JPS63301212A - Resin emulsion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for making resin emulsions and their products, particularly emulsions with improved mechanical stability. The present invention is suitable for mechanical applications such as emulsions applied on coating lines, especially adhesive coating lines where breakage of the emulsion can cause deposits on the equipment and require frequent shutdown of the line for cleaning. It is particularly useful when a stable emulsion is required.

Polar modification of tackifying hydrocarbon resins can result in modification of resin properties such as improved compatibility with polar polymers, ease of emulsification, emulsion stability, and adhesion to polar surfaces. can.

Grafting of unsaturated aldehydes, acids, etc. onto resins by thermal condensation methods is described, for example, in US Pat. Nos. 3,379,663 and 3,953,407. These methods require long heating times at high temperatures before emulsification.
Requires. Free radical grafting is described in U.S. Patent No. 3.27.
No. 9.925, No. 3.005.800, No. 3.161
, 620, these patents do not concern the production of emulsions.

The present inventors have now discovered a method for producing a modified resin emulsion that is stable and compatible with polar polymers.

According to the present invention, a resin emulsion is produced by forming an emulsion in a liquid resin of an aqueous solution of an unsaturated substance reactive with a resin, reacting the substance with the resin, and adding sufficient water to form an emulsion. It is manufactured by a manufacturing method consisting of a step of inverting the phase of the reacted resin to form an emulsion in water.

Although many different resins can be used in the process of the invention, hydrocarbon resins are preferred and the resins used preferably contain some unsaturation, as is the case with most commercially available resins. petroleum resins (aliphatic or aromatic or aliphatic/aromatic), resins produced by copolymerization of pure aromatic monomers (e.g. styrene or methylstyrene or vinyltoluene) with olefins and/or diolefins; derivatives, rosin derivatives,
Polyterpenes or their derivatives or coumarons
It is an indene resin.

Petroleum resin is produced by thermal decomposition of petroleum feedstock.
It is obtained by polymerization of a fraction having an atmospheric boiling point of 5°C to 410°C. The polymerization of the fraction can be carried out thermally or in the presence of a catalyst, for example a Friedel-Krach catalyst such as AlC1z.

Petroleum feedstocks are usually petroleum feedstocks such as light naphtha, heavy naphtha, kerosene, gas oil, vacuum gas oil and contain mixtures of C3 olefins and diolefins or C6 olefins and diolefins or C2 and Ch olefins and diolefins. The oil is cranked in the presence of steam, the preferred temperature is 600°C to 900°C
It is. The product obtained from this cranking typically has a boiling point of -15°C to 280°C, contains about 30-60% olefins, 10-30% diolefins and 20-50%
% aromatic hydrocarbons and 5-20% paraffins and naphthenes.

Preferably, the product is subjected to rectification to remove the C2-C1 light fraction and thermally removed to remove hydrocarbons such as cyclic diolefins including cyclopentadiene and methylcyclopetadiene as dimers. Subjected to soaking and distillation.

After heat soaking and distillation, the boiling point is usually 30-110
C., e.g. 30-80.degree. C., overhead naphtha is obtained. This overhead naphtha is mainly composed of isoprene and 1,3-cis-
and C, diolefins such as transpentadiene, O5-C6 monoolefins, and aromatic hydrocarbons such as benzene. Generally, the overhead naphtha has the following composition, although the exact composition obviously depends on the nature of the petroleum feedstock to be subjected to steam cracking.

IX Total paraffin 160-41.4 Total diolefin 35.5-14.5 Total olefin
33.5-13.0 Totally aromatic hydrocarbon 3
0.0~31.0 Isoprene 16.5~
6.5 Pentadiene-1,314,5-4.5 Cyclopentadiene 1.0-2.5 Alternatively, the feed is an olefinic aromatic hydrocarbon such as styrene, vinyltoluene, alpha-methylstyrene, indene. The C7 feed can be a mixture of the C7 feed, or the C2 feed can be a mixture of the C2 feed and the C7 feed, and these feeds can be polymerized. Alternatively, a mixture of the C6 feed and the pure aromatic monomers and/or terpenes listed above can be polymerized. Particularly suitable resins are aliphatic-aromatic resins obtained by polymerization of mixtures of olefins (especially C3 and C6 olefins and diolefins) and aromatic monomers (eg styrene, alpha-methylstyrene, vinyltoluene).

When carrying out thermal polymerization, the distillate, that is, the overhead naphtha, is
Polymerization is usually carried out at a temperature of 200°C to 280°C for 1 to 8 hours. When polymerizing in the presence of a Friedel-Krauch catalyst, the polymerization temperature can range, for example, from -80°C to 120°C, preferably from -10°C to 80°C, and the polymerization is carried out for 174 to 2 hours. .

For example, free materials such as aluminum trichloride, aluminum trichloride-aromatic hydrocarbon complex, aluminum tribromide, boron trifluoride, boron trifluoride-phenol complex, titanium trichloride, ethylaluminum chloride, and ferric chloride Dell
Craff catalysts can be used.

These catalysts can be used in solid or liquid or gaseous state. Usually the amount of catalyst used is from 0.05 to 3.0% by weight relative to the weight of the material to be polymerized;
Preferably it is 0.1 to 1.5% by weight.

After polymerization, residual catalyst can be removed, for example, by washing with an alkali or aqueous solution of ammonia or sodium carbonate, or by adding an alcohol, such as methanol, followed by filtration.

Unreacted hydrocarbon "raffinates" enriched in benzene and/or paraffins (unreacted olefins) and low molecular weight oily oligomers can be removed from the final resin by steam stripping or vacuum distillation. The final product is usually 06-250°C, especially 30°-
It has a softening point of 140°C.

Hydrogenated products of these resins can also be used if desired. Hydrogenation is carried out at 150° in a solvent such as an aliphatic saturated hydrocarbon, for example hexane or hebutane, using a catalyst such as nickel or Raney nickel supported on diatomaceous earth or alumina or silica gel or pumice support. ~250°C, preferably 200''~250°C
at a reaction temperature of from 30 to 250 bar, preferably from 50 to
It can be carried out at a hydrogen reaction pressure of 100 bar.

In general, preferred resins are aliphatic petroleum resins obtained by polymerizing a fraction having a boiling point of 1156 DEG to 60 DEG C. at normal pressure using a Friedel-Krauch catalyst.

The hydrocarbon resin is usually solid at ambient temperature and has an il of 500 to 3000, preferably 700 to 200.
It has an average molecular weight of 0. However, liquid or semi-liquid resins can also be used.

In the manufacturing process of the present invention, the resin must be rendered liquid if it is not already liquid.

For example, the resin is melted or dissolved in a solvent.

When melting a resin, it is only necessary to heat the resin just above its melting point; overheating the resin is undesirable. For petroleum resins, the melting point is usually between 0°C and 250°C.

Alternatively, the resin may be dissolved in a suitable solvent, such as paraffins or mixtures thereof, such as hexane, heptane, nonane, octane, or aromatic hydrocarbons, such as benzene, toluene, xylene, or olefins, such as heptene or nonene. can be dissolved.

The unsaturated material reactive with the resin is preferably a material that provides polar functionality in the resin after reaction, which provides improved emulsion stability. Examples of suitable substances are unsaturated acids,
anhydrides, amines and their salts.

Preferred materials are unsaturated organic carboxylates or unsaturated organic sulfonates; suitable unsaturated carboxylates or unsaturated sulfonates include group I metals of unsaturated carboxylic or sulfonic acids; Included are salts of group metals or ammonium, such as sodium or potassium salts. Suitable unsaturated carboxylic acids include acrylic acid, methacrylic acid, 21 acrylic acids or methacrylic acid dimers,
Unsaturated dicarboxylic acids and half esters thereof such as oleic acid, cis- and trans-crotonic acid and maleic acid, fumaric acid, itaconic acid, citraconic acid. Suitable unsaturated sulfonic acids include vinyl sulfonic acid,
Contains allyl sulfonic acid and styrene sulfonic acid.

An unsaturated substance is dissolved in water to form an aqueous solution.

The aqueous solution must be sufficiently thick so that the amount of water present in the resin/salt mixture produces a water-in-oil emulsion. 20% or less based on the weight of the resin,
More preferably, less than 16% by weight of water is present.

The aqueous solution is preferably added to the liquid resin with stirring, more preferably with high shear stirring, to ensure effective distribution of the aqueous solution into the liquid resin to form a water-in-oil emulsion. The amount of unsaturated material added is
It preferably corresponds to 0.1 to 10% by weight, more preferably 0.5 to 3% by weight, based on the weight of the resin. To facilitate the formation of water-in-oil emulsions, emulsifiers are also preferably added to the liquid resin, for example together with the aqueous solution of the carboxylate or sulfonate. The emulsifier must be an anionic or nonionic surfactant or a mixture thereof.

Suitable anionic surfactants include alkylaryl sulfone M salts, such as sodium or calcium alkylbenzenesulfonates; resin alcohol sulfates, such as sodium lauryl sulfate; phosphoric acid esters, such as mono- and di-esters of orthophosphoric acid. esters of sulfosuccinic acid; sodium salts of sulfated monoglycerides; sulfonates or sulfosuccinates of alkylpolyoxyalkylene oxide condensates or alkylphenol polyalkylene oxide condensates, including ammonium salts of nonylphenol polyethylene oxide sulfonic acid; It will be done.

Suitable nonionic surfactants include polyethylene oxide, fatty alcohols or alkylphenols reacted with ethylene oxide, such as oleyl alcohol reacted with 15 moles of ethylene oxide; alkylene oxide blocks such as blocks of ethylene oxide and propylene oxide; Certain polyalkylene oxide block copolymers; condensation products of fatty acids with hydroxyalkylamines, such as jetanolamine condensates and polyoxyethylene fatty acid amides; carboxylic acid esters, such as glycerol esters, polyoxyethylene esters, ethoxylated and glycols of fatty acids. Contains ester.

If used, the amount of emulsifier added is preferably from 0.1 to 10% by weight relative to the weight of the resin, for example 0.5
~5% by weight.

Once the water-in-oil emulsion is obtained, the unsaturated material is reacted with the resin. Preferably, the reaction takes place by introducing a free radical initiator into the emulsion. Suitable free radical initiators include organic peroxy compounds such as t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide and azo compounds such as 2-ethylhexanoate.
．． 2'-azobis(2-methylpropionitrile), 2
゜2'-azobis(2,4-dimethylvaleronitrile)
symmetrical azonitrile such as and unsymmetrical azonitrile such as 2-(tert-butylazo)-2-methylpropionitrile, water-soluble initiators such as ammonium persulfate or sodium persulfate or potassium persulfate or redox systems, i.e. sodium bisulfite. or hydroperoxides or persulfates linked to sodium formaldehyde sulfoxylate.

The amount of free radical initiator added is not critical, but preferably o,oot to 0.05% by weight, such as o,oot to 0.01% by weight, relative to the weight of the resin, is sufficient.

Alternatively, the reaction can be initiated by radiation.

The nature of the reaction is not clear, but it is believed that in the case of free radical initiation it may be grafting. but,
The inventors have discovered that when carrying out reactions by free radical initiation, it is preferable for the reaction mixture to be heated to a temperature of, for example, about 70° to 100°C in order for the reaction to occur at a reasonable rate. did. However, the temperature depends in part on the softening point of the resin (if melted) and the half-life of the free radical initiator used. If a redox system is used, heating may not be necessary.

The time for the reaction to complete varies, but typically the reaction is complete after 2 hours, and often after 1 hour.

The reaction mixture can be cooled, for example to a temperature of about 50° to 95°C, before adding the water or aqueous solution. Water or an aqueous solution is then added until the emulsion undergoes a phase inversion from a water-in-oil emulsion to an oil-in-water emulsion. Usually, 50% by weight or less, preferably 15% by weight or less of water is added based on the weight of the resin. If the substance reacting with the resin is an acid or anhydride, an aqueous solution of a neutralizing base can be advantageously used.

If the resin has been made into a liquid by the use of a solvent,
At this stage after phase inversion of the emulsion, the solvent is removed. This is accomplished by distillation, but other methods that can be used include steam stripping.

In one preferred embodiment, the production method of the present invention comprises (i) adding an aqueous solution of an unsaturated organic carboxylate or an unsaturated organic sulfonate to a liquid unsaturated resin, the amount of water being (ii) introducing a free radical initiator into the water-in-oil emulsion thereby produced to introduce unsaturated salts onto the resin bank bones. (iii) raising the temperature of the reaction mixture to cause grafting and, if necessary, to cause grafting; and (iii) adding a sufficient amount of water to phase invert the water-in-oil emulsion to a stable oil-in-water emulsion. It consists of a step of adding water or an aqueous solution.

In another embodiment, the resin emulsion of the present invention includes (i) 0.1 of an unsaturated substance reactive with the resin into the liquid resin;
(ii) introducing a free radical initiator to effect the reaction between the unsaturated material and the resin and, if necessary, increasing the temperature of the reaction mixture to effect the reaction. and (iii) a step of adding a neutralizing agent and water,
(iv) converting the water-in-oil emulsion into a stable oil-in-water emulsion, in which the amount of water is preferably 20% by weight or less relative to the weight of the resin, thereby producing a water-in-oil emulsion; and adding more water or aqueous solution until the mixture is mixed.

This embodiment of the process of the invention is of value primarily when the amount of reactive substances is relatively low and results in a modified resin that is difficult to emulsify per se. Materials useful in this embodiment are the same as those previously described for the present invention, the resin being liquid at ambient temperature or made liquid, for example by melting or dissolving in a solvent. Suitable unsaturated substances are the carboxylic and sulfonic acids mentioned above and their salts, the preferred amount being 0.5 based on the weight of the resin.
~5% by weight.

Thereafter, a free radical initiator is added to cause the unsaturated material to react with the unsaturated resin. In the next step water and optionally a neutralizing agent are added, preferably together with an emulsifier. The neutralizing agent used when the reactive substance is acidic is preferably an alkali metal hydroxide or an alkaline earth metal oxide or hydroxide, such as sodium hydroxide or potassium hydroxide or calcium oxide or water. It is added as an aqueous solution of a neutralizing agent, which can be calcium oxide or ammonium hydroxide. The amount of water added to the reaction mixture containing the grafted polymer is preferably not more than 20% by weight, based on the weight of the resin, more preferably 1% by weight, based on the weight of the resin.
It is 6% by weight or less.

At this stage a water-in-oil emulsion is produced. To obtain the desired product, more water or aqueous solution is added until the water-in-oil emulsion undergoes phase inversion into a stable oil-in-water emulsion.

Thereafter, if a solvent was used to make the resin liquid, that solvent is removed.

In both the main manufacturing method and alternative embodiments of the invention,
Optionally, unsaturated monomers are also dispersed into the liquid resin. 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, citraconic acid. Other suitable monomers include unsaturated carboxylic esters such as monoalkyl methacrylates, dialkyl methacrylates, alkyl crotonates, hydroxyalkyl acrylates, and hydroxyalkyl methacrylates.

The amount of unsaturated monomer added depends on the desired degree of grafting and the molecular weight of the monomer. These monomers are generally added to increase the functionality of the hydrocarbon resin, and ultimately these monomers improve the compatibility of the resin with the polymer.

The oil-in-water hydrocarbon resin emulsions produced by the present invention typically have small particle size, Coulter
r) Generally 1 μm or less, preferably 0.5 μm when measured using a N4 submicron particle size analyzer
It has a particle size of: high mechanical shear stability and high compatibility with polar polymers. The emulsions of the present invention are useful as tackifiers for adhesive polymer emulsions and are very useful in emulsion adhesive systems applied on high speed coating lines to reduce emulsion breakage, reduce deposits and Increase coating run time. Such adhesive polymer emulsions include acrylic polymers, styrene-butadiene rubber (SB
R), carboxylated SBR, polyvinyl acetate, and vinyl acetate/ethylene copolymer. The resin emulsion of the present invention can also be mixed with other polar emulsions such as acrylic resins to produce pressure sensitive adhesives.

The present invention will be explained below with reference to Examples. The first two examples are for comparison.

Unsaturated aliphatic/aromatic petroleum resin 200 which is a copolymer of 20% by weight styrene with a feed that is primarily C, olefins and diolefins and has a softening point of 30° C. on combustion.
After melting g at 55°C, Fenop
on) 26.7 g of EP-110 surfactant (30% by weight active ingredient aqueous solution). The surfactant is nonylphenol polyethylene oxide sulfonic acid (9
ammonium salt of mol ethylene oxide).

After dispersing the surfactant, while stirring at 55°C,
Water was added gradually until the emulsion underwent a phase inversion from a water-in-oil emulsion to an oil-in-water emulsion. Further water was added to adjust the solids content to 55% by weight.

The resulting resin emulsion had a particle size larger than 1 μm and separated into two phases after storage for 2 days at ambient temperature.

EXAMPLE 1 Example 1 was repeated. However, instead of 26.7 g of Fenopon EP-110, 8 g
Atlas G 3300 (calcium alkylbenzenesulfonate) was used.

The resulting emulsion had a particle size of less than 1 μm and showed no phase separation after storage for 6 months at ambient temperature. However, when evaluating its mechanical stability, the Haake Rotoviscometer (Haake Rotovisco-met)
It was found that the emulsion breaks down at a shear rate of 4000 sec-' as measured by er).

200 g of the resin used in Actual IL Moxibustion Example 1 was melted at 55°C,
．． 7 g of Fenopon EP −
110 was mixed with a solution containing 5 g of sodium crotonate.

After emulsifying this solution into a water-in-oil emulsion,
A solution of 0.01 g of tert-butyl peroxy-2-ethylhexanoate in g of dioctyl phthalate (as a dispersant for the free radical initiator) was added at 55° C. with stirring and under a nitrogen atmosphere. did. After dispersing the free radical initiator, the temperature was raised to 90° C. and the mixture was allowed to react for 1 hour under stirring.

The mixture was then cooled to 55° C. and warm water was added to the system until the emulsion phase inverted to an oil-in-water emulsion, and more water was added to obtain an emulsion with a solids content of 55% by weight.

The resulting emulsion had a particle size of 0.3 μm and showed no phase separation after storage for 6 months at ambient temperature. When its mechanical stability was evaluated, this emulsion was tested in a Haake Rotoviscometer (Haake Rotoviscometer).
shear rate limit (10,000 sec
-') was stable.

Large flame↓ 200 g of the resin used in Example 1 was melted at 70°C, and 0.0 g of methacrylic acid and 2 g of dioctyl phthalate were dissolved.
Mixed with t-butyl peroxy-2-ethylhexanoate of Olg under nitrogen atmosphere.

The mixture was heated at 90°C for 1 hour and 120°C for 30 minutes, then cooled to 55°C.

A concentrated solution of potassium hydroxide was then added to the molten resin to neutralize the acid.

This resin was then injected with 26.7 g of Fenobone (Fen).
ammonium salt of E P -115C nonylphenol polyethylene oxide sulfonic acid (15 moles ethylene oxide), aqueous solution containing 30% by weight of active ingredient]
mixed with.

After dispersing the surfactant, water was gradually added while stirring at 55°C until the emulsion phase inverted to an oil-in-water emulsion, and further water was added to form an emulsion with a solids content of 55% by weight. I got it.

The resulting emulsion had similar particle size and stability to the emulsion of Example 3.

The modified resin emulsions of Examples 3 and 4 were evaluated in two commercially available acrylic pressure sensitive adhesive (PSA) polymer latexes.
Showed improvement in loop tack and ball tack on polyethylene when used with V 205 and overall improvement when used with Acronal 85 D .

Claims (7)

[Claims] (1) A step of generating an emulsion in a liquid resin of an aqueous solution of an unsaturated substance reactive with the resin, a step of reacting the substance with the resin, and a step of adding sufficient water and inverting the phase of the emulsion to react. A method for producing a resin emulsion comprising the step of producing a resin-in-water emulsion. (2) The production method according to claim (1), wherein the unsaturated substance reactive with the resin is an organic carboxylate or an organic sulfonate. (3) (i) adding an aqueous solution of an unsaturated organic carboxylate or unsaturated organic sulfonate to a liquid unsaturated resin; and (ii) adding a free radical initiator to the water-in-oil emulsion thereby produced. (iii) adding a sufficient amount of water or an aqueous solution to the emulsion to cause grafting of the unsaturated salt on the resin backbone and, if necessary, increasing the temperature of the reaction mixture to cause grafting; A method for producing a resin emulsion comprising the step of phase inverting a water-in-oil emulsion into a stable oil-in-water emulsion. (4) (i) a step of introducing into the liquid resin an unsaturated substance reactive with the resin in an amount of 0.1 to 10% by weight based on the resin; (ii) a step of reacting the unsaturated substance with the resin; , (ii
i) adding water, thereby forming a water-in-oil emulsion; and (iv) adding further amounts of water or aqueous solution until the water-in-oil emulsion undergoes a phase inversion to a stable oil-in-water emulsion. A method for producing a resin emulsion, which consists of steps. (5) A resin emulsion produced by the production method according to any one of the claims. (6) Polymer emulsion and Claim No. (5)
A coating composition for providing a pressure-sensitive adhesive comprising a mixture with a resin emulsion as described in 1. (7) The pressure-sensitive adhesive coating according to claim (6), wherein the polymer emulsion is an emulsion of an acrylic polymer or a styrene-butadiene rubber or a carboxylated styrene-butadiene rubber or a polyvinyl acetate or a vinyl acetate-ethylene copolymer. Composition.