or aqueous solution until it is converted into a stable emulsion in water.

The basic value of this embodiment of the process is that the amount of reactant is relatively small, making the resulting modified resin itself difficult to emulsify. Useful materials for this embodiment are as described above for the present invention and the resin can be liquid at ambient temperature or can be made liquid, for example by melting or dissolving in a solvent. Suitable unsaturated materials are the aforementioned carboxylic acids and sulfonic acids and their salts and the preferred amounts are from 0.5 to 5% by weight, based on the weight of the resin.

A free group initiator is then added to cause the reaction of the unsaturated material and the unsaturated resin. In the next step it is preferred to add water and any neutralizing agent together with the emulsifier. It is preferable to add the neutralizing agent used when the reactants are acidic in the form of an aqueous solution of an alkali metal hydroxide or alkaline earth metal oxide or hydroxide, for example sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide or ammonium hydroxide. The amount of water added to the reaction mixture comprising the grafted polymer is preferably no more than 20% by weight, more preferably no more than 16% by weight, based on the weight of the resin.

At this stage a water emulsion in the oil is formed. To obtain the desired product, a larger amount of water or aqueous solution is added until the water emulsion in oil is converted to a stable oil emulsion in water. Then remove all solvent used to bring the resin into liquid.

In the main method and still another embodiment of the present invention, the unsaturated monomer may be dispersed in the liquid resin depending on the condition. Examples of unsaturated monomers that can be used include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconic acid and citraconic acid. Other suitable monomers include unsaturated carboxylic esters such as mono- and di-alkyl methacrylates, alkyl crotonates, hydroxy alkyl acrylates and methacrylates and the like.

The amount of unsaturated monomer added depends on the molecular weight of the monomer and the degree of grafting required. These monomers are generally added to increase the function of the hydrocarbon resin and in some cases they change the compatibility of the polymer with the resin.

Oil hydrocarbon resin emulsions in water produced by the present invention usually have a small particle size, measured using a coulter N4 ultrafine particle size analyzer with high mechanical shear stability and compatibility with polar polymers. It is small and preferably has a particle size of less than 0.5 microns.

They are useful as tackifiers for tacky polymer emulsions and are very useful for emulsion tack systems for use in high-speed coating lines that reduce oil breakage, produce less sediment and extend coating time further. Such sticky polymer emulsions include acrylic polymers, styrene-butadiene rubber (SBR), carboxylated SBR, polyvinyl acetate, and vinyl acetate-ethylene copolymers. The resin emulsion can also be mixed with other polar emulsions such as acrylic resins to produce pressure sensitive adhesives.

The invention is illustrated by the following examples, wherein the first two examples are by way of comparison.

Example 1

200 g of unsaturated aliphatic / aromatic petroleum resin, a feed copolymer having a softening point of 30 ° C., consisting mainly of C ₅ olefins and diolefins and 20 wt% of styrene, was dissolved at 55 ° C. and nonyl phenol-polyethylene oxide sulfonic acid (9 mol ethylene oxide) Is mixed with 26.7 g of fenopon EP-110 surfactant (30% by weight active ingredient in water) which is an ammonium salt of.

After dispersion of the surfactant, water was slowly added at 55 ° C. with stirring until the oil was converted from the water emulsion in oil to the oil emulsion in water. Further water was added to adjust the solids content to 55% by weight.

The resulting resin emulsion had a particle size larger than 1 micron and separated into two phases after two days storage at ambient temperature.

Example 2

Example 1 was repeated using 8 g of Atlas G3300, calcium alkyl benzene sulfonate instead of 26.7 g of Fenopon EP-110.

The particle size of the emulsion thus produced was less than 1 micron and phase separation did not occur after 6 months of storage at ambient temperature. However, examining its mechanical stability, it was found that when the emulsion was tested with a Haake rotoviscometer, it broke at a shear rate of 400 seconds ^-1 .

Example 3

The 200 g of the resin used in Example 1 was melted at 55 ° C. and mixed with a solution of 5 g sodium crotonate in 26.7 g of Fenopon EP-110.

After emulsifying the solution with water emulsion in oil, 0.01 g of tertiary-butylperoxy-2-ethyl hexanoate solution in 2 g of dioctyl phthalate (as dispersant for free radical initiator) was blanketed at 55 ° C. with a nitrogen blanket. Was added under stirring). After dispersing the free radical initiator, the temperature was raised to 90 ° C. and the mixture was reacted with stirring for 1 hour.

The mixture was then cooled to 55 [deg.] C. and hot water was added to the system until the emulsion converted to an oil emulsion in water, followed by further water to give an emulsion with a 55% solids content.

The particle size of the emulsion thus obtained was 0.3 microns and showed no phase separation after 6 months of storage at ambient temperature. Examination of its mechanical stability showed that the emulsion was stable within the shear rate range of the Haake Rotoviscometer (10,000 sec ^-1 ).

Example 4

200 g of the resin used in Example 1 was melted at 70 ° C. and mixed with 0.01 g tert-butylphenoxy-2-ethyl hexaneate in 4 g methacrylic acid and 2 g dioctyl phthalate under a blanket of nitrogen.

The mixture was heated at 90 ° C. for 1 hour and at 120 ° C. for 30 minutes. Then it was cooled to 55 ° C. A concentrated KOH solution was added to the molten resin to neutralize the acid.

The resin was mixed with 26.7 g of Fenopon EP-115 (ammonium salt of nonyl phenol polyethylene oxide sulfonic acid, 15 moles of ethylene oxide, 30% active ingredient in water). After dispersing the surfactant, water was added with stirring at 55 ° C. until the oil was converted into an oil emulsion in water, and further water was added to give an oil having a solid content of 55% by weight.

The emulsion thus obtained has a particle size and stability similar to those of Example 3.

The modified resin emulsions of Examples 3 and 4 were reviewed with two commercially available pressure sensitive adhesive (PSA) acrylic polymer latices and when using polyethylene, the loop tack was used with Acronal V205. The ball tack was improved, and the overall improvement was achieved with the Acronal 85D.

TABLE 1

Evaluation of the resin emulsion of Examples 3 and 4 as acrylic PSA latex tackifier (100 phr acrylic: 50 phr resin)

* Test method used

Claims (30)

Resin emulsion, consisting of forming an emulsion of an aqueous solution of an unsaturated substance that reacts with the resin in the liquid resin to react the substance with the resin and adding an amount of water sufficient to convert the emulsion into an emulsion of the reacted resin in water. How to prepare. The method of claim 1 wherein the unsaturated substance that reacts with the resin is an organic carboxylate or sulfonate. The method of claim 2 wherein the organic carboxylate or sulfonate is a Group 1 or 2 metal or ammonium salt of an unsaturated carboxylic acid or sulfonic acid. The process according to claim 2 or 3, wherein the carboxylic acid is acyl acid, methacrylic acid or cis- or trans-crotonic acid. 4. The process of claim 2 or 3 wherein the sulfonic acid is vinyl sulfonic acid, allylsulfonic acid or styrene sulfonic acid. The method of claim 1 wherein the amount of water provided in the aqueous solution does not exceed 20% by weight, based on the weight of the resin. 7. The method of claim 6, wherein the amount of water does not exceed 16% by weight based on the weight of the resin. 2. The process of claim 1 wherein the amount of aqueous solution of unsaturated material reacted with the resin is sufficient to provide 0.1 to 10 weight percent carboxylate or sulfonate based on the weight of the resin. (Iii) adding an unsaturated organic carboxylate or unsaturated organic sulfonate to the liquid unsaturated resin; (Ii) injecting a free radical initiator to graf the unsaturated salt in the resin backbone to the water emulsion in the oil thus formed and raising the temperature of the reaction mixture to cause grafting if necessary; (Iii) A method for producing a resin emulsion, comprising adding to the emulsion an amount of water or an aqueous solution sufficient to convert the water emulsion in oil into a stable oil emulsion in water. (Iii) injecting 0.1 to 10% by weight of an unsaturated substance reacting with the resin based on the weight of the resin into the liquid resin; (Ii) reacting an unsaturated substance with a resin; (Iii) adding water to form a water emulsion in the oil; (Iii) A method of producing a resin emulsion, which further comprises adding water or an aqueous solution until the water emulsion in oil is converted into a stable oil emulsion in water. The process of claim 10 wherein the unsaturated reactant is unsaturated carboxylic acid, anhydride or unsaturated organic sulfonic acid. 12. The method of claim 10 or 11, wherein the reactor free radical initiator is introduced into the mixture. The method of claim 10 wherein the neutralizing agent is injected with water in step (iii). The method of claim 10, wherein the carboxylic acid is acrylic acid, methacrylic acid, or cis- or trans-crotonic acid. The method of claim 10 wherein the sulfonic acid is alkyl sulfonic acid or styrenesulfonic acid. The method according to claim 10, wherein the amount of water added in step (iii) does not exceed 20% by weight based on the weight of the resin. 17. The method of claim 16, wherein the amount of water added does not exceed 16% by weight, based on the weight of the resin. The method of claim 1 wherein the resin is a petroleum resin. The method of claim 1 wherein the resin is a rosin derivative. The method of claim 1 wherein the resin was molten prior to adding the unsaturated reactant. The method of claim 1 wherein the emulsifier is also added to the liquid resin. 22. The method of claim 21 wherein the emulsifier is an sulfonate of an alkali sulphonate or an alkyl phenol polyalkylene oxide condensate. The method of claim 1 wherein after the unsaturated monomer has become liquid, it is also dispersed in the resin. The method of claim 23 wherein the unsaturated monomer is an ester of unsaturated carboxylic acid. A resin emulsion produced by the method of any one of the preceding claims. A method of using the resin emulsion of claim 25 as a tackifier for an adhesive polymer emulsion. 27. The method of claim 26, wherein the tacky polymer emulsion is an acrylic polymer, styrene-butadiene rubber, carboxylated styrene-butadiene rubber, polyvinyl acetate or vinyl acetate-ethylene copolymer. A coating composition for supplying a pressure sensitive adhesive comprising a mixture of a polymer emulsion and a resin emulsion of claim 25. 29. The pressure sensitive adhesive coating composition of claim 28 wherein the polymer emulsion is an emulsion of an acrylic polymer, styrene-butadiene rubber, carboxylated styrene-butadiene rubber, polyvinyl acetate or vinyl acetate-ethylene copolymer. 30. A method for producing a pressure sensitive adhesive material, comprising applying the coating composition of claim 28 or 29 to a substrate and drying to prepare an adhesive layer.