JP2608785B2 - Water-dispersible resin composition containing polysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a polysiloxane-containing water-dispersible resin composition.

[Conventional technology]

In order to obtain a water-dispersible resin containing a polysiloxane group, an emulsion of a polysiloxane compound (polydimethylsiloxane, polymethylvinylsiloxane, etc.) is prepared in advance, and an ethylenically unsaturated monomer is added to the emulsion in the presence of an emulsifier. There is a technique for obtaining a monomer by emulsion polymerization, and a technique for obtaining a polysiloxane-containing monomer unsaturated at one end and an ethylenically unsaturated monomer by emulsion polymerization using an emulsifier in the presence of an electrolyte. Examples of the former emulsifier include didecylbenzene sulfonate and the like (JP-A-50-109282), and examples of the latter emulsifier include dialkylsulfosuccinate and the like (JP-A-63-191807).

[Problems to be Solved by the Invention]

However, these polysiloxane-containing water-dispersible resin compositions have insufficient storage stability, and the polymer films produced from these water-dispersible resin compositions have insufficient water repellency and smoothness. There is a point.

[Means for Solving the Problems]

The present inventors have found that the storage stability of the polysiloxane-containing water-dispersed resin composition is good, and the polymer films produced from these water-dispersed resin compositions have improved water repellency and smoothness. The present invention has been achieved as a result of intensive research to develop a water-dispersible resin composition containing polysiloxane.

That is, the present invention relates to the general formula (Wherein, R ¹ represents a hydrogen atom or a methyl group, R ^2, R ³ .R ⁴ is carbon are each an alkyl group having 1 to 10 carbon atoms 3-25
Is an alkyl group. ) An amine imide compound (A ₁ ) and / or a general formula (In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms. R ⁵ is 4 to 28 carbon atoms.
Or a saturated or unsaturated aliphatic hydrocarbon group, or a (substituted) phenyl group. ) And an amine imide (A ₂ ) (Wherein X is a vinyl group, a (meth) acryloxy group or an allyl group, R ⁶ is a divalent hydrocarbon group, R ⁷ , R ⁸ , and R ⁹ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or phenyl. Base, n =
1 to 130. (B) and a copolymer of an ethylenically unsaturated monomer (C) copolymerizable therewith with the polysiloxane group-containing unsaturated monomer (B). It is a water-dispersed resin composition.

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

In the general formula (1), examples of the alkyl group having 3 to 25 carbon atoms of R ⁴ include propyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, and petanedecyl. , Hexadecyl, heptadecyl,
Examples thereof include linear or branched alkyl groups such as octadecyl, nonanidecyl and eicosyl groups. Among these, preferred is an alkyl group having a straight or branched chain having 7 to 15 carbon atoms.

In the general formula (2), as the saturated or unsaturated aliphatic hydrocarbon group having 4 to 28 carbon atoms of R ⁵ , butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, heptadecyl And alkyl groups or alkenyl groups such as hexadecyl, octadecyl, oleyl and eicosyl groups. Of these, preferred are saturated or unsaturated linear or branched aliphatic hydrocarbon groups having 10 to 18 carbon atoms. The substituted phenyl group has 1 carbon atom.
A phenyl group having 18 to 18 alkyl groups (cresyl, n-
Examples thereof include butylphenyl, t-butylphenyl, octylphenyl, nonylphenyl, dodecylphenyl and the like, an arylphenyl group (biphenyl and the like), an aralkylphenyl group (cumylphenyl, styrenated phenyl and the like) and the like. Among these, preferable one has 1 carbon atom.
A phenyl group having from 18 to 18 alkyl groups.

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

Specific examples of the compound represented by the general formula (2) include, for example, And so on.

The amine imide represented by the general formula (1) can be obtained by reacting a 1,2-epoxyalkane having 6 to 28 carbon atoms with a (meth) acrylate and an asymmetric dialkylhydrazine.

The amine imide compound represented by the general formula (2) is a glycidyl ether compound selected from an alkyl or alkenyl glycidyl ether compound having 4 to 28 carbon atoms or a (substituted) phenyl glycidyl ether compound and (meth)
It can be obtained by reacting an acrylate ester with an asymmetric dialkylhydrazine.

The amine imide represented by the general formula (1) or (2) may be used, if necessary, in the presence of a solvent such as an alcohol, a ketone, an ether or an aromatic hydrocarbon, in the presence of a (meth) acrylate, an asymmetric dialkylhydrazine and 1,2 −
Examples thereof include a method of simultaneously reacting three members of an epoxy alkane or a glycidyl ether compound, and a method of reacting a 1,2-epoxy alkane or glycidyl ether compound with an asymmetric dialkylhydrazine and then reacting with a (meth) acrylic ester.

In the general formula (3), examples of the divalent hydrocarbon group represented by R ⁶ include an alkylene group and a phenylene group, and examples of the alkylene group include an ethylene group, a propylene group, a butylene group and a hexylene group. Is a propylene group.

Further, in the general formula (3), R ⁷ , R ⁸ , and R ⁹ have 1 carbon atoms.
Examples of the alkyl group of 10 to 10 include a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group is preferable. Three of R ⁹ may be the same or different.

Specific examples of the monomer represented by the general formula (3) include, for example, And mixtures of two or more of these.

The ethylenically unsaturated monomer (C) used in the polysiloxane-containing water-dispersed resin composition of the present invention (hereinafter, referred to as the composition of the present invention) includes a hydrophobic ethylenically unsaturated monomer (I). ) And a hydrophilic ethylenically unsaturated monomer (II). Examples of (I) include the following monomers.

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 [(meth) acrylic acid Methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate]; glycols (ethylene glycol, propylene) (Meth) acrylate diesters of glycol, polypropylene glycol, 1,4-butanediol, etc.); glycidyl (meth) acrylate; di- or monoalkyl esters of maleic acid, itaconic acid, fumaric acid, etc .; hydroxy (meth) acrylate Caprolactone modified products of ethyl, etc.

c. Aromatic hydrocarbon monomers; styrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc.

d. Halogen-containing hydrocarbon monomers; vinyl chloride, vinylidene chloride, chlorostyrene, chloroprene and the like.

e. Aliphatic hydrocarbon monomer; ethylene, propylene, α-olefin, butadiene, isoprene and the like.

f. Vinyl ester monomer; vinyl acetate, vinyl propionate, etc.

g. (Meth) allyl ester monomers such as allyl acetate, diallyl phthalate and diallyl maleate;

(II) includes the following monomers.

h. Amino group- or amide group-containing unsaturated monomer; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, N
-Methylol (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, and the like.

i. 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).

j. Ester group-containing hydrophilic acrylic monomer; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate mono- or diester, polyethylene glycol lower alkyl ether ( (Meth) acrylic acid ester and the like.

k. Amine imide group-containing acrylic monomer (excluding the amine imides represented by formulas (1) and (2) of the present invention); N, N-dimethyl-N- (2-hydroxypropyl) amine methacrylimide; N, N, N-trimethylamine methacrylimide, and compounds of the general formula (1) described in JP-A-63-193031, etc. Ethylenically unsaturated monomer (C) used in the composition of the present invention As (I), a combination system of (I) and (II) is used.

The amine imide compound (A ₁ ) represented by the general formula (1) and / or the amine imide compound (A ₂ ) represented by the general formula ( ₂ ) and the polysiloxane-containing unsaturated monomer (B ), And the amount of the ethylenically unsaturated monomer (C) copolymerizable therewith is usually from 0.5 to 30 (A ₁ ) and / or (A ₂ ) based on the total weight of all the monomers.
%, Preferably 1 to 20%, (B) is usually 1 to 50%, preferably 5 to 50%, (C) is usually 20 to 98.5%, preferably
30-94%. If (A ₁ ) and / or (A ₂ ) is less than 0.5%, the emulsion stability of the composition of the present invention will be poor, and if it exceeds 30%, the water resistance of the dried coating film of the composition of the present invention will decrease. Further, if the content of (B) is less than 1%, the water repellency and smoothness of the composition of the present invention are not sufficient, and if it exceeds 50%, it is disadvantageous in terms of economy.

The composition of the present invention can be produced by an emulsion polymerization method or a method of dispersing a resin obtained after solution polymerization or bulk polymerization in water, and the like, and the emulsion polymerization method is preferred.

As the emulsion polymerization method, an amine imide compound (A ₁ ) represented by the general formula ( ₁ ) and / or an amine imide compound (A ₂ ) represented by the general formula (2) is used as an emulsifier, and if necessary, a pH adjuster or a polymerization chain is used. In the presence of a transfer agent, an unsaturated monomer (B) containing (A ₁ ) and / or (A ₂ ) and a polysiloxane group in the presence of a transfer agent, and an ethylenically unsaturated copolymerizable therewith It is obtained by polymerizing the monomer (C) in an aqueous medium.

As a method for dispersing the resin obtained after solution polymerization or bulk polymerization in water, an amine imide compound (A ₁ ) represented by the general formula ( ₁ ) and / or an amine imide compound (A ₂ ) And an unsaturated monomer (B) containing a polysiloxane group, and an ethylenically unsaturated monomer (C) copolymerizable therewith, are optionally subjected to various polymerizations in the presence of a polymerization chain transfer agent. It can be obtained by copolymerization in a solvent (alcohol, ketone, ether, aromatic hydrocarbon, etc.) or as it is depending on the starting method, and dispersing the obtained resin in an aqueous medium in the presence of a pH adjuster if necessary.

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

Examples of the polymerization chain transfer agent include mercaptans (dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, 2-mercaptoethanol, etc.), xanthogen disulfide, sulfur, nitroso compounds, amines and the like.

Examples of the aqueous medium include water, methanol, ethanol, isopropanol, acetone, ethylene glycol, diethylene glycol, triethylene glycol,
Organic solvents such as propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether may be used in combination.

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, the initiator is an azo compound [azobisisobutyronitrile, 2,2'-
Azobis (2,4-dimethylvaleronitrile), azobiscyanovaleric acid, 2,2-azobis (2-amidinopropane) hydrochloride, 2,2-azobis (2-amidinopropane) acetate, etc.], inorganic peroxide [peroxide Hydrogen oxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.], organic peroxides [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide acid peroxide, di (2-ethoxyethyl) peroxy] Dicarbonates] and redox catalysts (reducing agents such as alkali metal sulfites or bisulfites, ammonium sulfite, L-ascorbic acid, erythorbic acid, and oxidizing agents such as alkali metal persulfates, ammonium persulfate, peroxides) And a combination of two or more of these.

Addition of acid increases the hydrophilicity of the amine imide group. Accordingly, an acid can be added to the compounds of the general formulas (1) and (2) to increase hydrophilicity and to assist emulsification. Acids include organic or inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid,
Examples thereof include nitric acid, formic acid, acetic acid, propionic acid, lactic acid, (meth) acrylic acid, oxalic acid, citric acid, maleic acid, itaconic acid and adipic acid. 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 polymerization, but is usually performed before the polymerization.

In the method for producing the composition of the present invention, if necessary, other emulsifiers such as anionic surfactants such as alkyl sulfate ester salts, alkylaryl sulfonate salts, alkyl phosphate ester salts or fatty acid salts, and alkyl amine salts. , Cationic surfactants such as alkyl quaternary ammonium salts, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, pluronic type surfactants, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters An ionic surfactant, an amphoteric surfactant of carboxylate type (amino acid type, betaine type, etc.) or sulfonate type can be used in combination. The amount of these emulsifiers used is preferably 50% or less of the weight of the amine imide compound represented by the general formula (1) and / or the amine imide compound represented by the general formula (2) constituting the composition of the present invention.

In the method for producing the composition of the present invention, a protective colloid such as polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose can be used for the purpose of stabilizing the emulsion. The protective colloid agent is used in an amount of the amine imide compound represented by the general formula (1) and / or the general formula (2) constituting the composition of the present invention.
20% or less of the weight of the amine imide represented by

As the 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, a monomer emulsion addition method and the like.

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

If necessary in the composition of the present invention, an antifoaming agent, a viscosity modifier, a film-forming aid, a preservative, a freeze stabilizer, a crosslinking agent, a plasticizer,
You may add additives, such as an adhesive, an antistatic agent, a pigment, and a dye.

The composition of the present invention is suitable as an adhesive, a coating agent, a sealing agent, etc., and can be applied to wood, metal, paper, cloth, and other inorganic substances such as concrete by a method such as adhesion, coating, electrodeposition and impregnation. Applicable. For example, "Emulsion / Latex Handbook" (published by Taiseisha in March 1975), 5th edition, Processing of emulsion / latex (P.565-
P.903) and "Introduction to Emulsion Applications" (August 1973)
Published by The Polymer Society of Japan) Chapter 7 Application as Adhesives-
It can be used for the purposes and usages described in Chapter 12, Other Uses (P.69 to P.157).

〔Example〕

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

Example 1 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, 20 g of an amine imide (AI-3), 3 g of acetic acid, 2,2-azobis (2-amidino) were used. Propane) Hydrochloride 1 g was charged, and after nitrogen substitution, 30 g of polysiloxane-containing unsaturated monomer (SI-3, n = 11), 75 g of styrene, and 75 g of n-butyl acrylate were stirred at a temperature of 70 to 80 ° C. Polymerization was carried out by dropping the mixed monomer from the dropping funnel for 3 hours to obtain a milky white polymer emulsion (monomer conversion rate: 99% or more, solid content;
(About 43%).

Example 2 216 g of ion-exchanged water, 15 g of amine imide (AI-4), 2.5 g of acetic acid, 0.75 g of 2,2-azobis (2-amidinopropane) hydrochloride were charged in the same apparatus as in Example 1, and after nitrogen substitution. A mixture of 30 g of polysiloxane-containing unsaturated monomer (SI-3, n = 24), 45 g of methyl methacrylate, 48 g of n-butyl acrylate, and 12 g of 2-hydroxyethyl methacrylate under stirring at a temperature of 70 to 80 ° C. The monomer was added dropwise from the dropping funnel over 3 hours to carry out polymerization to obtain a composition of the present invention which was a good milky white polymer emulsion (monomer conversion: 99% or more, solid content: about 41.5%).

Example 3 In the same apparatus as in Example 1, 70 g of ion-exchanged water, 4.8 g of an amine imide (AI-5), 12 g of an unsaturated monomer containing polysiloxane (SI-3, n = 11), 17 g of styrene, and acrylic acid 21 g of ethyl, 6 g of 2-hydroxyethyl acrylate, 1 lactic acid
g and 2,2-azobis (2-amidinopropane) hydrochloride (0.6 g) were charged, emulsified with stirring, replaced with nitrogen and replaced with 70 to 75 g.
Emulsified at 30 ° C for 30 minutes. Subsequently, 200 g of ion-exchanged water, 11.2 g of an amine imide (AI-5), 28 g of a polysiloxane-containing unsaturated monomer (SI-3, n = 11), 38 g of styrene, 48 g of ethyl acrylate, 14 g of 2-hydroxyethyl acrylate,
Lactic acid 1.5g and 2,2-azobis (2-amidinopropane)
Emulsified liquid consisting of 1.4 g of hydrochloride in a nitrogen atmosphere
Polymerization was carried out by dropping from a dropping funnel at 70 to 75 ° C. for 3 hours to obtain a composition of the present invention which was a milky white good polymer emulsion (monomer conversion rate: 99% or more, solid content: about 43%). .

Example 4 In the same manner as in Example 1, 70 g of ion-exchanged water, 6 g of amine imide (AI-9), 6 g of polysiloxane-containing unsaturated monomer (SI-3, n = 65), 24 g of methyl methacrylate were added to the apparatus.
24 g of n-butyl acrylate and 0.3 of azobiscyanovaleric acid
Then, g was charged, the mixture was emulsified with stirring, and the atmosphere was replaced with nitrogen. Subsequently, 200 g of ion-exchanged water, 14 g of amine imide (AI-9), unsaturated monomer containing polysiloxane (SI
-3, n = 65) 14 g, methyl methacrylate 65 g, n-butyl acrylate 56 g, and azobiscyanovaleric acid 0.7 g were added dropwise at 80 to 90 ° C. under a nitrogen atmosphere to carry out polymerization.
Milky white good polymer emulsion (monomer conversion: 9
A composition according to the invention of 9% or more, solids content; approx. 43%) was obtained.

Example 5 A device similar to that of Example 1 was charged with 270 g of ion-exchanged water, 15 g of an amine imide (AI-10), 3 g of lactic acid and 1 g of azobiscyanovaleric acid, and after nitrogen substitution, the mixture was stirred at 80 to 90 ° C.
And polysiloxane-containing unsaturated monomer (SI-3, n = 1
1) 15g, methyl methacrylate 100g, ethyl acrylate 70
Was mixed dropwise from the dropping funnel over 3 hours to carry out polymerization to obtain a composition of the present invention which was a good milky white polymer emulsion (monomer conversion: 99% or more, concentration: about 43%).

Comparative Example 1 In Example 1, emulsion polymerization was carried out in the same manner as in Example 1 except that sodium dihexylsulfosuccinate was used as an emulsifier instead of the amine imide compound, and a milky white polymer emulsion (monomer conversion rate: 99% or more, concentration; About 43%).

Test Example 1 The following tests were performed on the compositions of the present invention of Examples 1 to 5 and the composition of Comparative Example 1. Table 1 shows the results.

(1) Storage stability test 50 g of the polymer emulsion obtained from each of Examples 1 to 5 and Comparative Example 1 was taken in a glass bottle, sealed, and kept at -10 ° C for 6 hours.
The number of times until the emulsion was broken was measured with one cycle of 0 ° C. × 6 hours.

(2) Water resistance test The polymer emulsions obtained from Examples 1 to 5 and Comparative Example 1 were spread on a glass plate and dried at 20 ° C for 24 hours.
The film was dried at 60 ° C. for 8 hours to produce a film having a thickness of 0.2 mm. The water resistance of this film was tested by the water drop test method of JIS-K6828.

(3) Water repellency test The polymer emulsions obtained from Examples 1 to 5 and Comparative Example 1 were spread on a glass plate and dried at 20 ° C. for 24 hours.
The film was dried at 60 ° C. for 8 hours to produce a film having a thickness of 0.2 mm. The contact angle of the film to water was measured.

[Effect of the Invention] The composition of the present invention has the general formula (1) and / or (2)
Since the amine imide represented by (1) is used as an emulsifier, the emulsifier does not bleed out due to aging, the stability of the polymer emulsion is good, and long-term storage and freeze-thaw properties are improved.

The film or coating produced from the composition of the present invention exhibits excellent water repellency, oil repellency, smoothness, water resistance, solvent resistance, and weather resistance, and when the composition of the present invention is heated to 150 ° C. or higher. The water resistance and solvent resistance of the film or coating produced by crosslinking the amine imide compound in the resin by thermal decomposition are remarkably improved.

The composition of the present invention is a water-based paint, an adhesive, a sealing agent,
It can be used for paper processing, fiber processing, fiber modification, floor polishing, soil erosion prevention, concrete, mortar mixing, etc.

Claims (3)

(57) [Claims] 1. A 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, and R ⁴ is 3 to 25 carbon atoms.
Is an alkyl group. ) An amine imide compound and / or a general formula Wherein 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. R ⁵ is a C 4 to 28 carbon atom.
Or a saturated or unsaturated aliphatic hydrocarbon group, or a (substituted) phenyl group. An amine imide compound represented by the formula (b): (In the formula, X is a vinyl group, (meth) acryloxy group or allyl group, R ⁶ is a divalent hydrocarbon group, R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, an alkyl group having 1 to 10 carbon atoms or phenyl. Base, n =
1 to 130. And (c) a copolymer of an ethylenically unsaturated monomer copolymerizable therewith with a polysiloxane group-containing unsaturated monomer represented by the formula (1): Resin composition. 2. The composition according to claim 1, wherein the polysiloxane-containing water-dispersible resin composition comprises an emulsion polymer of (a), (b) and (c). 3. The amount of (a), (b) and (c) used is 0.5 to 30% of (a) based on the total weight of all monomers, and (b)
The composition according to claim 1 or 2, wherein (c) is 20 to 98.5%.