JPS6234947A - Waer dispersion type resin composition - Google Patents

Abstract

PURPOSE:A water dispersion type resin composition suitable as adhesive, etc., providing a dried film of coating with improved water resistance and adhesivity, comprising an emulsified polymer of a specific sulfuric ester (salt) and a hydrophobic ethylenic unsaturated monomer coplymerizable with it. CONSTITUTION:(A) 10-20wt% sulfuric ester (salt) shown by the formula (R is H or methyl; A is alkylene; n is >=2; M is monovalent or bivalent cation; m is valence of M, preferably >=2 propylenes exist in nA and M is Ka, K, ammonium, etc.,) as an emulsifying agent, (B) 60-99.9wt% hydrophobic ethylenic unsaturated monomer copolymerizable with the component A, such as (meth) acrylonitrile, styrene, and if necessary, (C) 0-20wt% hydrophilic ethylenic unsatu rated monomer are subjected to emulsion copolymerization in an aqueous medi um in the presence of an electrolyte and optionally a polymerization chain transfer agent, to give the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to water-dispersible resin compositions useful as adhesives and coatings.

[Conventional technology]

Polymerizable emulsifiers such as (meth) are used during emulsion polymerization of ethylenically unsaturated monomers for the purpose of improving performance such as water resistance and adhesion of dried coating films of water-dispersed resin compositions made of emulsion polymers, that is, polymer emulsions. Nurphonate containing an allyl group (allyl group and/or meta-lylyl group is abbreviated, the same expression will be used hereinafter) (Japanese Unexamined Patent Publication No. 7468/1983)
There is a technique using aromatic (meth)acrylate containing a nurphonic acid group (Japanese Patent Application Laid-open No. 198716/1983).

[Problem that the invention seeks to solve]

However, when using (meth)allyl group-containing sulfonates, sulfonic acid group-containing aromatic (meth)acrylates, etc., there is a problem that the water resistance and adhesion of the dried coating film of the polymer emulsion are insufficient. .

[Means for solving problems]

The present inventors have conducted intensive studies to develop a water-dispersed resin composition that has a dry coating film with excellent water resistance and adhesive properties, and whose usefulness as an adhesive, coating agent, etc. has been dramatically increased. As a result, we have arrived at the present invention.

The present invention is based on the general formula (wherein R is hydrogen or a methyl group. A is an alkylene group. n is an integer of 2 or more. M is a monovalent or divalent cation. m is 1 Sulfuric ester (an integer of ~2, representing the valence of the cation M)
salt) (A), a hydrophobic ethylenically unsaturated monomer copolymerizable with the salt (Bl), and optionally a hydrophilic ethylenically unsaturated monomer (C); A water-dispersible resin composition suitable for adhesives and coatings.

In the sulfuric ester V (salt) (A) represented by the general formula (1) used in the present invention, the alkylene group of A is an alkylene group having 2 to 4 carbon atoms, such as ethylene group, propylene group, etc. and butylene groups. These alkylene groups together with oxygen form oxyalkylene groups,
The n oxyalkylene groups may be of the same type or different types (block or random). Preferred are oxypropylene groups and combination groups (block, random) of oxyethylene groups and oxypropylene groups, and particularly preferred are oxypropylene groups in which n oxyalkylene (OA) groups have two or more oxypropylene groups. It is a group that exists.

n is 2 or more, preferably 2 to 80, particularly preferably 3
It is an integer between ~15.

Mo divalent or divalent cations include hydrogen, alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium,
Examples include organic amine cations (alkanolamine cations, lower alkylamine cations, etc.). Preferred among these are alkali metals (especially sodium and potassium) and ammonium.

Specific examples of the sulfuric acid ester/I/(salt) used in the present invention include compounds represented by the following formula.

In the formula below, EO represents C2H,,0, and PO represents 03H,0.

(a) Sulfate ester base-containing acrylic acid polyalkylene gellicol ester CH2= 0H-COO (EO% 5o3Na
(2) CH220H-000-+PO), o(E
O%803K (3) (Block) CH2= C! H-C! 00 (EO), (PO womb-8
03Na(4)(random) 01(2=CH-COO(POOH03NH4,(5
) (b) Entel sulfate base-containing methacrylic acid polyalkylene gelinol Entel CH3? CH2-C-COO+PO almost 803NH, (6) CH3 OH,, = 0-000(PO)2(EO+-8o3N
a (8) (random) CH8 CH2=C-COO+PO+1-803Na(9)CH
3 0H2= CC0O-(-PO”) to (EO-
)-i-803Na O□ (random) Sulfuric acid ester represented by general formula (1))v (salt) (A)
For example, (1) a method of adding alkylene oxide to (meth)acrylic acid and converting it into a sulfuric ester using a sulfating agent and, if necessary, a salt; (II) polyalkylene glycol monosulfuric acid ester) V (salt) and (meth) It is manufactured by esterifying acrylic acid and making a salt if necessary.

In the method (I), the method of adding alkylene oxide to (meth)acrylic acid includes a method of adding alkylene oxide to (meth)acrylic acid, hydroxyethyl or hydroxypropyl)V (meth)acrylate, a method of adding alkylene oxide to (meth)acrylic acid, Examples include a method of dehydrating and condensing polyalkylene glycol with an acid. Examples of the sulfating agent include fuming sulfuric acid, sulfuric acid, chlorosulfuric acid, and sulfamic acid. Examples of methods for converting into salts include neutralizing with alkali metal or alkaline earth metal hydroxides, aqueous ammonia, organic amines, and the like. If sulfamic acid is used as the sulfating agent, this operation is not necessary since it forms a salt.

Hydrophobic ethylenically unsaturated monomer (B
) are listed below.

(a) Nitrile group-containing monomer: 1 (meth)acrylonitrile, etc. (])) Nistel of unsaturated carboxylic acid [(meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, etc.]
: Alkyl/l/ having an alkyl group having 1 to 20 carbon atoms (methyl, ethyl, butyl, 2-ethylhexyl group, etc.)
(meth)acrylate; glycidi)V (meth)acrylate; glyco-/L/(ethylene glycol, 1.4
- di(meth)acrylates of butanediol, polypropylene glycol polyoxypropylene bispheno-1-/L/A, etc.); dialkyl esters of maleic acid, fumaric acid or itaconic acid, half esters, etc. (6) Halogen-containing monomers Body: vinyl chloride, vinylidene chloride, chloroprene, chlorostyrene, etc. (d) Styrenic monomer: styrene, α-methylstyrene, vinyl/V) toluene,
(e) Aliphatic hydrocarbon monomers such as divinylbenzene: ethylene, propylene, butadiene, isoprene, etc.) vinyl esters or (meth)allyl enethers: vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate, diallyl male The hydrophilic monomer (C') used as necessary, such as ate, is
The following are examples.

(g) Unsaturated carboxylic acids or salts thereof: (meth)acrylic acid, maleic acid, fumaric acid, etc. and their salts (alkali metal salts, ammonium salts, etc.) (h) Amides of unsaturated carboxylic acids: (meth)acrylamide , N-methylol (meth)acrylamide, etc. (i) Other hydroxyethyl (meth)acrylate) hydroxypropylene) V (meth)acrylate polyoxyethylene glycol mono- or di(meth)acrylate, polyoxyethylene lower alkyl ether/I/ (meth)acrylate, dimethylaminoethyl)V (meth)acrylate, etc. 0 to 20%, preferably (A) 0.5 to 10%, (B
) is 80 to 99.5 inches, and (C') is 0 to 10 inches.

If (A) is less than 0.01%, the storage stability of the composition of the present invention will be poor.

When (A) exceeds 20, the water resistance of the dried coating film of the composition of the present invention decreases. When (B) is less than 60%, the water resistance of the dried coating film of the composition of the present invention decreases, and 99. If it exceeds 'J%, the storage stability of the composition of the present invention will deteriorate. If (0) is more than 20, the water resistance of the dried coating film of the composition of the present invention will be poor. The composition of the present invention uses sulfuric acid ester (salt) (A) as an emulsifier, and pH adjustment etc. Hydrophobic ethylenically unsaturated monomer (B) and optionally hydrophilic unsaturated monomer (C) are added to an aqueous system by various polymerization initiation methods in the presence of the desired electrolyte and, if necessary, a polymerization chain transfer agent. Obtained by emulsion copolymerization in a medium.

Electrolytes for the purpose of pH adjustment include acids (hydrochloric acid, phosphoric acid, acetic acid, cono-phosphoric acid, boric acid, carbonic acid, etc.), their salts (sodium hydrogen carbonate, sodium acetate, sodium chloride, sodium tripolyphosphate, etc.), and Examples include bases [alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), aqueous ammonia, amines, etc.].

Examples of polymerization modifiers include mercaptans (primary dodecyl mercaptan, tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan mercaptan, etc.), cyclam disulfide, xanthogen disulfide, sulfur, selenium, substituted honuphine, and decagenides (carbon tetrachloride, etc.). ), amines, Schiff's bases, and nitroso compounds.

Examples of methods for initiating polymerization include methods by irradiation with electron beams, gamma rays, or ultraviolet rays, methods by heating, and methods using an initiator. In the method using an initiator, initiators include persulfates (ammonium persulfate, etc.); peroxy compounds (benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.); azo initiators (azobisisobutyronitrile, etc.); ); Redotsukunu-based initiators (combinations of oxidizing agents such as persulfates and peroxy compounds with reducing agents such as sulfites, ferrous sulfates, Rongalit, L-ascorbic acid), and the like.

Examples of the aqueous medium include water or a mixed solvent of water and a water-soluble organic solvent (methanol, isopropanol, acetone, etc.).

The polymerization method may be any known polymerization method, such as a batch continuous polymerization method. Known polymerization methods include a bulk charging method, monomer temperature addition method, and monomer emulsion addition method.

In the above various polymerization methods, the polymerization temperature is determined by the polymerization method,
It varies depending on the type of monomer to be copolymerized, but
Usually -5 to 150°C, preferably 10 to 90°
It is C.

In the various polymerization methods mentioned above, for the purpose of stabilizing emulsion polymerization, protective colloids (partially saponified polyvinyl alcohol, hydroxyethyl cellulose nat), ordinary emulsifiers without copolymerizability [anionic activators (sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, ammonium polyoxyethylene alkyl ether sulfate, etc.) and/or nonionic activators (polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polypropylene glycol ethylene oxide adduct) )] can be used in combination, but it is not preferable to use a large amount because it goes against the purpose of the present invention.

The composition of the present invention may optionally include 1 antifoaming agent 1 viscosity modifier, film forming aid, filler, pigment, dye, preservative, freeze stabilizer, crosslinking agent, plasticizer, adhesive, antistatic agent, etc. Additives such as agents may also be added.

The compositions of the invention are suitable as adhesives, coating agents, etc. For example, "Emulsion Latex Handbook" [August 1975, published by Taiseisha] 17) Volume 5 Processing of Emulsion Latex (P565~:,90
8) It can be used for various uses and applications as described in 8). As an adhesive, "Polymer Latex Adhesive J (June 1984, published by Kobunshi Publishing Association)"
Chapter ■ (Liquid Adhesives and Their Applications), Chapter V (Contact Adhesives and Their Applications), Chapter ■ (Adhesives and Their Applications), Chapter 1 (LOM Adhesives and Their Applications) It can be used or used for various purposes.

〔Example〕

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

Example 1 Into a reaction vessel equipped with a stirrer, dropping funnel, nitrogen inlet, thermometer, and reflux condenser, 117.5 g of ion-exchanged water,
Sodium bicarbonate O, 08g, ammonium persulfate 0
．． 16 j9 , 22 g of styrene, 18 g of butyl acrylate, and 1.6 g of the sulfuric acid ester salt of formula (9) were charged and emulsified with stirring, and after nitrogen substitution, polymerization was carried out at 75° C. for 30 minutes with stirring. Continued ion exchange water 184.5g, formula (9)
56 g of ethel sulfate, 0.28 sodium bicarbonate
g, ammonium persulfate 0.5Jj9, styrene 77g
An emulsion consisting of 63 g of butyl acrylate was added dropwise from a dropping funnel over 2 hours, and polymerization was carried out at 80°C with stirring. After adding 18 g of a 1-part aqueous solution of ammonium persulfate, the temperature was raised to 85°C and polymerization was carried out for 2 hours. Concentration 4
A polymer emulsion (composition of the invention) having a weight of 1% and a viscosity of 15 cps was obtained.

Example 2 In a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen inlet, a thermometer, and a reflux condenser, 117.5 g of ion-exchanged water, 016 g of potassium persulfate, 20 g of methyl methacrylate,
20 g of butyl acrylate and 1.6 g of sulfuric acid NTE/I/salt of formula (5) were charged, stirred and emulsified, and after nitrogen substitution, 75 g
Polymerization was carried out at °C for 30 minutes. Continued ion exchange water 1B
An emulsion consisting of 4.5 jq, sulfuric acid xy of formula (5), 5.6 g of Te/L/salt, 0.569 g of potassium persulfate, 69 g of methyl methacrylate, 69.9 g of butyl acrylate, and 2 g of acrylic acid was added through a dropping funnel. The mixture was added dropwise over 2 hours, and polymerization was carried out at 80°C with stirring. After adding 18 g of a 1-toch potassium persulfate aqueous solution, the temperature was raised to 85°C and polymerization was carried out for 2 hours, resulting in a concentration of 41% by weight and a viscosity of 10 cp.
A polymer emulsion of s (composition of the present invention) was obtained.

Example 8 A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen inlet, a thermometer and a reflux condenser was charged with 117.5,9.
0.16 g of potassium persulfate, vinyl acetate V 209, 20 g of butyl methacrylate, and 1.6 g of the sulfuric ester salt of formula OI were charged and emulsified with stirring, and after purging with nitrogen, polymerization was performed at 75° C. for 30 minutes. Continued ion exchange water 184.5
g1 200 sulfate ester salt 56g, potassium persulfate 0
．． 56 g of vinyl acetate/l/68 g of a butyl methacrylate combined emulsion (composition of the present invention) was obtained.

Comparative Example 1 Emulsion polymerization was carried out according to the method of Example 1 using the same weight of sodium dodecylallyl nurphosuccinate in place of the ethel salt sulfate used as the emulsifier in Example 1, resulting in a polymer with a concentration of 41% by weight and a viscosity of 35 cps. A combined emulsion was obtained.

Comparative Example 2 Sulfuric acid ester/L/ used as an emulsifier in Example 1
Using the same weight of sodium acryloyloxynonylbenzene sulfonate instead of +i, emulsion polymerization was carried out according to the method of Example 1, and the concentration was 40% by weight, and the viscosity was 15%.
A polymer emulsion of cps was obtained.

Comparative Example 3 Instead of the sulfuric acid ether salt used as the emulsifier in Example 2, the same weight of dodecylmetali! Emulsion polymerization was carried out using ammonium resulfosuccinate according to the method of Example 2 to obtain a polymer emulsion having a concentration of 40 and a viscosity of 35 cps.

Comparative Example 4 Emulsion polymerization was carried out according to the method of Example 2 using the same weight of sodium methacryloyloxynonylbenzenesulfonate instead of the sulfuric ester salt used as the emulsifier in Example 2, resulting in a polymer with a concentration of 40 coefficient and a viscosity of 15 cps. A combined emulsion is obtained.

Test Example 1 The compositions of the present invention of Examples 1 to 8 and the polymer emulsions of Comparative Examples 1 to 4 were deposited on a glass plate to a dry film thickness of 0.
．． The resin film was coated to a thickness of 2 mm and dried at 25° C. for 24 hours and then at 60° C. for 5 hours to form a resin film on a glass plate.

Using the glass plate on which this resin film was formed and the resin film peeled from the glass plate, a water resistance test, an adhesion test, a bending resistance test, a water resistance strength test, and a water resistance adhesion test were conducted according to the following methods. The test results are shown in Table-1.

Water resistance test: The glass plate on which the resin film was formed was immersed in water for 120 hours, and the resin film was observed.

○...The resin film remains transparent and does not become cloudy.

△...Resin Kui/Rem is slightly cloudy, but 8 point hiragana type can be seen through.

×: The resin film is cloudy and the 8-point hiragana type cannot be seen through.

Adhesion test: The adhesion between the glass plate and the film was measured using a tensile strength tester at 180° peel strength.

Flexing resistance test: The number of times the film was bent at 180° until it broke was measured.

Water resistance strength test: The tensile strength at break of the film after being immersed in water for 48 hours was compared with the tensile strength at break of the film before immersion.

○... Film whose strength decreases when immersed in water is less than 5 inches △... Film whose strength decrease when immersed in water is 5 factors or more and less than 50 inches ×... Film whose strength decrease when immersed in water is 50 Water resistant adhesion test: The glass plate on which the resin film was formed was
Immersed in water for 40 hours and observed the presence or absence of peeling. ○...Floating, no peeling △...Partial peeling, peeling ×...Full surface peeling [Effects of the invention] Composition of the present invention Compared to conventional polymer emulsions, the water resistance and adhesiveness of the soft film coating of the polymer emulsion are significantly improved. In addition, the dried coating film has high bending resistance and high water resistance.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R is hydrogen or a methyl group. A is an alkylene group. n is an integer of 2 or more. M is a monovalent or divalent cation. m is an integer of 1 to 2 and represents the valence of the cation M. Suitable for adhesives and coatings characterized by being composed of an emulsion polymer of a polymerizable hydrophobic ethylenically unsaturated monomer (B) and optionally a hydrophilic ethylenically unsaturated monomer (C) Water-dispersed resin composition. 2. The composition according to claim 1, wherein two or more oxypropylene groups are present in the n oxyalkylene (OA) groups of (A) represented by general formula (1). 3, the amounts of (A), (B), and (C) are 0.1 to 20% for (A) and 6 for (B) based on the total weight of all monomers.
The composition according to claim 1 or 2, wherein (C) is 0 to 99.9% and 0 to 20%.