JPS6036162B2 - Method for producing synthetic resin emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a synthetic resin emulsion.

Conventionally, synthetic resin emulsions have been synthesized using low-molecular-weight emulsifiers such as alkyl sulfonates, alkyl sulfates, and alkyl carboxylates as emulsifiers, but since the emulsifiers are mixed directly into the emulsion as impurities, The film made from the emulsion is water resistant,
It had the disadvantage of poor heat resistance, poor weather resistance, etc.

In addition, since the above-mentioned emulsifier is mixed, the foaming property is large, and especially when the paint is synthesized from the Umami emulsion, it foams violently when applied, making it difficult to apply it uniformly.
There were also drawbacks such as pinholes occurring in the film due to defoaming. Furthermore, when an acrylic monomer was used as the synthetic resin, the emulsifier alone produced a large amount of aggregates and only an emulsion with poor mechanical stability was obtained.

The purpose of the present invention is to react stably without generating aggregates during emulsion polymerization, and the obtained emulsion has low foaming property, high defoaming property, and mechanical stability.
The object of the present invention is to provide a method for producing a synthetic resin emulsion which has excellent pigment miscibility and whose film obtained from the emulsion has excellent water resistance, heat resistance, weather resistance, etc.

That is, the gist of the present invention is to provide a neutralized product obtained by ring-opening an anhydrous maleated isoprene resin having an acid value of 20 to 350 and neutralizing it with an amino alcohol compound. The present invention relates to a method for producing a synthetic resin emulsion, comprising emulsion polymerization of a radically polymerizable monomer using the emulsifier. The isoprene resin used in the present invention is a polymer mainly composed of isoprene, and may be a copolymer with a homopolymer of isoprene or a small amount of a copolymerizable monomer such as butadiene or 1,3 pentadiene. . If the molecular weight of isoprene resin is too small, the emulsifying ability will be reduced when an anhydrous maleic compound is subjected to an addition reaction to form an emulsifier, and if the molecular weight is too large, the viscosity will be high when dissolved in water, resulting in a small amount of Therefore, the number average molecular weight is preferably 500 to 150,000, and 1,000 to 1
00,000 is more preferred. Examples of the maleic anhydride compound used in the present invention include maleic anhydride derivatives such as maleic anhydride, maleic anhydride monomethyl ester, and maleic anhydride diethyl ester, and maleic anhydride is preferably used.

In the present invention, the above-mentioned isoprene resin and the above-mentioned maleic compound are subjected to an addition reaction to form an anhydrous maleated isoprene resin, and any known method may be adopted for this synthesis method, for example, isoprene resin and Methods such as heating to a high temperature (approximately 20,000 ℃) while simulating an anhydrous maleic compound, or adding isoprene resin and anhydrous maleic compound to a solvent and heating to a high temperature (approximately 200 oo) while stirring may be adopted. Although the reaction can be carried out without a catalyst during this synthesis, it is preferable to add a peroxide catalyst such as benzoyl peroxide. In the present invention, when the acid value of the anhydrous maleinated isoprene resin is less than 20, the emulsifying ability becomes low and a good emulsion cannot be obtained, and when the acid value is greater than 350,
As the emulsifying ability decreases, the water resistance of the film made from the obtained emulsion decreases, so the anhydrous maleinated isoprene resin with an acid value of 20 to 350 is used, and more preferably 50. ~200.
And in the present invention, the above-mentioned anhydrous maleinated physophore. The ring resin is ring-opened and then neutralized with an amino alcohol compound, and the resulting neutralized product is used as an emulsifier in emulsion polymerization. The method for ring-opening the anhydrous maleated isoprene resin is not particularly limited, and any known method may be adopted, such as heating in the presence of water, monohydric alcohol, amine compound, epoxy compound, etc. However, it is preferable to heat in the presence of water or a monohydric alcohol, and if the heating temperature is low, the ring reaction will be slow, and if it is high, gelation will occur easily.
~180q○ is preferable, more preferably 80~150q
○. The above-mentioned monohydric alcohols are compounds having one hydroxyl group in the molecule, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, phenol, benzyl alcohol, methyl cellosolve, butyl cellosolve, hydrubitol, and ethyl glycol monoacetate. can give.

In addition, examples of the above-mentioned amine compounds include methylamine,
Examples include alkylamines such as ethylamine, butylamine, diethylamine, and triethylamine; alkoxyalkylamines such as dimethomo, ethylamine, and diethoxoethylamine; and cyclic amines such as morpholine.

Furthermore, the ring-opened anhydrous maleinated isoprene resin as described above is then neutralized with an amino alcohol compound, but the amino alcohol compound is a compound having an amino group and a hydroxyl group on different carbon atoms in the molecule. For example, ethanolamine, diethanolamine,
Triethanolamine, N-methylmonoethanolamine, N,N. Diethyl monoethanolamine, 2-aminof.

Ro/zin-1-ol, 2-oxy-2-methylpropylamine, 1-aminobro/zin-2,3-diol,
2-aminopropane-1,3-diol, 2-amino-
2-methylpro/gnol, 2-amino-1,3-dioxybutane, 1-aminobentan-4-ol, 1,2
-diaminopropan-3-ol and the like. Any known method may be used for the neutralization, and is easily carried out by, for example, adding and mixing the amino alcohol compound to ring-opened anhydrous maleinated isoprene resin.

The radically polymerizable monomers used in the present invention are monomers that are generally used in emulsion polymerization, such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Alkyl esters of acrylate such as methyl methacrylate, alkyl methacrylate such as butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, styrene, Q-methylstyrene, vinyl acetate, vinyltoluene,
Examples include vinylpyridine, butadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile, etc., and these monomers may be used alone or as a mixture of two or more. , itaconic acid, acrylamide, methacrylamide, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and other hydrophilic monomers are used in combination. It's okay. In the present invention, any known emulsion polymerization method may be employed, except for using the above-mentioned neutralized anhydrous maleated isoprene resin as an emulsifier. For example, emulsion polymerization may be carried out by irradiation with radical-generating radiation such as gamma rays and electron beams, or by adding a radical polymerization initiator. Examples of the radical polymerization initiator include penzoyl peroxide, cumene hydroperoxide, peroxide Peroxides such as hydrogen, azo compounds such as azobisisobutyronitrile, persulfate compounds such as ammonium persulfate and potassium persulfate, perchloric acid compounds, combinations of the above persulfate compounds and reducing sulfoxy compounds, Examples include redox catalysts such as a combination of a chloric acid compound and a reducing sulfoxy compound.

The monomers, polymerization initiator, etc. may be added by any known method such as a batch addition method, a divided addition method, a continuous addition method, a monomer addition method, an emulsion addition method, etc.

In addition, in order to make the reaction proceed smoothly, methods such as purging the reaction system with nitrogen, purifying the reaction system after the reaction is completed to remove residual monomers, and adding special catalysts are used. Good too.

If necessary, conventionally known anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers, water-soluble polymer emulsifiers such as carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, butyl cellosolve, butyl carbitol, etc. may be used in combination. good.

In the present invention, emulsion polymerization is carried out using an anhydrous maleinated isoprene resin which has been ring-opened and then neutralized with an amino alcohol compound as an emulsifier. Because of its large emulsification capacity, it is suitable for use as an emulsifier for emulsion polymerization.
During polymerization, there is no generation of aggregates, and the polymerization is carried out stably, and the resulting emulsion has excellent mechanical stability, storage stability, pigment miscibility, etc., and has high adhesive strength.

Furthermore, since the emulsifier used in the present invention is a polymer and there is no need to use low molecular weight emulsifiers such as alkyl sulfonates and alkyl sulfates during emulsion polymerization, the film made from the synthesized emulsion is It has excellent water resistance, heat resistance, weather resistance, etc.

Further, since the anhydrous maleinated isoprene resin is neutralized with an amino alcohol compound, the synthesized emulsion has low foaming property and high antifoaming property. Furthermore, the synthesized emulsion has excellent miscibility with other water-soluble resins, and can be modified by being used in combination with epoxy resins, phenol resins, urea resins, melamine resins, etc., depending on the purpose of use. Furthermore, by adding a desiccant such as cobalt naphthenate or magnesium naphthenate, which are commonly used in paints, the water resistance and oil resistance of the film can be further improved. Therefore, in the production method of the present invention, it is possible to produce an emulsion that can be used in paints, adhesives, resin processing, etc. and exhibits excellent performance. Next, examples of the present invention will be described. The method for measuring acid value etc. is as follows. 1 Acid value The sample was dissolved in toluene ethyl alcohol (7/3) and titrated with 0.1 N potassium hydroxide solution using phenolphthalein as an indicator to determine the acid value.

2 Average particle size It was measured by turbidity method using Sakurada method.

3. Foaming and anti-foaming properties Ten samples of emulsion were supplied into a 20-piece graduated cylinder with a common stopper, shaken for 1 minute using a shaker, and foaming properties were determined by measuring the foam volume immediately after that. .

After shaking, the foam volume was measured after the mixture was allowed to stand still for 10 minutes, and the defoaming property was determined. Note that the foam volume is expressed as [(volume of combined foam emulsion) - (volume of true emulsion)]. 4
Gel formation: The emulsion was passed through an 80-mesh wire mesh to examine gel formation.

5 Soak the water-resistant emulsion film in 2000 ion exchange water,
Those with no decrease in transparency were considered to have good water resistance, and those with whitening were considered to have poor water resistance.

6. Alkali resistance The emulsion film was immersed in a 20o0 1% by weight aqueous sodium hydroxide solution, the transmittance and water absorption were measured, and a film with a low transmittance and a high water absorption was judged to have poor alkali resistance.

Example 1 In a separable flask equipped with a simulator, a thermometer, a cooling tube, and a nitrogen introduction tube, isoprene resin with an average molecular weight of 29,000 (manufactured by Kuraray Co., Ltd., trade name LIR-30) 20
The inside of the system was replaced with nitrogen by supplying 0.0 mt and 40 mn of maleic anhydride.

Next, the temperature was raised to 195 to 200 q0 while shaking, and the mixture was reacted for 8 hours to obtain a yellow solid maleinized isoprene resin composition.

The acid value of the resulting composition was 95. Twenty minutes of the above composition was fed into a separable flask equipped with a broiler, a thermometer, a cooling tube, a nitrogen introduction tube, and a dropping funnel, and the system was purged with nitrogen. Next, the temperature was raised to 9,000 degrees Celsius while holding a light, and after supplying 10 tons of water and keeping it at 90 qo for 3 hours, 90 tons of water, 5 tons of monoethanolamine, and 15 tons of butyl cellosolve were supplied to prepare the above composition. Neutralized and dissolved. Next, add 80 g of butyl methacrylate, and add 30 g of butyl methacrylate while stirring.
After purging with nitrogen for a minute, 30 minutes of ion-exchanged water in which 0.1 hours of potassium persulfate had been dissolved was added, the temperature was raised to 7,000℃, and the mixture was reacted for 6 hours. The reaction proceeded uniformly and no gel was generated. The solid content of the obtained emulsion was 39%, and the particle size of the emulsion was 160 mm. Also, the super foaming property is 0.2
The antifoaming property was 0. Further, the obtained emulsion was applied onto a glass plate and left at room temperature for 3 days to obtain a sheet having a film thickness of about 200 mm.

The obtained sheet was hard and transparent, and its water resistance was good with no change at all after 9 hours. In addition, the alkali resistance was good, with a transmittance of 94% and a water absorption rate of 8% after 9 hours of use.
Examples 2 to 8 Maleated isoprene resin compositions were obtained in the same manner as in Example 1 except that the isoprene resin used in Example 1 and maleic anhydride were used in the predetermined amounts shown in Table 1.

The acid value of the resulting composition was measured and the results are shown in Table 1.
The resulting composition was neutralized and dissolved in the same manner as in Example 1 using the amino alcohol compounds shown in Table 1.

An emulsion was obtained in the same manner as in Example 1 using the obtained neutralized solution and predetermined amounts of ion-exchanged water, potassium persulfate, butyl cellosolve, butyl methacrylate, butyl acrylate, and styrene shown in Table 1. Ta.

The polymerization proceeded uniformly and no gel was formed. The solid content, particle size, foaming properties, and sea-dissolving properties of the obtained emulsion were measured and are shown in Table 1. Next, a sheet was prepared from the obtained emulsion in the same manner as in Example 1, and a transparent hard sheet was obtained.

In addition, when the water resistance was measured after 9 mornings, all were found to be good. Example 9 Maleated isoprene resin composition 2 obtained in Example 1
After supplying the separable flask used in Example 1 with the same separable flask and purging the system with nitrogen, 140q0
The salt was raised to .

Then, butyl cellosolve was supplied for 10 hours and 140 hours for 3 hours.
After keeping 0, water 105 min and jetanolamine 5
The above composition was neutralized and dissolved by supplying water. Next, Example 1
When emulsion polymerization was carried out in the same manner as in Example 1, the reaction proceeded uniformly and no gel was formed. The solid content of the obtained emulsion was 40.0%, and the particle size was 260 mm. The foaming property was 0.8', and the antifoaming property was 0.3'. Also, in the same manner as in Example 1, the thickness was 200 mm.
When a Buddha sheet was produced, a transparent hard sheet was obtained, and the water resistance after 9 cycles was also good. Comparative Examples 1 to 3 The maleinized isoprene resin compositions obtained in Example 1 are shown in Table 1.

Neutralization and melting were carried out in the same manner as in Example 1 using aqueous ammonia, triethylamine, and sodium hydroxide.
Emulsion polymerization was carried out in the same manner as in Example 1 using the obtained neutralized melt.

Polymerization proceeded uniformly and no gel was generated. The solid content, particle size, foaming property, and antifoaming property of the obtained emulsion were measured and shown in Table 1. Next, a sheet having a film thickness of about 200 mm was produced from the obtained emulsion in the same manner as in Example 1.

The resulting sheet was hard and transparent. Next, water resistance and alkali resistance were measured and the results are shown in Table 1. Table 1

Claims (1)

[Scope of Claims] 1. A neutralized product obtained by ring-opening an anhydrous maleic isoprene resin with an oxidation rate of 20 to 350, which is obtained by adding an anhydrous maleic compound to an isoprene resin, and then neutralizing the ring with an amino alcohol compound. 1. A method for producing a synthetic resin emulsion, comprising emulsion polymerization of a radically polymerizable monomer using as an emulsifier. 2 The number average molecular weight of the isoprene resin is 500 to 1500
00. The manufacturing method according to claim 1. 3. The manufacturing method according to claim 1, wherein the oxidation is 50 to 200. 4 When ring opening occurs in the presence of water or monohydric alcohol, 50 to 1
The manufacturing method according to claim 1, which is carried out by heating to 80°C.