JP6228487B2 - Trifunctional viscosity modifier - Google Patents

Description

  The present invention relates to a viscosity modifier having a high viscosity at a low share.

  Various additives are added to resin emulsions used for paints, inks, adhesives and adhesives (hereinafter, resin emulsions refer to liquids containing only resin components in solvents) In particular, a viscosity modifier that adjusts the viscosity and viscosity of the liquid is often added as one of them. Resin emulsion compositions for these applications (hereinafter, resin emulsion compositions refer to liquids containing various additives in resin emulsions) are low at high shares from the viewpoint of improving workability when sprayed with a sprayer. When viscosity is low, high viscosity is required. This is because when spraying with a sprayer, the low viscosity is easier to spray, and when spraying and adhering to the object, the higher viscosity is less likely to cause “sag”. In general, this viscosity is called thixotropic property. Therefore, if thixotropic viscosity is not obtained in the resin emulsion composition to be used, it leads to deterioration in workability and deterioration of the product appearance for the above-mentioned use.

  Typical examples of existing well-adjusted viscosity modifiers include natural viscosity modifiers such as carboxymethyl cellulose and hydroxyethyl cellulose, alkali thickening viscosity modifiers such as polyacrylic acid and polyacrylic acid-containing copolymers, And so-called urethane type viscosity adjusting agents obtained by reacting an isocyanate compound with a polyol compound (see, for example, Patent Documents 1 to 3). However, each of the above existing viscosity modifiers has advantages and disadvantages, and it is difficult to say that they have sufficient performance.

  For example, with regard to natural viscosity modifiers and alkali thickening type viscosity modifiers, adding these to aqueous resins such as resin emulsions gives thixotropic viscosity to aqueous resins. In this case, the water resistance of the coating film is deteriorated. In addition, regarding urethane type viscosity modifiers, when added to aqueous resins such as resin emulsions, the water resistance when water-based resins are used as coatings is good. A thixotropic viscosity cannot be obtained. Therefore, so far, natural viscosity modifiers, alkali thickening type viscosity modifiers, and urethane type viscosity modifiers are often used in combination, and have been used in a form that compensates for each other's drawbacks.

  In recent years, some urethane-type viscosity modifiers have been developed that provide a thixotropic viscosity to resin emulsions and the like that have improved the disadvantages so far (see, for example, Patent Document 4). However, although the performance is improved as compared with the conventional product, the effect may not be sufficient. In particular, if the viscosity at the time of low shear is not sufficient, problems such as dripping occur at the time of forming a coating film of the aqueous resin as described above, and thus there is a need for a viscosity modifier that provides a further high low shear viscosity.

Japanese Patent No. 3902913 JP 2012-041475 A Japanese Patent No. 3938427 Japanese Patent No. 4650967

  Therefore, the problem to be solved by the present invention is to provide a viscosity modifier with good water resistance that has a high viscosity at a low share as compared with a conventionally used viscosity modifier.

Thus, as a result of intensive studies, the present inventors have reached the present invention.
That is, this invention is a viscosity regulator characterized by consisting of the compound represented by following General formula (1).

(In the formula, R ^{1 to} R ³ each independently represent a divalent hydrocarbon group having 4 to 16 carbon atoms, and R ^{4 to} R ⁶ each independently represent a hydrocarbon group having 12 to 36 carbon atoms. And x to z each independently represents a number of 10 to 500, and A ^{1 to} A ³ each independently represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms.)

  The effect of the present invention is to provide a viscosity modifier with good water resistance that has a high viscosity at a low share.

It is a graph which shows the viscosity at the time of a low share in the vinyl acetate emulsion containing the viscosity modifier of this invention. In 0.01 / s, from the order of increasing viscosity, compound A (◯), compound B (□), comparative product I (−), comparative product II (Δ) and blank (（) are represented. Here, 1 part by mass of a viscosity modifier is added to 100 parts by mass of the vinyl acetate emulsion (resin solid content: 44% by mass). It is a graph which shows the viscosity at the time of a low share in the vinyl acetate emulsion containing the viscosity modifier of this invention. In order of increasing viscosity at 0.01 / s, compound A (◯), compound B (□), compound C (*), comparative product I (−), comparative product II (Δ) and blank (◇) Represent. Here, 2 parts by mass of a viscosity modifier is added to 100 parts by mass of the vinyl acetate emulsion (resin solid content: 44% by mass). It is a graph which shows the viscosity at the time of a low share in the acrylic emulsion containing the viscosity modifier of this invention. At 0.01 / s, from the order of increasing viscosity, compound B (□), compound D (◯), compound E (Δ), comparative product III (−), and blank (◇) are represented. Here, 0.4 parts by mass of a viscosity modifier is added to 100 parts by mass of the acrylic emulsion (resin solid content: 50% by mass).

  The viscosity modifier of the present invention is a compound represented by the following general formula (1).

(In the formula, R ^{1 to} R ³ each independently represent a divalent hydrocarbon group having 4 to 16 carbon atoms, and R ^{4 to} R ⁶ each independently represent a hydrocarbon group having 12 to 36 carbon atoms. And x to z each independently represents a number of 10 to 500, and A ^{1 to} A ³ each independently represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms.)

R ^{1 to} R ³ of the compound represented by the general formula (1) each independently represent a divalent hydrocarbon group having 4 to 16 carbon atoms, specifically, an aliphatic group having 4 to 16 carbon atoms. Examples thereof include a hydrocarbon group or an alicyclic hydrocarbon group, or an aromatic hydrocarbon group having 6 to 16 carbon atoms. These hydrocarbon groups may be any group within the range of 4 to 16 carbon atoms, but are groups obtained by removing two isocyanate groups from the diisocyanate compound represented by the general formula (3) described later. Is preferred. This will be described in detail in the description of the diisocyanate compound described later.
In the present specification, “divalent” means having two sites to be bonded, for example, “divalent hydrocarbon group” means a hydrocarbon group having two sites to be bonded. Represent.

  The compound represented by the general formula (1) may be synthesized by any known synthesis method, but an AO adduct of isocyanurate and a monohydric alcohol (AO is alkylene) A method of synthesizing using an abbreviation of oxide as a raw material is preferable because it is simple and inexpensive. In this synthesis method, isocyanurate may also be synthesized using any known synthesis method, but a method of obtaining it as a trimer of diisocyanate is preferable because it is simple and inexpensive. The isocyanurate used as a preferable raw material of the viscosity modifier of the present invention is a compound represented by the following general formula (2), and the diisocyanate which is a preferable raw material of the isocyanurate is a compound represented by the following general formula (3). is there.

(In the formula, R ^{1 to} R ³ each independently represents a divalent hydrocarbon group having 4 to 16 carbon atoms.)

(In the formula, each Q independently represents a divalent hydrocarbon group having 4 to 16 carbon atoms.)

Examples of the diisocyanate represented by the general formula (3) include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Aliphatic diisocyanates such as 2,2-dimethylpentane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate; metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tri Diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmeta Diisocyanate (MDI), toluidine diisocyanate (TODI), metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylxylylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, 1,4-naphthalene diisocyanate (1,4- NDI), 1,5-naphthalene diisocyanate (1,5-NDI), 2,6-naphthalene diisocyanate (2,6-NDI), 2,7-naphthalene diisocyanate (2,7-NDI), 2,2′- Aromatic diisocyanates such as dimethyldiphenylmethane-4,4′-diisocyanate and diphenyldimethylmethane-4,4′-diisocyanate; isophorone diisocyanate ( Alicyclic diisocyanates such as PDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated metaxylylene diisocyanate, hydrogenated paraxylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate; biphenyl diisocyanate, 3,3′-dimethylbiphenyl Biphenyl diisocyanate such as diisocyanate may be mentioned. The isocyanurate represented by the general formula (2) is obtained from the above-described diisocyanate represented by the general formula (3), and Q in the general formula (3) is represented by the general formula (2) and the general formula ( This corresponds to R ^{1 to} R ³ in 1). These hydrocarbon groups R ^{1 to} R ³ may be any group within the range of 4 to 16 carbon atoms, but as described above, these are groups obtained by removing two isocyanate groups from the diisocyanate compounds exemplified above. It is preferable.

R ^{1 to} R ³ are independent groups, and any of the above-described diisocyanates may be combined with any isocyanurate, but since it is easy to produce, three of the same diisocyanates are used. Isocyanurate obtained as a monomer is preferred. Among the diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates are preferred, and hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated metaxylylene diisocyanate, hydrogenated paraxylylene diene. More preferred are isocyanate, hydrogenated tetramethylxylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexyl. Methane diisocyanate (hydrogenated MDI) is more preferred, and hexamethylene diisocyanate (HDI) is most preferred. Arbitrariness.

A ^{1 to} A ³ of the compound represented by the general formula (1) are groups derived from an AO adduct of a monohydric alcohol which is a raw material used when synthesizing the compound represented by the general formula (1), Represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms. For example, ethylene group, propylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylmethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 3-methylpropylene group, 1 , 1-dimethylethylene group, 2,2-dimethylethylene group, 1,2-dimethylethylene group, 1-ethylethylene group, 2-ethylethylene group, propylmethylene group, isopropylmethylene group and the like, and A ¹ to A ³ is an independent group. Among them, ethylene group, propylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylmethylene group, butylene group are preferable, ethylene group, propylene group, 1-methylethylene group, 2-methylethylene. Groups are more preferred, with ethylene groups being most preferred.

  Xz of the compound represented by the general formula (1) represents the degree of addition polymerization of AO of the AO adduct of a monohydric alcohol which is a raw material used when the compound represented by the general formula (1) is synthesized. It is an independent number between 10 and 500. Further, there is no problem even if x, y, and z are different numbers, but since the production is easy, the same number is preferable, and if it is less than 10, it may not be dissolved in an emulsion or the like. If it exceeds 1, a high low shear viscosity effect cannot be obtained. x to z are preferably 30 to 350, more preferably 50 to 300, and still more preferably 50 to 200.

Here, the x A ^{1 in the} compound represented by the general formula (1) may be the same or different, and in the case of being different, two or more types may be used, either block polymerization or random polymerization. The same is true for y A ² and z A ³ , and x A ¹ , y A ² and z A ³ are independent and have the same composition. Or different. Among them, the lower the ethylene group content, the more difficult it is to dissolve in the resin emulsion. Therefore, among the total of x A ¹ , y A ² and z A ³ , ethylene The group is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 95 mol% or more.

R ^{4 to} R ⁶ of the compound represented by the general formula (1) are groups derived from an alcohol of an AO adduct of a monohydric alcohol which is a raw material used when the compound represented by the general formula (1) is synthesized. Yes, it represents a hydrocarbon group having 12 to 36 carbon atoms, and specifically represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 12 to 36 carbon atoms. Examples of such a group include saturated aliphatic hydrocarbon groups such as dodecyl group, isododecyl group, secondary dodecyl group, tridecyl group, isotridecyl group, secondary tridecyl group, tetradecyl group, isotetradecyl group, secondary tetradecyl group, Pentadecyl, isopentadecyl, secondary pentadecyl, hexadecyl, isohexadecyl, secondary hexadecyl, heptadecyl, isoheptadecyl, secondary heptadecyl, octadecyl, isooctadecyl, secondary octadecyl, nonadecyl Group, isononadecyl group, secondary nonadecyl group, icosyl group, isoicosyl group, secondary icosyl group, eicosyl group, isoeicosyl group, secondary eicosyl group, heicosyl group, isohenicosyl group, secondary henocosyl group, docosyl group, isodocosyl group, 2 Class doko Group, tricosyl group, isotricosyl group, secondary tricosyl group, tetracosyl group, isotetracosyl group, secondary tetracosyl group, pentacosyl group, isopentacosyl group, secondary pentacosyl group, hexacosyl group, isohexacosyl group, secondary hexacosyl group, heptacosyl group, Isoheptacosyl group, secondary heptacosyl group, octacosyl group, isooctacosyl group, secondary octacosyl group, nonacosyl group, isononacosyl group, secondary nonacosyl group, triacontyl group, isotriacontyl group, secondary triacontyl group, hentriacontyl group, iso Hentriacontyl group, secondary Hentriacontyl group, dotriacontyl group, isodotriacontyl group, secondary dotriacontyl group, tritriacontyl group, isotritriacontyl group, secondary tritriacontyl group, Tratriacontyl group, isotetratriacontyl group, secondary tetratriacontyl group, pentatriacontyl group, isopentatriacontyl group, secondary pentatriacontyl group, hexatriacontyl group, isohexa Examples of the 2-position branched alkyl group include a 2-hexyldecyl group, a 2-octyldecyl group, a 2-octyldodecyl group, and a 2-decyltetradecyl group. Group, 2-dodecylhexadecyl group, 2-tetradecyloctadecyl group, 2-hexadecyleicosyl group and the like.

  Examples of unsaturated aliphatic hydrocarbon groups include dodecenyl, isododecenyl, secondary dodecenyl, tridecenyl, isotridecenyl, secondary tridecenyl, tetradecenyl, isotetradecenyl, and secondary tetradecenyl. , Pentadecenyl group, isopentadecenyl group, secondary pentadecenyl group, hexadecenyl group, isohexadecenyl group, secondary hexadecenyl group, heptadecenyl group, isoheptadecenyl group, secondary heptadecenyl group, octadecenyl group, iso Octadecenyl group, secondary octadecenyl group, nonadecenyl group, isononadecenyl group, secondary nonadecenyl group, icocenyl group, isoicocenyl group, secondary icocenyl group, eicocenyl group, isoeicosenyl group, secondary eicocenyl group, heneicosenyl group, isohenico group Cenyl group, 2 Henicosenyl group, heneicosenyl group, isoheneecocenyl group, secondary heneecocenyl group, dococenyl group, isodococenyl group, secondary dococenyl group, tricocenyl group, isotricosenyl group, secondary tricocenyl group, tetracocenyl group, isotetracocenyl group, 2 Secondary tetracosenyl group, pentacocenyl group, isopentacocenyl group, secondary isopentacocenyl group, hexacocenyl group, isohexacocenyl group, secondary hexacocenyl group, heptacocenyl group, isoheptacocenyl group, secondary heptacocenyl group, octacocenyl group Group, isooctacosenyl group, secondary octacocenyl group, nonacocenyl group, isononacocenyl group, secondary nonacocenyl group, triacontenyl group, isotriacontenyl group, secondary triacontenyl group, hentriacontenyl group, isohent Acontenyl group, secondary hentria contenyl group, dotria contenyl group, isodotria contenyl group, secondary dotria contenyl group, tritria contenyl group, isotritria contenyl group, secondary tritria contenyl group, tetra Triacontenyl group, isotetratriacontenyl group, secondary tetratriacontenyl group, pentatriacontenyl group, isopentatriaconenyl group, secondary pentatriacontenyl group, hexatriacontenyl group, isohexatria Examples thereof include a contenyl group and a secondary hexatriacontenyl group.

  Aromatic hydrocarbon groups include both aromatic hydrocarbon groups consisting of simple aromatic rings and polycyclic aromatic hydrocarbon groups consisting of heterocycles, such as phenyl, benzyl, tolyl, xylyl and Monosubstituted or disubstituted compounds such as a naphthyl group can be mentioned. As the hydrocarbon group that the mono- or di-substituted product of this aromatic hydrocarbon group may have as a substituent, the total carbon number of the mono- or di-substituted product of the aromatic hydrocarbon group as a whole If it is 12 to 36, there is no problem whether it is an aliphatic group, an aromatic group, a straight chain or a branched chain.

  Examples of the alicyclic hydrocarbon group include monosubstituted or disubstituted products such as a cyclopropyl group, a cyclobutyl group, a cyclobutenyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, and a cyclohexenyl group. The monocyclic or disubstituted product of the monocyclic alicyclic hydrocarbon group may have a monocyclic or disubstituted monocyclic alicyclic hydrocarbon group as the hydrocarbon group that the monocyclic or disubstituted product may have as a substituent. If the total number of carbon atoms in the whole body is 12 to 36, there is no problem whether it is an aliphatic group, an aromatic group, a straight chain or a branched chain.

R ^{4 to} R ⁶ of the compound represented by the general formula (1) are each an independent group, and may be different or the same, but are preferably the same because of easy production. Further, when the total number of carbon atoms in the hydrocarbon group of R ^{4 to} R ⁶ is 12 or less, a high low shear viscosity may not be obtained, and when it exceeds 36, it is relatively difficult to obtain raw materials. R ^{4 to} R ⁶ are preferably an aliphatic hydrocarbon group, more preferably a 2-position branched alkyl group or a secondary alkyl group, and still more preferably 24 to 32 carbon atoms.

The AO adduct of monohydric alcohol, which is a raw material used when synthesizing the compound represented by the general formula (1), has the above-mentioned AO as R ⁴ OH, R ⁵ OH and R ⁶ OH, respectively. x, y and z addition-polymerized compounds. The molecular weight of these compounds is calculated from the measured hydroxyl value (OHV) of the product, and the molecular weight is preferably 500 to 30,000. Especially, 2,000-15,000 are preferable and 3,000-8,000 are more preferable.

  The resin emulsion composition of the present invention comprises the viscosity modifier of the present invention contained in an aqueous resin emulsion (latex), dispersion (suspension, dispersion) or the like. Specific examples of the resin component of the resin emulsion include vinyl acetate, acrylic, styrene, and halogenated olefin resins. As vinyl acetate, in addition to vinyl acetate alone, for example, vinyl acetate / styrene, vinyl acetate / (meth) acrylic acid, vinyl acetate / (meth) acrylic acid ester, vinyl acetate / vinyl chloride, vinyl acetate / acrylonitrile, vinyl acetate / Maleic acid (ester), vinyl acetate / fumaric acid (ester), vinyl acetate / ethylene, vinyl acetate / propylene, vinyl acetate / isobutylene, vinyl acetate / vinylidene chloride, vinyl acetate / cyclopentadiene, vinyl acetate / crotonic acid, acetic acid Examples include vinyl / acrolein, vinyl acetate / veova, vinyl acetate / alkyl vinyl ether, and the like.

  Examples of acrylics include (meth) acrylic acid (esters), (meth) acrylic acid (ester) / styrene, (meth) acrylic acid (ester) / vinyl acetate, (meth) acrylic acid (ester) / vinylidene chloride , (Meth) acrylic acid (ester) / allylamine, (meth) acrylic acid (ester) / vinylpyridine, (meth) acrylic acid (ester) / N, N-dimethylaminoethyl ester and (meth) acrylic acid (ester) / N, N-diethylaminoethyl vinyl ether and the like.

  As styrene, in addition to styrene alone, for example, styrene / acrylonitrile, styrene / fumaronitrile, styrene / maleonitrile, styrene / cyanoacrylate, styrene / phenyl vinyl acetate, styrene / chloromethylstyrene, styrene / dichlorostyrene, styrene / Vinylcarbazole, styrene / N, N-diphenylacrylamide, styrene / methylstyrene, styrene / acrylonitrile / methylstyrene, styrene / acrylonitrile / vinylcarbazole, styrene / maleic acid and the like.

  Examples of halogenated olefins include vinyl chloride, vinylidene chloride, vinyl chloride / maleic acid (ester), vinyl chloride / fumaric acid (ester), vinyl chloride / vinyl acetate, vinyl chloride / vinylidene chloride, vinylidene chloride / vinyl acetate, and the like. And vinylidene chloride / vinyl benzoate. Other emulsions include, for example, urethane resin emulsion, silicone resin emulsion, epoxy resin emulsion, fluororesin emulsion, SBR emulsion, SB emulsion, ABS emulsion, NBR emulsion, CR emulsion, VP emulsion, BR emulsion, MBR emulsion and IR emulsion etc. are mentioned.

  In the resin emulsion used in the present invention, the solid content of the resin component listed above is preferably 30 to 80% by mass, more preferably 40 to 60% by mass of the resin emulsion. When it is 30% by mass or less or 80% by mass or more, the thickening / gelling effect may not be obtained when the viscosity modifier of the present invention is blended.

  The resin emulsion can be generally prepared by using one or more anionic, cationic or nonionic emulsifiers, and emulsifying and emulsion-polymerizing the monomer and water. The amount of the emulsifier added is not particularly limited, but is preferably about 0.1 to 6 parts by mass with respect to 100 parts by mass of the monomer. If a persulfate type initiator is used, an emulsifier may not be necessary. Generally, the average molecular weight of these resin emulsions is not particularly specified, but is preferably about 100,000 to 15 million, more preferably 500,000 to 10 million.

  The viscosity modifier of the present invention dissolves or disperses in water and exhibits a viscosity-adjusting effect. The addition amount is not particularly specified, but the usual addition amount is 0.01 to 100 mass parts of the resin emulsion and the entire dispersion. 10 mass parts is preferable and 0.05-5 mass parts is more preferable. As a method of use, it may be blended directly into a resin emulsion, dispersion, etc., or it can be blended after being diluted with water or a solvent so as to have an appropriate viscosity before blending. For example, when the viscosity modifier of the present invention is used for a resin emulsion for paints, the viscosity modifier of the present invention is one or two of water, methanol, ethanol, propanol, butanol, etc., in order to facilitate work. After diluting with the above mixed solvent, it may be added to the kneading step, or may be added to any other step.

  When the viscosity modifier of the present invention is diluted with water or a solvent so as to have an appropriate viscosity and then blended into the resin emulsion, the viscosity modifier of the present invention is 0.01 to 100 parts by mass of the resin solid content. It is preferable to mix | blend so that it may become 34 mass parts, and it is still more preferable to mix | blend so that it may become 0.03-13 mass parts.

  Since the viscosity modifier of the present invention is nonionic, it is also effective for resin emulsions that are alkaline. They can be added at the same time as antifoaming agents, pigment dispersants and other surfactants.

  Further, the resin emulsion composition of the present invention comprises an antioxidant, an ultraviolet absorber, a water resistant agent, an antiseptic / antibacterial agent, an insecticidal fungicide, a dispersant, an antifoaming agent, a deodorant, a fragrance, an extender, a dye and A pigment or the like may be contained or mixed. Other aqueous applications in which the viscosity modifier of the present invention is effective include coating agents for paper, leather and fibers, cleaning agents, adhesives, waxes, polishing agents, cosmetics, cosmetics for toilets, pharmaceuticals and agricultural chemicals. It is done.

Hereinafter, the present invention will be specifically described by way of examples.
(Method for Synthesizing Compound A)
342.2 g (0.002) of a compound (Mw = 7074) obtained by reacting 1 mol of 2-tetradecyloctadecanol with 150 mol of EO in a 500 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. 0484 mol), 0.22 g (0.06 wt% of the total solid content) of dibutylhydroxytoluene was charged, and dehydrated at 120 to 130 ° C. for 2 hours under reduced pressure (1.3 kPa or less). Next, the mixture was cooled to 75 to 80 ° C., 7.8 g (0.0154 mol) of hexamethylene diisocyanurate (Mw = 505), which is a trimer of hexamethylene diisocyanate, was added, and the mixture was heated at 80 to 90 ° C. for 2 hours under a nitrogen stream. Reaction was performed to obtain a reaction product. This is designated Compound ^{_{A (R 1 ~R 3: C}} 6 H 12, R 4 ~R 6: iC 32 H 65, A 1 ~A 3: C 2 H 4, x~z: 150).
Compounds B to E were produced in the same manner as Compound A by changing the raw materials and the amounts charged, and Table 1 shows in detail the raw materials used in producing each compound and the amounts charged.

(Comparative product I)
340.5 g (Mw = 7074, 0.0481 mol) of 150 EO adduct of 1 mol of 2-tetradecyloctadecanol (iC32-OH) was added to a 500 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. ) And 0.22 g of dibutylhydroxytoluene (0.06 wt% of the total solid content), and dehydrated at 120 to 130 ° C. for 2 hours under reduced pressure (1.3 kPa or less). Then, 9.3 g (Mw = 639, 0.0146 mol) of an adduct type trifunctional triisocyanate of trimethylolpropane (TMP) and hexamethylene diisocyanate (HDI) was added and reacted at 80 to 90 ° C. for 2 hours under a nitrogen stream. The obtained reaction product was designated as Comparative Example I.

(Comparative product II)
A 200 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer is charged with 100 g (0.01 mol) of polyoxyethylene glycol having a weight average molecular weight of 10,000 and 30 mol of ethylene oxide of 2-octyldodecyl alcohol. 32.4 g (0.02 mol) was charged, and 3.4 g (0.02 mol) of hexamethylene diisocyanate was added thereto, and reacted at 80 to 90 ° C. for 3 hours. The obtained urethane type viscosity modifier was designated as Comparative Example II.

(Comparative product III)
Into a 500 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, 186.0 g (0.009 mol) of polyoxyethylene glycol having a weight average molecular weight of 20,000, C12-14 secondary alcohol was added. 13.1 g (0.018 mol) of an ethylene oxide 12 mol adduct was charged, and 3.0 g (0.018 mol) of hexamethylene diisocyanate was added thereto, followed by reaction at 75 to 85 ° C. for 2 hours. The obtained urethane type viscosity modifier was designated as Comparative Example III.

<Evaluation with vinyl acetate emulsion>
Compounds A to C and comparative products I and II were added to a vinyl acetate emulsion and evaluated in the emulsion. The measurement sample is prepared by adding compounds A to C and comparative products I and II in the amounts shown in Table 2 with respect to 100 parts by mass of the vinyl acetate emulsion.
First, the viscosity was measured, the Ti value was calculated, and the thixotropic property of each viscosity modifier was investigated. The results are shown in Table 2. In addition, since the kind of rotor used with a viscometer changes with the magnitude | sizes (measurement range) of a viscosity, the kind of rotor used for each sample was also shown in Table 2. The vinyl acetate emulsion used is Movinyl 504N (resin solid content 44% by mass) from Nippon Synthetic Chemical Industry.
Viscosity measurement condition measuring instrument: B8H type viscometer (manufactured by Tokyo Keiki Co., Ltd.)
Measurement temperature: 25 ° C

  Here, the Ti value will be described. The Ti value is an index that has been used to express thixotropic properties in many patent documents so far, and shows a larger value as the viscosity at a lower share increases and the viscosity at a higher share decreases. Indicates that the tropic property is high. However, this index is difficult to see the difference in low share, and its effect is difficult to see when used as an index for judging whether it is a viscosity modifier having a high low shear viscosity (see the results in Table 2). Moreover, in the said measuring method, when it is high viscosity, a measurement will become difficult. Therefore, in Example 2, it was impossible to measure the viscosity by the above method, but this does not mean that Example 2 cannot be used (see FIG. 2).

Then, next, by looking at the viscosity curve representing the relationship between the viscosity and the shear rate, the level of viscosity at a low share was confirmed. The results are shown in FIGS. FIG. 1 shows data obtained by adding 1 part by mass of a viscosity adjusting agent to 100 parts by mass of a vinyl acetate emulsion (including water), and FIG. 2 shows 2 types of viscosity adjusting agent for 100 parts by mass of the vinyl acetate emulsion (including water). Data with parts by mass added is shown.
Viscosity curve measuring condition measuring instrument: rheometer Physica MCR301 (manufactured by Anton Paar)
Measuring jig: CP50-1
Measurement temperature: 25 ° C

  As a result, compared with Comparative Product I and Comparative Product II that have been conventionally used as viscosity modifiers, the isocyanurate type trifunctional viscosity modifier (compounds A to C) of the present invention is highly evaluated in the vinyl acetate emulsion. It was found to exhibit a low shear viscosity.

<Evaluation with acrylic emulsion>
Next, compounds B, D and E, and comparative product III were added to the acrylic emulsion and evaluated with the acrylic emulsion. The measurement sample is prepared by adding compounds B, D and E, and comparative product III in the addition amounts shown in Table 3 with respect to 100 parts by mass of the acrylic emulsion.
First, similarly to the evaluation with a vinyl acetate emulsion, the viscosity was measured, the Ti value was calculated, and the thixotropic property of each viscosity modifier was investigated. The results are shown in Table 3. The rotor used for each sample was different depending on the viscosity, which is also shown in Table 3. The acrylic emulsion used is Movinyl 727 (resin solid content 50 mass%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
Viscosity measurement condition measuring instrument: B8H type viscometer (manufactured by Tokyo Keiki Co., Ltd.)
Measurement temperature: 25 ° C

However, as described above in the evaluation of the vinyl acetate emulsion, it is difficult to see the effect of using the Ti value as an index for judging whether it is a viscosity modifier having a high low shear viscosity, and the same can be said for the acrylic emulsion.
Therefore, the viscosity curve representing the relationship between the viscosity and the shear rate was continuously measured. The results are shown in FIG. FIG. 3 shows data obtained by adding 0.4 parts by mass of a viscosity modifier to 100 parts by mass of an acrylic emulsion (including water).
Viscosity curve measuring condition measuring instrument: rheometer Physica MCR301 (manufactured by Anton Paar)
Measuring jig: CP50-1
Measurement temperature: 25 ° C

As a result, the isocyanurate type trifunctional viscosity modifiers (compounds B, D, E) of the present invention are higher and lower in evaluation with acrylic emulsions than the comparative product III that has been conventionally used as a viscosity modifier. It was found to show shear viscosity.
From the above results, it can be said that the product of the present invention is an unprecedented viscosity modifier that has a high viscosity at low shear.

  The viscosity modifier of the present invention expresses a higher low shear viscosity as compared with conventionally used viscosity modifiers. Therefore, it is considered that the performance of resin emulsions used for paints, inks, adhesives, pressure-sensitive adhesives, etc. can be effectively improved and used in a wider range.

Claims (5)

A viscosity modifier comprising a compound represented by the following general formula (1).

(In the formula, R ^{1 to} R ³ each independently represent a divalent hydrocarbon group having 4 to 16 carbon atoms, and R ^{4 to} R ⁶ each independently represent a hydrocarbon group having 12 to 36 carbon atoms. And x to z each independently represents a number of 10 to 500, and A ^{1 to} A ³ each independently represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms.) ^2. The viscosity modifier according to claim 1, wherein 50 mol% or more of the total of x A ¹ , y A ^2, and z A ^{3 in} the general formula (1) is an ethylene group. The viscosity modifier according to claim 1 or 2, wherein R ^{4 to} R ^{6 in} the general formula (1) are a 2-position branched alkyl group or a secondary alkyl group.   The viscosity regulator according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is a reaction product of an isocyanurate and an alkylene oxide adduct of a monohydric alcohol.   The resin emulsion composition which contains 0.01-10 mass parts of viscosity adjusting agents in any one of Claims 1-4 with respect to 100 mass parts of resin emulsions.

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