JP5135515B2 - Paint additive and coating composition containing the same - Google Patents

Description

  The present invention relates to a coating additive and a coating composition containing the same. In particular, paint additives that are applied to the exterior surface of buildings and are suitable as paint contamination reducing agents for reducing coating film contamination (mainly coating film contamination reduction in water-based paints) due to room temperature drying or heat drying The present invention relates to a coating composition containing the same.

  Additives for coatings added for the purpose of imparting hydrophilicity to the coating film and washing away contaminants due to rain, etc. Water-swelling properties such as starch-polyacrylate grafted products and polyoxyethylene chain-containing polyurethane resins Polymer (Patent Document 1), Compound obtained by polymerizing ethylene oxide or propylene oxide on glycerin or pentaerythritol (Patent Document 2), non-reducing di- or trisaccharide alkylene oxide adduct and dimer (Patent Document 2) Document 3) is known.

JP-A-2-123176 JP-A-11-279454 JP 2004-224945 A

The paint additives described in Patent Documents 1 and 2 have a problem that the water resistance of the coating film is remarkably lowered and the contamination reducing property disappears in a short period of time. Further, even the paint additive described in Patent Document 3 cannot be said to have a sufficient pollution reducing property over a long period of 1 to 2 years.
That is, an object of the present invention is to provide an additive for paints that can form a coating film excellent in water resistance and long-term contamination reduction.

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 coating additive of the present invention is that it contains the polyoxyalkylene compound (Y) represented by the general formula (1).

_{S 1 -L-D-L (} -S 2 -L-D-L) q -S 1 (1)

However, _{S 1} is a group represented by the general formula (2), _{S 2} is a group represented by the general formula (3), radical D is represented by the general formula (4), L 6 to 20 carbon atoms The diisocyanate reaction residue, q represents an integer of 0 to 5.

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, and Z is two from glycols having 2 to 15 carbon atoms The residue except the hydroxyl group of, O is an oxygen atom, H is a hydrogen atom, n is an integer of 2-50, t is an integer of 2-4, m represents an integer of 5-35, S ₁ unit and S ₂ The total number of OA included in the unit is an integer of 10 to 100, and S ₁ , S ₂ , D, L, R, (OA) n, Q, n, and m may be the same or different.

In addition, the characteristics of the paint additive of the present invention are obtained from a chemical reaction of 1 mol part of the non-reducing di- or trisaccharide (a1) and 10 to 100 mol parts of the alkylene oxide (a2) having 2 to 4 carbon atoms. 1 mol part of compound (a12),
0.5 to 0.86 mole part of the compound (a32) obtained from the chemical reaction of 1 mole part of the glycol (a3) having 2 to 15 carbon atoms and 10 to 70 mole parts of the alkylene oxide (a2) having 2 to 4 carbon atoms; ,
The gist is that a polyoxyalkylene compound having a structure that can be produced by a chemical reaction with 1.0 to 1.71 parts by mole of a diisocyanate (a4) having 6 to 20 carbon atoms is an essential component.

  The gist of the coating composition of the present invention is that it comprises a coating material and the above-mentioned coating additive, and contains 0.1 to 5% by weight of the coating additive based on the weight of the coating material.

  The additive for paints of the present invention greatly reduces the contact angle of water on the coating film, and is extremely excellent in its sustainability, and maintains extremely excellent contamination reduction and water resistance over a long period of time. That is, the coating additive of the present invention can form a coating film excellent in water resistance and long-term contamination reduction. The paint additive of the present invention is extremely effective even with a small amount of use, and does not reduce the original properties of the paint. Therefore, the paint additive of the present invention is extremely useful for paints to be painted outdoors such as outer walls or paints for factory processed panels used for outer walls or the like (particularly aqueous emulsion paints).

  In addition, since the coating composition of the present invention contains the above-mentioned additive for coatings, the contact angle of water on the coating film is greatly reduced, and its durability is extremely excellent. Maintains excellent contamination reduction and water resistance. That is, the coating composition of the present invention can form a coating film excellent in water resistance and long-term contamination reduction. Therefore, the coating composition of the present invention is extremely useful as a coating composition used outdoors such as an outer wall (particularly an aqueous emulsion coating).

  In General formula (1), L represents the reaction residue (group represented by -CO-NH-X-NH-CO-) of diisocyanate.

X may be alkylene, cycloalkylene, arylene, aralkylene (arylalkylene) or the like. Moreover, a part of hydrogen atoms contained in these groups may be substituted with a halogen atom and / or an alkoxy having 1 to 6 carbon atoms, and these groups are oxa groups (—O—) or It may be bonded with 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.

  q is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, particularly preferably an integer of 1 to 3, and most preferably an integer of 1 to 2. Within this range, the long-term contamination reduction property of the coating film is further improved.

  In the general formulas (2) and (3), as the di- or trisaccharide that can constitute the residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, Examples thereof include sucrose, trehalose, isotrehalose, isosaccharose, gentianose, raffinose, meretitol, planteose and the like. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of long-term pollution reduction, etc., more preferably sucrose, trehalose and raffinose, and particularly preferably sucrose from the viewpoint of supply and cost. is there.

  In the general formulas (2) to (4), examples of the oxyalkylene group (OA) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Of these, oxypropylene is preferred, and oxypropylene and oxybutylene are preferably mixed from the viewpoint of water resistance, etc., but oxypropylene and / or oxybutylene and oxybutylene are preferred from the viewpoint of contact angle with water and contamination reduction. It may be mixed with ethylene.

  When plural kinds of oxyalkylene groups are contained in OA, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and content ratio of these oxyalkylene groups, but the block shape or block shape and random shape It is preferable that the combination of these is included.

  In the general formulas (2) and (3), when a mixture of oxypropylene and / or oxybutylene and oxyethylene is included, the content ratio (mol%) of oxyethylene is based on the total number of moles of oxyalkylene groups. 1-10 are preferable, More preferably, it is 2-9, Most preferably, it is 3-8, Most preferably, it is 4-7. 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 contains an oxyethylene group, it is preferable that the oxyethylene group is directly bonded to the reaction residue (Q). Further, when the OA includes a plurality of types of oxyalkylene groups, it is preferable to include a block shape.

  Examples of the residue (Z) obtained by removing two hydroxyl groups from a glycol having 2 to 15 carbon atoms include alkylene, cycloalkylene, and arylene.

  As alkylene, C2-C6 alkylene etc. are used, and ethylene, propylene, butylene, hexamethylene, etc. are mentioned.

  Examples of cycloalkylene include cycloalkylene having 6 to 9 carbon atoms, and examples thereof include cyclohexylene, methylcyclohexylene, and trimethylcyclohexylene.

As the arylene, arylene having 6 to 15 carbon atoms or the like is used, and phenylene, methylphenylene, ethylphenylene, tetramethylphenylene, xylylene, naphthylene, biphenylylene, dimethylbiphenylylene, anthrylene, phenanthrylene,-(ph) -CH _2- A group represented by (ph)-, a group represented by-(ph) -C (CH ₃ ) _2- (ph)-, and a group represented by-(ph) -CH ₂ CH _2- (ph)- Group and a group represented by —CH ₂ — (ch) —CH ₂ — and the like.

Of these Z, alkylene and arylene are preferable, ethylene, propylene, hexamethylene and groups represented by-(ph) -C (CH ₃ ) _2- (ph)-are more preferable, and propylene is particularly preferable. It is.

  n is preferably an integer of 2 to 50, more preferably an integer of 5 to 47, particularly preferably an integer of 7 to 43, and most preferably an integer of 10 to 40. Within this range, the water resistance and long-term contamination reduction of the coating film are further improved.

  t is preferably an integer of 2 to 4, more preferably 3. Within this range, the long-term contamination reduction property of the coating film is further improved.

  m is preferably an integer of 5 to 35, more preferably an integer of 7 to 33, and most preferably an integer of 10 to 30. Within this range, the long-term contamination reduction property of the coating film is further improved.

The total number of OA contained in the S ₁ unit and S ₂ unit is preferably an integer of 10 to 100, more preferably an integer of 20 to 90, particularly preferably an integer of 30 to 80, most preferably 40 to 70. It is an integer. Within this range, the water resistance and long-term contamination reduction of the coating film are further improved.

As the polyoxyalkylene compound (Y) represented by the general formula (1), a compound obtained from a chemical reaction of a non-reducing di- or trisaccharide (a1) and a C2-C4 alkylene oxide (a2) ( a12)
A compound (a32) obtained from a chemical reaction of a glycol having 2 to 15 carbon atoms (a3) and an alkylene oxide having 2 to 4 carbon atoms (a2);
Examples include polyoxyalkylene compounds having a structure that can be produced by a chemical reaction with a diisocyanate (a4) having 6 to 20 carbon atoms. That is, a polyoxyalkylene compound having a structure that can be produced by this chemical reaction may cause distribution in the number of oxyalkylene groups, n, m, q, etc. In this case, strictly speaking, a plurality of types of polyoxyalkylene It becomes a mixture of compounds, and this mixture contains the polyoxyalkylene compound represented by the general formula (1). Even in this case, the manufacturing method is not limited.

  In the compound (a12), the use amount (mole part) of the alkylene oxide (a2) is preferably 10 to 100, more preferably 1 mol part of the non-reducing di- or trisaccharide (a1). It is 20 to 90, particularly preferably 30 to 80, and most preferably 40 to 70. Within this range, the long-term contamination reduction and water resistance of the coating film are further improved.

  In the compound (a32), the usage amount (mole part) of the alkylene oxide (a2) is preferably 10 to 70 moles, more preferably 20 to 20 moles per mole part of the glycol (a3) having 2 to 15 carbon atoms. 70, particularly preferably 20-60, most preferably 30-50. Within this range, the long-term contamination reduction property of the coating film is further improved.

  The amount (mole) of the polyoxyalkylene glycol (a32) used is preferably 0.5 to 0.86, more preferably 0.5 to 0.83, particularly 1 mol part of the compound (a12). Preferably it is 0.67-0.80, Most preferably, it is 0.67-0.75. Within this range, the long-term contamination reduction and water resistance of the coating film are further improved.

  As usage-amount (mol part) of C6-C20 diisocyanate (a4) with respect to 1 mol part of compound (a12) of a non-reducing di- or trisaccharide and alkylene oxide, it is 1.0-1. 71 is preferable, more preferably 1.0 to 1.67, particularly preferably 1.33 to 1.6, and most preferably 1.33 to 1.5. Within this range, the long-term contamination reduction and water resistance of the coating film are further improved.

  As the non-reducing di- or trisaccharide (a1), the same disaccharide or trisaccharide that can constitute the reaction residue (Q) in the general formula (1) 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. Among these, PO is preferable, and mixing of PO and BO is preferable from the viewpoint of water resistance of the coating film. However, mixing of PO and / or BO and EO is preferable from the viewpoint of contact angle with water and reduction of contamination. But you can.

Examples of the glycol (a3) having 2 to 15 carbon atoms include alkylene diols (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol, hexamethylene glycol, etc.), cycloalkylene diol (cyclohexyl glycol and di (hydroxymethyl) cyclohexane, etc.), and arylene diols (hydroquinone, catechol and bisphenol _{A {HO-C 6 H 4} -C (CH 3) 2 -C 6 H 4 -OH} , and the like. Of these, alkylene diols and arylene diols are preferable, ethylene glycol, propylene glycol, hexamethylene glycol and bisphenol A are more preferable, and propylene glycol is particularly preferable. It is a call.

  Examples of the diisocyanate (a4) 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.

Of these diisocyanates, alkylene diisocyanates, cycloalkylene diisocyanates and arylene diisocyanates are preferred, more preferably hexamethylene diisocyanate, diisocyanates represented by OCN- (tmch) -CH ₂ -NCO (isophorone diisocyanate) and xylylene diisocyanate, Hexamethylene diisocyanate is preferred.

  In the chemical reaction of the non-reducing disaccharide or trisaccharide (a1) and the alkylene oxide (a2), when multiple types of alkylene oxide are used, the order of reaction (block, random and combinations thereof) and the use ratio are as follows: Although there is no limitation, it is preferable to include a block shape or a combination of a block shape and a random shape. When EO is contained, the use ratio (mol%) of EO is preferably 1 to 10, more preferably 2 to 9, particularly preferably 3 to 8, most preferably based on the total number of moles of alkylene oxide. Is 4-7. When EO and PO or / and BO are included, it is preferable to react PO and / or BO after the reaction of EO to the di- or trisaccharide (a1).

  In the chemical reaction of glycol (a3) and alkylene oxide (a2), when a plurality of types of alkylene oxide are used, the order of reaction (block, random, and combinations thereof) and the use ratio are not limited, but block or It is preferable to include a combination of a block shape and a random shape. When EO is used, the use ratio (mol%) of EO is preferably from 1 to 10, more preferably from 2 to 9, particularly preferably from 3 to 8, most preferably 4 based on the total number of moles of alkylene oxide. ~ 7.

  The chemical reaction of the non-reducing disaccharide or trisaccharide (a1) and the alkylene oxide (a2) and the chemical reaction of the glycol (a3) and the alkylene oxide (a2) may be any of anionic polymerization, cationic polymerization, or coordinated anionic polymerization. It may be implemented in the form of 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 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, trimethylamine) Ethylenediamine and tetramethylethylenediamine) and Lewis acids (such as stannic chloride and boron trifluoride) are used. Of these, alkali metal hydroxides and tertiary amine compounds are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.

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

  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. } (JP-A-53-123499, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (JP-B-49-14359, etc.), a method using an ion exchange resin (JP-A-51 No. 23211, etc.) 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, it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring. The reaction atmosphere is preferably an atmosphere of inert gas (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.

  A reaction solvent is preferably used for the chemical reaction 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 using a reaction solvent, the amount used (% by weight) is preferably 20 to 200 based on the weight of the compound (a12) produced by the reaction of the di- or trisaccharide (a1) and the alkylene oxide (a2). More preferably, it is 40-180, Most preferably, it is 60-150.

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 (Y). 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.

  Examples of the polyoxyalkylene compound include compounds having a structure that can be produced by a chemical reaction between the compound (a12) in Table 1, the compound (a32) in Table 1, and the diisocyanate (a4) in Table 1. (A1) is a non-reducing di- or trisaccharide, (a2) is alkylene oxide, (a3) is glycol, PO is propylene oxide, EO is ethylene oxide, and BO is butylene oxide. Q1 is sucrose, Q2 is trehalose, Q3 is raffinose, DEG is diethylene glycol, DPG is dipropylene glycol, HG is hexamethylene glycol, BPA is bisphenol A, L1 is hexamethylene diisocyanate, L2 is Isophorone diisocyanate, L3 represents xylylene diisocyanate.

  Among these, No. A polyoxyalkylene compound represented by any one of 4 to 9 and 12 to 18 is preferred, and more preferably It is a polyoxyalkylene compound represented by any one of 5 to 8 and 13 to 17, particularly preferably any one of 4, 6 and 13.

The coating additive of the present invention contains, as necessary, components other than the polyoxyalkylene compound (Y) such as known additives (viscosity adjusting agent, antifoaming agent, wetting agent, film forming adjusting agent, etc.). be able to.
As a viscosity modifier, SN thickener 601 and 612 (manufactured by San Nopco Co., Ltd.) and the like, as an antifoaming agent, SN deformer 180 and 260 (manufactured by San Nopco Co., Ltd.), etc. Texanol (manufactured by Eastman Chemical Co., Ltd.) and the like can be mentioned as a film-forming modifier such as San Nopco Co., Ltd. In addition, when it contains an additive, as these content, all are 0.1-30 weight% based on the weight of a polyoxyalkylene compound (Y).

  The paint additive of the present invention can be applied to both aqueous paints and non-aqueous paints, and among these, it is suitable for water-based paints, and particularly suitable for aqueous emulsion paints. Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints.

  The timing for adding the paint additive of the present invention to the paint is as follows: (1) when the pigment is dispersed, (2) when the resin component and various additives are added to the dispersed pigment, and (3) further coating is performed. There are just before, but any of them may be used.

  The addition amount (% by weight) of the paint additive of the present invention is preferably 0.1 to 5, more preferably 0.2 to 4.5, particularly preferably 0.3 to, based on the weight of the paint. 4, more particularly preferably 0.5 to 3.5, most preferably 0.7 to 3. Within this range, good long-term contamination reduction properties are likely to be obtained, and it is difficult to adversely affect the water resistance of the coating film (original properties of the paint).

  The paint to which the additive for paint of the present invention is added can be applied to an object to be coated by a usual method, such as brush coating, roller coating, air spray coating, airless coating, roll coater coating, and flow coater coating. Methods etc. can be applied.

   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.

<Example 1>
In a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, pressurizing with nitrogen and depressurization with a vacuum pump, trehalose {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter the same} 342 parts (1 mol part) and DMF {Mitsubishi Gas Chemical Co., Ltd., hereinafter the same} After 1000 parts are charged, nitrogen gas is used to pressurize to 0.4 MPa with a gauge pressure and discharge to 0.02 MPa (hereinafter referred to as nitrogen) Abbreviated as substitution) was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 720 parts (10 mole parts) of BO was added dropwise at the same temperature over 2 hours, followed by further stirring at the same temperature for 2 hours. Subsequently, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain a trehalose / BO 10 molar adduct (S101). The water content was 0.01% (according to Karl Fischer method, the same applies hereinafter).

  In the same pressure-resistant reaction vessel as above, dipropylene glycol {reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as DPG, hereinafter the same} 134 parts (1 mole part) and potassium hydroxide {reagent grade, Wako Pure The amount used by Yakuhin Kogyo Co., Ltd. is shown as a pure equivalent amount excluding moisture. same as below. } After adding 6.0 parts, nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and 3480 parts (60 mole parts) of PO was then added dropwise at the same temperature over 8 hours, and stirring was further continued at the same temperature for 3 hours to react the remaining PO. Next, after adding 50 parts of deionized water at 90 ° C., 200 parts of KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. The filter was filtered using 2 filter papers {manufactured by Toyo Filter Paper Co., Ltd.} to remove Kyoward 700, and dehydrated at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa for 1 hour (hereinafter abbreviated as Kyoward treatment and dehydration) To obtain a DPG / PO60 molar adduct (D101). The moisture was 0.02%.

  In a reaction vessel capable of stirring, heating and cooling, 3108 parts (0.86 mol part) of DPG / PO 60 mol adduct (D101), hexamethylene diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., hereinafter abbreviated as HDI). same as below. } 287.3 parts (1.71 mol parts) were charged and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 5 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 1062 parts (1.0 mol part) of trehalose / BO 10 mol adduct (S101), heated to 110 ° C. with stirring for 1 hour, and stirred at the same temperature for 5 hours. Continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y1). And this polyoxyalkylene compound (Y1) was made into the coating additive (1) of this invention as it was.

<Example 2>
To a pressure-resistant reaction vessel similar to that in Example 1, 342 parts (1 mol part) of trehalose and 1000 parts of DMF were added and nitrogen substitution was repeated three times. Then, the temperature was raised to 100 ° C. with stirring, and then PO870 parts (15 mole parts) were dropped over 3 hours at the same temperature, and further 360 parts (5 mole parts) of BO were dropped over 2 hours at the same temperature. Stirring was continued for 4 hours. Next, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain a trehalose / PO15 mol / BO5 mol adduct (S102). The moisture was 0.02%.

  After charging 106 parts (1 part by mole) of diethylene glycol {reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as DEG, hereinafter the same} and 6.0 parts of potassium hydroxide into the same pressure resistant reactor as above. The nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 440 parts (10 mole parts) of EO was added dropwise at the same temperature over 2 hours, and stirring was further continued at the same temperature for 1 hour. Next, the temperature was raised to 110 ° C., then, 3480 parts (60 mol parts) of PO was added dropwise at the same temperature over 6 hours, and stirring was further continued at the same temperature for 3 hours to react the remaining PO. Next, Kyoward treatment and dehydration were performed to obtain an adduct (D102) of DEG / EO 10 mol / PO 60 mol. The moisture was 0.02%.

  In a reaction vessel which can be stirred, heated and cooled, DEG / EO10 Mo / PO60 mol adduct (D102) 3342 parts (0.83 mol parts), isophorone diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., hereinafter, abbreviated as IPDI) To do. same as below. } 370.7 parts (1.67 mole part) was charged and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 5 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 1572 parts (1.0 mol part) of trehalose PO 15 mol / BO 5 mol adduct (S102), heated to 110 ° C. with stirring for 1 hour, and kept at the same temperature for 5 hours. Stirring was continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y2). And this polyoxyalkylene compound (Y2) was made into the additive (2) for coating materials of this invention as it was.

<Example 3>
342 parts (1 mole part) of purified granulated sugar {sucrose made by Taiyo Co., Ltd., hereinafter the same} and 1000 parts of DMF were added to the pressure-resistant reaction vessel similar to Example 1, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1740 parts (30 mole parts) of PO was added dropwise over 3.5 hours at the same temperature, and stirring was further continued for 4 hours at the same temperature. Next, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain a sucrose / PO 30 mol adduct (S103). The moisture was 0.01%.

  In the same pressure resistant reactor as above, hexamethylene glycol {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HG, hereinafter the same} 106 parts (1 mole part) and 5.0 parts of potassium hydroxide were charged. Then, dehydration was performed at 60 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, 2100 parts (50 mol parts) of PO was added dropwise at 100 ° C. over 5 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 2 hours to react the remaining PO. Next, Kyoward treatment and dehydration were performed to obtain an HG / PO 50 molar adduct (D103). The moisture was 0.02%.

  In a reaction vessel capable of stirring, heating and cooling, 2414 parts (0.8 mole part) of HG / PO adduct (D102), xylylene diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., hereinafter abbreviated as XDI). same as below. } 300.8 parts (1.6 mole parts) were charged, and the nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 5 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 2082 parts (1.0 mol part) of sucrose / PO 30 mol adduct (S103), heated to 110 ° C. with stirring for 1 hour, and stirred at the same temperature for 5 hours. Continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y3). And this polyoxyalkylene compound (Y3) was made into the coating additive (3) of this invention as it is.

<Example 4>
Into a pressure resistant reactor similar to that in Example 1, 2082 parts (1 mole part) of sucrose / PO 30 mole adduct (1 mole part) and 5.0 parts of potassium hydroxide were added, and then 0.6-1. It dehydrated under reduced pressure of 3 kPa. Subsequently, 580 parts (10 mol parts) of PO was added dropwise at 100 ° C. over 2 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 2 hours to react the remaining PO. Next, Kyoward treatment and dehydration were carried out to obtain a sucrose / PO40 molar adduct (S104). The moisture was 0.02%.

  After charging 134 parts (1 mole part) of DPG and 6.0 parts of potassium hydroxide into the same pressure resistant reactor as above, nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 2320 parts (40 mole parts) of PO was added dropwise at the same temperature over 6 hours, and stirring was further continued at the same temperature for 3 hours to react the remaining PO. Subsequently, Kyoward treatment and dehydration were performed to obtain a DPG / PO 40 molar adduct (D104). The moisture was 0.02%.

  In a reaction vessel capable of stirring, heating and cooling, 1841 parts (0.75 mole part) of DPG / PO 40 mole adduct (D104) and 252 parts (1.5 mole part) of HDI were charged, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 5 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 2662 parts (1.0 mol part) of sucrose / PO 40 mol adduct (S104), heated to 110 ° C. over 1 hour with stirring, and stirred at the same temperature for 5 hours. Continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y4). And this polyoxyalkylene compound (Y4) was made into the coating additive (4) of this invention as it was.

<Example 5>
Into a pressure resistant reactor similar to that of Example 1, 2082 parts (1 mole part) of sucrose / PO 30 mole adduct (1 mole part) and 6.0 parts of potassium hydroxide were added, and then 0.6 to 1. It dehydrated under reduced pressure of 3 kPa. Next, 1160 parts (20 mole parts) of PO was added dropwise at 100 ° C. over 3 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 2 hours to react the remaining PO. Next, Kyoward treatment and dehydration were performed to obtain a sucrose / PO 50 mol adduct (S105). The moisture was 0.01%.

  228 parts (1 mole part) of bisphenol A {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.} and 1000 parts of DMF were added to a pressure-resistant reaction vessel similar to that in Example 1, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1740 parts (30 mole parts) of PO was added dropwise over 3.5 hours at the same temperature, and stirring was further continued for 4 hours at the same temperature. Next, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain a bisphenol A / PO 30 molar adduct (D105). The moisture was 0.01%.

  A reaction vessel capable of stirring, heating, and cooling was charged with 1319 parts (0.67 mole parts) of bisphenol A / PO 30 mole adduct (D105) and 223.4 parts (1.33 mole parts) of HDI, and nitrogen substitution was repeated three times. It was. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 5 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 3242 parts (1.0 mol part) of sucrose / PO 50 mol adduct (S105), heated to 110 ° C. with stirring for 1 hour, and stirred at the same temperature for 5 hours. Continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y5). And this polyoxyalkylene compound (Y5) was made into the additive (5) for coating materials of this invention as it was.

<Example 6>
Into a pressure resistant reactor similar to that in Example 1, 2082 parts (1 mole part) of sucrose / PO 30 mole adduct (1 mole part) and 7.0 parts of potassium hydroxide were added, and then 0.6 to 1. It dehydrated under reduced pressure of 3 kPa. Subsequently, 1740 parts (30 mole parts) of PO was added dropwise at 100 ° C. over 4 hours while maintaining the reduced pressure, and the stirring was further continued at 120 ° C. for 2 hours to react the remaining PO. Next, Kyoward treatment and dehydration were carried out to obtain a sucrose / PO 60 mol adduct (S106). The moisture was 0.01%.

  After charging 134 parts (1 mole part) of DPG and 3.0 parts of potassium hydroxide into a pressure resistant reactor similar to that of Example 1, nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1160 parts (20 mol parts) of PO was added dropwise at the same temperature over 5 hours, and stirring was further continued at the same temperature for 3 hours to react the remaining PO. Next, Kyoward treatment and dehydration gave DPG / PO20 molar adduct (D106). The moisture was 0.01%.

  A reaction vessel capable of stirring, heating and cooling was charged with 647 parts (0.5 mol part) of DPG / PO 20 mol adduct (D106) and 222 parts (1.0 mol part) of IPDI, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 4 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 3822 parts (1.0 mol part) of sucrose / PO 60 mol adduct (S106), heated to 110 ° C. with stirring for 1 hour, and stirred at the same temperature for 5 hours. Continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y6). And this polyoxyalkylene compound (Y6) was made into the additive (6) for coating materials of this invention as it was.

<Example 7>
Into a pressure resistant reactor similar to that in Example 1, 2082 parts (1 mole part) of sucrose / PO 30 mole adduct (1 mole part) and 7.0 parts of potassium hydroxide were added, and then 0.6 to 1. It dehydrated under reduced pressure of 3 kPa. Subsequently, PO2320 parts (40 mole parts) were added dropwise at 100 ° C. over 5 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 2 hours to react the remaining PO. Next, Kyoward treatment and dehydration were performed to obtain a sucrose / PO 70 mol adduct (S107). The moisture was 0.01%.

  Into the same pressure-resistant reaction vessel as above, 106 parts of HG (1 mol part) and 1.0 part of potassium hydroxide were added, followed by dehydration at 60 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, 580 parts (10 mol parts) of PO was added dropwise at 100 ° C. over 2 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 2 hours to react the remaining PO. Subsequently, Kyoward treatment and dehydration were performed to obtain an HG / PO 10 molar adduct (D107). The moisture was 0.01%.

  In a reaction vessel capable of stirring, heating, and cooling, 343 parts (0.5 mol part) of HG / PO 10 mol adduct (D107) and 222 parts (1.0 mol part) of IPDI were charged, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 4 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 4402 parts (1.0 mol part) of sucrose / PO 70 mol adduct (S107), heated to 110 ° C. with stirring for 1 hour, and stirred at the same temperature for 5 hours. Continued. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y7). And this polyoxyalkylene compound (Y7) was made into the additive (7) for coating materials of this invention as it was.

<Example 8>
342 parts (1 mole part) of purified granulated sugar and 1500 parts of DMF were added to the same pressure resistant reaction vessel as in Example 1, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 220 parts (5 mol parts) of EO was added dropwise over 2 hours at the same temperature, and 4350 parts (75 mol parts) of PO were further added dropwise over 6 hours at the same temperature. Thereafter, stirring was continued for 2 hours at the same temperature. Subsequently, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain an adduct (S108) of sucrose / EO 5 mol / PO 75 mol. The moisture was 0.01%.

  After putting 106 parts (1 mole part) of DEG and 1.0 part of potassium hydroxide into the same pressure resistant reactor as above, nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 290 parts (5 mole parts) of PO was dropped over 2 hours at the same temperature, and 360 parts (5 mole parts) of BO was dropped over 2 hours at the same temperature. The stirring was continued for 1 hour at the same temperature. Next, Kyoward treatment and dehydration were carried out to obtain an adduct of DEG / PO5 mol / BO5 mol (D108). The moisture was 0.02%.

  In a reaction vessel capable of stirring, heating and cooling, 507 parts (0.67 mol part) of DEG / PO5 mol / BO5 mol adduct (D108) and 295.3 parts (1.33 mol part) of IPDI were charged, and nitrogen substitution was performed. Repeated times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 4 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 4912 parts (1.0 mol part) of sucrose / EO 5 mol / PO 75 mol adduct (S108), heated to 110 ° C. over 1 hour while stirring, Stirring was continued for an hour. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y8). And this polyoxyalkylene compound (Y8) was made into the coating additive (8) of this invention as it was.

<Example 9>
Raffinose {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., the same applies hereinafter) 504 parts (1 mol part) and DMF 1500 parts were added to the same pressure-resistant reaction vessel as in Example 1, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, then, PO 5220 parts (90 mole parts) were added dropwise at the same temperature over 7 hours, and stirring was further continued for 4 hours. Next, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain a raffinose / PO 90 molar adduct (S109). Moisture is 0.01
%Met.

  After charging 134 parts (1 mole part) of DPG and 3.5 parts of potassium hydroxide into a pressure resistant reactor similar to that of Example 1, nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1450 parts (25 mole parts) of PO was added dropwise at the same temperature over 5 hours, and stirring was further continued at the same temperature for 3 hours to react the remaining PO. Next, Kyoward treatment and dehydration were carried out to obtain a DPG / PO 25 molar adduct (D109). The moisture was 0.01%.

  In a reaction vessel capable of stirring, heating and cooling, 1188 parts (0.75 mole part) of DPG / PO 25 mole adduct (D109) and 282 parts (1.5 mole part) XDI were charged, and the nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 4 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., charged with 5724 parts (1.0 mol part) of raffinose / PO 90 mol adduct (S109), heated to 110 ° C. with stirring for 1 hour, and stirred at the same temperature for 5 hours. Continued. Thereafter, the disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y9). And this polyoxyalkylene compound (Y9) was made into the coating additive (9) of this invention as it was.

<Example 10>
To a pressure resistant reaction vessel similar to that in Example 1, 504 parts (1 mole part) of raffinose and 1500 parts of DMF were added, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 440 parts (10 parts by mole) of EO and 10220 parts (90 parts by weight) of PO were added dropwise at the same temperature over 7 hours, and stirring was further continued for 4 hours. Next, DMF was removed under reduced pressure of 1.3 to 13 kPa at 120 ° C. to obtain an adduct (S110) of raffinose / EO 10 mol / PO 90 mol. The moisture was 0.01%.

  After charging 134 parts (1 mol part) of DPG and 4.5 parts of potassium hydroxide into a pressure-resistant reaction vessel similar to that in Example 1, nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 2030 parts (35 mole parts) of PO was dropped at the same temperature over 6 hours, and stirring was further continued at the same temperature for 3 hours to react the remaining PO. Next, Kyoward treatment and dehydration gave DPG / PO35 molar adduct (D110). The moisture was 0.01%.

  A reaction vessel capable of stirring, heating and cooling was charged with 1731 parts (0.8 mole part) of DPG / PO35 mole adduct (D110) and 268.8 parts (1.6 mole part) of HDI, and the nitrogen substitution was repeated three times. . Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 4 hours at the same temperature. Thereafter, the mixture was cooled to 80 ° C., 6164 parts (1.0 mol part) of raffinose / EO 10 mol / PO 90 mol adduct (S110) was charged, and the temperature was raised to 110 ° C. over 1 hour while stirring. Stirring was continued for an hour. Thereafter, disappearance of the isocyanato group was confirmed to obtain a polyoxyalkylene compound (Y10). And this polyoxyalkylene compound (Y10) was made into the additive (10) for coating materials of this invention as it was.

<Comparative Example 1>-Corresponding to the invention described in Patent Document 2-
In the same pressure-resistant reaction vessel as in Example 1, 106 parts (1 mole part) of diethylene glycol and 1.5 parts of potassium hydroxide were added, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 140 ° C. while stirring, and 2200 parts (50 mole parts) of EO was added dropwise at the same temperature over 8 hours, followed by stirring for 30 minutes at the same temperature to react with the remaining EO. Next, Kyoward and dehydration were carried out to obtain polyethylene glycol (number average molecular weight 2300) (HS1). Then, this polyoxyalkylene compound (HS1) was used as a comparative coating additive (H1) as it was.

<Comparative example 2>
In the same reaction vessel as in Example 1, 2300 parts (1 mole part) of polyethylene glycol (HS1) was charged and dehydrated at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa for 1 hour. Subsequently, after cooling to 50 ° C., 112 parts (0.67 mol parts) of HDI was added, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. over 1 hour with stirring, and stirring was continued for 7 hours at the same temperature. After confirming disappearance of the isocyanate group, a polyoxyalkylene compound (HY1) was obtained. Then, this polyoxyalkylene compound (HY1) was used as a coating additive (H2) for comparison as it was.

<Comparative Example 3>-Corresponding to the invention described in Patent Document 3-
In the same reaction vessel as in Example 1, 3242 parts (1.0 mol part) of sucrose / PO 50 mol adduct (S105) was charged and dehydrated at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa for 1 hour. Next, after cooling to 50 ° C., 111 parts (0.5 mole part) of IPDI was added, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 100 ° C. with stirring for 1 hour, and stirring was continued for 8 hours at the same temperature. After confirming the disappearance of the isocyanate group, a polyoxyalkylene compound (HY2) was obtained. The polyoxyalkylene compound (HY2) was used as a comparative coating additive (H3) as it was.

  Using paint additives obtained in the examples and comparative examples, paint compositions were prepared, and long-term contamination reduction {contact angle with water (initial and after immersion treatment)}, water resistance and outdoor exposure test (white) The difference in degrees, -ΔL) was evaluated and the results are shown in Table 3.

The relationship between the contact angle of the paint film with water and the pollution reduction is well known (public-private joint research “Development of technology for structural fouling”, Ministry of Construction Public Works Research Institute Chemical Laboratory ), The smaller the contact angle, the better the contamination reduction (contamination resistance, the ease of carrying away dirt adhered to the surface by water droplets due to rainfall).
In addition, the test paint pieces are immersed in deionized water for 24 hours and then dried, and the coating film that maintains the contact angle with water of 50 degrees or less even after the accelerated durability test is measured. There is a report that it is difficult {Nobuhiro Kenmochi, “Surface Properties and Contamination of Paints for Exterior Walls”, Paint Engineering, 28, [4] 147 (1993); Toshikazu Nakaya, “Development of Antifouling Paints for Architecture "JETI, 42, [5] 8 (1994)}.
Therefore, the pollution reduction ability and its sustainability index (long-term pollution reduction ability) were evaluated by contact angle with water, and the contamination resistance of the coating film was evaluated by measuring the whiteness by an outdoor exposure test.

<Adjustment of paint and test paint pieces> Conforms to JISK 5600-2-5: 1999 (1) Standard paint Excel auto homogenizer with impeller blades in the grinding and letdown processes with the raw material composition shown in Table 2 ( Nippon Seiki Co., Ltd. model ED) was used as the paint. The obtained paint was confirmed to be free of particles of 5 microns or more by the crush gauge method (conforming to JISK5600-2-5: 1999), and this aqueous emulsion paint was used as a standard paint.

1: Dispersant manufactured by San Nopco Co., Ltd. 2: Thickener manufactured by San Nopco Co., Ltd. 3: Defoamer manufactured by San Nopco Co., Ltd. 4: Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. 5: Dainippon Ink & Chemicals, Inc. Acrylic emulsion manufactured by Sanyo Co., Ltd. 6: Preservative manufactured by San Nopco Co., Ltd. 7: Film-forming regulator manufactured by Eastman Chemical Co., Ltd. 8: Thickener manufactured by San Nopco Co., Ltd.

(2) Evaluation paint To 98.5 parts of the standard paint, 1.5 parts of the paint additive obtained in Examples or Comparative Examples was added, and an Excel auto homogenizer (impeller blade) was used, and the room temperature (20-30) C.) at 2000 rpm for 3 minutes to prepare an evaluation paint.
A blank paint was prepared in the same manner as described above except that 1.5 parts of the paint additive was changed to 1.5 parts of deionized water.

(3) Test piece Polyester film degreased with acetone {trade name: Lumirror 75-S10, manufactured by Panac Co., Ltd., with a thickness of 0.1 mm cut to 10 × 8 cm and used. }, The coating thickness when wet was set to 200 μm, and after applying the evaluation paint or the blank paint, the control room (hereinafter abbreviated as the temperature control room) adjusted to 25 ° C. and 60% relative humidity for 10 days. It dried and it was set as the test coating piece.

<Performance evaluation>
1. Contact angle with water Take a 1 x 5 cm test piece from the test piece, drop 0.02 ± 0.005 mL of deionized water onto the surface of the coating, and contact the water drop after 1 minute. Was used as the initial contact angle. The contact angle was measured in a temperature control room using a contact angle meter CAA manufactured by Kyowa Chemical.

2. Contact angle after immersion treatment (sustainability promotion test)
A test piece having a size of 1 × 5 cm was taken from the test piece and immersed in deionized water at 25 ° C. for 14 days. Next, after drying for 36 hours in a temperature-controlled room (25 ° C., 60% relative humidity), the contact angle with water was measured in the same manner as described above, and this was defined as the contact angle after the immersion treatment.

3. After taking a test piece having a size of 5 × 5 cm from a paint piece for water resistance test and immersing it in deionized water at 25 ° C. for 14 days, it is lifted from the water, and the number of blisters generated on the surface of the coating film and The size and the like were determined according to the following criteria, and this was evaluated as water resistance.

A: No blister.
○: There are some blisters having a diameter of about 0.1 mm.
Δ: Some blisters with a diameter of 0.5 mm or more.
X: There are many blisters with a diameter of 0.5 mm or more.

4). Difference in whiteness (-△ L value, outdoor dripping test)
A test plate (prepared by spray-coating each evaluation paint with a wet film thickness of 1.5 mm on a 10 x 30 cm stainless steel plate and drying it) is 18 m above ground (6th floor) in Tokai City, Aichi Prefecture. (On the roof of the building) equipped with an outdoor rain dripping test stand (stainless steel, 80 cm long, 110 cm wide, with a roof with a 5 mm deep rain collecting groove at an interval of 5 mm (having an inclination of 30 degrees with respect to the horizontal plane)). Install the paint surface vertically and with the paint surface facing true north, and let the rainwater from the rain collecting groove on the roof flow along the paint surface. From the beginning of January 2007 to January 2008 The test was conducted for about 12 months until the end of the month. Then, after rubbing off dust, dirt, etc. adhering to the surface of the test coating piece with a wet cotton cloth, the whiteness (L2) was measured. Then, a value obtained by subtracting the whiteness (L1) of the test coating piece before exposure from the whiteness (L2) was defined as a difference in whiteness (absolute value: -ΔL). It shows that pollution resistance is so favorable that-(DELTA) L is small. As a whiteness measurement tester, SPECTRO COLOR METERMODEL PF-10 manufactured by Nippon Denshoku Industries Co., Ltd. was used.

  From Table 3, the additive for paints of the present invention (Examples 1 to 10) is different from the additive for paints of Comparative Examples 1 to 3 in the contact angle with water, particularly the difference in contact angle before and after the immersion treatment. And the difference in whiteness was extremely small, and it was confirmed that the long-term contamination reduction and its sustainability were extremely high. The paint additive of the present invention also has good water resistance and did not deteriorate the original properties of the paint.

  The paint additive of the present invention can be applied to both aqueous paints and non-aqueous paints, and among these, it is suitable for water-based paints, and particularly suitable for aqueous emulsion paints. Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints. The paint additive of the present invention is extremely useful for paints (especially aqueous emulsion paints) to be painted outdoors such as outer walls.

Claims (4)

A paint additive comprising a polyoxyalkylene compound (Y) represented by the general formula (1).

_{S 1 -L-D-L (} -S 2 -L-D-L) q -S 1 (1)

However, _{S 1} is a group represented by the general formula (2), _{S 2} is a group represented by the general formula (3), radical D is represented by the general formula (4), L 6 to 20 carbon atoms The diisocyanate reaction residue, q represents an integer of 0 to 5.

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, and Z is two from glycols having 2 to 15 carbon atoms The residue except the hydroxyl group of, O is an oxygen atom, H is a hydrogen atom, n is an integer of 2-50, t is an integer of 2-4, m represents an integer of 5-35, S ₁ unit and S ₂ The total number of OA included in the unit is an integer of 10 to 100, and S ₁ , S ₂ , D, L, R, (OA) n, Q, n, and m may be the same or different. The paint additive according to claim 1, wherein the non-reducing di- or trisaccharide reaction residue (Q) is a sucrose reaction residue. 1 mole part of the compound (a12) obtained from a chemical reaction of 1 mole part of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2) having 2 to 4 carbon atoms,
0.5 to 0.86 mole part of the compound (a32) obtained from the chemical reaction of 1 mole part of the glycol (a3) having 2 to 15 carbon atoms and 10 to 70 mole parts of the alkylene oxide (a2) having 2 to 4 carbon atoms; ,
A paint additive comprising a polyoxyalkylene compound having a structure that can be produced by a chemical reaction with 1.0 to 1.71 mole parts of a diisocyanate (a4) having 6 to 20 carbon atoms as an essential component. A paint composition comprising a paint and the paint additive according to any one of claims 1 to 3, and containing the paint additive in an amount of 0.1 to 5% by weight based on the weight of the paint.