JP5266448B2 - Viscosity adjusting agent for water-based paint and paint comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous coating that has a big sag prevention effect, and does not have a bad influence on leveling property, popping prevention and water resistance, etc., and to provide a viscosity modifier added to the coating. <P>SOLUTION: This viscosity modifier for the aqueous coating includes a polyoxyalkylene compound represented by following formula (1): S<SP POS="POST">1</SP>-L(-U-L-S<SP POS="POST">2</SP>-L)<SB POS="POST">q</SB>-U-L-S<SP POS="POST">1</SP>(1), wherein S<SP POS="POST">1</SP>is a group represented by formula (2), S<SP POS="POST">2</SP>is a group represented by formula (3), L is a reaction residue of diisocyanate or diglycidyl ether, U is a group represented by formula (4), q is 0-2. Wherein Q is nonreducing disaccharide or trisaccharide, OA is oxyalkylene, Z is alkylene or arylene, n is 3-50, t is 2-4, and m is 5-25. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a viscosity modifier for water-based paints and a paint containing the same.

  In recent years, paints have rapidly become water-based, and there is a remarkable trend toward water-based thermosetting paints in industrial paint lines. In the near future, almost all automobile base coats and intermediate paints will become water-based. It has become. However, the main component of the solvent of water-based paints is water, so the effect of reducing the viscosity of the paint is low. To enable spray coating, the paint concentration (ratio of resin, pigment components, etc. in the paint) must be set low. In many cases, it is unavoidable. In this case, there is a problem that a problem that the paint sags (drops) after spray coating occurs. In order to prevent this, a viscosity adjusting agent (anti-sagging agent) is added, but this causes a negative cycle that further increases the viscosity. In addition, due to the strong hydrophilicity of the viscosity modifier, there is a problem that the water resistance of the coating film formed by the addition of the viscosity modifier decreases, and the development of a viscosity modifier that can solve these problems is desired. It was.

  As means for solving these problems, a core / shell type emulsion resin (A) having a crosslinked core and a hydrophobic shell, a viscosity modifier (B) having a bulky hydrophobic group at the end, and a relatively large amount Water-based paints (Patent Document 1) containing a hydrophobic solvent (C) and water-based paints (Patent Document 2) to which polyoxyalkylene urethane resins having strong hydrophobic alkyl groups at both ends are added are proposed. Yes.

Republished 2007-126134 JP 2001-254068 A

  In the water-based paint described in Patent Document 1, the use of a special emulsion resin and the use of a relatively large amount of a hydrophobic solvent tend to increase the price of the paint, and the use of a hydrophobic solvent is a problem. There is a case.

On the other hand, in the water-based paint described in Patent Document 2, the hydrophilicity of the polyoxyalkylene chain must be increased because of the influence of the hydrophobic groups at both ends constituting the urethane resin, resulting in a decrease in water resistance. There is a problem that there are cases. In addition, since the thickening mechanism is due to the networking of the emulsion resin, there is a problem that the leveling property is inevitably adversely affected if the dripping prevention effect is large.
Accordingly, an object of the present invention is to provide a water-based paint that can provide a large sag-preventing effect and that does not adversely affect leveling properties, anti-cracking properties, water resistance, and the like, and a viscosity modifier added thereto.

  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 feature of the viscosity modifier for paints of the present invention is that it contains the polyoxyalkylene compound (Y1) represented by the general formula (1).

^{S 1 - LG (-U- LG -S} 2 - LG) q -U- LG -S 1 (1)

However, ^{S 1} is the general formula a group represented by (2), based on ^{S 2} is represented by the general formula (3), LG is reactive residue of a diglycidyl ether of 10 to 50 carbon atoms, U is formula The group represented by (4), q represents 0, 1 or 2.

Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, OA is an oxyalkylene group having 2 to 4 carbon atoms, Z is an alkylene group or arylene having 2 to 15 carbon atoms A group, O is an oxygen atom, H is a hydrogen atom, n is an integer of 3 to 50, t is an integer of 2 to 4, m is an integer of 5 to 25, and OA of S ¹ unit or S ² unit the total number is an integer of ^{10~100, S 1, S 2,} LG, U, (OA) n, (OA) m, Q, n, m may be identical to or different from each other.

Moreover, the characteristics of the manufacturing method of the viscosity modifier for coatings of this invention are the non-reducible di- or trisaccharide (a1) 1 mol part, C2-C4 alkylene oxide (a2) 10-100 mol part, A step (1) of obtaining a compound (a12) from the chemical reaction (1) of:
A step (2) of obtaining a compound (a32) from a chemical reaction (2) of 1 mol part of a glycol (a3) having 2 to 15 carbon atoms and 10 to 50 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms; and Compound (a12) 1 mol part, Compound (a32) 0.1-0.75 mol part, C10-50 diglycidyl ether (a5) 0.5-1.5 mol part The point is that it includes the step (3) of obtaining the polyoxyalkylene compound (Y1) from the chemical reaction (4).

  The paint of the present invention is characterized by comprising an aqueous base paint and the above viscosity modifier, and the content of the viscosity modifier is 1 to 5% by weight based on the weight of the aqueous base paint and the viscosity modifier. The point is summarized.

  The viscosity adjusting agent for water-based paints according to the present invention provides a large sag-preventing effect and does not adversely affect leveling properties, anti-skid properties, water resistance, and the like.

  According to the method for producing a viscosity adjusting agent for paints of the present invention, the above viscosity adjusting agent can be obtained efficiently.

  Since the coating material of the present invention contains the above-described viscosity modifier, a large sag-preventing effect is obtained, and leveling properties, anti-cracking properties, water resistance and the like are improved.

Examples of the reaction residue (LD) of the diisocyanate having 6 to 20 carbon atoms include a group represented by —CO—NH—X—NH—CO—.

X includes alkylene, cycloalkylene, arylene, and aralkylene (arylalkylene), and a part of the hydrogen atoms contained in these groups is substituted with a halogen atom and / or alkoxy having 1 to 6 carbon atoms or the like. These groups may be bonded to each other through an oxa group (—O—) or a sulfonyl group (—SO ₂ —).

  Examples of the alkylene include alkylene having 4 to 8 carbon atoms, and examples include butylene, hexamethylene, and 2-ethylhexylene.

As the cycloalkylene, cycloalkylene having 6 to 15 carbon atoms and the like are used, and cyclohexylene, dicyclohexylene, methylcyclohexylene, trimethylcyclohexylene, nonylcyclohexylene,-(ch) -CH _2- (ch)- A group represented by —CH ₂ — (ch) —CH ₂ —, a group represented by — (ch) —C (CH ₃ ) ₂ — (ch) —, — (ch) —CH Examples include a group represented by ₂ CH ₂ — (ch) — and a group represented by — (tmch) —CH ₂ —. Note that (ch) represents cyclohexylene and (tmch) represents trimethylcyclohexylene (the same applies hereinafter). In addition to these, a group represented by-(ch) -O- (ch)-, a group represented by-(ch) -SO _2- (ch)-, chlorocyclohexylene, methoxycyclohexylene and the like can also be used. .

Arylene having 6 to 15 carbon atoms is used as arylene, and includes phenylene, tolylene, methylphenylene, ethylphenylene, tetramethylphenylene, xylylene, nonylphenylene, naphthylene, biphenylylene, dimethylbiphenylylene, anthrylene, phenanthrylene,-(ph ) -CH _2- (ph)-group,-(ph) -C (CH ₃ ) _2- (ph)-group,-(ph) -CH ₂ CH _2- (ph) And a group represented by —CH ₂ — (ch) —CH ₂ — and the like. In addition, (ph) represents phenylene (hereinafter the same). In addition to these, a group represented by-(ph) -O- (ph)-, a group represented by-(ph) -SO _2- (ph)-, bromophenylene, chloronaphthylene, chlorobiphenylene and methoxy Phenylene and the like can also be used.

  As the aralkylene, aralkylene having 7 to 18 carbon atoms is used, and examples thereof include phenylethylene, tolylbutylene, ethylphenylethylene, xylylhexylene, nonylphenylethylene, naphthylbutylene, biphenylylethylene and phenanthrylpropylene. It is done. In addition to these, bromophenylethylene, chlorobiphenylylethylene, methoxyphenylethylene, butoxynaphthylbutylene, diethoxybiphenylylethylene, and the like can also be used.

Of these X, alkylene, cycloalkylene and arylene are preferred, hexamethylene, a group represented by-(tmch) -CH _2- and xylylene, and particularly preferred is hexamethylene.

As the reaction residue of diglycidyl ether of 10 to 50 carbon atoms (LG), it includes residues epoxy groups diglycidyl ether of 10 to 50 carbon atoms and ring-opening reaction.

As a reaction residue of such diglycidyl ether, 2,11-dihydroxy-4,9-dioxadodecylene {—CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ( _OH) CH 2 -}, 2,6,10- trihydroxy-4,8-di oxa undecylenic _{{-CH 2 CH (OH) CH} 2 OCH 2 CH (OH) CH 2 OCH 2 CH (OH) CH 2 - }, 2,10-dihydroxy-4,8-dioxa-6,6-dimethylundecylene {—CH ₂ CH (OH) CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH (OH) CH ₂ —} , 2,13- dihydroxy-4,11-di oxa-tetramethyl decylene _{{-CH 2 CH (OH) CH} 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OCH 2 CH ( _H) CH 2 -}, 2,10- dihydroxy-4,8-dioxa-6-hydroxymethyl-6-ethyl undecylenic _{{-CH 2 CH (OH) CH} 2 OCH 2 C (C 2 H 5) (CH 2 OH) CH ₂ OCH ₂ CH (OH) CH ₂ —}, 2,10-dihydroxy-4,8-dioxa-6,6-bishydroxymethylundecylene {—CH ₂ CH (OH) CH ₂ OCH ₂ C (CH ₂ OH) ₂ CH ₂ OCH ₂ CH (OH) CH ₂ —}, and polyoxyalkylene (glycol / alkylene oxide adduct, etc., having 4 to 44 carbon atoms, alkylene having 2 to 4 carbon atoms) reaction of diglycidyl ether Examples include residues.

  q is 0, 1 or 2. Within this range, the surface activity (leveling properties, prevention of cracking, etc.) is further improved as well as the viscosity adjusting function.

  Examples of di- or trisaccharides that can form a residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide include sucrose, trehalose, isotrehalose, iso Saccharose, gentianose, raffinose, meletitose, planteose and the like are included. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of viscosity adjusting function, more preferably sucrose, trehalose and raffinose, and sucrose is particularly preferable from the viewpoint of supply ability and cost.

Among the alkylene group having 2 to 15 carbon atoms or the arylene group (Z), as alkylene, alkylene having 2 to 9 carbon atoms or the like is used, and ethylene, 3-oxapentylene (—CH ₂ CH ₂ OCH ₂ CH ₂ -), propylene, 3-oxa-2,4-dimethyl-pentylene _{(-CH 2 CH (CH 3)} OCH (CH 3) CH 2 -), butylene, hexamethylene, cyclohexylene, methylene-cyclohexylene-methylene (- CH ₂ C ₆ H ₁₀ CH ₂ —), methylcyclohexylene, trimethylcyclohexylene and the like.

Among (Z), as arylene, arylene having 6 to 15 carbon atoms is used, and phenylene, methylphenylene, ethylphenylene, tetramethylphenylene, xylylene, naphthylene, biphenylylene, dimethylbiphenylylene, anthrylene, phenanthrylene,-( ph) -CH _2- (ph)-group,-(ph) -C (CH ₃ ) _2- (ph)-group,-(ph) -CH ₂ CH _2- (ph )-And a group represented by -CH _2- (ch) -CH _2- (ph represents a phenylene group and ch represents a cyclohexenyl group).

Among these (Z), alkylene and arylene are preferable, and ethylene, propylene, hexamethylene, and a group represented by-(ph) -C (CH ₃ ) _2- (ph)-are particularly preferable. Is propylene.

  Examples of the oxyalkylene group (OA) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Of these, oxyethylene and oxypropylene are preferable from the viewpoint of the viscosity adjusting function, and more preferably a mixture of oxypropylene and oxyethylene. Moreover, oxypropylene and oxybutylene are preferable from the viewpoint of water resistance among the basic performances of the paint, and more preferably a mixture of oxypropylene and oxybutylene.

  When (OA-) n or (OA-) m contains a plurality of types of oxyalkylene groups, there is no limitation on the bonding order (block shape, random shape, and combinations thereof) and the content ratio of these oxyalkylene groups. .

  In the general formulas (2) and (3), when oxypropylene and / or oxybutylene and oxyethylene are included, the content ratio (mol%) of oxyethylene is 4 based on the total number of moles of oxyalkylene groups. Is preferably 10 to 10, more preferably 4 to 8. In this case, it is preferable that oxypropylene and / or oxybutylene is located at the end away from the reaction residue (Q). That is, when (OA-) n contains an oxyethylene group, it is preferable that the oxyethylene group is directly bonded to the reaction residue (Q). Moreover, when (OA-) n contains a plurality of types of oxyalkylene groups, it may contain either a block shape or a random shape.

  In the general formula (4), when oxypropylene and / or oxybutylene and oxyethylene are included, the content ratio (mol%) of oxyethylene is preferably 4 to 10 based on the total number of moles of oxyalkylene groups. More preferably, it is 4-8. In this case, it is preferable that the oxyethylene is located at the end away from the alkylene group or the arylene group (Z). That is, when (OA-) m contains an oxyethylene group, it is preferable that the oxyethylene group is bonded to the end away from (Z). Moreover, when (OA-) m contains a plurality of types of oxyalkylene groups, it may contain either a block shape or a random shape.

  n is preferably an integer of 3 to 50, more preferably an integer of 5 to 45, particularly preferably an integer of 10 to 45, and most preferably an integer of 15 to 40. Within this range, the viscosity adjustment function is further improved.

  t is preferably an integer of 2 to 4, more preferably 3. Within this range, the viscosity adjustment function is further improved.

  m is preferably an integer of 5 to 25, more preferably an integer of 7 to 23, particularly preferably an integer of 7 to 20, and most preferably an integer of 10 to 20. Within this range, the viscosity adjustment function is further improved.

The total number of OA contained in the S ¹ unit or S ² unit is preferably an integer of 10 to 100, more preferably an integer of 15 to 90, particularly preferably an integer of 15 to 80, most preferably 20 to 80. It is an integer. Within this range, the viscosity adjustment function is further improved.

  The viscosity modifier for water-based paints of the present invention may further contain a polyoxyalkylene compound (Y2) represented by the general formula (5).

_{^{S 1 -L (-S 2 -L)}} q -S 1 (5)

^{However, S 1,} S ^2, q is the general formula (1) and the same, L is the reaction residue of diglycidyl ether of the reaction residues (LD), or 10 to 50 carbon atoms diisocyanates having 6 to 20 carbon atoms (LG ) .

The total number of OA contained in the S ¹ unit or S ² unit is preferably an integer of 10 to 100, more preferably an integer of 20 to 100, particularly preferably an integer of 25 to 95, most preferably 30 to 30. An integer of 95. Within this range, the viscosity adjustment function is further improved.

  When the polyoxyalkylene compound (Y2) is contained, the content (% by weight) is preferably 10 to 150, more preferably 30 to 120, particularly preferably based on the weight of the polyoxyalkylene compound (Y1). 50-100. Within this range, the viscosity adjustment function is further improved.

The polyoxyalkylene compound (Y1) represented by the general formula (1) and the polyoxyalkylene compound (Y2) represented by the general formula (5) can be produced by applying a known chemical reaction.
For example, the polyoxyalkylene compound (Y1) represented by the general formula (1) includes 1 mole part of a non-reducing di- or trisaccharide (a1) and an alkylene oxide (a2) 10 to 100 having 2 to 4 carbon atoms. The step (1) of obtaining the compound (a12) from the chemical reaction (1) in the molar part;
A step (2) of obtaining a compound (a32) from a chemical reaction (2) of 1 mol part of a glycol (a3) having 2 to 15 carbon atoms and 10 to 50 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms; and Compound (a12) 1 mol part, Compound (a32) 0.1-0.75 mol part, C10-50 diglycidyl ether (a5) 0.5-1.5 mol part From the chemical reaction (4), it can be produced by a method including the step (3) of obtaining the polyoxyalkylene compound (Y1).

In addition , in chemical reaction (4), the usage-amount (mol part) of compound (a32) is 0.1 or more and less than 0.5, and the usage-amount (mole part) of diglycidyl ether (a5) is 0.5 or more and less than 1. In this case , in addition to the polyoxyalkylene compound (Y1), a polyoxyalkylene compound (Y2) is by-produced.

  Even in the production method other than the case of the above usage amount, when obtaining the polyoxyalkylene compound (Y1) represented by the general formula (1), the polyoxyalkylene compound (Y2) represented by the general formula (5) May be produced as a by-product, but may be used as it is as a mixture.

In addition to obtaining the polyoxyalkylene compound (Y2) represented by the general formula (5) together with the polyoxyalkylene compound (Y1) as described above, the step of obtaining the compound (a12) from the chemical reaction (1) (1) ); And 1 mol part of the compound (a12) and 0.5 to 0.75 mol part of the diisocyanate (a4) having 6 to 20 carbon atoms, or 1 mol part of the compound (a12) and carbon It can be produced by a method including the step (4) of obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (6) with 0.5 to 0.75 mol parts of several 10 to 50 diglycidyl ether (a5).

  That is, the polyoxyalkylene compound (Y1) and polyoxyalkylene compound (Y2) produced by these chemical reactions may have a distribution in the number of oxyalkylene groups, n, m, q, etc. In this case, Strictly speaking, it becomes a mixture of plural kinds of polyoxyalkylene compounds, and in this mixture, the polyoxyalkylene compound (Y1) represented by the general formula (1) and the polyoxyalkylene compound represented by the general formula (5) (Y2) is included.

  In the step (1) for obtaining the compound (a12), the use amount (mole part) of the alkylene oxide (a2) is preferably 10 to 100 per 1 part by mole of the non-reducing di- or trisaccharide (a1). More preferably, it is 15-90, Most preferably, it is 15-80, Most preferably, it is 20-80. Within this range, the viscosity adjustment function is further improved.

  In the step (2) for obtaining the compound (a32), the use amount (mole part) of the alkylene oxide (a2) is preferably 10 to 50 moles relative to 1 mole part of the glycol (a3) having 2 to 15 carbon atoms. More preferably, it is 14-46, Most preferably, it is 14-40, Most preferably, it is 20-40. Within this range, the viscosity adjustment function is further improved.

  In the step (3) of obtaining the polyoxyalkylene compound (Y1), the amount of the compound (a32) used (mol part) is preferably 0.1 to 0.75 with respect to 1 mol part of the compound (a12). More preferably, it is 0.15-0.72, Especially preferably, it is 0.17-0.7, Most preferably, it is 0.2-0.7. Within this range, the viscosity adjustment function is further improved.

  In addition, in the step (3), when it is desired to suppress the by-product of the polyoxyalkylene compound (Y2), the amount (mole part) of the compound (a32) used is 0. 5-0.75 is preferable, More preferably, it is 0.53-0.72, Especially preferably, it is 0.53-0.7, Most preferably, it is 0.55-0.7.

In the step (3), the amount (mole part) of the diglycidyl ether (a5) used is preferably 0.5 to 1.5, more preferably 0.6 to 1 part by mole of the compound (a12). 1.4, particularly preferably 0.7 to 1.4, most preferably 0.8 to 1.3. Within this range, the viscosity adjustment function is further improved.

In the step (3), if you want to suppress the by-production of the polyoxyalkylene compound (Y2), as the amount of diglycidyl ether (a5) (parts by mol), relative to compound (a12) 1 part by mol, 1-1.5 are preferable, More preferably, it is 1-1.4, Most preferably, it is 1.1-1.4, Most preferably, it is 1.1-1.3.

  In the step (4), the use amount (mole part) of the diisocyanate (a4) or diglycidyl ether (a5) is preferably 0.5 to 0.75, more preferably 1 mol part of the compound (a12). Is 0.53 to 0.72, particularly preferably 0.53 to 0.7, and most preferably 0.55 to 0.7. Within this range, the viscosity adjustment function is further improved.

  As the non-reducing disaccharide or trisaccharide (a1), the same disaccharide or trisaccharide that can constitute the reaction residue (Q) can be used, and the preferred range is also the same.

  As the alkylene oxide (a2), an alkylene oxide having 2 to 4 carbon atoms can be used, and examples thereof include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof. Of these, ethylene oxide and propylene oxide are preferable from the viewpoint of the viscosity adjusting function, and a mixture of propylene oxide and ethylene oxide is more preferable. In addition, propylene oxide and butylene oxide are preferable from the viewpoint of water resistance among the basic performances of the paint, and more preferable is a mixture of propylene oxide and butylene oxide.

  In the chemical reaction (1) of the non-reducing disaccharide or trisaccharide (a1) and the alkylene oxide (a2) in the step (1), when a plurality of types of alkylene oxide are used, the reaction order (block, random and these) The combination) and the use ratio are not limited, but it is preferable to include a block shape or a combination of a block shape and a random shape. Moreover, when it contains EO, as for the usage-amount (mol%) of EO, 4-10 are preferable based on the total number of moles of alkylene oxide, More preferably, it is 4-8. When EO and PO or / and BO are included, it is preferable to react PO and / or BO after the reaction of di- or trisaccharide (a1) with EO.

  In the chemical reaction (2) of the glycol (a3) having 2 to 15 carbon atoms and the alkylene oxide (a2) in the step (2), when a plurality of types of alkylene oxide are used, the reaction order (block, random and these) The combination) and the use ratio are not limited, but it is preferable to include a block shape or a combination of a block shape and a random shape. When EO is used, the use ratio (mol%) of EO is preferably 4 to 10, more preferably 4 to 8, based on the total number of moles of alkylene oxide. In this case, it is preferable to react ethylene oxide after reacting propylene oxide and / or butylene oxide.

As the glycol (a3) having 2 to 15 carbon atoms, alkylene diol {ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol, hexamethylene glycol, cyclohexyl glycol, methyl Cyclohexyl glycol, trimethylhexyl glycol and di (hydroxymethyl) cyclohexane etc.} and arylenediol {hydroquinone, catechol, methylhydroquinone, ethylhydroquinone, tetramethylhydroquinone, xylylene glycol, naphthalene glycol, biphenyl glycol, dimethylbiphenyl glycol, anthracene biphenyl, Phenanthrenebiphenyl, bisphenol F {HO—C ₆ H ₄ —CH ₂ —C ₆ H ₄ -OH}, 1,2- bis (4-hydroxyphenyl) ethane _{{HO-C 6 H 4 -CH} 2 CH 2 -C 6 H 4 -OH} and bisphenol _{A {HO-C 6 H 4} - C (CH ₃ ) ₂ -C ₆ H ₄ —OH} etc.}. Among these, ethylene glycol, propylene glycol, hexamethylene glycol and bisphenol A are preferable, and propylene glycol is more preferable.

  Examples of the diisocyanate (a3) having 6 to 20 carbon atoms include alkylene diisocyanate, cycloalkylene diisocyanate, arylene diisocyanate, and aralkylene diisocyanate.

  Examples of the alkylene diisocyanate include alkylene diisocyanates having 4 to 8 carbon atoms, such as butylene diisocyanate, hexamethylene diisocyanate and 2-ethylhexylene diisocyanate.

As the cycloalkylene diisocyanate, cycloalkylene diisocyanate having 6 to 15 carbon atoms and the like are used, and cyclohexylene diisocyanate, dicyclohexylene diisocyanate, methylcyclohexylene diisocyanate, trimethylcyclohexylene diisocyanate, nonylcyclohexylene diisocyanate, OCN- (ch)- CH ₂ - diisocyanate represented by (ch) -NCO, OCN-CH 2 - (ch) a diisocyanate represented by _{-CH 2 -NCO, OCN- (ch)} -C (CH 3) 2 - (ch) - diisocyanate represented by _{NCO, OCN- (ch) -CH 2} CH 2 - diisocyanate represented by (ch) diisocyanate represented by -NCO and OCN- (tmch) -CH ₂ -NCO (isophorone diisocyanate) Doors and the like. In addition to these, diisocyanates represented by OCN- (ch) -O- (ch) -NCO, diisocyanates represented by OCN- (ch) -SO _2- (ch) -NCO, chlorocyclohexylene diisocyanate and methoxycyclohexyl Sylene diisocyanate and the like can also be used.

As the arylene diisocyanate, arylene diisocyanate having 6 to 15 carbon atoms is used, and phenylene diisocyanate, tolylene diisocyanate, methylphenylene diisocyanate, ethylphenylene diisocyanate, tetramethylphenylene diisocyanate, xylylene diisocyanate, nonylphenylene diisocyanate, naphthylene diisocyanate, Biphenylylene diisocyanate, dimethyl biphenylylene diisocyanate, antolylene diisocyanate, phenanthrylene diisocyanate, diisocyanate represented by OCN- (ph) -CH _2- (ph) -NCO, OCN- (ph) -C (CH ₃ ) ₂ Diisocyanate represented by-(ph) -NCO, OCN- (ph) -CH ₂ CH _2- (ph) -NCO And diisocyanate represented by OCN—CH ₂ — (ch) —CH ₂ NCO—. Other than these, diisocyanate represented by OCN- (ph) -O- (ph) -NCO, diisocyanate represented by OCN- (ph) -SO _2- (ph) -NCO, bromophenylene diisocyanate, chloronaphthylene Isocyanate, chlorobiphenylene diisocyanate, methoxyphenylene diisocyanate, and the like can also be used.

  As the aralkylene diisocyanate, aralkylene diisocyanate having 7 to 18 carbon atoms is used, and phenylethylene diisocyanate, tolyl butylene diisocyanate, ethylphenylethylene diisocyanate, xylylhexylene diisocyanate, nonylphenylethylene diisocyanate, naphthyl butylene diisocyanate, biphenylylethylene. Examples include diisocyanate and phenanthrylpropylene diisocyanate. Besides these, bromophenylethylene diisocyanate, chlorobiphenylylethylene diisocyanate, methoxyphenylethylene diisocyanate, butoxynaphthyl butylene diisocyanate, diethoxybiphenylylethylene diisocyanate, and the like can also be used.

Among these diisocyanates, alkylene diisocyanate, cycloalkylene diisocyanate and arylene diisocyanate are preferable, and diisocyanate (isophorone diisocyanate represented by hexamethylene diisocyanate (hereinafter referred to as HDI) or OCN- (tmch) -CH ₂ -NCO is more preferable. (Hereinafter referred to as IPDI) and xylylene diisocyanate (hereinafter referred to as XDI), particularly preferably hexamethylene diisocyanate.

  As the diglycidyl ether (a5) having 10 to 50 carbon atoms, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane And diglycidyl ether and pentaerythritol diglycidyl ether, and polyalkylene glycol diglycidyl ether (polyoxyethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether and polyoxytetramethylene ether glycol diglycidyl ether, etc.) And those having 10 to 50 carbon atoms). Of these, 1,4-butanediol diglycidyl ether and polyoxypropylene glycol diglycidyl ether are preferable, and polyoxypropylene glycol diglycidyl ether is more preferable.

  Chemical reaction (1) of non-reducing di- or trisaccharide (a1) and alkylene oxide (a2) and chemical reaction (2) of glycols (a3) and (a2) having 2 to 15 carbon atoms are anionic polymerization, It may be carried out in any form such as cationic polymerization or coordination anionic polymerization. These polymerization forms may be used alone or in combination according to the degree of polymerization.

A reaction catalyst can be used for the chemical reaction (1, 2) with the alkylene oxide (a2). In addition, when using the amide demonstrated below as a reaction solvent, it is not necessary to use a reaction catalyst.
As the reaction catalyst, a conventionally used alkylene oxide addition reaction catalyst or the like can be used. Alkali metal or alkaline earth metal hydroxides (potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (Potassium methylate and cesium ethylate), alkali metal or alkaline earth metal carbonates (potassium carbonate, cesium carbonate, barium carbonate, etc.), tertiary amines having 3 to 24 carbon atoms (trimethylamine, trioctylamine, Triethylenediamine and tetramethylethylenediamine) and Lewis acids (such as stannic chloride and boron trifluoride) are used. Of these, alkali metal hydroxides and tertiary amines are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.

  When a reaction catalyst is used, the amount used (% by weight) is the total weight of the non-reducing disaccharide or trisaccharide (a1) and alkylene oxide (a2), or the total of glycol (a3) and alkylene oxide (a2). Based on the weight, 0.05 to 2 is preferable, more preferably 0.1 to 1, and particularly preferably 0.2 to 0.6.

  When using a reaction catalyst, it is preferable to remove the reaction catalyst from the reaction product. As the method, an alkali adsorbent such as a synthetic aluminosilicate {for example, trade name: Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd. , "KYOWARD" is a registered trademark of the company} (Japanese Patent Laid-Open No. 53-123499, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (Japanese Patent Publication No. 49-14359) And a method using an ion exchange resin (Japanese Patent Laid-Open No. 51-23211) and a method of filtering a carbonate formed by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000).

  The end point of removal of the reaction catalyst is preferably a CPR (Controlled Polymerization Rate) value of 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. CPR is measured in accordance with JIS K1557-4: 2007.

  As the reaction vessel for the chemical reaction (1, 2), it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring. The reaction atmosphere is preferably an inert gas atmosphere (such as argon, nitrogen and carbon dioxide) in which the inside of the reaction apparatus is vacuumed or dried before introducing the alkylene oxide (a2) into the reaction system. Moreover, as reaction temperature (degreeC), 80-150 are preferable, More preferably, it is 90-130. The reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, more preferably 0.5 or less.

  The end point of the reaction can be confirmed by the following method. That is, when the reaction temperature is kept constant for 15 minutes, the reaction end point is set when the decrease in the reaction pressure (gauge pressure) is 0.001 MPa or less. The required reaction time is usually 4 to 12 hours.

  It is preferable to use a reaction solvent for the chemical reaction (1) of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). As the reaction solvent, those having no active hydrogen are preferred, and more preferably non-reducing disaccharides or trisaccharides (a1), alkylene oxides (a2) and products (a12) produced by these reactions are dissolved. Is preferred.

As such a reaction solvent, alkyl amides having 3 to 8 carbon atoms and heterocyclic amides having 5 to 7 carbon atoms can be used.
Examples of the alkylamide include N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-propylacetamide, 2-dimethylaminoacetaldehyde dimethylacetal and the like.

  Examples of the heterocyclic amide include N-methylpyrrolidone, N-methyl-ε-caprolactam, and N, N-dimethylpyrrolecarboxylic acid amide.

  Of these, alkylamide and N-methylpyrrolidone are preferred, DMF, N, N-dimethylacetamide and N-methylpyrrolidone are more preferred, DMF and N-methylpyrrolidone are most preferred, and DMF is most preferred.

  When a reaction solvent is used, the amount used (% by weight) is 20 to 20 based on the weight of the compound (a12) produced by the chemical reaction (1) between the di- or trisaccharide (a1) and the alkylene oxide (a2). 200 is preferable, 40 to 180 is more preferable, and 60 to 150 is particularly preferable.

  When a reaction solvent is used, it is preferable to remove the reaction solvent after the reaction. The residual amount (% by weight) of the reaction solvent is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.01 or less, based on the weight of the polyoxyalkylene compound (Y1). is there. The residual amount of the reaction solvent can be determined by gas chromatography using an internal standard substance.

As a method for removing the reaction solvent, vacuum distillation, adsorption removal and the like can be applied, and it is preferable to further remove by adsorption after vacuum distillation.
As conditions for distilling off under reduced pressure, conditions such as distilling off at 100 to 150 ° C. under reduced pressure of 0.6 to 27 kPa can be applied.
As the adsorption removal, a method of treatment using an alkali adsorbent {eg, trade name: Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd.} such as synthetic aluminosilicate can be applied. For example, when using KYOWARD 700, the addition amount (% by weight) of the alkali adsorbent is about 0.1 to 10 based on the weight of the compound (a12), the processing temperature is about 60 to 120 ° C., and the processing time is About 0.5 to 5 hours. Subsequently, the residual amount of the reaction solvent can be reduced by removing the alkali adsorbent by filtration using filter paper or filter cloth.

In the chemical reaction (5) (addition reaction), when an isocyanate (aliphatic or alicyclic di-isocyanate etc .; for example, HDI, IPDI ) having a low reaction rate is used, a reaction catalyst is used for the purpose of shortening the reaction time. Can do. As the reaction catalyst, dibutyltin dilaurate, stannous octoate, triethylenediamine and the like are common.

For the chemical reaction (5), a sealed container capable of heating, cooling and stirring can be used. 70-150 are preferable and, as for reaction temperature (degreeC), More preferably, it is 90-130. The reaction atmosphere is preferably a dry inert gas atmosphere. In addition, the reaction end point can be confirmed by the following method or the like. That is, in the isocyanato group content measuring method using a dioxane solution of di-n-butylamine, the end point of the reaction is the time when the isocyanato group content is 0.01% by weight or less.

  A reaction catalyst can be used for the chemical reaction (4) and the chemical reaction (6) (epoxy ring-opening reaction). Such a catalyst is the same as that used for the chemical reaction (1, 2) with the alkylene oxide (a2), and a known catalyst (Japanese Patent Application Laid-Open No. 2004-224945) can be applied.

  The end point of the reaction can be performed by the disappearance of the epoxy group. The epoxy group is quantified by cetyltrimethylammonium bromide (CTAB) method (JIS K7236) in which hydrogen halide (HB) is generated from perchloric acid and a quaternary ammonium salt (CTAB) and reacted with the epoxy group. : Conforming to ISO3001: 1999) is applicable.

  Chemical reaction (4) and chemical reaction (6) are the same epoxy ring-opening reaction as chemical reaction (1) and chemical reaction (2), and the reaction apparatus, catalyst and removal thereof are also the same.

Examples of the polyoxyalkylene compound (Y1) include compounds shown in Table 1. {The compounds described in columns 1 to 18 are to be read as reference compound (Y1) ′. } . Examples of the polyoxyalkylene compound (Y2) include compounds shown in Table 2.

Q1 represents a sucrose reaction residue, Q2 represents a trehalose reaction residue, and Q3 represents a raffinose reaction residue. P represents oxypropylene, E represents oxyethylene, and B represents oxybutylene. These subscripts represent the number of moles per mole of a non-reducing di- or trisaccharide residue {general formula (1 ) Corresponding to the total number of OA contained in S ¹ unit or S ² unit. In OA, / means a block shape, and • means a random shape.

  Further, DEG represents a reaction residue of diethylene glycol, DPG represents a reaction residue of dipropylene glycol, HG represents a reaction residue of hexamethylene glycol, and BPA represents a reaction residue of bisphenol A. P represents oxypropylene, E represents oxyethylene, B represents oxybutylene, and these subscripts represent the number of moles per mole of alkylene or arylene (Z) {2 of m in the general formula (4), respectively. Represents a double value (2 m)}. In OA, / means a block shape, and • means a random shape.

LD in the column (a4) corresponds to LG {reference compound (Y1) ′} in the general formula ( 1) or L in the general formula (5), D1 is a reaction residue of hexamethylene diisocyanate, and D2 is isophorone. The reaction residue of diisocyanate, D3 represents the reaction residue of xylylene diisocyanate.

Further, LG in the column (a5) corresponds to LG in the general formula (1) or L in the general formula (5), and G1 is polyoxyethylene (1.5 mol), polyoxypropylene (15 mol), polyoxy The reaction residue of ethylene (1.5 mol) (pluronic type in which polyoxyethylene blocks are added to both ends of polyoxypropylene) glycol diglycidyl ether, G2 is the reaction residue of 1,6-hexanediol diglycidyl ether G3 represents a reaction residue of polyoxypropylene glycol (3 mol) diglycidyl ether, and G4 represents a reaction residue of polyoxypropylene glycol (7 mol) diglycidyl ether.
Q corresponds to general formula (1) or (5) .

Among these polyoxyalkylene compounds (Y1), No. Polyoxyalkylene compounds are preferred are represented by 20,21,22,23,25,27,29,30,31,33,35,40,42 or 43, more preferably No. 22,25,29,31,40 or polyoxyalkylene compound represented by 43, particularly preferably No. A polyoxyalkylene compound represented by 25 or 40.

  Of these polyoxyalkylene compounds (Y2), No. The polyoxyalkylene compounds represented by 46, 48, 49, 50, 56, 59, 60, 63 or 65 are preferred, and more preferably It is a polyoxyalkylene compound represented by 46, 48, 50, 60 or 63.

  In the viscosity modifier for coatings of the present invention, known additives (antifoaming agents, wetting agents, film-forming regulators) are necessary as components other than the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2). Etc.) and / or a solvent or the like.

  SN Deformer 180 and 184 (manufactured by San Nopco) as defoaming agents, SN Wet 125, 126 and 984 (manufactured by San Nopco) as wetting agents, and Texanol (Eastman) as film forming regulators. “Texanol” manufactured by Chemical Corporation is a registered trademark of Yoshimura Oil Chemical Co., Ltd.).

  When these additives are contained, the content (% by weight) thereof is preferably 1 to 20 based on the weight of the polyoxyalkylene compound (Y1).

  As the solvent, water, a water-soluble organic solvent, or the like can be used. Examples of water include ion exchange water, distilled water, tap water, and industrial water. Examples of the water-soluble organic solvent include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropanol), ketones having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), and ethers having 2 to 6 carbon atoms (dimethyl ether). , Ethyl cellosolve and butyl cellosolve) and ether esters having 4 to 6 carbon atoms (e.g., butyl cellosolve acetate), and the like.

  When the solvent is contained, the content (% by weight) is preferably 1 to 30 based on the weight of the polyoxyalkylene compound (Y1).

  When the viscosity modifier for water-based paints of the present invention contains a polyoxyalkylene compound (Y2), an additive and / or a solvent, there is no limitation on the production method as long as these can be mixed uniformly with the polyoxyalkylene compound (Y1). For example, a polyoxyalkylene compound (Y1), a polyoxyalkylene compound (Y2), an additive, and / or a solvent are added at 20 to 80 ° C. in the presence or absence of an inert gas (nitrogen gas or the like). A method of stirring and mixing at a degree can be applied.

  The viscosity adjusting agent for paints of the present invention can be applied to water-based paints, and among these, it is suitable for water-based emulsion paints, and is particularly suitable for thermosetting water-based paints (such as automotive topcoat water-based paints). Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints.

  Since the viscosity modifier for water-based paints of the present invention is excellent in surface activity and the like, it can be used as an additive for improving the viscosity of paints. Tension reducing agent (including curtain flow coatability improver and spray optimization agent), antifoaming agent (including foam suppressor, foam breaker and foam stabilizer), anti-icing agent, anti-fogging agent, fingerprint adhesion prevention It can be widely used as an agent, an anti-skinning agent (a water-based paint prevents the phenomenon of solidification of the surface of the paint during storage in a container) and other paint additives, and can also be used as these raw materials.

  The amount of use (% by weight) of the viscosity modifier for paints of the present invention is appropriately determined according to the application and the like. For example, when used for water-based paints, the amount is 1 based on the weight of the water-based base paint and viscosity modifier. -5 is preferable, More preferably, it is 1.5-4.5, Most preferably, it is 2-4.

  The timing of adding the viscosity modifier for paint of the present invention to the paint is also during the paint production process (for example, paint resin dissolution process, emulsion dilution process, pigment dispersion process, or process of blending various additives into the paint). Good.

  The paint of the present invention preferably contains a flaky filler in addition to the above viscosity modifier. When the flaky filler is contained, the flaky filler and the secondary hydroxyl group present in the saccharide constituting the polyoxyalkylene compound (Y1, Y2) are hydrogenated during coating at a room temperature (approximately 20 ° C.) to around 40 ° C. Viscosity is imparted to the water-based paint by bonding, while the above-mentioned hydrogen bond disappears at the time of heat curing, and the surface activity inherent in the polyoxyalkylene compound (Y1, 2) is exhibited. It is considered that defects such as armpits are prevented and an effect excellent in leveling property (smoothness) is exhibited. In addition, since the viscosity modifier of the present invention has few hydrophilic parts (secondary hydroxyl groups and oxyethylene groups present in saccharides), the water resistance of the formed coating film is hardly lowered.

  As the flake filler, aluminum flake pigment, colored aluminum flake pigment, metal titanium flake pigment, stainless steel flake pigment, plate-like iron oxide pigment, metal oxide-coated mica pigment, metal oxide-coated silica flake pigment, metal oxide-coated glass Examples include flake pigments and graphite.

  The paint containing the viscosity adjusting agent for paints of the present invention can be applied to an object to be coated by a usual method, such as brush coating, roller coating, bell coating, air spray coating, airless coating, roll coater coating and flow. Coating methods such as coater coating can be applied. The drying method may be normal drying or baking drying, and baking drying is performed according to a conventional method, for example, using an electric hot air dryer, an indirect hot air oven, a direct hot air oven, a far infrared oven, etc. It can be carried out by holding the coating film at 250 ° C. for several tens of seconds to 30 minutes.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”. However, Examples 9 to 12, 15, 16, 18, and 19 shall be read as Reference Examples 9 to 12, 15, 16, 18, and 19, respectively.

<Production Example 1>
In a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, pressurizing with nitrogen, and depressurization with a vacuum pump, 342 parts (1 mol part) of refined granulated sugar {Sucrose manufactured by Taiyo Co., Ltd.), N, N-dimethylformamide (DMF) {Mitsubishi Gas Chemical Co., Ltd., hereinafter the same} 1000 parts were added. Next, the operation of pressurizing with nitrogen gas to 0.4 MPa and discharging until 0.02 MPa was repeated three times (hereinafter abbreviated as “nitrogen replacement”). Thereafter, the temperature was raised to 100 ° C. while stirring, and then 580 parts (10 mole parts) of propylene oxide (PO) was dropped over 4 hours at the same temperature, and stirring was further continued for 4 hours at the same temperature to leave the remaining PO. Completely reacted (hereinafter, description of the operation for completely reacting the remaining PO etc. is abbreviated as “reacted”). Next, using an oil diffusion vacuum pump {MODEL SW-150, manufactured by Sato Vacuum Co., Ltd.}, DMF is removed at a reduced pressure of 1.3 to 13 kPa at 120 ° C. (hereinafter abbreviated as “DMF removed”). As a result, a sucrose / PO 10 molar adduct (S1) was obtained.

<Production Example 2>
In the same pressure resistant reaction vessel as in Production Example 1, 922 parts (1 mole part) of sucrose / PO adduct (S1) and potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. It is displayed as the net equivalent converted amount. Thereafter, the same} 3 parts were added and replaced with nitrogen, and further dehydrated at 120 ° C. using an oil diffusion vacuum pump under reduced pressure of 0.6 to 1.3 kPa (hereinafter abbreviated as “dehydration”). Next, 580 parts (10 mole parts) of (PO) was dropped and reacted at 100 ° C. with reduced pressure to obtain a polymer. Next, after adding 25 parts of deionized water (approximately 2% by weight of the polymer, hereinafter the same) at 90 ° C., KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd., “KYOWARD” is registered by the company) Trademark} 45 parts (amount of about 3% by weight of the polymer, hereinafter the same) was added and stirred for 1 hour at the same temperature. 2 Filter paper (manufactured by Toyo Filter Paper Co., Ltd.) is used to remove the Kyodo word, and further dehydrated at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa (hereinafter abbreviated as “Kyo word treatment”). To obtain a sucrose / PO20 molar adduct (S2).

<Production Example 3>
In a pressure resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of sucrose / PO 10 mole adduct (S1) and 5 parts of potassium hydroxide were added for dehydration. Subsequently, 1740 parts (30 mole parts) of (PO) was dropped and reacted at 100 ° C. with reduced pressure. Next, Kyoward treatment was performed to obtain a sucrose / PO 40 mol adduct (S3).

<Production Example 4>
In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of sucrose / PO 10 mole adduct (S1) and 7.5 parts of potassium hydroxide were added for dehydration. Subsequently, 2100 parts (50 mole parts) of (PO) were dropped and reacted at 100 ° C. with reduced pressure. Next, Kyoward treatment was performed to obtain a sucrose / PO 60 mol adduct (S4).

<Production Example 5>
In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of sucrose / PO 10 mole adduct (S1 mole) and 10 parts of potassium hydroxide were added for dehydration. Subsequently, 4060 parts (70 mol parts) of (PO) were dropped and reacted at 100 ° C. with reduced pressure. Next, Kyoward treatment was performed to obtain a sucrose / PO 80 mol adduct (S5).

<Production Example 6>
In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of sucrose / PO 10 mole adduct (S1) and 2.6 parts of potassium hydroxide were added for dehydration. Subsequently, 370 parts (5 mol parts) of 1,2-butylene oxide (BO) was dropped and reacted at 100 ° C. with reduced pressure. Next, Kyoward treatment was performed to obtain an adduct (S6) of sucrose / PO10 mol / BO5 mol.

<Production Example 7>
In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of sucrose / PO 10 mole adduct (S1) and 11 parts of potassium hydroxide were added for dehydration. Subsequently, 176 parts (4 mol parts) of ethylene oxide (EO) was added dropwise and reacted at 100 ° C. with reduced pressure. Further, 4408 parts (76 mole parts) of (PO) was dropped and reacted. Next, Kyoward treatment was performed to obtain an adduct (S7) of sucrose / PO 10 mol / EO 4 mol / PO 76 mol.

<Production Example 8>
In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of sucrose / PO 10 mole adduct (S1) and 12 parts potassium hydroxide were added for dehydration. Subsequently, 176 parts (4 mol parts) of ethylene oxide (EO) was added dropwise and reacted at 100 ° C. with reduced pressure. Further, 4988 parts (86 mole parts) of (PO) was dropped and reacted. Next, Kyoward treatment was performed to obtain an adduct (S8) of sucrose / PO10 mol / EO4 mol / PO86 mol.

<Production Example 9>
To a pressure resistant reactor similar to Production Example 1, 504 parts (1 mole part) of raffinose {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1500 parts of DMF were added and replaced with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and 1160 parts (20 mole parts) of (PO) was dropped and reacted at the same temperature. Next, DMF was removed to obtain a raffinose / PO 20 molar adduct (S9).

<Production Example 10>
In a pressure resistant reaction vessel similar to Production Example 1, 1664 parts (1 mole) of raffinose / PO 20 mole adduct (S9) and 8 parts of potassium hydroxide were added for dehydration. Subsequently, (PO) 2320 (40 mol parts) was dropped and reacted at 100 ° C. with reduced pressure. Next, Kyoward treatment was performed to obtain a raffinose PO 60 mol adduct (S10).

<Production Example 11>
In the same pressure resistant reaction vessel as in Production Example 1, 106 parts (1 part by mole) of diethylene glycol {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “deg”} and 1.5 parts of potassium hydroxide were added. Thereafter, the atmosphere was replaced with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 812 parts (14 mole parts) of (PO) were dropped and reacted at the same temperature. Next, Kyoward treatment was carried out to obtain a deg / PO14 molar adduct (U1).

<Production Example 12>
Into the same pressure-resistant reaction vessel as in Production Example 1, 918 parts (1 mole part) of deg / PO 14 mole adduct (U1) and 3.5 parts of potassium hydroxide were charged, and then purged with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 928 parts (16 mole parts) of (PO) was dropped and reacted at the same temperature. Next, Kyoward treatment was performed to obtain a deg / PO 30 molar adduct (U2).

<Production Example 13>
Into the same pressure-resistant reaction vessel as in Production Example 1, 918 parts (1 mole part) of deg / PO 14 mole adduct (U1) and 6 parts of potassium hydroxide were added, and then purged with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 2088 parts (36 mole parts) of (PO) were dropped and reacted at the same temperature. Next, Kyoward treatment was performed to obtain a deg / PO 50 molar adduct (U3).

<Production Example 14>
In a pressure resistant reactor similar to Production Example 1, dipropylene glycol {reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “dpg”} 134 parts (1 mole part) and 1.5 parts of potassium hydroxide Then, nitrogen was substituted. Thereafter, the temperature was raised to 100 ° C. with stirring, and then 580 parts (10 mole parts) of (PO) was dropped and reacted at the same temperature. Next, Kyoward treatment was performed to obtain a dpg / PO10 molar adduct (U4).

<Production Example 15>
Into a pressure-resistant reaction vessel similar to Production Example 1, 714 parts (1 mol part) of dpg / PO 10 mol adduct (U4) and 2.5 parts of potassium hydroxide were added, followed by nitrogen substitution and dehydration. Thereafter, the temperature was raised to 100 ° C. with stirring, and then 580 parts (10 mole parts) of (PO) was dropped and reacted at the same temperature. Next, Kyoward treatment was performed to obtain a dpg / PO20 molar adduct (U5).

<Production Example 16>
Into a pressure-resistant reaction vessel similar to Production Example 1, 714 parts (1 mol part) of dpg / PO 10 mol adduct (U4) and 4.5 parts of potassium hydroxide were added, followed by nitrogen substitution and dehydration. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1508 parts (26 mole parts) of (PO) were dropped and reacted at the same temperature. Furthermore, 176 parts (4 mol parts) of (EO) was dropped and reacted. Next, Kyoward treatment was performed to obtain a dpg / PO36 mol / EO4 mol adduct (U6).

<Production Example 17>
Into a pressure resistant reactor similar to Production Example 1, 714 parts (1 mol part) of dpg / PO 10 mol adduct (U4) and 5 parts of potassium hydroxide were added, followed by nitrogen substitution and dehydration. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1856 parts (32 mole parts) of (PO) were dropped and reacted. Furthermore, 176 parts (4 mol parts) of (EO) was dropped and reacted. Next, Kyoward treatment was performed to obtain a dpg / PO42 mol / EO4 mol adduct (U7).

<Production Example 18>
Into a pressure-resistant reaction vessel similar to Production Example 1, 134 parts (1 mole part) of dpg and 1.5 parts of potassium hydroxide were added, and then purged with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 754 parts (13 mole parts) of (PO) were dropped and reacted at the same temperature. Further, 132 parts (3 parts by mole) of (EO) were dropped and reacted to obtain an adduct of dpg / PO13 moles / EO3 moles (EO 1.5 moles—PO15 moles—1.5 moles of pluronic glycol). Next, 112.2 parts (2 mole parts) of potassium hydroxide was added as a 50% aqueous solution and then dehydrated. Further, 189.6 parts (2.05 mol parts) of epichlorohydrin {manufactured by Kashima Chemical Co., Ltd.} was added dropwise at 40 ° C. with stirring for 3 hours. Further, the mixture was stirred at the same temperature for 3 hours and then subjected to Kyoward treatment to obtain pluronic glycol (EO 1.5 mol-PO 15 mol-EO 1.5 mol) diglycidyl ether (g1). The epoxy equivalent was 570 (g / eq).

<Example 1>
In a reaction vessel capable of stirring, heating, cooling, and depressurization by a vacuum pump, 4506 parts (3 mol parts) of sucrose / PO 20 mol adduct (S2) obtained in Production Example 2 and dpg / PO 36 mol obtained in Production Example 16 / EO 4 mol adduct (U6) 4796 parts (2 mol parts) and 14 parts of sodium hydroxide (an amount that is about 0.1% of the final total charge amount) were charged and dehydrated. Thereafter, 4560 parts (4 mole parts) of pluronic glycol (EO 1.5 mole-PO15 mole-EO 1.5 mole) diglycidyl ether (g1) obtained in Production Example 18 was added and reacted at 130 ° C. for 6 hours to form an epoxy group. The disappearance was confirmed. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound (Y101). And this polyoxyalkylene compound (Y101) was used as the viscosity modifier (1) for water-based paints of this invention.

<Examples 2 to 8>
“Sucrose / PO 20 mol adduct (S2) 4506 parts (3 mol parts)”, “dpg / PO 36 mol / EO 4 mol adduct (U6) 4796 parts (2 mol parts)” and “Pluronic glycol (EO 1.5 mol − PO15 mol-EO 1.5 mol) diglycidyl ether (g1) 4560 parts (4 mol parts) "was changed to the compounds shown in Table 3 and the number of moles used, respectively. Oxyalkylene compounds (Y102) to (Y108) and viscosity modifiers (2) to (8) of the present invention were obtained.
In addition, the usage-amount of sodium hydroxide was adjusted so that it might become about 0.1% of a total preparation amount.

<Example 9>
In the same reaction vessel as in Example 1, 3688 parts (4 mol parts) of sucrose / PO 10 mol adduct (S1) obtained in Production Example 1 and 3006 parts of deg / PO 50 mol adduct (U3) obtained in Production Example 13 (3 mol parts) and 1008 parts (6 mol parts) of HDI (d1) were charged and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour with stirring, and stirring was continued for 6 hours at the same temperature. After confirming disappearance of the isocyanate group, a polyoxyalkylene compound (Y109) was obtained. And this polyoxyalkylene compound (Y109) was used as the viscosity modifier (9) of this invention as it was.

<Examples 10 to 12>
"Sucrose / PO 10 mol adduct (S1) 3688 parts (4 mol parts)", "deg / PO 50 mol adduct (U3) 3006 parts (3 mol parts)" and HDI (d1) 1008 parts (6 mol parts) " Were changed to the compounds shown in Table 3 and the number of moles used, respectively, in the same manner as in Example 9, polyoxyalkylene compounds (Y110) to (Y112) and the viscosity modifiers (10) to (10) of the present invention ( 12) was obtained.

<Example 13>
“Sucrose / PO 20 mol adduct (S2) 4506 parts (3 mol parts)”, “dpg / PO 36 mol / EO 4 mol adduct (U6) 4796 parts (2 mol parts)” and “Pluronic glycol (EO 1.5 mol − PO15 mol-EO 1.5 mol) diglycidyl ether (g1) 4560 parts (4 mol parts) ", respectively, raffinose PO 60 mol adduct (S10) 19920 parts (5 mol parts) obtained in Production Example 10, production example The same procedure as in Example 1 except that 714 parts (1 mol part) of the dpg / PO 10 mol adduct (U4) obtained in 14 and 4560 parts (4 mol part) obtained in Production Example 18 were used. , Polyoxyalkylene compound (Y113) {(S10) 2 mole part, (U1) 1 mole part and (g1) 2 mole part reactant} and polyoxyalkylene compound (Y201) { S10) to obtain a 3 molar parts, and (g1) a mixture of reactants} of 2 molar parts (Y1Y201) and viscosity modifier of the present invention (13).

<Examples 14 to 16>
“Sucrose / PO 20 mol adduct (S2) 4506 parts (3 mol parts)”, “dpg / PO 36 mol / EO 4 mol adduct (U6) 4796 parts (2 mol parts)” and “Pluronic glycol (EO 1.5 mol − PO15 mol-EO 1.5 mol) Diglycidyl ether (g1) 4560 parts (4 mol parts) "was changed to the compounds shown in Table 3 and the number of moles used, respectively, as in Example 1 and Example 9. Polyoxyalkylene compound (Y114) {(S5) 3 mol part, (U4) 2 mol part and (g4) 4 mol part reactant} and polyoxyalkylene compound (Y202) {(S5) 3 mol part And (g4) 2 mole parts of reactant} (Y1Y202), polyoxyalkylene compound (Y115) {(S7) 3 mole parts, (U1) 2 mole parts and (d2) 4 moles. Part of reactant} and polyoxyalkylene compound (Y203) {(S7) 3 mole part and (d2) 2 mole part reactant} (Y1Y203), polyoxyalkylene compound (Y116) {(S8) 2 Mole part, (U4) 1 mole part and (d1) 2 mole part reactant} and polyoxyalkylene compound (Y204) {(S8) 4 mole part and (d1) 3 mole part reactant} ( Y1Y204) and the viscosity modifier (14-16) of the present invention were obtained.

<Example 17>
In the same reaction vessel as in Example 1, 6456 parts (7 mol parts) of sucrose / PO 10 mol adduct (S1) obtained in Production Example 1, and dpg / PO36 mol / EO 4 mol adduct (U6) obtained in Production Example 16 were used. ) 9592 parts (4 mole parts) and 10 parts of sodium hydroxide were charged and dehydrated. Thereafter, 1856 parts (8 mole parts) of 1,6-hexanediol diglycidyl ether (g2) was added and reacted at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound (Y117).

  Further, 12172 parts (2 mole parts) of sucrose / PO 10 mole adduct (S8) obtained in Production Example 8 and 10 parts of sodium hydroxide were charged into a reaction vessel similar to that in Example 1, and dehydrated. Thereafter, 580 parts (1 mole part) of Glicier PP-300P (g4) was added and reacted at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound (Y205).

  67 parts of polyoxyalkylene compound (Y117) and 33 parts of polyoxyalkylene compound (Y205) were uniformly mixed at about 25 ° C. to obtain a polyoxyalkylene compound (Y1Y205). And this polyoxyalkylene compound (Y1Y205) was used as the viscosity modifier (17) of the present invention.

<Example 18>
In the same reaction vessel as in Example 1, 4506 parts (3 mol parts) of sucrose / PO 20 mol adduct (S2) obtained in Production Example 2 and 1836 parts of deg / PO 14 mol adduct (U1) obtained in Production Example 11 (2 mol parts) and 672 parts (4 mol parts) of HDI (d1) were charged and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. with stirring for 1 hour, and stirring was continued at the same temperature for 6 hours. After confirming disappearance of the isocyanate group, a polyoxyalkylene compound (Y118) was obtained.

  Furthermore, 10648 parts (4 mole parts) of sucrose / PO 40 mole adduct (S3) obtained in Production Example 3 and 504 parts (3 mole parts) of HDI (d1) were charged into the same reaction vessel as in Example 1, and nitrogen substitution was performed. Repeated 3 times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 6 hours at the same temperature. After confirming the disappearance of the isocyanate group, a polyoxyalkylene compound (Y206) was obtained.

  50 parts of the polyoxyalkylene compound (Y118) and 50 parts of the polyoxyalkylene compound (Y206) were uniformly mixed at about 25 ° C. to obtain a polyoxyalkylene compound (Y1Y206). And this polyoxyalkylene compound (Y1Y206) was used as the viscosity modifier (18) of the present invention.

<Example 19>
In the same reaction vessel as in Example 1, 9044 parts (7 mol parts) of sucrose / PO10 / BO5 mol adduct (S6) obtained in Production Example 6 and dpg / PO20 mol adduct (U5) obtained in Production Example 15 were used. 5176 parts (4 mole parts) and 1776 parts (8 mole parts) of IPDI (d2) were charged and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. with stirring for 1 hour, and stirring was continued for 6 hours at the same temperature. After confirming disappearance of the isocyanate group, a polyoxyalkylene compound (Y119) was obtained.

  Furthermore, 15288 parts (4 mol parts) of sucrose / PO 60 mol adduct (S4) obtained in Production Example 4 and 20 parts of sodium hydroxide were charged into a reaction vessel similar to that in Example 1, and dehydrated. Thereafter, 1740 parts (3 mole parts) of glyciere PP-300P (g4) was added and reacted at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound (Y207).

  46 parts of the polyoxyalkylene compound (Y119) and 54 parts of the polyoxyalkylene compound (Y207) were uniformly mixed at about 25 ° C. to obtain a polyoxyalkylene compound (Y1Y207). This polyoxyalkylene compound (Y1Y207) was used as the viscosity modifier (19) of the present invention.

  d1 represents HDI, d2 represents IPDI, and d3 represents XDI (both manufactured by Sumika Bayer Urethane Co., Ltd.). g2 is 1,6-hexanediol diglycidyl ether {1,6HD-DEP (D), manufactured by Yokkaichi Chemical Co., Ltd., epoxy equivalent 116 g / eq}, g3 is polyoxypropylene glycol (3 mol) diglycidyl ether {epiol P-200, manufactured by NOF Corporation, epoxy equivalent of 155 g / eq, “Epiol” is a registered trademark of the company}, g4 is polyoxypropylene glycol (7 mol) diglycidyl ether {Gliciere PP-300P, Sanyo Chemical Kogyo Co., Ltd., epoxy equivalent of 290 g / eq, “Glicier” is a registered trademark of the same company}, and each molecular weight is a value obtained by doubling each epoxy equivalent.

<Comparative Example 1>
SN thickener 603 (manufactured by Sannopco, urethane-modified polyether, active ingredient 40%) was used as a comparative viscosity modifier (H1).

<Comparative example 2>
SN thickener 613 (manufactured by San Nopco, modified polyacrylic acid, active ingredient 20%) was used as a comparative viscosity modifier (H2).

Using the raw materials and the amounts used shown in Table 4, they were mixed and dispersed with an Excel auto homogenizer equipped with impeller blades to prepare an evaluation paint. Moreover, the blank coating material was prepared like the above except not using a viscosity modifier.
In addition, based on JISK5600-2-5: 1999, it confirmed that the coating material for evaluation and the blank coating material did not have a particle | grain of 5 micrometers or more.
The evaluation paint and the blank paint were evaluated for anti-sagging and anti-flaking properties and are shown in Table 5.

* 1 Water-soluble acrylic resin “Boncoat” manufactured by Dainippon Ink and Chemicals, Inc. is a registered trademark of the company.
* 2 Water-soluble melamine resin, “Cymel”, manufactured by Mitsui Cyanamid Co., Ltd. is a registered trademark of Cytec Technology Corporation.
* 3 Aluminum flake “Alpaste” manufactured by Toyo Aluminum Co., Ltd. is a registered trademark of the company.
* 4 “Nopco”, an antifoam agent manufactured by San Nopco, is a registered trademark of Cognis Deutschland, Geselsyaft, Mito, Besyulenktel, Haftung, und, Company, Comandate, Geselsyaft.
* 5 Viscosity modifiers in Examples and Comparative Examples

<Evaluation of sag prevention>
For evaluation cup or blank paint with ion exchange water for Ford Cup No. 4 (conforming to JIS K-5600-2-2) is sprayed over the entire stainless steel plate (250 mm × 100 mm, 0.5 mm thickness) diluted to 20 seconds (25 ° C.) and degreased with acetone. Using a gun {Wider W-88 cup gun (Iwata Paint Co., Ltd.), hereinafter the same}, a coating film having a film thickness difference is formed (film thickness gradient coating, atmospheric conditions: 25 ° C., 40% relative humidity). ). Subsequently, the coating plate was stood still at 60 degrees and allowed to stand, and after 5 minutes of standing, the sagging condition of the coating film was checked, and the limit sagging film thickness [the film thickness immediately before starting sagging, after baking and drying, the electromagnetic fine film thickness meter { Measured with Orem Co., Ltd., SEM-100 type}. Unit: μm] was compared. A higher value means better sag prevention.

<Evaluation of armpit prevention>
For the evaluation paint or blank paint with ion exchange water, Ford Cup No. 4 (conforming to JIS K-5600-2-2) is diluted to 20 seconds (25 ° C.) and degreased with acetone (250 mm × 100 mm, 0.5 mm thickness) with a spray gun. After coating with a film thickness gradient, setting for 10 minutes (25 ° C., 40% relative humidity), baking at 140 ° C. for 10 minutes to form a coating film with a difference in film thickness, Was evaluated and this value was defined as anti-flammability. The higher this value, the better the anti-flammability.
Note that when the film thickness is changed by applying an inclined coating to form a coating film with a difference in film thickness, and baking and drying is performed, a film is generated from a thin part to a thick part. It means the film thickness at the beginning, and was measured with an electromagnetic fine film thickness meter {manufactured by Orwell Co., Ltd., SEM-100 type} (unit: μm).

From the evaluation results, the viscosity modifiers for water-based paints according to the present invention (Examples 1 to 8, 13, 14, 17 ) were remarkably superior in anti-skid properties compared to Comparative Examples 1 and 2. In addition, the sagging resistance is remarkably improved as compared with the blank, and the balance between sagging prevention and sagging resistance, which has been said to be incompatible with each other, was extremely well balanced.

The viscosity adjusting agent for water-based paints of the present invention can be applied to water-based paints, and among these, it is particularly suitable for thermosetting water-based paints (automobile topcoat water-based paints, building material water-based paints, etc.). Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints. The viscosity modifier for water-based paints of the present invention is extremely useful for water-based thermosetting paints containing flaky fillers such as aluminum flakes.

Claims (6)

A viscosity modifier for water-based paints comprising a polyoxyalkylene compound (Y1) represented by the general formula (1).

^{S 1 - LG (-U- LG -S} 2 - LG) q -U- LG -S 1 (1)

However, ^{S 1} is the general formula a group represented by (2), based on ^{S 2} is represented by the general formula (3), LG is reactive residue of a diglycidyl ether of 10 to 50 carbon atoms, U is formula The group represented by (4), q represents 0, 1 or 2.

Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, OA is an oxyalkylene group having 2 to 4 carbon atoms, Z is an alkylene group or arylene having 2 to 15 carbon atoms A group, O is an oxygen atom, H is a hydrogen atom, n is an integer of 3 to 50, t is an integer of 2 to 4, m is an integer of 5 to 25, and OA of S ¹ unit or S ² unit the total number is an integer of ^{10~100, S 1, S 2,} LG, U, (OA) n, (OA) m, Q, n, m may be identical to or different from each other. Furthermore, the viscosity modifier of Claim 1 formed by containing the polyoxyalkylene compound (Y2) represented by General formula (5).

_{^{S 1 -L (-S 2 -L)}} q -S 1 (5)

^{However, S 1,} S ^2, q is the general formula (1) and the same, L is the reaction residue of diglycidyl ether of the reaction residues (LD), or 10 to 50 carbon atoms diisocyanates having 6 to 20 carbon atoms (LG ) . The viscosity modifier according to claim 1 or 2, wherein the non-reducing disaccharide or trisaccharide reaction residue (Q) is a sucrose reaction residue. Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing disaccharide or trisaccharide (a1) and 10 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
A step (2) of obtaining a compound (a32) from a chemical reaction (2) of 1 mol part of a glycol (a3) having 2 to 15 carbon atoms and 10 to 50 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms; and Compound (a12) 1 mol part, Compound (a32) 0.1-0.75 mol part, C10-50 diglycidyl ether (a5) 0.5-1.5 mol part A process for producing a viscosity modifier for water-based paints, comprising the step (3) of obtaining a polyoxyalkylene compound (Y1) from the chemical reaction (4). It consists of a water-based base paint and the viscosity modifier according to any one of claims 1 to 3, and the content of the viscosity modifier is 1 to 5% by weight based on the weight of the water-based base paint and the viscosity modifier. Paint characterized by. The paint according to claim 5, wherein the water-based base paint is a heat curable paint and is a paint containing a flaky filler.