JPS58108283A - Viscoelasticity regulator and regulation using the same - Google Patents

Abstract

PURPOSE:To obtain a viscoelasticity regulator free from putrefaction and fungi generation, with good flow characteristics, high heat resistance and low cost, useful for aqueous dispersions such as ink, etc., by carrying out a graft polymerization, to a polyether, of a specific amount of a water-soluble monomer having functional group(s) such as carboxyl group, etc. CONSTITUTION:The amounts of the components A, B and C are as follows: A...10-90wt%, B+C...10-90wt%, B/B+C...>=50mol%. A graft polymerization, to (A) a polyether, of (B) a water-soluble ethyenic unsaturated monomer having carboxyl, amide, sulfonic acid group(s), etc., a second ethylenic unsaturated monomer having functional group(s) capable of being converted to carboxyl group(s) by hydrolysis and, if required (C) a third monomer is carried out. The resulting product may be hydrolysed followed by, if necessary, incorporating (D) a crosslinking agent thus obtaining the objective regulator. When put to practical use, 0.0001-100pts.wt. of the above regulator together with 100pts.wt. of an adhesivity-imparting component is incorporated in an aqueous dispersion to be regulated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a viscoelastic modifier and a method of using the same. More specifically, the present invention relates to a viscoelasticity modifier that is inexpensive, provides favorable flow characteristics, and has excellent heat resistance, and does not cause spoilage or I, and a method for using the same. Conventionally, droxyethyl cellulose, carboxymethyl cellulose, methiμ cellulose, sodium alginate, guar gum, sodium polyacrylate, etc. have been used as adhesive elasticity modifiers for paints, inks, paper manufacturing, cosmetics, printing pastes, etc.
Hydroxyethylcellulose, poxymethylcellulose, methylcellulose, and sodium alginate, which are used in aqueous dispersions for Pauling mud, etc., are all natural products or chemically modified materials made from natural products, but they are all extremely harmful. Corruption or so! It has a major drawback in that it is prone to celiac formation, and to prevent this, it is necessary to use a preservative that is effective against living organisms. In addition, conventional natural, semi-synthetic, and synthetic dry elasticity modifiers have poor fluidity and... It has the disadvantage that improvements in repelling properties, coating properties, etc. are insufficient or insufficient. It is also known to mix a graft copolymer of a water-soluble polyalkylene oxide polymer and a vinyl μ monomer in an amount of 3 to 19 times the amount of the tackifying resin to form a water-dispersible hot-melt adhesive composition. Although such adhesive compositions are useful for special applications in which easy resolubility in water is desired, their markedly poor water resistance makes them unsuitable as commonly used adhesives, and they also have poor heat resistance. Also inferior.

The present inventors have conducted repeated research to improve these drawbacks, and as a result, they have arrived at the present invention.

That is, the present invention uses polyether tvQQ, a water-soluble ethylenically unsaturated monomer CB-1) having a carboxyl group, an amide group, or a sulfonic acid group, and a functional compound that can be induced into a carpoxyl group by decomposition of water. ← Ethylenically unsaturated monomer 6) selected from the group consisting of ethylenically unsaturated monomers (B-2) with rL and other monomers 0 if necessary, Q, ■ and 0 Q in the total is 10-
90% by weight, the total of ■ and 0 is 10 to 90% by weight, and 8) in the total of ■ and 0 is 50 mol% or more, 0 is 50 mol
v cyMv graft polymerization, and when (B-2) is used as (■), it is a viscoelastic modifier for an aqueous dispersion (excluding paints) consisting of a graft polymer obtained by hydrolyzing CB-2). be. The polyether IvlA) constituting the graft polymer used in the present invention is particularly limited, and includes active hydrogen-containing polyethers such as acols, bonic acids, amines, amides, and urethanes. monster rf aμ
Examples include kylene oxide V-do addition polymers. Specific examples of these active hydrogen-containing compounds include the following. methanol, ethanol, probanol μ, gutanol,
Pentanol~, Ncropentanol, Hexanol N, Cyclohexanol N, Octano-I, Deci/L'7/1
Saturated monohydric alcohols such as /co μ, lauri 7 real alcohol, myristyl alcohol μ, cetyl alcohol p1, stearyl rare ~ co μ, ethylene glycol μ monobutyl ether, diethylene glycol monobutyl ether/I
/l1 Ethylene glycol, propanedioh ~, putanedioh μ, pentanedio μ, hexanedione, decanedio μ, bi7' nacol, glycerin, ? tantriol, hexanetriol, and erythritol, pentitol, hequinitol, such as pentaerythritol, sonolevitol,
and saturated polyhydric alcohols such as polyglycerin and polyvinyl alcohol, and polysaccharides such as cellulose, starch, dextrin, and guar gum. High-molecular polyhydric alcohols such as carbon dioxide and its derivatives. Vinyl alcohol, alcohol μ, crotyl alcohol, oleyl alcohol, cinnamyl 7/L/coy
Aromatic alcohols such as unsaturated alcohols such as v-hydroxyethyl methacrylate/l'LD1, benzyl alcohols, pendyl alcohols, triphenyl carbinooles, phenylethynoleas and IV nato, phenols, and hydroquinones. The right phenols are represented by derivatives such as lephonic acid and its salts, catechol, bilogalou μ, cresol, ditrophenol, aminophenol, naphthol and phenol μ, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethyl. Monobasic saturated carboxylic acids such as acetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, lauric acid, stearic acid, etc. and oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, dimer acid, butane tricarpon Polybasic saturated carboxylic acids such as i゛shun, unsaturated carboxylic acids such as acrinoleic acid, oleic acid, vinylacetic acid, maleic acid, fumanoleic acid, phenylacetic acid, benzoic acid, toluic acid, phthalic acid,
Aromatic carboxylic acids such as naphthoic acid and cinnamic acid.

Primary amines such as methylamine, ethylamine, probylamine, petite lamine, lauriμ amine, stearylamine, oleylamine, allylamine, aniline, dimethylamine, jetynoleamine, dipropyμamine, digtylamine, dilauri! Secondary amines such as reaamine, distearylamine, and diolei I-leamine; gliamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Amides in the form obtained by the dehydration condensation reaction of 1. carboxylic acids and ammonia or the above-mentioned amines, such as honolemamide, acetamide, propionic acid amide, butyric acid amide, valeric acid amide, caproic acid amide, stearic acid amide, acrylamide, Acid amides such as oxalic acid amide, succinic acid amide, malonic acid amide, glutaric acid amide 6 Substituted amides such as 6 N-ethylpropionamide. Polyamides are typified by polyamides produced by dehydration condensation of polybasic acids such as adipic acid and dimer acid and polyamines such as diethylenetriamine.

Monoisocyanates such as methyl isocyanate, ethyl isocyanate, propyμ isocyanate, petit μ isocyanate, polyfunctional isocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenyl remethane diisocyanate, hexamethylene diisocyanate, alcohols or amines, poly A mono- or polyurethane compound obtained by reacting an ether polyol and a polyol μ compound with a polyester polyol made of a polybasic acid. Oxycarboxylic acids such as glycolic acid and lactic acid, alkaline amines such as monoethanolamine, diethanolone, triethanolamine, and aminomethylpropanol, and amino acids such as glycine, alanine, and lysine, and acid alkanols such as lauric acid monoethanol μamide. Compounds with two or more active hydrogens, such as μamide, can also be used. These active hydrogen compounds (anolekylene oxide to be added include ethylene oxide, propylene oxide, and butylene oxide), and these may be used alone or in combination of two or more. Among these, ethylene oxide and propylene oxide are preferred. The addition method of alkylene oxide to the species may be random or block.Also, polyether/L' (AC is the addition method of alkylene oxide to the compound having active hydrogen described in 1). In addition to polyethers obtained by the addition polymerization method, there are also polyethers obtained by dehydration condensation using polyhydric anolecol acids, anolekali, or metal oxides as catalysts, such as polyethylene glycol, glycerin, and sodium hydroxide as catalysts at about 250°C.
Polyether obtained by demetallizing salt reaction of polyhydric alcohol apcolate obtained by reacting polyhydric alcohol with hydrogenated alkali metal or alkali metal and polyhalogen compound. For example, an addition reaction between a polyester obtained by heating sodium acholate obtained by reacting ethylene glycol p with sodium hydride and dichloroethane and a compound having an unsaturated bond with a polyhydric anolecolate obtained by heating dichloroethane to 150°C or higher. For example, a polyether obtained by reacting glycerin and acetylene at about 250° C. and 15 atm using boron trifluoride as a catalyst. Also included are polyethers obtained using various methods such as polyethers. If necessary, these polyethers can be used by modifying their unterminated hydroxyl by various methods. Modification methods for unterminated hydroxyl groups include esterification using a monobasic acid such as acetic acid or stearic acid, etherification using a lhydric alcohol such as propylμ alcohol or stearyl alcohol, or etherification using a monoisocyanate such as ophthalmyl alcohol. Urethane prepolymers of diisocyanates such as decyl isocyanate, phenyl isocyanate, or monohydric alcohols, monobasic acids, tertiary niamines, etc. For example, methanol, laurinorea I record/
L' or diisoprobylamine and xylylene diisocyanate with an isocyanate group of about 2 to
There are methods such as urethanization using a conventional method using a urethane prepolymer that is reacted using a 25-fold molar amount. These polyethers can also be crosslinked into dimers using polyfunctional isocyanates, polybasic acids, or polyfunctional epoxy resins.

The molecular weight of polyether/l'(A) is usually 200 to 2,0
00,000, preferably 10,000 to 800,000, more preferably 2,000 to 100,000. Regarding the molecular weight per active hydrogen to which apkylene oxide is added, it is usually 1.5 to 2 million, preferably 500 to 800,000, and more preferably 1000 to 1.
00,000, and the number of alkylene oxide adducts per active hydrogen is usually 3 to 45,000, preferably 1.
0 to 18,000, more preferably 20 to 2,300. If the molecular weight per active hydrogen is less than 150, the effect of adding glyether will be small and it will not be possible to impart desirable flow properties, and if the molecular weight is greater than 2 million, the viscosity will be too high and it will be difficult to impart desirable flow properties. I can't. Preferred among these are alkylene oxide addition polymers of l-valent and divalent saturated alcohols, alkylene-Oquinde addition polymers of l-base and divalent saturated carboxylic acids, and alkylene oxide adducts of primary amines and secondary amines. , an alkylene oxide adduct of a polyamide consisting of a monobasic acid or a dibasic acid and a polyamine, and an alkylene oxide addition polymer of a polyurethane consisting of a monoisocyanate or diisocyanate and a polyalkylene oxide. More preferably 2
Alkylene oxide addition polymers of alcohols, alkylene oxide addition polymers of dibasic acids, alkylene oxide addition polymers of primary amines, alkylene oxide addition polymers of polyamides consisting of dibasic acids and polyamines, and diisocyanates and polyamines. This is a μkylene oxide-1 additive of polyurethane consisting of Kylene oxide. The ethylenically unsaturated monomer ■ (hereinafter referred to as monomer ■ or ■) constituting the graft polymer includes carpoquin μ group, amide, etc., which can be used directly from the graft polymer obtained by polymerization. A water-soluble monomer CB-1) (hereinafter referred to as monopaper (B-1) or CB-1) having a snorefonic acid group or a snolephonic acid group can be hydrolyzed to form a carboxyl group. An ethylenically unsaturated monomer (B-2) (hereinafter referred to as monomer (B-2) or (B-2)) having a functional group that can be induced into a monomer CB-1 can be used. ) The following are specific examples: L (Meth)acrylic acid (means acrylic acid and methacrinoleic acid. The same expression will be used hereinafter.) Carpoquinyl, which is typified by ethylenically unsaturated mono- or polycarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Group-containing monomer. 2. Sodium (meth)acrylate,
Water-soluble salts of ethylenically unsaturated mono- or polycarbonic acids such as (meth)acrylic acid trimethy7leamine salt, (meth)acrylate, triethanol μ-amine salt, sodium maleate, sodium itaconate, and methylamine maleate salt. Carboxylic acid group-containing monomers represented by (alkali metal salts, ammonium salts, amine salts, etc.). a (meth)acrylic amide group-containing monomers such as amide. 4 Vinylsulfonic acid, allylsulfonic acid, vinyltonoleenesulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, sulfopropy/L/(meth)acrylate, 2-hydroxy-3-(
A sulfonic acid group-containing monomer substituted with aliphatic or aromatic vinyl sulfonic acids such as meth)acryloyloxypropylsulfonic acid. aJ: A sulfonic acid group-containing monomer such as an alkali metal salt, ammonium salt, or amine salt of the sulfonic acid group-containing monomer. Among these, preferred ones can be easily imparted with water solubility;
It is easy to adjust the degree of polymerization, and it is easy to obtain a high grafting rate (
More preferred are meth)acrylic acid, maleic acid, fumaric acid, styrene paraphonic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and their sodium, potassium or ammonium salts, and (meth)acrylamide. are (meth)acrylic acid, maleic acid and (meth)acrylamide. Specific examples of monomer (B-2.) include the following. L Carboxylic anhydride group-containing monomer such as maleic anhydride and itaconic anhydride. 2 Alkyl esters of ethylenically unsaturated carboxylic acids such as meth/l/(meth)acrylate, ethyl(meth)acrylate, 2-ethylhexy/L/(meth)acrylate. a A nitrile group-containing monomer such as (meth)acrylonitrile. Among these, preferred ones are easily hydrolyzable;
Maleic anhydride, methyl (meth)acrylate, from which a graft polymer can be easily obtained and a high grafting rate can be obtained.
Among these are ethyl(meth)acrylate, and more preferred are maleic anhydride and methyl/L/(meth)acrylate. The graft polymer of the present invention may be one obtained by copolymerizing water-soluble monomer (1) with another ethylenically unsaturated monomer 0 (hereinafter referred to as monomer 0 or 0). Examples of such monomer 0 include the following, in addition to the apyl ester of ethylenically unsaturated carboxylic acid and the nitrile group-containing monomer listed in the monomer (B-2) above. It will be done. 1,C)1. Ethylenically unsaturated alcohols such as (meta)aliμ alcohol, hydroxyethyl/1
/(methacrylate, hydroxyprobyl (meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)noacrylate, triethylene glycol mono(meth)acrylate, tripropylene glycol μ mono(meth)acrylate, poly Oxyethylene-oxypropylene glycol mono(meth)acrylate (Polyoxyethylene-oxypropylene glycol halon or block may be used. The same applies hereinafter.) Alkylene glycols such as glycerin 7-(meth)acrylate, polyalkylene glycol μ, polyhydric Polyol/I/ethylenically unsaturated esters such as alcohol μ, polyoxyethylene-oxypropylene glycol 7-(meth)alinolether (
Monomers containing hydroxyl groups or ethers, such as ethylenically unsaturated ethers (the terminal hydroxyl groups may be etherized or esterified). 2. ．． N-methylacrylamide, N-propy/L/7
Acrylamide, N-hexynyl acrylamide, N,N-
Dimethylacrylamide, N,N-dipropylacrylamide, N-methylol(meth)acrylamide, N-
Hydroxyethyl (meth)acrylic reamide, N,N-
Dihydroxymethyiv (meth)acrylamide%N,N
- Ethylenically unsaturated N-mono- or diaμ-kyl substituted (meth) such as dihydroxyethyl (meth)acrylamide
Amide group-containing monomers represented by vinyl lactams such as acrylamide and N-vinylpyrrolidone. a dimethylaminoethyl/I/(meth)acrylate,
Amino group-containing esters of ethylenically unsaturated mono- or dicarboxylic acids, such as diethyl μ aminoethyl (meth)acrylate, morpholinoethyl/L/(meth)acrylate, and dimethyl rareminoethyl fumarate. 4. Amino group-containing monomers represented by heterocyclic vinyl compounds such as 2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine, and N-vinylimidazole. KN,N,N-}limethylol-quaternary ammonium base-containing monomer represented by N-(meth)acryloyloxyethylammonium chloride, 2-hydroxy, 3-(meth)acryloyloxypropyltrimethylammonium chloride, etc. ．． G Water-insoluble monomers such as styrene, ethylene, phlopyrene, butene, and vinyl chloride.

7 Vinyl acetate, (meth)allyl acetate, etc. 1/7
Unsaturated alcohol esthetics/re. 8 Divinylbenzene, trivinylbenzene, divinylethylene glycol, divinylμ sulfone. Di- or polyvinyl compounds such as divinyl ether and divinyl ether, bisacrylamide such as N,N-methylenebis(meth)acrylamide, ethylene glycol/re, polyethylene glycol, polypropylene glycol, polyoxyethylene-oxypropylene glycol, glycerin , unsaturated di- or polyester compounds of polyols such as trimethylolpropane and pentaerythritol and unsaturated mono- or polyoleponic acids such as (meth)acrylinoleic acid, maleic acid and fumanolenic acid, glycerindigrindyl, unsaturated di- or polyester compounds of polyepoxides such as polyepoxides such as trimethylolpropane triglycidyl ether and unsaturated carboxylic acids such as (meth)acrylic acid; ) Allinoleether compounds, di-matahori(meth)alinolester compounds of polycarbonate/leponic acids such as diallyl phthalate, diallyl adipate, mono(meth)acrylic ethers of polyols such as polyethylene glycol μ-monoaryl μ-ether acrylate, and unsaturated carboxyls. Ester compounds with acids, and di(meth)acrylates with hydroxyethyl/L/(meth)acrylate and xylylene diisocyanate [Shunriki μ, polyisocyanates such as Bamip Esthe μ and hydroxyl diisocyanate-containing monomers] At least 2
of pieces! i, Compounds having a combinable double bond.

a glycidi A/(meth)acrylate, N-methyμ-
A compound having at least one polymerizable double bond represented by /1/(meth)acrylamide and at least one functional group capable of reacting with a carpoxy/1/ group, a hydroxyl group, or an amide group. Among these, preferred is methyl (meth), which is easily copolymerized and can easily obtain a high grafting rate.
acrylates, alkyl esters of (meth)acrylic acids such as μ, hydroxyethyl IV (meth)acrylates,
Ethylenically unsaturated esters of polyols such as polyoxyethylene-oxypropylene glycol mono(meth)acrylate N-methylacrylamide, N,N-
N-mono- or dialkynol-substituted acrylamides such as dimethyl acrylamide, vinyl lactams such as N-vinylpyrrolidone, esters of ethylenically unsaturated alcohols such as styrene, vinyl acetate, divinyl-ethylene glycol-7, divinyl sulfone, etc. polyvinyl compounds, and bisacrylinoleamides such as N,N-methylenebis(meth)acrylamide, more preferably alkyl esters of (meth)acrylic acid such as methyl/L/(meth)acrylate, hydroxyethyl l
Ethylenically unsaturated esters of polyols such as poly(meth)acrylates, vinyllactams such as N-bi=ypyrrolidone, styrene, vinyl acetate, divinylethylene glycol, divinylbenzene, and N,N-methylenebis(meth) ) is acrylamide. Unsaturated monomers with two or more unsaturated double bonds can impart water resistance or change in flow properties to graft polymers. Furthermore, the graft polymer of the present invention may be used for the purpose of imparting water resistance and changing flow characteristics to the above-mentioned Oμ, if necessary.
Alternatively, the following crosslinking agent 0 [hereinafter referred to as crosslinking agent O or 0] which can crosslink with Q may be used in combination. As such a crosslinking agent, a compound having at least two reactive functional groups or a compound capable of forming an ionic crosslink can be used, and specific examples thereof include the following. Hydroxides of polyvalent metals such as calcium hydroxide, calcium chloride, canolecium carbonate, calcium oxide, magnesium chloride, magnesium oxide, aluminum chloride, lead chloride, and nickel chloride, and those of groups ■, ■, and ■ of the periodic table. , halides, carbonates, oxides and acetates, borates such as borax, and alcoholates of polyvalent metals such as aluminum isopropylate. aldehydes such as formalin and glyoxal;
polyepochine compounds such as ethylene glycol diglycidi μ ether and glycerin diglycidi~etherp,
haloepoxyanolecanes, such as epichlorohydrin;
and compounds having at least 12 functional groups that can react with carboxy μ groups, hydroxyl groups, or amide groups, typified by polyisocyanate compounds such as xylylene diisocyanate and tolylene diisocyanate. Among these, preferred are polyvalent metal hydroxides such as aluminum, magnesium or aluminum, halide carbonates and oxides, borates such as borax, and polyepoxy compounds such as ethylene glycol diglycidyl ether. and haloepoxy alkanes such as chlorinated phosphorus, more preferably hydroxides, halides, carbonates and oxides of polyvalent metals such as calcium, magnesium or aluminum,
borates, such as borax, and polyepoxy compounds, such as ethylene glycol diphosphonate. In the graft polymer of the present invention, polyate/L'(
The ratio of A) to monomer ■ and monomer O is
The total of the monomers ■ and 0 is 10-90\preferably 20-80%. The total is 20~
80%, more preferably Q is 20-70%. The sum of ■ and 0 is used for 3NO%. If (f) is less than 10%, fluidity decreases, and if it exceeds 90%, water resistance and thickening properties decrease, which is not preferable. When copolymerizing or graft polymerizing other ethylenically unsaturated monomers 0, 0 is used in less than 50 mol%, preferably less than 35 mol%, more preferably less than 257 μ% of the total of 0 and 0, And when using an unsaturated monomer having two or more polymerizable double bonds as 0 or an unsaturated monomer having one polymerizable double bond and a functional group that reacts with Q or ■, C ) is less than 107 μ% of the total of ■ and (Q), preferably less than 67 μ%, more preferably less than 3%. is basically non-thermofusible, and excellent heat resistance can be obtained.If 0 exceeds the above range, the flow $JJ properties will deteriorate and the heat resistance of the resulting graft polymer will also decrease, which is undesirable. When CB-2) is used as the mercury 0, it becomes the range 1 after hydrolysis. You can make it so that The preferred amount of crosslinking agent 0 to be used differs depending on the type of crosslinking agent 00, but it is usually less than 107 μ%, preferably less than 67 μ%, more preferably 3 mol, based on the total of e), C) and 0. If the amount of the crosslinking agent exceeds the range 1, the fluidity will decrease, which is not preferable. Products using a crosslinking agent within this range have improved water resistance and fluidity is slightly lower than those using no crosslinking agent, but the thickening effect is significantly greater. Ordinary graft polymerization methods can be used to polymerize polyether Q, monomer (1) and, if necessary, other monomer (0), such as methods using polymerization catalysts, ultraviolet rays, electron beams, radiation, etc. The method using a polymerization catalyst is preferred because it can easily obtain a polymer. Specific examples of polymerization catalysts include redox catalysts such as sulfate salts such as ammonium persulfate, sodium persulfate and potassium persulfate, ceric salts such as ceric ammonium nitrate, and hydrogen peroxide catalysts, or azobisisobutyl Examples include radical polymerization catalysts such as lonitrinole and benzoyl peroxide. Among these, preferred are persulfate-based, ceric salt-based, and hydrogen peroxide-based redox catalysts, which provide a high grafting rate and favorable viscoelasticity. In the polymerization of the present invention, if necessary, as a polymerization solvent,
Water, water-soluble organic solvents such as methanol, ethanol, acetone, methyl ethyl alcohol, and dimethynoleformamide, water-insoluble organic solvents such as toluene, xylene, and mixtures thereof can be used. ．． In particular, when (B-1) is used as (2), a polymerization solvent is required because the graft polymer of the polyether loses heat meltability as the polymerization progresses. Preferred polymerization solvents are water and mixtures of water and the above-mentioned water-soluble organic solvents.
In addition, acetaldehyde, chloroform,
Additives such as carbon tetrachloride and dodecylmercabutane may also be used. Further, in the present invention, when a polymerization catalyst is used, the market temperature varies depending on the type of catalyst, but is usually 10 to 150°C, preferably 20 to 100°C. Examples of polymerization methods include, for example, a method in which L(F), ■, 0 and a polymerization catalyst are simultaneously mixed and reacted; N,@
and a method of reacting while dropping the polymerization catalyst into the mixed system of C), while e) and 0 are simultaneously dropped into the mixed system of aH and the polymerization catalyst, or one of e) and 0 is dropped first and the other after. A method of reacting, a method of reacting while dropping a mixture of 0,0 and a polymerization catalyst into 4.1A),
A method of dropping a mixture of a polymerization catalyst and the remaining monomers into a mixed system of &Q and either ■ or 0, G amount, a polymerization catalyst, and the remaining 9 monomers into a mixed system of either ■ or 0 A method in which 7Q and either (1) or (Q are polymerized and then the remaining monomers are further reacted,
There are various polymerization methods, and the properties and performance of the resulting graft polymers vary depending on the desired performance.The preferred polymerization method can be selected depending on the desired performance. Hydrolysis carried out in the present invention can be carried out using conventional methods. For example, to a polymer containing monomer CB-2) or an aqueous solution thereof, sodium hydroxide, hydroxide, potassium hydroxide, and water as necessary may be added, and the mixture may be stirred and hydrolyzed, usually at 10 to 100°C. (B-2) e is used as monomer (f), CB-2
) remains unhydrolyzed, and this unhydrolyzed (B
-2) may correspond to other monomer 0. In the graft polymer of polyether 1v (f) and monomer ① and other monomer O in the present invention, the carboxyl group may be in the form of free, salt, or partially neutralized partial salt. ．． However, in graft polymerization, water or a mixture of water and a water-soluble organic solvent is used as the polymerization solvent (
If a monomer containing a carboxylic acid group is used as B-1), the graft polymer produced during polymerization may have poor solubility in water, and (is preferably a water-soluble salt or partial salt of sodium, potassium or ammonium, etc.) to increase its water solubility and then polymerize it.Also, from the viewpoint of ease of handling and ease of dissolution, the obtained graft polymer may be used as a salt or partial salt. Partial salts are preferred.Salts include salts of alkali metals such as sodium and potassium, ammonium salts, and alkali metals such as monomethylamine, dimethynoleamine, trimethylamine, etc.
Amines, such as alkanolamines such as amines, monoethanolamines, diethanolamines, triethanolamines, or heterocyclic amines such as monoleforin?
Examples include salt. Among these salts, anolekali metal salts and ammonium salts are preferred from the viewpoint of solubility and applicability. The salt form may be one obtained by polymerizing the salt form as CB-1), or it may be made into a salt after polymerization, or it may be polymerized using CB-2) and hydrolyzed to form a salt. It can be anything. The method for using crosslinking agent 0 is to add 0 to the polymerization system before, during or after the polymerization reaction, and usually add 10 to 20
Crosslinking is carried out by a reaction at 0°C, preferably 20 to 180°C, according to a conventional method. Alternatively, a graft polymer that does not contain 0'f: may be added to the aqueous separation liquid, and then 0 may be further added to the aqueous dispersion to cause it to cross and dissolve. The viscosity of the graft polymer used in the present invention is generally 2 to 50 cps, preferably 3 to 5 s, and more preferably 5 to 1000 cps as a viscosity of a 61% aqueous solution. A certain m 2Cp
If it is less than S, the thickening effect is low and 50,000 cps
If it exceeds this value, it is difficult to obtain favorable flow characteristics and is therefore undesirable. Grafting efficiency of the backbone polymer of the water-soluble ethylenically unsaturated monomer used in the present invention [(grafted backbone polymer amount (
lFr)/Amount of backbone polymer (1?r))
-100%, more preferably lO -100%.
Grafting efficiency of stem polymers can be measured by solvent extraction or fractional precipitation. The type of solvent used for this separation varies depending on the type and type of monomers ① and 0 used and must be selected appropriately. To explain in more detail how to measure graft efficiency, for example, a dilute aqueous solution (concentration 10% by weight or less) of a graft polymer consisting of polyethylene oxide and sodium acrylate is mixed with a dilute aqueous solution (concentration 10% by weight or less) about 10 times
The solution containing the precipitated polymer is centrifuged to collect the supernatant, and the remaining precipitated polymer is Transfer to a Soxhlet extractor and extract using methanol for 11 minutes. Methanol is distilled off from the extract and the clear liquid recovered above to obtain unreacted polyether. Calculate the grafting efficiency of this υ stem polymer. The amount of the viscoelasticity modifier of the present invention to be used is usually α000l to 100 parts, preferably α000l to 100 parts (parts by weight, the same shall apply hereinafter) of the adhesion-imparting component in the aqueous dispersion containing the adhesive component. (10005 to 50 parts, more preferably 0001 to 50 parts)
25 copies will be used. If the amount used is more than 100 parts, the water resistance of the adhesion-imparting component will be significantly reduced, making it difficult to use in normal applications, and if it is less than 00,001 parts, a sufficient flowability improvement effect cannot be obtained. The viscoelasticity adjusting agent of the present invention may be used as a solution or after drying and pulverizing.It is used by adding it to an aqueous dispersion and mixing it in the same way as a normal thickener. The viscoelasticity modifier of the present invention also includes antioxidants, ultraviolet absorbers, waterproofing agents, preservatives, insecticides, fungicides, dispersants, antifoaming agents, deodorants, fragrances, fillers, dyes, and It may contain or be mixed with pigments. The viscoelasticity modifier of the present invention is useful for adjusting the viscoelastic behavior of water or aqueous solutions or dispersions containing inorganic or organic substances, such as natural and synthetic latex, various synthetic materials {☆ 1 fat emulsions, inorganic salt aqueous solutions, water-soluble resin aqueous solutions, aqueous slurries and colloidal dispersions of water-insoluble inorganic and organic substances, and mixed compositions thereof, specifically for adhesives and food additives. It can be used for printing, printing paste, cosmetics, polling mud, cement compounding, resin mortar, etc. The viscoelasticity modifier of the present invention provides a polyether with a force μ boxy p
It is a grafted product of water-soluble ethylenically unsaturated monomers containing amide, sulfonic acid, and sulfonic acid groups.It is non-thermally meltable, has high heat resistance, does not rot or spoil, and is inexpensive. It can use raw materials and exhibits favorable viscoelastic properties, such as excellent thickening properties, leveling properties, fluidity, and coating properties. It is also possible to add a crosslinking component to give the product a crosslinked structure, giving it greater viscosity than conventional thickeners such as methylcellulose. The performance and effects described in L cannot be obtained at all with polyether μ alone, a polymer of a permanently soluble ethylenically unsaturated monomer alone, or a salt thereof, or a mixture thereof. Although the present invention will be explained using Examples above, the present invention is not limited thereto. In addition, in the following examples, parts mean parts by weight. Examples 1 to 7 Graft polymer [1] Molecular weight of about 400 obtained by randomly adding ethylene oxide and propylene oxide to stearic acid at a molar ratio of 9:1 in a reaction apparatus equipped with a stirrer, a thermometer and a nitrogen blowing tube.
0 polyether/L/100 parts, acrylamide 15 parts, acrylic acid 80 parts, sodium acrylate 30 parts,
4 parts of sodium styrene snolephonate and 525 parts of water
After stirring and purging with nitrogen, 35 parts of ammonium persulfate 10% aqueous solution and 03 parts of sodium bisulfite 10% aqueous solution were added at 50'C and reacted at 50'C for 5 hours, followed by 8'Zl parts of water. A 50% aqueous sodium oxide solution was added to neutralize with stirring to obtain a pale yellow aqueous solution of graft polymer (I).The viscosity (25°C) of the 5% aqueous solution was 49C1)S.Graft polymer [π] In the same reactor as in Example 1, 100 parts of polyether with a molecular weight of about 6500, which is obtained by adding ethylene oxide to diethanolamine, 60 parts of acrylic acid, and methacrylic acid Iv
After adding 10 parts of sodium methacrylate, 15 parts of sodium methacrylinoleate, and 600 parts of water and purging with nitrogen under stirring, 4 parts of a 10% aqueous solution of ammonium persulfate and 4 parts of a 10% aqueous solution of sodium bisulfite were added at 30°C, and the mixture was heated at 30°C for lθ hours. After the reaction, add 50% aqueous sodium hydroxide solution of 6a7#r and add about 7
The mixture was stirred at 0'C to perform neutralization and partial hydrolysis to obtain a pale yellow aqueous solution of the graft polymer (self). The viscosity of the 5% aqueous solution was 128 cps. Graft polymer CI [[] 500 parts of acyhinic acid and 555 parts of tetraethylenepentamine
A polyether with a molecular weight of about 35,000 was synthesized by adding 1 ethylene oxide 'tf. 35 parts of this polyether, 43 parts of acrylic acid, 19 parts of sodium methacrylate, 3 parts of hydroxyethyl methacrylate, and 570 parts of water were placed in the same reactor as in Example 1, dissolved under stirring, and replaced with nitrogen. Add α4 parts of vitamin CIO solution and 05 parts of 35% aqueous hydrogen peroxide solution, stir and react at 40'C for 6 hours, then add 4 parts of 50% sodium hydroxide aqueous solution and 2.21 parts of water. Oxidizing power! Neutralize by adding lesium,
A light brown aqueous solution of the graft polymer (b) was obtained. The viscosity (25°C) of the 5% aqueous solution was 730 cps. Graft polymer CM) Dry polyethylene glycol/L/(molecular m approx. 200
0) 116 parts of xylylene diisocyanate 1α5 parts were reacted in a xylene solution at 120°C, and after xylene was removed, a polyurethane resin with a molecular weight of about 63a0σ) was obtained. 70 parts of this polyurethane resin was placed in the same reactor as in the example.
Add 39 parts of methacrylic acid, 10 parts of sodium acrylate, 1 part of methyacrylate/L/L, 1 part of N,N-methylenebisacrylamide α, and 620 parts of water, dissolve with stirring, and after purging with nitrogen, heat at 50°C to dissolve 0.5 parts of vitamins. After adding CtO% aqueous solution and 4 parts of hydrogen peroxide 35% aqueous solution and reacting with stirring at 50°C for 6 hours, 32 parts of sodium hydroxide 50% aqueous solution was added and stirred to perform partial neutralization, resulting in a slightly yellow and transparent solution. An aqueous solution of the graft polymer (b) was obtained. Viscosity of 5% aqueous solution (2
5℃) was 218 cps. Further, when 5 parts (solid content) of the graft polymer (2) was dissolved in 45 parts of water and the solution was added dropwise to 800 parts of methanol (7 parts) with stirring, a white flocculent solid was precipitated. The solution containing this flocculent solid was centrifuged at 600 rpm for 30 minutes to separate the supernatant. The remaining flocculent solid was transferred to a Soxhlet extractor and extracted with methanol for 8 hours. From the extract and the above supernatant, 500 to 15 ffill {l? , Methanol was distilled off at 30-80°C to obtain 52 parts of polyether μα. In addition, the solid remaining in the Soxhlet extractor is gm*l1F, 70
It was dried at ℃ for 5 hours to obtain 4.40 parts of white solid. The grafting efficiency of the backbone polymer was 7a4%. Graft polymer (V) In the same reaction apparatus as in Example 1, ethylene oxide and propylene oxide were added to ethylene glycol in a molar ratio of 70:30.
95 parts of polyether with a molecular weight of about 9800 randomly added with 75 parts of acrylic acid, 3 parts of sodium methacrylate
After adding 600 parts of water and stirring with nitrogen, add 5 parts of vitamin CIO% aqueous solution and 04 parts of 35% hydrogen peroxide aqueous solution at 50°C, stir and react at 50°C for 5 hours, and then add 8a and 3 parts of water. A 50% aqueous solution of sodium oxide was added and stirred to effect neutralization, yielding a slightly pale yellow transparent aqueous solution of the graft polymer. The viscosity (25°C) of the 5% aqueous solution was 110 cps. Graft polymer [■] In the same reaction apparatus as in Example 1, ethylene oxide and propylene oxide were added to 1,4-butanediode μ at a mole ratio of 70.
:30 randomly added polyether/l/95 parts with a molecular weight of about 8,500, 70 parts of acrylamide and 66 parts of water.
Add 0 parts of hydrogen peroxide, 35% aqueous solution of hydrogen peroxide and 5 parts of vitamin C, 10% aqueous solution at 50°C, and stir and react at 50°C for 6 hours. A 50% aqueous sodium hydroxide solution was added and stirred to hydrolyze acrylamide, resulting in a pale yellow and cloudy graft polymer (b).
An aqueous solution of was obtained. The viscosity of the 5% aqueous solution was 75 cps. Graft polymer [■] 50 parts of polyethylene oxide having a molecular weight of about 6,000, 20 parts of methyl acrylate, 5 parts of vinyl acetate, and 71 parts of styrene were placed in the same reactor as in Example 1, and after stirring and purging with nitrogen, the temperature was 50°C.
Then, 25 parts of ammonium persulfate io% aqueous solution and 02 parts of sodium bisulfite 10% aqueous solution were added, and the mixture was heated at 50°C.
After reacting with stirring for an hour, 220 #r of water was added and dissolved, and 209 parts of a 50% aqueous sodium hydroxide solution was added to hydrolyze 90% of methyl acrylate and vinyl acetate, resulting in a slightly yellowish-white graft polymer. An aqueous solution of (d) was obtained. The viscosity of the 5% aqueous solution was 83 cps. 1 Graft polymers I to ■ of the present invention and ratio 4ji 2 examples include sodium polyacrylinoleate (■) (average molecular weight: about 500,
000), polyethylene oxide Q (average molecular weight approximately 15
0,000), a mixture of ■ and ■ in a weight ratio of 1:1, methylcellulose (A) (average molecular weight of about 30,000), and an unhydrolyzed product (Xll) of the graft polymer (A). A viscoelasticity modifier was added to the emulsion (concentration 50%) and the flow characteristics were measured, and a coating test was conducted using a roll coater using graft polymers (I), @, (B) and comparative examples. The results are shown in Table 1.

Claims (1)

[Scope of Claims] L Polyether Iv (A) and a water-soluble ethylenically unsaturated monomer CB-1 having a carboxyl group, an amyl group or a sulfonic acid group, and which can be induced into a carboxy μ group by hydrolysis An ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers (B-2) having a functional group (B-2) and, if necessary, other monomers 0, ), e) and 0, Q is 10 to 90
Weight%, the total of ■ and 0 is lθ ~ 90% by weight, and in the total of ■ and O, ■ is 507 μ% or more 1, 0 is 50 mol. When (B-2) is used, a graft polymer obtained by hydrolyzing CB-2) and, if necessary, a crosslinker {. Aqueous dispersion consisting of 0 beach agents (
A viscoelastic modifier for paints (excluding paints). 2. The viscoelasticity according to claim 1, wherein the cross-linked sieving agent 0 is a polyvalent metal compound capable of forming ionic crosslinks, a polyexoxidized α-aldehyde, a haloepoxytelkane, or a polyisocyanate compound. Adjustment agent. a) Polyether Iv (A) is an alkyl oxide addition polymer of alcohols, levonic acids, amines, amides or urethanes. 1'1 Claim 1
or the viscoelastic modifier according to any one of Item 2. Tun Polyether Iv (A), a water-soluble ethylenically unsaturated monomer (B-1) having a carpoxyl group, an amide group or a sulfonic acid group, and by hydrolysis Kuka/Reboki S/
Ethylenically unsaturated monomer (B-2) selected from the group consisting of ethylenically unsaturated monomers (B-2) having a functional group that can be induced into /1/ group → rumored ethylenically unsaturated monomer■ and other monomers as necessary 0 and 0, in the total of e and 0, ■ is 10-90% by weight, ■
The total of and 0 is 10-90% by weight, and in the total of (f) and C), (f) is 50 mol% or more, and 0 is 50 mol%"≦
When (B-2) is used, a graft polymer obtained by hydrolyzing CB-2) or a viscoelasticity modifier consisting of this graft polymer and a crosslinking agent O is used. , α0001 to 1 per 100 parts by weight of the adhesion-imparting component in an aqueous dispersion containing the adhesion-imparting component.
Method for adjusting the viscoelasticity of an aqueous dispersion by adding 00 parts by weight.