JP2597137B2 - Reactive emulsifier and water-dispersed resin composition - Google Patents

Description

The present invention relates to a reactive emulsifier and a water-dispersible resin composition.

[Conventional technology]

Uses a reactive emulsifier as an emulsifier for aqueous emulsion polymerization of unsaturated compounds, improves the water resistance of the resulting polymer film and eliminates the problem of river pollution by leaving the emulsifier in the wastewater when taking out the polymer by breaking the emulsion. For this purpose, there is a technique that attempts to incorporate a reactive emulsifier into a polymer.

Examples of the reactive emulsifier include quaternary ammonium salts containing a (meth) allyl group (JP-A-60-784947).

[Problems to be solved by the invention]

However, these reactive emulsifiers are not satisfactory in emulsion polymerization stability, and in particular, have a problem that the water resistance and adhesiveness of a polymer film produced from the obtained polymer emulsion are not sufficient.

[Means for solving the problem]

The present inventors are a reactive emulsifier having a good emulsion polymerization stability, and a polymer film made from a polymer emulsion having improved water resistance and adhesion, a reactive emulsifier and an ethylenic As a result of intensive studies to develop a water-dispersed resin composition comprising an emulsion polymer with an unsaturated monomer, the present invention has been achieved.

That is, the present invention relates to the general formula (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms. Z is 4 to 24 carbon atoms.
Having a saturated or unsaturated linear or branched chain of
Represents a fatty acid residue or an oxyacid residue. A) a reactive emulsifier comprising the amine imide (A) and an emulsion polymer of the amine imide (A) and the ethylenically unsaturated monomer (B) copolymerizable with the amine imide. This is a water-dispersed resin composition.

In the general formula (1), as the alkyl group having 1 to 10 carbon atoms of R ² and R ^3, a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, hexyl, -Ethylhexyl, octyl group and the like. Preferred among these are methyl, ethyl and n- or isopropyl groups.

In the general formula (1), Z is a fatty acid residue or an oxyacid residue (having a fatty acid residue or an oxyacid residue) having a saturated or unsaturated linear or branched chain having 4 to 24 carbon atoms. Examples of the fatty acid having a saturated or unsaturated straight or branched chain having 4 to 24 carbon atoms which constitutes a fatty acid or an oxyacid, from which the COOH group has been removed, include butyric acid, valeric acid, isovaleric acid, and capron. Acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
Arachidic acid, behenic acid, oleic acid, eicosenoic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid and the like. Examples of the oxyacid include hydroxycaproic acid, hydroxycapric acid, hydroxylauric acid, hydroxypalmitic acid hydroxystearic acid, hydroxyarachidic acid, and ricinoleic acid. Among these, preferred are those having 8 to 18 carbon atoms.
Having a saturated or unsaturated linear or branched chain of
Fatty acids or oxyacids.

Specific examples of the compound represented by the general formula (1) include, for example, And so on.

The amine imide represented by the general formula (1) of the present invention comprises glycidyl (meth) acrylate, an asymmetric dialkylhydrazine, [Wherein Z is the same as that represented by the general formula (1).
R ⁴ is an alkyl group having 1 to 10 carbon atoms. And the ester compound represented by the following formula:

In the asymmetric dialkylhydrazine, that is, N, N-dialkylhydrazine, the alkyl group is the same or different and has 1 to 10 carbon atoms and is a linear or branched alkyl group, such as asymmetric dimethylhydrazine, diethylhydrazine, isopropylhydrazine, n-butylhydrazine, diisobutylhydrazine, dioctylhydrazine and the like. Among them, preferred are linear or branched alkyl groups having 1 to 5 carbon atoms, which are the same or different, and particularly preferred is asymmetric dimethylhydrazine.

In formula (2), examples of the alkyl group having 1 to 10 carbon atoms for R ⁴ include the same groups as the alkyl groups for R ² and R ³ in formula (1).

Examples of the fatty acid constituting the ester compound of the general formula (2) include those having 4 carbon atoms constituting the residue Z in the general formula (1).
Fatty acids or oxyacids similar to fatty acids or oxyacids having up to 24 saturated or unsaturated straight or branched chains.

A method wherein the amine imide represented by the general formula (1) is reacted simultaneously with glycidyl (meth) acrylate, an asymmetric dialkylhydrazine and an ester compound in the presence of a solvent, if necessary, a method wherein glycidyl (meth) acrylate and asymmetric dialkyl are used. A method in which hydrazine is reacted and then the ester compound is reacted is exemplified.

The solvent used as necessary is not particularly limited as long as the raw material is dissolved and the reaction is not inhibited, and examples thereof include aliphatic alcohols, aromatic alcohols, ketones, ethers, aromatic hydrocarbons, amides, nitriles, and the like, and two or more of these. And mixtures thereof. Preferred are aliphatic alcohols and aromatic alcohols, particularly preferred are aliphatic alcohols.

The amount of the solvent used is usually 0 based on the total weight of the raw materials.
500500%, preferably 50-300%.

The reaction is usually carried out under stirring and, if necessary, under an atmosphere of an inert gas (such as nitrogen).

 After completion of the reaction, it can be used as it is or after purification.

Amineimide compounds have an infrared absorption (IR) spectrum,
And its structure can be confirmed by nuclear magnetic resonance (NMR) spectrum.

The water-dispersed resin composition of the present invention (hereinafter referred to as the composition of the present invention) comprises an amine imide (A) represented by the general formula (1) and an ethylenically unsaturated monomer copolymerizable therewith. It can be produced by the emulsion polymerization of B). Examples of the ethylenically unsaturated monomer (B) copolymerizable with the amine imide (A) include a hydrophobic ethylenically unsaturated monomer (I) and a hydrophilic ethylenically unsaturated monomer (II). Can be Examples of (I) include the following monomers.

(A) a nitrile group-containing monomer; (meth) acrylonitrile and the like.

(B) unsaturated carboxylic acid [(meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, etc.] ester monomer; (meth) acrylic acid ester having an alkyl group having 1 to 20 carbon atoms [eg, (meth) ) Methyl acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate dodecyl acrylate, etc.]; glycol (ethylene glycol, (Meth) acrylic acid diester of propylene glycol, polypropylene glycol, 1,4-butanediol, etc .; glycidyl (meth) acrylate; maleic acid, itaconic acid,
Di- or monoalkyl esters such as fumaric acid;

(C) aromatic hydrocarbon monomers; styrene, α-methylstyrene, vinyltoluene, divinylbenzene and the like.

(D) conjugated diolefin-based monomers; butadiene, isoprene, chloroprene and the like.

(E) Halogen-containing hydrocarbon monomers; vinyl chloride, vinylidene chloride and the like.

(F) Aliphatic hydrocarbon monomers; ethylene, propylene, α-olefin and the like.

(G) Vinyl ester monomers; vinyl acetate, vinyl propionate, and the like.

(H) (meth) allyl ester monomers such as allyl acetate, diallyl phthalate and diallyl maleate;

(II) includes the following monomers.

(I) an amide group-containing acrylic monomer; (meth) acrylamide, N-methylolacrylamide and the like.

(J) unsaturated carboxylic acids and salts thereof; (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and the like and salts thereof (alkali metal salts, ammonium salts, amine salts and the like).

(K) ester group-containing hydrophilic acrylic monomers; ethylene glycol (meth) acrylate monoester, propylene glycol (meth) acrylate monoester, polyethylene glycol (meth) acrylate mono- or diester, polyethylene glycol lower alkyl ether (Meth) acrylic acid esters and the like.

(1) Amine amide group-containing acrylic monomer (excluding the amine imide represented by the general formula (1) of the present invention); N, N-dimethyl-N- (2-hydroxypropyl) amine methacrylimide, N, N , N-trimethylamine methacrylimide and the like The ethylenically unsaturated monomers (B) copolymerizable with the amine imide compound (A) include (I) and (I) and (I)
The combination system of I) is used.

The polymerization amount of the amine imide (A) represented by the general formula (1) constituting the composition of the present invention and the ethylenically unsaturated monomer (B) copolymerizable therewith is the total weight of all the monomers. (A) is usually 0.1-20%, (B) is 80
99.9%, preferably (A) 0.5-10%, (B) 90%
~ 99.5%. If (A) is less than 0.1%, the composition of the present invention has poor emulsion stability. When (A) exceeds 20%, the water resistance of the dried coating film of the composition of the present invention decreases.

The composition of the present invention uses an amine imide (A) represented by the general formula (1) as an emulsifier, and is prepared by various polymerization initiation methods in the presence of a pH adjuster and, if necessary, a polymerization chain transfer agent. By subjecting an ethylenically unsaturated monomer (B) copolymerizable with the above to emulsion polymerization in an aqueous medium.

Acids (hydrochloric acid, phosphoric acid, acetic acid, succinic acid,
Boric acid, carbonic acid, etc.), salts thereof (sodium bicarbonate, sodium acetate, sodium chloride, sodium tripolyphosphate, etc.), and bases [alkali metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), ammonium hydroxide, Amines].

Examples of the polymerization chain transfer agent include mercaptans (such as dodecyl mercaptan, tetradecyl mercaptan, and hexadecyl mercaptan), xanthogen disulfide, sulfur, nitroso compounds, and amines.

As the aqueous medium used to obtain the composition of the present invention, an organic solvent such as methanol, isopropanol, and acetone may be used in addition to water.

Examples of the polymerization method include a method of irradiating an electron beam or an ultraviolet ray, a method of heating, and a method of using an initiator. In the method using an initiator, an azo compound (azobisisobutyronitrile, 2,2 ′
Azobis (2,4-dimethylvaleronitrile), azobiscyanovaleric acid, 2,2-azobis (2-amidinopropane) hydrochloride, etc.), inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide Sodium sulfate, etc.), organic peroxides (benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide peroxide, di (2-ethoxyethyl) peroxydicarbonate) and redox catalysts (alkali metal sulfite Or a combination of a reducing agent such as a salt or bisulfite, ammonium sulfite, L-ascorbic acid, erythorbic acid and an oxidizing agent such as alkali metal persulfate, ammonium persulfate and peroxide] and two or more of these. Is raised.

In the method for producing the composition of the present invention, if necessary, other emulsifiers, for example, anionic surfactants such as alkyl sulfates, alkyl aryl sulfonates, alkyl phosphates or fatty acid salts, and alkylamine salts , Cationic surfactants such as alkyl quaternary ammonium salts, nonionic surfactants such as polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, or pluronic types, carboxylate types (amino acid types, betaine types, etc.) or An amphoteric surfactant such as a sulfonic acid salt type can be used in combination, but a large amount would defeat the purpose of the present invention, and therefore it is preferably 50% or less by weight of the emulsifier of the present invention.

It is known that when an acid is added, the amine imide group becomes cationic and hydrophilic. Accordingly, an acid can be added to the compound of the general formula (1) to increase the hydrophilicity and assist the emulsifying property. Examples of the acid include organic or inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, lactic acid, (meth) acrylic acid, oxalic acid, citric acid, maleic acid, itaconic acid, and adipic acid. Can be
The amount of the acid is usually 0.3 to 1.5 times the mol of the amine imide group. The acid may be added before or after the emulsion polymerization, but is usually performed before the emulsion polymerization.

In the method for producing the composition of the present invention, a protective colloid agent for the purpose of stabilizing emulsion polymerization, for example, partially saponified polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like can be used. When used, it is contrary to the purpose of the present invention, so that it is preferably at most 20% based on the weight of the emulsifier of the present invention.

As a polymerization method, any of a batch polymerization method and a continuous polymerization method can be used by a known polymerization method. Known polymerization methods include a batch charging method, a monomer addition method, and a monomer emulsion addition method.

The polymerization temperature varies depending on the polymerization method, the type of the monomer to be polymerized, the emulsified state, etc., but is usually -5 to 100.
° C, preferably 10-90 ° C.

In the composition of the present invention, if necessary, an antifoaming agent, a viscosity modifier, a film-forming aid, a preservative, a freeze stabilizer, a crosslinking agent, a plasticizer, an adhesive, an antistatic agent, a pigment, a dye, and the like. May be added.

〔Example〕

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

Example 1 A four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 128 g of methyl laurate, 36 g of asymmetric dimethylhydrazine, and 62 g of isopropyl alcohol, and heated to 40 to 50 ° C with stirring. At the same temperature, 85 g of glycidyl methacrylate was added dropwise over 2 hours, followed by 60-70 ° C.
For 6 hours. A white amine imide (Al-4) was obtained in a quantitative yield except for isopropyl alcohol. This is designated as reactive emulsifier 1 of the present invention.

Example 2 Using the same reactor as in Example 1, methyl caprylate 30
g, 12 g of asymmetric dimethylhydrazine, and 72 g of isopropyl alcohol, and heated to 30 to 40 ° C. with stirring. At the same temperature, 26 g of glycidyl acrylate was added dropwise over 1 hour, followed by stirring at 60 to 70 ° C. for 8 hours. Except for isopropyl alcohol, a white amine imide (Al-2) was obtained in a quantitative yield. This is designated as reactive emulsifier 2 of the present invention.

Example 3 In the same manner as in Example 1, isopropyl alcohol 12
In the presence of 5 g, 109 g of methyl palmitate, 24 g of asymmetric dimethylhydrazine and 57 g of glycidyl methacrylate were reacted to obtain a white amine imide (Al-5) in a quantitative yield except for isopropyl alcohol. This is designated as reactive emulsifier 3 of the present invention.

Example 4 In the same manner as in Example 1, isopropyl alcohol 99
In the presence of g, 59 g of methyl oleate, 12 g of asymmetric dimethylhydrazine and 28 g of glycidyl methacrylate were reacted to obtain a pale yellow amine imide (Al-7) at a quantitative yield except for isopropyl alcohol. This is designated as reactive emulsifier 4 of the present invention.

Example 5 In the same manner as in Example 1, isopropyl alcohol 70
In the presence of g, 125 g of methyl hydroxystearate, 12 g of asymmetric dimethylhydrazine and 28 g of glycidyl methacrylate were reacted to obtain a white amine imide (Al-9) in a quantitative yield except for isopropyl alcohol. This is designated as reactive emulsifier 5 of the present invention.

Examples 6 to 10 In a reactor equipped with a stirrer, a dropping funnel, a nitrogen inlet tube, a thermometer and a reflux condenser, 270 g of ion-exchanged water, an emulsifier of the present invention (1
5) 8.5 g, 0.36 g of sodium hydrogen carbonate and 0.8 g of sodium persulfate are charged, and after purging with nitrogen, a mixed monomer of 90 g of styrene and 90 g of butyl acrylate is dropped at 70 to 80 ° C. over 2 hours from a dropping funnel at 70 to 80 ° C. Then, the composition of the present invention, which was a good milky white polymer emulsion having a monomer conversion of 99% or more, was obtained.

The emulsion polymerizability and the water resistance, adhesion, mechanical stability and freeze stability of the emulsion prepared from the polymer emulsion of the composition of the present invention were examined. Table 1 shows the test results.

Examples 11 to 15 In a reactor equipped with a stirrer, a dropping funnel, a nitrogen inlet tube, a thermometer and a reflux condenser, 216 g of ion-exchanged water, an emulsifier of the present invention (1
5) Charge 6.4 g, 0.8 g of acetic acid and 0.7 g of azobiscyanovaleric acid, and after replacing with nitrogen, add a mixed monomer of 80 g of methyl methacrylate and 65 g of isobutyl acrylate at 90 to 95 ° C under stirring for 3 hours from a dropping funnel. And polymerized by dropping over
The composition of the present invention was obtained as a milky white good polymer emulsion having a monomer conversion of 99% or more.

The emulsion polymerizability and the water resistance, adhesion, mechanical stability and freeze stability of the emulsion prepared from the polymer emulsion of the composition of the present invention were examined. Table 2 shows the test results.

(Polymerization Stability) The polymer emulsion, which is the composition of the present invention, was filtered through a 150-mesh wire gauze, and the residue was washed with water and dried, and the weight of the coagulated product was expressed as% of the weight of the charged monomer.

(Water resistance) The polymer emulsion as the composition of the present invention was spread on a glass slide and dried at 60 ° C. for 8 hours and further at 20 ° C. for 24 hours to prepare a 0.2 mm thick film. The water resistance of this film was tested by the water drop test method of JIS-K6828.

(Adhesion) The 180 ° C peel strength at 40 ° C of a glass / film (reinforced with cotton cloth) of the film prepared by the method described in the section “Water resistance of film” was measured at a pulling speed of 100 mm / min.

(Mechanical stability) 200 g of the polymer emulsion of the composition of the present invention was placed in a beaker, stirred at 10,000 rpm for 30 minutes with a homomixer, and the formed coagulated product was filtered off through a 150-mesh wire net and washed with cold water. After drying. This dry weight was expressed in% with respect to the weight of the solid content in the collected emulsion.

(Freezing stability) 50 g of the polymer emulsion of the composition of the present invention was taken in a glass bottle and sealed, and the mixture was kept at -10 ° C for 12 hours and at 35 ° C for 12 hours.
As a cycle, the number of times until the emulsion was frozen and destroyed was measured.

[Effect of the Invention] When emulsion polymerization of a polymerizable unsaturated compound is performed using the emulsifier of the present invention, a polymer emulsion having good emulsion polymerization stability can be produced.

The polymer emulsion obtained by incorporating the emulsifier of the present invention has excellent stability, long-term storage, and improved freeze-thaw properties.

When the polymer is taken out from the polymer emulsion of the composition of the present invention, effects such as hardly flowing out of the emulsifier into the wastewater are also exerted.

The emulsifier of the present invention can also be used for producing synthetic resins, synthetic fibers, and synthetic rubber.

Films or coatings made from the compositions of the present invention exhibit excellent antistatic properties, water resistance and adhesion.

When the composition of the present invention is heated to 150 ° C. or higher, crosslinking of the amine imide in the thermal field occurs, and the solvent resistance and water resistance of the obtained film or coating are significantly improved.

The composition of the present invention obtained by applying the emulsifier of the present invention is applied to inorganic materials such as concrete in addition to wood, metal, paper, cloth, etc. by methods such as adhesion, coating, electrodeposition, and impregnation. it can.

The composition of the present invention obtained by applying the emulsifier of the present invention can be used for aqueous paints, adhesives, paper processing, textile processing, fiber modification, floor polish, soil erosion prevention, concrete, and mortar admixture. It can be used for such purposes.

Claims (3)

(57) [Claims] (1) General formula (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms. Z is 4 to 24 carbon atoms.
Having a saturated or unsaturated linear or branched chain of
Represents a fatty acid residue or an oxyacid residue. A) a reactive emulsifier comprising an amine imide represented by the formula: 2. The general formula (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms. Z is 4 to 24 carbon atoms.
Having a saturated or unsaturated linear or branched chain of
Represents a fatty acid residue or an oxyacid residue. A water-dispersible resin composition comprising an emulsion polymer of the amine imide (A) and an ethylenically unsaturated monomer (B) copolymerizable with the amine imide (A). 3. The polymerization amount of (A) and (B) is 0.1 to 20%, and (B) is 80 to 9 based on the total weight of all monomers.
3. The composition according to claim 2, which is 9.9%.