JP2009073938A - Viscosity improving agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a viscosity improving agent giving excellent finish characteristics (smoothness, vividness, and sag preventing property). <P>SOLUTION: The viscosity improving agent contains a copolymer comprising the following monomers as essential constituents: (a) (meth)acrylic acid (acrylate); (b) a monomer represented by a formula (1) (wherein R<SB>1</SB>is a hydrogen atom or a methyl group, R<SB>2</SB>and R<SB>3</SB>are each a hydrogen atom, methyl group or ethyl group, R<SB>4</SB>is a 25-60C normal/branched chain hydrocarbon group, and n is an integer of 3-60); (c) alkyl(meth)acrylate having a 1-4C alkyl group; and (d) a multifunctional monomer. Based on the total weight of the respective monomer units (a)-(d), the content of the unit (a) is 0.1-50 wt.%, the content of the unit (b) is 5-60 wt.%, the content of the unit (c) is 5-60 wt.%, and the content of the unit (d) is 0.05-5 wt.%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

   The present invention relates to a viscosity improver.

Conventionally, as viscosity improvers, polymer type viscosity improvers {alkyl-modified polycarboxylic acid (Patent Document 1), cyano group-containing alkyl-modified polycarboxylic acid (Patent Document 2) and amino group-containing alkyl-modified polycarboxylic acid (patent Literature 3); as a constituent monomer, none of them contains a polyfunctional monomer} or the like.
Japanese Patent Laid-Open No. 11-246799 JP 2001-279158 A JP 2003-253596 A

Conventional polymer viscosity improvers have a problem that the smoothness, sharpness, and sagging prevention (finishing property) of the coating film are insufficient.
That is, an object of the present invention is to provide a viscosity improver capable of imparting excellent finishing properties (smoothness, sharpness, and sagging prevention).

（式中、Ｒ^１は水素原子又はメチル、Ｒ^２及びＲ^３は水素原子、メチル又はエチル、Ｒ^４は炭素数２５〜６０の直鎖又は分岐の炭化水素基、ｎは３〜６０の整数、Ｃは炭素原子、Ｈは水素原子、Ｏは酸素原子を表す。）で表される単量体（ｂ）と、
アルキル基の炭素数が１〜４であるアルキル（メタ）アクリレート（ｃ）と、
多官能単量体（ｄ）とを必須構成単量体とする共重合体を含有してなり、
（ａ）〜（ｄ）の各単量体単位の合計重量に基づいて、（メタ）アクリル酸（塩）（ａ）単位の含有量が０．１〜５０重量％、単量体（ｂ）単位の含有量が５〜６０重量％、単量体（ｃ）単位の含有量が５〜６０重量％、多官能単量体（ｄ）単位の含有量が０．０５〜５重量％である点を要旨とする。 The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems. That is, the viscosity improver of the present invention is characterized by (meth) acrylic acid (salt) (a),

Wherein R ¹ is a hydrogen atom or methyl, R ² and R ³ are hydrogen atoms, methyl or ethyl, R ⁴ is a linear or branched hydrocarbon group having 25 to 60 carbon atoms, and n is an integer of 3 to 60 , C is a carbon atom, H is a hydrogen atom, and O is an oxygen atom)) (b)
An alkyl (meth) acrylate (c) having 1 to 4 carbon atoms in the alkyl group;
Containing a copolymer having a polyfunctional monomer (d) as an essential constituent monomer;
Based on the total weight of the monomer units (a) to (d), the content of the (meth) acrylic acid (salt) (a) unit is 0.1 to 50% by weight, the monomer (b) The unit content is 5 to 60% by weight, the monomer (c) unit content is 5 to 60% by weight, and the polyfunctional monomer (d) unit content is 0.05 to 5% by weight. The point is summarized.

  The viscosity improver of the present invention exhibits excellent finishing properties (smoothness, sharpness and sagging prevention).

<(Meth) acrylic acid (salt) (a)>
(Meth) acrylic acid (salt) (a) means acrylic acid, methacrylic acid, acrylate or methacrylate.
Examples of the salt include alkali metal (sodium, potassium, lithium, etc.) salt, alkaline earth metal (magnesium, calcium, etc.) salt, ammonium salt, alkanolamine (monoethanolamine, diethanolamine, triethanolamine etc.) salt and carbon number 1 -4 alkylamine (such as methylamine, ethylamine, propylamine and butylamine) salts and the like.
Of these (meth) acrylic acids (salts), acrylic acid, methacrylic acid, and ammonium methacrylate are preferable, acrylic acid and methacrylic acid are more preferable, and methacrylic acid is particularly preferable.

<Monomer (b)>
Of R ¹ , methyl is preferable from the viewpoint of finish.
Of R ² and R ³ , a hydrogen atom and methyl are preferable, and a hydrogen atom is more preferable from the viewpoint of finish.
Examples of the linear or branched hydrocarbon group (R ⁴ ) having 25 to 60 carbon atoms include linear alkyl, branched alkyl, linear alkenyl, and branched alkenyl.
As linear alkyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, n-hentriacontyl, n-dotriacontyl, n-tritriacontyl, n-tetratria Contil, n-pentatriacontyl, n-hexatriacontyl, n-heptatriacontyl, n-octatriacontyl, n-nonatriacontyl, n-tetracontyl, n-pentacontyl and n-hexacontyl Etc.

  Examples of the branched alkyl include isopentacosyl, isohexacosyl, isoheptacosyl, isooctacosyl, isononacosyl, isotriacontyl, isotetracontyl, isopentacontyl and isohexacontyl.

  Examples of linear alkenyl include n-pentacocenyl, n-hexacocenyl, n-heptacocenyl, n-octacocenyl, n-nonacocenyl, n-triacontenyl, n-tetracontenyl, n-pentacontenyl and n-hexacontenyl. It is done.

  Examples of branched alkenyl include isopentacosenyl, isohexacocenyl, isoheptacosenyl, isooctacocenyl, isononacocenyl, isotriacontenyl, isotetracontenyl, isopentacontenyl, and isohexacontenyl.

  Of these, linear alkyl and linear alkenyl are preferable from the viewpoint of finish, etc., more preferably linear alkyl, and particularly preferably n-triacontyl, n-tetracontyl and n-pentacontyl.

  n is an integer of 3 to 60, preferably an integer of 10 to 50, and more preferably an integer of 20 to 40. Within this range, the finish is further improved.

  As the monomer (b), n-pentacosanol ethylene oxide 3-60 mol adduct (meth) acrylate, n-hexacosanol ethylene oxide 3-60 mol adduct (meth) acrylate, n-triacontanol (Meth) acrylate of ethylene oxide 3-60 mol adduct, (meth) acrylate of n-tetracontanol ethylene oxide 3-60 mol adduct, (meth) acrylate of n-pentacontanol ethylene oxide 3-60 mol adduct and n- Examples include (meth) acrylates of 3 to 60 mol adducts of hexacontanol ethylene oxide. Among these monomers, n-hexacosanol ethylene oxide 3-60 mol adduct (meth) acrylate, n-triacontanol ethylene oxide 3-60 mol adduct (meth) acrylate and n-tetracontanol ethylene oxide (Meth) acrylates of 3 to 60 mol adducts are preferred, more preferably (meth) acrylates of 3 to 60 mol of adducts of n-hexacosanol ethylene oxide and (meth) acrylates of 3 to 60 mol of adducts of n-tetracontanol ethylene oxide (meta ) Acrylate.

<Alkyl (meth) acrylate (c)>
Examples of the alkyl (meth) acrylate (c) having 1 to 4 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Examples include butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and n-butyl (meth) acrylate are preferred from the viewpoint of finish, etc., particularly preferably methyl (meth) acrylate and ethyl. (Meth) acrylate and n-propyl (meth) acrylate.
In addition, (meth) acrylate means an acrylate or a methacrylate.

<Polyfunctional monomer (d)>
The polyfunctional monomer (d) can be copolymerized with (meth) acrylic acid (a), monomer (b) and alkyl (meth) acrylate (c), and has at least 2 ethylenically unsaturated double bonds. It is not particularly limited as long as it is a monomer having one unit, bifunctional monomer (d1) {monomer having two ethylenically unsaturated double bonds}, trifunctional monomer (d2) {ethylenic unit Monomers having 3 saturated double bonds}, 4-8 functional monomers (d3) {monomers having 4-8 ethylenically unsaturated double bonds}, and the like.

Examples of the bifunctional monomer (d1) include di (meth) acrylate of a polyol (pd11) and di (meth) acrylate of a polyol (pd12) alkylene oxide adduct.
As the polyol (pd11), 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl Examples include -1,3-diol, tricyclodecane dimethylol, cyclohexane diol, cyclohexane dimethylol, hydrogenated bisphenol A, hydrogenated bisphenol F, pentaerythritol, trimethylolpropane, and glycerin.

The polyol alkylene oxide adduct is not limited as long as it is an alkylene oxide adduct of polyol (pd12), but is preferably within the following range.
Examples of the polyol (pd12) include ethylene glycol, propylene glycol, 1,2-butanediol, 2,3-butanediol, hydroquinone, bisphenol A, and bisphenol F in addition to the above-described polyol (pd11).

  The number of moles of alkylene oxide added is preferably 2 to 100, more preferably 4 to 80, and particularly preferably 6 to 60 with respect to 1 mole of polyol (pd12).

Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like).
In addition, 1 type or 2 types may be sufficient as an alkylene oxide, and when using 2 types, any of block, random, or these mixture may be sufficient. When two types are used, it is preferable to include ethylene oxide, and the content (mol%) of ethylene oxide is preferably 30 to 99.9, more preferably 50 to 99.9, particularly based on the number of moles of all alkylene oxides. Preferably it is 70-99.9.

  Examples of the trifunctional monomer (d2) include tri (meth) acrylate of polyol (pd2) and tri (meth) acrylate of a polyol alkylene oxide adduct.

  Examples of the polyol (pd2) include dipentaerythritol, tripentaerythritol, diglycerin, triglycerin, ditrimethylolpropane, tristrimethylolpropane, cyclohexanetetraol and the like in addition to the above-described polyol (pd12).

The number of moles of alkylene oxide added is preferably 3 to 200, more preferably 6 to 150, and particularly preferably 9 to 100 with respect to 1 mole of polyol (pd2).
The alkylene oxide is the same as described above (one type or two types may be included, including the contents when two types are used).

  Examples of the 4- to 8-functional monomer (d3) include tetra- to octa- (meth) acrylate of polyol (pd3) and tetra- to octa- (meth) acrylate of a polyol alkylene oxide adduct.

  Examples of the polyol (pd3) include sorbitan, tetrapentaerythritol, hexapentaerythritol and the like in addition to the above-described polyol (pd2).

The number of moles of alkylene oxide added is preferably from 3 to 200, more preferably from 6 to 150, and particularly preferably from 9 to 100, based on 1 mole of the polyol (pd3).
The alkylene oxide is the same as described above (one type or two types may be included, including the contents when two types are used).

  Of these polyfunctional monomers (d), from the viewpoint of finish, the bifunctional monomer (d1) and the trifunctional monomer (d2) are preferable, and polyoxyalkylene glycol di (meta) is more preferable. ) Acrylate, tri (meth) acrylate of glycerin alkylene oxide adduct, tri (meth) acrylate of trimethylolpropane alkylene oxide adduct and tri (meth) acrylate of pentaerythritol alkylene oxide adduct, particularly preferably polyoxyalkylene glycol di Tri (meth) acrylates of (meth) acrylates and glycerin alkylene oxide adducts, most preferably polyoxyalkylene glycol di (meth) acrylates.

  As monomers constituting the copolymer, in addition to (meth) acrylic acid (salt) (a), monomer (b), alkyl (meth) acrylate (c) and polyfunctional monomer (d), Other ethylenically unsaturated monomers (e) may be included.

<Other ethylenically unsaturated monomers (e)>
Other ethylenically unsaturated monomers (e) include (meth) acrylic acid (a), monomer (b), alkyl (meth) acrylate (c) and polyfunctional monomer (d). The monomer is not particularly limited as long as it is a monomer that can be polymerized, and known monomers {for example, Patent Document 2, Patent Document 3, Japanese Patent Application Laid-Open No. 2004-27208, etc.} can be used.

  Among these other ethylenically unsaturated monomers, from the viewpoint of finish, etc., ethylenically unsaturated carboxylic acid (salt), polyoxyalkylene (alkylene oxide addition mole number 2 to 100) (meth) acrylic acid mono Ester, alkoxy polyalkylene glycol (alkylene oxide addition mole number 2 to 100) (meth) acrylic acid ester, hydroxyalkyl (meth) acrylate, dihydroxyalkyl (meth) acrylate and ethylenically unsaturated amide are more preferable. Crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, polyoxyethylene (ethylene oxide addition mole number 2-100) mono (meth) acrylate, C1-6 aliphatic alcohol ethylene oxide adduct ( With ethylene oxide (Meth) acrylate having 2 to 100 moles), hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, dihydroxyethyl (meth) acrylate, dihydroxypropyl (meth) acrylate and (meth) acrylamide, in particular Preferably maleic acid, fumaric acid, polyoxyethylene (2-100 ethylene oxide addition moles) mono (meth) acrylate, hydroxyethyl (meth) acrylate, dihydroxyethyl (meth) acrylate, dihydroxypropyl (meth) acrylate and (Meth) acrylamide.

  (Meth) acrylic acid (salt) (a), monomer (b), alkyl (meth) acrylate (c), polyfunctional monomer (d) and other ethylenically unsaturated monomers (e) , One or more of each may be used.

The content (% by weight) of (meth) acrylic acid (salt) (a) units is (meth) acrylic acid (salt) (a), monomer (b), alkyl (meth) acrylate (c), and many. Total weight of each monomer unit of the functional monomer (d) {hereinafter abbreviated as “weight of (a) to (d)”. } Is preferably 0.1 to 50, more preferably 1 to 45, and particularly preferably 7 to 40.
The content (% by weight) of the monomer (b) unit is preferably 5 to 60, more preferably 10 to 55, particularly preferably 20 to 50 based on the weight of (a) to (d). .
The content (% by weight) of the alkyl (meth) acrylate (c) unit is preferably 5 to 60, more preferably 7 to 50, particularly preferably 10 to 40 based on the weight of (a) to (d). It is.
The content (% by weight) of the polyfunctional monomer (d) unit is preferably 0.05 to 5, more preferably 0.07 to 4, particularly preferably based on the weight of (a) to (d). Is 0.1-3.
When the copolymer has another monomer (e) as a constituent unit, the content (% by weight) of the other monomer (e) unit is based on the weight of (a) to (d). 1-100 are preferable, More preferably, it is 5-70, Most preferably, it is 10-40.
Within these ranges, the finish and the like are further improved.

  The copolymer is a known polymerization method {emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, etc. (for example, Patent Document 2, Patent Document 3 and Japanese Patent Application Laid-Open No. 2004-27208); Solution polymerization is preferred, more preferably solution polymerization}.

The viscosity improver of the present invention may contain a solvent (an organic solvent and / or water).
Examples of the organic solvent include alcohol and ether.
As alcohol, C1-C8 monool, C2-C12 diol, etc. are contained.
Examples of monools include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isobutyl alcohol, isopropyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, and 2-ethylhexyl alcohol.
Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.
Examples of ethers include ethers having 2 to 12 carbon atoms, such as dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, triethylene glycol monobutyl ether, Examples include ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.

When the solvent is contained, the content (% by weight) is preferably 10 to 10,000, more preferably 40 to 5000, and particularly preferably 100 to 3000, based on the weight of the copolymer.
When the organic solvent and water are contained, the content weight ratio (organic solvent / water) is preferably 10/90 to 99/1, more preferably 20/80 to 98/2, and particularly preferably 30/70 to 97/3.

The viscosity improver of the present invention includes other additives {viscosity improvers other than the present invention, antifoaming agents, dispersants, leveling agents, wetting agents, film-forming aids, antiseptics, fungicides, and water resistance agents. Etc.} (for example, additives described in JP-A No. 54-80349).
When other additives are contained, the total content (% by weight) thereof is preferably 1 to 70, more preferably 2 to 60, and particularly preferably 3 to 50, based on the weight of the copolymer. .

The viscosity improver of the present invention can be used to improve the viscosity of various aqueous liquids (particularly paints and the like). The aqueous liquid may be any of an aqueous solution, a water emulsion, an aqueous dispersion, and the like.
The viscosity improver of the present invention is suitable for water emulsions and water-based paints among various aqueous liquids.
As the water emulsion, an emulsion for water-based paint is suitable.
As the water-based paint, water-based emulsion paints are suitable, and industrial emulsion paints, and then industrial emulsion paints excluding automobile paints, particularly water-based emulsion paints for construction, building materials, PCM or heavy anticorrosion are suitable.

The water emulsion and water dispersion are composed of an emulsion and other additives.
Water-based emulsion paints (particularly industrial emulsion paints) are composed of emulsions, aqueous resins, curing agents, pigments, organic solvents, water, and other additives.
As emulsion, acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, acrylic styrene resin emulsion, silicone resin emulsion, urethane resin emulsion, epoxy resin emulsion, fluororesin emulsion, SB latex, SBR latex, ABS latex, NBR latex And CR latex.

  Examples of the aqueous resin include acrylic resin, vinyl resin, oil-free alkyd resin, oil-modified alkyd resin, phenol resin, and epoxy resin.

  Examples of the curing agent include di-, tri-, tetra-, penta- or hexa-methylol melamine and methyl etherified products thereof, urea-formaldehyde condensate, urea-melamine condensate, and the like.

Pigments include inorganic pigments (calcium carbonate, titanium oxide, satin white, barium sulfate, talc, zinc oxide, gypsum, silica, ferrite, etc.) and organic pigments (carbon black, quinacridone red, phthalocyanine blue, polystyrene pigments, etc.) In addition, metallic pigments (aluminum flakes, copper flakes, mica-like iron oxides, mica, scale-like powders in which mica is coated with a metal oxide, and the like) can also be used.
As the organic solvent, the same organic solvents as described above can be used.
As other additives, the same additives as described above can be used.

The viscosity improver of the present invention may be added to the grinding stage (kneading step) or may be added to the let-down stage (adjustment step).
When the viscosity improver of the present invention is added to an aqueous liquid (particularly emulsion paint), the content (% by weight) of the viscosity improver is preferably 0.01 to 10, more preferably based on the weight of the emulsion paint. Is 0.05 to 5, particularly preferably 0.03 to 3. Within this range, the finish is further improved.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, with a part or% means a weight part or weight%.
<Example 1>
Monomer comprising 45 parts of methacrylic acid, 5 parts of acrylic acid, 5 parts of methacrylate of 40-mole adduct of n-pentacosyl alcohol ethylene oxide, 44.95 parts of ethyl methacrylate and 0.05 part of trimethacrylate of 60-mole glycerin ethylene oxide adduct The body mixture and 50 parts of a 1% butyl glycol solution of 2,2′-azobisisobutyronitrile were added dropwise to 350 parts of butyl glycol at a constant rate over 1.5 hours from the dropping funnel. Stir to react. The reaction temperature was kept at 80-90 ° C. After maintaining at the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain viscosity improver 1 {copolymer concentration: 20%} of the present invention.

<Example 2>
A monomer mixture consisting of 40 parts of methacrylic acid, 20 parts of acrylate of 20 moles of adduct of n-hexacontyl alcohol ethylene oxide, 39.9 parts of methyl acrylate and 0.1 parts of triacrylate of 30 moles of trimethylolpropane ethylene oxide, Stir uniformly while dropping 50 parts of a 2,2′-azobisisobutyronitrile solution in 0.5% ethyl glycol at a constant rate from each addition funnel over 1.5 hours to 350 parts of ethyl glycol. Reacted. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain viscosity improver 2 {copolymer concentration: 20%} of the present invention.

<Example 3>
Monomer comprising 0.1 part of acrylic acid, 60 parts of methacrylate of adduct of 50 moles of n-hexacosyl alcohol ethylene oxide, 36.9 parts of ethyl methacrylate and 3 parts of dimethacrylate of 30 moles of 1,4-butanediol ethylene oxide adduct Body mixture and 50 parts of a 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile 1% ethyl diglycol solution) from a dropping funnel at a constant rate over a period of 1.5 hours. The reaction was carried out with uniform stirring while dropping into 350 parts, and the reaction temperature was maintained at 80 to 90 ° C. After the completion of dropping, the reaction temperature was kept at the same temperature for 3 hours and then cooled to 40 ° C. {Concentration of copolymer: 20%} was obtained.

<Example 4>
A monomer mixture consisting of 1 part of acrylic acid, 50 parts of methacrylate of n-triacontyl alcohol ethylene oxide 10 mol adduct, 44 parts of ethyl methacrylate and 5 parts of diacrylate of ethylene glycol ethylene oxide 100 mol adduct, and 2,2 ′ -Stir uniformly while dropping 50 parts of 1% butyl glycol solution of azobis [2- (hydroxymethyl) propionitrile] into 350 parts of butyl glycol at a constant rate over 1.5 hours from the dropping funnel. Reacted. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity modifier 4 {copolymer concentration: 20%} of the present invention.

<Example 5>
A monomer mixture consisting of 20 parts of methacrylic acid, 19.5 parts of methacrylate of 60 moles of adduct of n-pentacontyl alcohol ethylene oxide, 60 parts of propyl methacrylate and 0.5 parts of dimethacrylate of 15 moles of ethylene glycol ethylene oxide, and 2 , 2'-azobisisobutyronitrile and 50 parts of a 1% methyltriglycol solution were added to 350 parts of methyltriglycol at a constant rate from a dropping funnel over a period of 1.5 hours, and the mixture was stirred and reacted uniformly. It was. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain viscosity improver 5 {copolymer concentration: 20%} of the present invention.

<Example 6>
A monomer mixture comprising 30 parts of methacrylic acid, 29 parts of an acrylate of n-pentacosyl alcohol ethylene oxide 3 mol adduct, 40 parts of methyl methacrylate and 1 part of a triacrylate of pentaerythritol ethylene oxide 90 mol adduct, and 2,2 ′ -50 parts of a 1% butyl glycol solution of azobisisobutyronitrile was allowed to react with stirring uniformly while being dropwise added to 350 parts of butyl glycol at a constant rate over 1.5 hours from the dropping funnel. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 6 {copolymer concentration: 20%} of the present invention.

<Example 7>
50 parts of methacrylic acid, 43 parts of acrylate of 5 moles of n-tetracontyl alcohol propylene oxide / 40 moles of ethylene oxide (block copolymer), 5 parts of ethyl acrylate and 2 parts of diacrylate of 70 moles of ethylene glycol ethylene oxide adduct While adding dropwise the monomer mixture and 50 parts of a 1% butyl glycol solution of 2,2′-azobisisobutyronitrile to 350 parts of butyl glycol at a constant rate from a dropping funnel over a period of 1.5 hours, uniformly Stir to react. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain viscosity improver 7 {copolymer concentration: 20%} of the present invention.

<Example 8>
45 parts of methacrylic acid, 44.7 parts of an acrylate of 10 moles of n-triacontyl alcohol propylene oxide / 40 moles of ethylene oxide (random copolymerization), 10 parts of ethyl methacrylate and 15 moles of adduct of ethylene glycol ethylene oxide 3 parts of a monomer mixture and 50 parts of a 2,2′-azobisisobutyronitrile 0.5% butyl glycol solution were added from a dropping funnel at a constant rate over a period of 1.5 hours, 350 parts of butyl glycol. While dropping, the mixture was reacted with uniform stirring. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 8 {concentration of copolymer: 20%} of the present invention.

<Example 9>
45 parts of methacrylic acid, 47.7 parts of methacrylate of 10 moles of isotriacontyl alcohol butylene oxide and 40 moles of ethylene oxide (block copolymer), 7 parts of ethyl acrylate and 15 moles of ethylene glycol ethylene oxide and 5 moles of propylene oxide ( (Random Copolymerization) A monomer mixture composed of 0.3 part of dimethacrylate and 50 parts of a 2% 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile solution in 1% methyl glycol) The reaction was carried out with uniform stirring while being added dropwise to 350 parts of methyl glycol at a constant rate over 1.5 hours, and the reaction temperature was maintained at 80 to 90 ° C. After maintaining the same temperature for 3 hours after completion of the addition, 40 After cooling to 0 ° C., the viscosity improver 9 {copolymer concentration: 20%} of the present invention was obtained.

<Example 10>
A single unit consisting of 20 parts of methacrylic acid, 10 parts of acrylic acid, 55 parts of methacrylate of 50-mole adduct of n-tetracontyl alcohol ethylene oxide, 14.93 parts of butyl acrylate and 0.07 part of tetraacrylate of 40-mole pentaerythritol ethylene oxide adduct. The monomer mixture and 50 parts of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile in 1% isopropyl alcohol) were added from the dropping funnel at a constant rate over a period of 1.5 hours. The reaction temperature was kept at 70 to 80 ° C. The reaction temperature was kept at the same temperature for 3 hours after the completion of the dropping, and then cooled to 40 ° C., and the viscosity improver 10 { Copolymer concentration: 20%} was obtained.

<Example 11>
Of methacrylic acid 39.4 parts, n-hexacosyl alcohol ethylene oxide 35 mol / propylene oxide 5 mol adduct (random copolymer) 45.5 parts methacrylate, ethyl methacrylate 14.4 parts, ethylene glycol ethylene oxide 15 mol adduct A monomer mixture consisting of 0.7 parts of dimethacrylate and 1 part of methacrylamide and 50 parts of a 1% aqueous solution of sodium persulfate were dropped into 350 parts of water at a constant rate from a dropping funnel over a period of 1.5 hours. The reaction was carried out with uniform stirring. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 11 {concentration of copolymer: 20%} of the present invention.

<Example 12>
23 parts of methacrylic acid, 56 parts of acrylate of 30 moles of n-triacontyl alcohol ethylene oxide and 10 moles of propylene oxide (random copolymerization), 18.9 parts of butyl methacrylate, triacrylate of 90 moles of glycerin ethylene oxide adduct 2.1 Butyl glycol 350 at a constant rate over 1.5 hours from a dropping funnel and a monomer mixture consisting of 40 parts of acrylamide and 40 parts of acrylamide and 50 parts of a 1% butyl glycol solution of 2,2′-azobisisobutyronitrile. While dripping to the part, it was made to react by stirring uniformly. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 12 {copolymer concentration: 20%} of the present invention.

<Example 13>
Methacrylic acid 36.7 parts, n-pentacontyl alcohol ethylene oxide 30 mol adduct methacrylate 50 parts, ethyl acrylate 11.6 parts, 1,4-butanediol ethylene oxide 40 mol adduct dimethacrylate 1.7 parts and 2- A monomer mixture composed of 70 parts of hydroxyethyl acrylate and 50 parts of a 1% butyl diglycol solution of 2,2′-azobisisobutyronitrile were each added from a dropping funnel at a constant rate over a period of 1.5 hours. While dropping into 350 parts of diglycol, the reaction was carried out with uniform stirring. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 13 {copolymer concentration: 20%} of the present invention.

<Example 14>
Dimethacrylate of 33.5 parts of methacrylic acid, 53.2 parts of acrylate of isotetracontyl alcohol ethylene oxide 7 mole adduct, 12.4 parts of ethyl methacrylate, 30 moles of ethylene glycol ethylene oxide and 5 moles of propylene oxide (random copolymerization) A monomer mixture consisting of 0.9 part, 4 parts of 2,3-dihydroxypropyl methacrylate and 1 part of acrylamide and 50 parts of a 1% butyl diglycol solution of 2,2′-azobisisobutyronitrile are added dropwise. While dropping from a funnel at a constant rate over 1.5 hours to 350 parts of butyl diglycol, the reaction was carried out with uniform stirring. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 14 {copolymer concentration: 20%} of the present invention.

<Example 15>
50 parts of methacrylic acid, 10 parts of methacrylate of 50 moles of isopentacontyl alcohol ethylene oxide, 39.2 parts of ethyl acrylate, 0.8 parts of dimethacrylate of 20 moles of ethylene glycol ethylene oxide, 40 parts of maleic acid, 30 parts of methacrylamide And 30 parts of 2-hydroxyethyl acrylate and 50 parts of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile in 0.5% isopropyl alcohol) from the dropping funnel. The reaction was conducted with uniform stirring while being added dropwise to 350 parts of isopropyl alcohol at a constant rate over 1.5 hours, and the reaction temperature was maintained at 70 to 80 ° C. After maintaining the same temperature for 3 hours after completion of the addition, 40 After cooling to ° C., the viscosity improver 15 of the present invention {copolymer concentration: 2 0%} was obtained.

<Example 16>
A monomer mixture consisting of 7 parts of methacrylic acid, 39 parts of methacrylate of 40 moles of adduct of n-triacontyl alcohol ethylene oxide, 50 parts of ethyl methacrylate and 4 parts of diacrylate of 90 moles of ethylene glycol ethylene oxide, and 2,2 ′ -50 parts of a 1% ethyl diglycol solution of azobisisobutyronitrile was reacted with uniform stirring while being dropwise added to 350 parts of ethyl diglycol from a dropping funnel at a constant rate over 1.5 hours. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 16 {copolymer concentration: 20%} of the present invention.

<Example 17>
Methacrylic acid 38.5 parts, n-tetracontyl alcohol ethylene oxide 30 mol adduct methacrylate 44 parts, propyl methacrylate 16.5 parts, ethylene glycol ethylene oxide 25 mol adduct dimethacrylate 1 part and 2,3-dihydroxypropyl acrylate A monomer mixture consisting of 10 parts and 50 parts of a 1% ethyl diglycol solution of 2,2′-azobisisobutyronitrile at a constant rate from the dropping funnel over a period of 1.5 hours, 350 parts of butyl glycol While dropping, the mixture was reacted with uniform stirring. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain the viscosity improver 17 {copolymer concentration: 20%} of the present invention.

<Comparative Example 1>
1100 parts of water, 169.9 parts of methacrylic acid, 44.6 parts of methacrylate of 60 mol adduct of butyl alcohol ethylene oxide, 58.5 parts of butyl acrylate, 5.6 parts of decyl acrylate, and polyoxyethylene (25 mol adduct of ethylene oxide) stearyl While stirring a mixture of 21.2 parts of ether sulfate sodium salt, 100 parts of a 0.2% aqueous solution of potassium persulfate was added dropwise at a constant rate over 3 hours to cause a reaction. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain a comparative viscosity improver 1 {concentration of copolymer: 20%, alkyl-modified polycarboxylic acid described in Patent Document 1}. .

<Comparative example 2>
A monomer mixture consisting of 200 parts of acrylic acid, 71 parts of methacrylic acid and 40 parts of acrylonitrile and 12 parts of a 5% aqueous sodium persulfate solution were respectively added dropwise to 1232 parts of water at a constant rate over a period of 1.5 hours. The reaction was carried out with uniform stirring. The reaction temperature was kept at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C., and a viscosity improver 2 for comparison {concentration of copolymer: 20%, cyano group-containing alkyl-modified polycarboxylic acid described in Patent Document 2} Got.

<Comparative Example 3>
1100 parts of water, 111 parts of methacrylic acid, 28 parts of butyl acrylate, 28 parts of methacrylamide, 28 parts of acrylate of 50 mol adduct of octyl alcohol ethylene oxide, 83 parts of styrene, polyoxyethylene (ethylene oxide 12 mol adduct) lauryl ether phosphate diester While stirring a mixture of 10 parts of sodium salt and 12 parts of polyoxyethylene (ethylene oxide 25 mol adduct) lauryl ether, 100 parts of 0.2% aqueous solution of potassium persulfate was added dropwise at a constant rate for 3 hours to react. The reaction temperature was maintained at 80-90 ° C. After maintaining the same temperature for 3 hours after the completion of dropping, the mixture was cooled to 40 ° C. to obtain a comparative viscosity modifier 3 {concentration of copolymer: 20%, alkyl-modified polycarboxylic acid described in Patent Document 1}. .

The performances of the viscosity improvers obtained in Examples 1 to 17 and Comparative Examples 1 to 3 (smoothness, sharpness, sagging prevention and high shear viscosity reduction) were evaluated by the following methods, and the results are shown in Table 1. It was.
<Sag prevention>
(1) Preparation of emulsion paint for evaluation (thermosetting industrial emulsion paint) 2.5 parts for evaluation sample {viscosity improver}, 180 parts acrylic emulsion (Boncoat EC-898, manufactured by Dainippon Ink and Chemicals) , 206 parts of water-soluble acrylic resin (Boncoat 3980, manufactured by Dainippon Ink Chemical Co., Ltd.), 52 parts of water-soluble melamine resin (Cymel 370, manufactured by Mitsui Cyanamid Co., Ltd.), titanium dioxide (Taipaque CR-95, Ishihara Sangyo ( 170 parts, butyl glycol 60 parts, deionized water 440 parts and antifoaming agent (SN deformer 399, San Nopco Co., Ltd.) 4 parts were uniformly mixed to obtain an adjustment solution.
Viscosity of this adjustment solution {Ford Cup NO. 4 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.)} was diluted with deionized water to obtain an emulsion paint for evaluation so that the time was 60 seconds.

(3) Coating Emulsion paint for evaluation is applied to a degreased tin plate (20 cm x 30 cm, thickness: 0.3 mm) by air spray coating (Wider W-88 Cupgun, Iwata Coating Machine Co., Ltd., film thickness gradient coating, exhaust Pressure: 4 kg / cm ² ) to obtain a coated tin plate.
In air spray coating, the discharge amount was changed so that the film thickness was 30 μm, trial coating was performed, and then main coating was performed.

(3) Evaluation Standing the painted tin plate vertically, setting in the booth for 10 minutes (booth temperature: 25 ° C, relative humidity: 75% RH), and observing the dripping condition of the paint immediately afterwards with the naked eye It was evaluated with.
○: There is no paint dripping △: There is a little paint dripping ×: There are many paint dripping traces

<Smoothness>
After evaluating the sagging prevention property, the coated tin plate was left to stand in a 150 ° C. oven for 30 minutes to obtain a baked tin plate. After the baking tin plate was cooled to room temperature (about 25 ° C.), the surface of the coating film was observed with the naked eye and evaluated according to the following criteria.
○: Almost no repelling or craters Δ: There are a few repellings or craters ×: There are many repellings or craters

<Vividness>
Subsequent to the evaluation of the smoothness, the surface of the coating film was measured at 6 locations each for 20 ° gloss (gloss meter VGS-300A, manufactured by Nippon Denshoku Industries Co., Ltd.), and the average value thereof was defined as sharpness. It shows that it is excellent in the sharpness, so that this value is high.

<High shear viscosity reduction>
The viscosity at 1000 (1 / S) of the emulsion paint for evaluation was measured with a rheometer (manufactured by HAAKE, Rheostress RS75). It shows that it is excellent in the high shear viscosity decreasing property, so that this value is low.

注１）調整溶液を希釈して評価用エマルション塗料を得るために用いた脱イオン水の量（部）
注２）ブランク：評価用サンプル｛粘性改良剤｝の代わりに脱イオン水を用いた以外、実施例及び比較例と同様に評価した。

Note 1) Amount of deionized water used to dilute the adjustment solution to obtain an emulsion paint for evaluation (parts)
Note 2) Blank: Evaluated in the same manner as in Examples and Comparative Examples except that deionized water was used instead of the evaluation sample {viscosity improver}.

  The viscosity improver of the present invention was extremely superior to the viscosity improver of the comparative example in terms of finish (smoothness, sharpness and sagging prevention) and high shear viscosity-reducing properties.

  The viscosity improver of the present invention can be used to improve the viscosity of various aqueous liquids (particularly paints and the like). The viscosity improver of the present invention is suitable for water-based paints among various aqueous liquids, and further suitable for water-based emulsion paints, particularly industrial emulsion paints (PCM, heavy anticorrosion paints, etc.).

Claims (5)

(Meth) acrylic acid (salt) (a);

Wherein R ¹ is a hydrogen atom or methyl, R ² and R ³ are hydrogen atoms, methyl or ethyl, R ⁴ is a linear or branched hydrocarbon group having 25 to 60 carbon atoms, and n is an integer of 3 to 60 , C is a carbon atom, H is a hydrogen atom, and O is an oxygen atom)) (b)
An alkyl (meth) acrylate (c) having 1 to 4 carbon atoms in the alkyl group;
Containing a copolymer having a polyfunctional monomer (d) as an essential constituent monomer;
Based on the total weight of the monomer units (a) to (d), the content of the (meth) acrylic acid (salt) (a) unit is 0.1 to 50% by weight, the monomer (b) The unit content is 5 to 60% by weight, the monomer (c) unit content is 5 to 60% by weight, and the polyfunctional monomer (d) unit content is 0.05 to 5% by weight. A viscosity improver characterized by that. Polyfunctional monomer (d) is polyoxyalkylene glycol di (meth) acrylate, glycerin alkylene oxide adduct tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate and pentaerythritol alkylene oxide addition The viscosity improver according to claim 1, which is at least one selected from the group consisting of tri (meth) acrylates. Furthermore, the viscosity improving agent of Claim 1 or 2 containing a solvent. The water emulsion containing the viscosity improving agent in any one of Claims 1-3. A water-based emulsion paint for building, building material, PCM or heavy corrosion protection, comprising the viscosity improver according to claim 1.