JPS6011734B2 - Emulsifier for synthetic resin - Google Patents

Description

[Detailed description of the invention] The present invention relates to an emulsifier for synthetic resins.

More specifically, the present invention relates to a new and useful emulsifier for synthetic resins containing an amine oxide group-containing polymer compound as an essential component. Various surfactants are used as emulsifiers for synthetic resins, but ``when taking out the resin, it is necessary to perform treatments such as salt folding and water washing, which is troublesome.

In this case, if washing with water is not sufficient, some of the emulsifier remains in the resin, causing undesirable effects such as deterioration of physical properties, especially deterioration of water resistance. The present inventors have conducted extensive research into emulsifiers that do not have such drawbacks, and have thus arrived at the present invention.

That is, the present invention relates to the general formula (where R is hydrogen or a methyl group; R' and R'' are each independently an alkyl group having 1 to 4 carbon atoms; x is a divalent bonding group; n is a number of 0 or 1) This emulsifier for synthetic resins is characterized by containing as an essential component a polymer compound having a structural unit represented by:

In the present invention, the polymer compound having the structural unit represented by the above general formula (abbreviated as structural unit A) is one in which the structural unit A is preferably contained in the polymer compound in an amount of 30% or more. It may be a polymer containing 100% A, or a copolymer containing structural units A and structural units other than A.

Structural units other than A include copolymerizable monomers in the form of monomers, such as styrene compounds, fatty acid esters of pinyl alcohol, (hydroxy)alkyl esters of (meth)acrylic acid, (meth)acrylamide, Examples include fatty acid pinylether and (meth)acrylonitrile. The above polymer or copolymer can be prepared by the method described in Tokuiso Sho 49-68291, namely by the general formula (where R is hydrogen or a methyl group; R and R'' are each independently an alkyl group having 1 to 4 carbon atoms; × is a divalent bonding group;
It can be obtained by oxidizing a polymer compound having a structural unit (n is a number of 0 or 1).

These compounds specifically include N,N-dimethylaminomethylstyrene, N,N-dimethylaminomethylstyrene, N,N-dimethylaminoethylisoproben, and N,N-dimethylaminomethylstyrene.
-dimethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, N,N-diethylaminoethyl acrylate, N-(N',N'-dimethylaminoethyl)acrylamide, N,N-dimethylaminopropionate vinyl, N, Polymers and copolymers of amine oxides of compounds such as N-dimethylaminoethyl (polyethoxy)acrylate. Among these, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, etc. are preferred from the viewpoint of ease of synthesis. The emulsifier of the present invention can be used in combination with a conventional emulsifier if necessary, and both anionic and nonionic emulsifiers can be used.

The amount used is preferably 0 to 50% (weight) based on the emulsifier of the present invention. The amount of the emulsifier used in the present invention is 0.1 to 20% (by weight), preferably 0.5 to 10% (by weight) based on the synthetic resin to be emulsified.

The method of use is the same as for ordinary emulsifiers, but since the emulsifier of the present invention is thermally decomposable, it is preferable to use it at a molecular weight of 10,000 or less. The emulsifier of the present invention can be used as an emulsifier for emulsion polymerization, such as vinyl acetate emulsion, rubber emulsion (
SBR, NBR. (acrylic rubber, etc.), acrylic emulsions, emulsifiers for condensed polymer compounds, emulsifiers, and emulsions of polyesters, polyamides, polyurethanes, and epoxy resins.

The emulsifier of the present invention is thermally decomposable and heated (120 to 13
0qo), it is decomposed into a water-insoluble resin part and a water-soluble part mainly composed of hydroxylamine.

Therefore, unlike conventional emulsifiers, there is no need for salting out or washing with water to remove the emulsifier, making the operation simple. Furthermore, when used as a baking resin (for example, in paint), it decomposes and becomes hydrophobic, resulting in a product with good water resistance. The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Various resin emulsions were prepared by weighing resin in a beaker and adding an aqueous solution of an emulsifier while stirring at room temperature according to the following formulation examples.

Details are shown in Table 1. Table 1'1 - Mixing example Resin 4 parts by weight Distilled water
58″ emulsifier
2 parts by weight [2- Emulsifier A: B: C: D: A: Mixture of 4:1 (by weight) of 10 mole adduct of nonylphenol-ethylene oxide EmiF: Sodium dodecylbenzenesulfonate: Nonylphenol ethylene oxide Mixture of 10 moles of adduct = 3:1 (by weight) Example 2 4 parts of the emulsifier B in Example 1 (as an active ingredient) was placed in a 4-volume flask equipped with a condenser, a condenser, a monomer dropping funnel, and a thermometer. amount), ammonium persulfate 0.2 part, sodium bicarbonate 0.07 part, t-dodecylmethylcaptan 1 part
．． After replacing the system with nitrogen gas, 67 parts of vinyl acetate monomer was added dropwise over 3 hours while adjusting the temperature to 70°C and 2°C under the ocean.
The students were taught at the same temperature for 1 hour.

The obtained polyvinyl acetate was No. 11. Subsequently, the emulsifier and resin composition were changed and resin emulsion No. 1 was prepared in the same manner as above. 12 to 17 were created.

These details are summarized in Table 2.

Table 2 {11 Emulsifier G: Sulfate salt of 20 mole adduct of linear C,2 alcohol ethylene oxide (2- Explanation of abbreviations of resin composition VAC: Vinyl acetate BMA:
n-butyl methacrylate St:
Styrene ACN:
Acrylonitrile BA:
n-Butyl acrylate HEMA: Hydroxyethyl methacrylate Example 3 No. obtained in Examples 1 and 2
．． 1~No. The physical properties of No. 17 emulsions were measured and the results are shown in Table 3.

Table 3*1. Weigh out 5 ounces of emulsion, and weigh 60 qo of 5 ounces.
Dry under reduced pressure for an hour, and the steam residue (%) is 0. Example 4 Resin emulsion No. 4 prepared in Example 2 was left at room temperature for one month and its appearance was observed with the naked eye. When changing the post-processing method (processing method for removing the resin) for 15 to 17 (acrylic rubber latex), the physical properties of the removed resin (
We measured how the viscosity and water pressure resistance changed.

The results are shown in Table 4.

4'11 Post-processing method a: Process for 130q02 hours while pressing in an autoclave.

b: Salt out by adding sodium sulfate.

. After that, wash with water (0 to 10 times). ■Viscosity Measured with 10% toluene solution at 20q0 using a BL type viscometer {31 Water resistance Measured according to JISLI079 Sample preparation method Koyama Tissog method: Over-knife method Number of coatings: 1 time Sample: 70 denier nylon taffeta hardener :
Addition amount of 3% isocyanate (NCO%=7.5) (evening/final): 4.3 Drying:
10000 x 1 minute Water repellent treatment: 1 part silicone 1-2% solution Cure: 15
Based on the results of 0 x 2 minutes or more, those heat-treated using the emulsifier of the present invention were treated with salt and washed with water for 5 minutes using a conventional emulsifier.
It shows the same water resistance (water pressure resistance) as the one that has been tested ~10 times, and does not require troublesome salting or water washing.

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, R is hydrogen or a methyl group; R', R'' are each independently an alkyl group having 1 to 4 carbon atoms; An emulsifier for synthetic resins, comprising as an essential component a polymer compound having a structural unit represented by a bonding group (n is a number of 0 or 1).