JP2012107088A - Resin-modifying agent, modified resin composition containing the same and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-modifying agent that has hydrolysis resistance and can impart hydrophilicity coating films without deteriorating the water resistance of the coating films.SOLUTION: The resin-modifying agent includes a polyoxyalkylene compound represented by one of formulae (1) to (3) as an essential component: (G-)S (1); (G-)-S-L{-S(-G)-L}-S(-G)(2); and (G-)-S-L{-U-L-S(-G)-L}-U-L-S(-G)(3) [wherein, S is a group of formula 4: Q{-(OA-)}; t is 2 to 4; L is a diglycidyl ether residue; U is a group of formula 5: Z{-(OA-)O-}; q is 0 to 1; G is glycidyl or H; at least one of G is glycidyl, wherein Q is a non-reducible di- or tri-saccharide residue; OA is oxyalkylene; Z is alkylene or arylene; n is 5 to 30; t is 2 to 4; m is 5 to 20; the total number of OA contained in the group (S) of formula 4 is 20 to 100].

Description

  The present invention relates to a resin modifier, a modified resin composition containing the same, and a coating material.

  Ethylene oxide adducts of alkylamines and alkylamides (Patent Document 1) and non-reducing as paint additives for imparting hydrophilicity to the coating film after cationic electrodeposition coating and preventing water droplets from remaining on the coating film A dimeric or trisaccharide multimeric glycidyl ether compound (Patent Document 2) is known.

JP 2002-226778 A JP 2007-119653 A

  In the paint additive described in Patent Document 1, when the paint film is pulled up from the paint bath in the step after the cationic electrodeposition coating, the paint additive flows down from the paint film, or the paint additive is washed away during washing with water. There is a problem that it is easy to do and hardly remains in the coating film. On the other hand, when the amount used is increased in order to increase the remaining amount, there are problems such as adversely affecting the water resistance (rust resistance) of the coating film.

  The coating additive described in Patent Document 2 has a problem in that since an ether bond derived from a dihalide is used for multimerization, it tends to be subject to hydrolysis, resulting in a decrease in performance.

  That is, the object of the present invention is to have hydrolysis resistance and impart hydrophilicity (drying unevenness) to the coating film (coating resin) without impairing the water resistance (rust resistance) of the coating film (coating resin). It is to provide a resin modifier (coating resin modifier) that can be used.

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 resin modifier of the present invention is that the polyoxyalkylene compound (Y) represented by any one of the general formulas (1) to (3) is an essential component.

(G-) _t S (1)

(G-) _t-1 SL {-S (-G) _t-2 -L} _q- S (-G) _t-1 (2)

(G-) _t-1 SL {-ULS (-G) _t-2 -L} _q -ULS (-G) _t-1 (3)

  However, S is group represented by General formula (4), t is an integer of 2-4, L is the reaction residue of C10-50 diglycidyl ether, U is represented by General formula (5) Group q represents 0, 1 or 2, and G represents a glycidyl group or a hydrogen atom, but in each general formula, at least one G is a glycidyl group.

Q {-(OA-) _n } _t (4)

Z {-(OA-) _m O} _2- (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, Z is an alkylene group or arylene having 2 to 15 carbon atoms Group, O represents an oxygen atom, n represents an integer of 5 to 30, t represents an integer of 2 to 4, m represents an integer of 5 to 20, and OA contained in the group (S) represented by the general formula (4) Is an integer of 20 to 100, and when a plurality of S, L, U, (OA) n, (OA) m, Q, Z, q, n, m, and t are contained in one molecule, a plurality of Each of the pieces may be the same or different.

  A feature of the modified resin composition of the present invention is that it contains a resin and the above resin modifier, and contains 5 to 40% by weight of a resin modifier based on the weight of the resin and the resin modifier. This is the summary.

  The gist of the characteristics of the coating material of the present invention is that it contains the above-mentioned modified resin composition.

  The coating composition of the present invention is characterized by containing a coating material and the above resin modifier, and containing 0.5 to 5% by weight of a resin modifier based on the weight of the coating material and the resin modifier. This is the summary.

A feature of the production method of the present invention is a method for producing the above resin modifier,
Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing di- or trisaccharide (a1) and 20 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms And a method (1) comprising a step (2) of obtaining a polyoxyalkylene compound (Y1) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 3 mol parts of an epihalohydrin (a3);

Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing di- or trisaccharide (a1) and 20 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
Compound (a124) is obtained from chemical reaction (3) of 1 mol part of compound (a12) and 0.5 to 0.67 mol part of diglycidyl ether (a4) having 10 to 50 carbon atoms; and step (3); A method (2) comprising a step (4) of obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (4) of the compound (a124) and 1 to 3 mole parts of an epihalohydrin (a3); or

Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing di- or trisaccharide (a1) and 20 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
A step (5) of obtaining a compound (a52) from a chemical reaction (5) of 1 mol part of a glycol having 2 to 15 carbon atoms (a5) and 10 to 40 mol parts of an alkylene oxide having 2 to 4 carbon atoms (a2);
Chemical reaction (1) of 1 mol part of compound (a12), 0.5 to 0.67 mol part of compound (a52) and 1 to 1.33 mol part of diglycidyl ether (a4) having 10 to 50 carbon atoms A step (6) of obtaining a compound (a12524) from the above (6); and a step (7) of obtaining a polyoxyalkylene compound (Y3) from a chemical reaction (7) of 1 to 3 mole parts of the compound (a12524) and epihalohydrin (a3). The point which consists of method (3) makes it a summary.

  The resin modifier (coating resin modifier) of the present invention has excellent hydrolysis resistance and can be applied to a coating film (coating resin) without impairing the water resistance (rust prevention) of the coating film (coating resin). Hydrophilicity (drying unevenness resistance) can be imparted.

  Since the modified resin composition of the present invention contains the above-described resin modifier (coating resin modifier), it has excellent hydrolysis resistance and water resistance (rust resistance) of the coating film (coating resin). ) Can be imparted hydrophilicity (drying unevenness) to the coating film (coating resin).

  Since the coating material of the present invention contains the above-mentioned modified resin composition, it has excellent hydrolysis resistance and the coating film (coating resin) without impairing the water resistance (rust prevention) of the coating film (coating resin) ) Can be imparted with hydrophilicity (drying unevenness).

  Since the coating composition of the present invention contains the above-mentioned resin modifier, it has excellent hydrolysis resistance, and the coating film (coating) without impairing the water resistance (rust resistance) of the coating film (coating resin) Resin) can be given hydrophilicity (drying unevenness).

  The production method of the present invention is an optimum method for producing the above resin modifier.

The group (S) represented by the general formula (4) will be described.
Examples of saccharides that can constitute a residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of non-reducing di- or trisaccharides include sucrose, trehalose, isotrehalose, isosaccharose, gentianose , Raffinose, meretitol and planteose. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of hydrophilicity and the like, more preferably sucrose and trehalose, and sucrose is particularly preferable from the viewpoint of supply ability and cost.

  Examples of the oxyalkylene group (OA) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Among these, oxyethylene, oxypropylene, and a mixture thereof are preferable from the viewpoint of hydrophilicity and water resistance, and a mixture of oxyethylene and oxypropylene is more preferable from the viewpoint of hydrophilicity (dry unevenness resistance).

  When oxypropylene and / or oxybutylene and oxyethylene are included, the content ratio (mol%) of oxyethylene is preferably 2 to 8, more preferably 4 to 6, based on the total number of moles of oxyalkylene groups. It is. 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). In addition, when (OA-) n includes 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 the oxyalkylene groups.

  n is preferably an integer of 5 to 30, more preferably an integer of 5 to 28, particularly preferably an integer of 8 to 25, and most preferably an integer of 10 to 25. Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

  t is preferably an integer of 2 to 4, more preferably 3 or 4, and particularly preferably 3. Within this range, the water resistance (rust resistance) and hydrophilicity (drying unevenness) of the coating film are further improved. T corresponds to t in the general formulas (1) to (3) and also corresponds to the number of primary hydroxyl groups of a di- or trisaccharide. For example, 3 for sucrose, 2 for trehalose, 4 for meretitose. It is.

  The total number of OA contained in the group (S) represented by the general formula (4) is preferably an integer of 20 to 100, more preferably an integer of 20 to 90, particularly preferably an integer of 30 to 80, most preferably. It is an integer of 30-70. Within this range, the water resistance (rust resistance) and hydrophilicity (drying unevenness) of the coating film are further improved.

  The reaction residue (L) of the diglycidyl ether having 10 to 50 carbon atoms includes a residue obtained by ring-opening reaction of two epoxy groups possessed by the diglycidyl ether having 10 to 50 carbon atoms.

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.

The group (U) represented by the general formula (5) will be described.
Among the alkylene group or arylene group (Z) having 2 to 15 carbon atoms, as the alkylene group, 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-dimethylpentylene (—CH ₂ CH (CH ₃ ) OCH (CH ₃ ) CH ₂ —), butylene, hexamethylene, cyclohexylene, methylenecyclohexylenemethylene ( _{-CH 2 C 6 H 10 CH 2} -), and the like methyl cyclohexylene and trimethyl cyclohexylene.

Among the alkylene group or arylene group (Z), as the arylene group, arylene having 6 to 15 carbon atoms is used, and phenylene, methylphenylene, ethylphenylene, tetramethylphenylene, xylylene, naphthylene, biphenylylene, dimethylbiphenylylene, Anthrylene, phenanthrylene, a group represented by-(ph) -CH _2- (ph)-, a group represented by-(ph) -C (CH ₃ ) _2- (ph)-,-(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).

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

  The oxyalkylene group (OA) having 2 to 4 carbon atoms is the same as above, but oxyethylene and oxypropylene are preferable from the viewpoint of hydrophilicity, and more preferably a mixture of oxypropylene and oxyethylene. On the other hand, from the viewpoint of water resistance, oxypropylene and oxybutylene are preferable, and a mixture of oxypropylene and oxybutylene is more preferable.

  When a plurality of types of oxyalkylene groups are contained in (OA-) m, the bonding order (block shape, random shape, and combinations thereof) and content ratios of these oxyalkylene groups are not limited.

  When oxypropylene and / or oxybutylene and oxyethylene are included, the content ratio (mol%) of oxyethylene is preferably 5 to 10 based on the total number of moles of oxyalkylene groups. 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 portion away from the alkylene group or the arylene group (Z).

  m is preferably an integer of 5 to 20, more preferably an integer of 7 to 20, particularly preferably an integer of 7 to 18, and most preferably an integer of 10 to 15. Within this range, the water resistance (rust resistance) of the coating film is further improved.

  q is 0 or 1. Within this range, water resistance (rust resistance) as well as hydrophilicity (drying unevenness) are further improved.

  G represents a glycidyl group or a hydrogen atom. In general formula (1), at least one G among t G is a glycidyl group. In the general formula (2), at least one G out of {(t−1) × 2 + (t−2) × q} G is a glycidyl group. In the general formula (3), at least one G out of {(t−1) × 2 + (t−2) × q} G is a glycidyl group.

  The polyoxyalkylene compound (Y) represented by any one of the general formulas (1) to (3) can be produced by applying a known chemical reaction.

For example, among the polyoxyalkylene compounds (Y), the polyoxyalkylene compound (Y1) represented by the general formula (1) has 1 mole part of a non-reducing di- or trisaccharide (a1), 2 to 2 carbon atoms. Step (1) to obtain compound (a12) from chemical reaction (1) with alkylene oxide (a2) 20-100 mol part of 4; and 1 mol part of compound (a12) and epihalohydrin (a3) 1-3 mol part It can manufacture by the method (1) etc. which include the process (2) which obtains a polyoxyalkylene compound (Y1) from the chemical reaction (2).

  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, from the viewpoint of dryness resistance of the coating film, EO, a mixture containing EO and PO are preferable, and a mixture containing EO is more preferable.

  Moreover, when using multiple types of alkylene oxides, the order of reaction (block, random and combinations thereof) and the usage rate are not limited, but it is preferable to include a block or a combination of block and random. .

  Moreover, when it contains EO, 2-8 are preferable based on the total number of moles of alkylene oxide, and, more preferably, it is 4-6, based on the total number of moles of EO. When EO and PO or / and BO are included, it is preferable to react PO and / or BO after the reaction of EO to (a1).

  Examples of epihalohydrin include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferred.

  In the step (1), the amount (mole part) of the alkylene oxide (a2) used is preferably 20 to 100, more preferably 20 to 1 part by mole of the non-reducing di- or trisaccharide (a1). 90, particularly preferably 30 to 80, and most preferably 30 to 70 (the same applies to the following methods). Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

In the step (2), the usage amount (mol part) of the epihalohydrin (a3) is 1 mol part of the compound (a12) {non-reducing disaccharide or trisaccharide (a1)}.
1 to 3 is preferable, more preferably 1 to 2, particularly preferably 1 to 1.8, and most preferably 1.2 to 1.8. Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

Among the polyoxyalkylene compounds (Y), the polyoxyalkylene compound (Y2) represented by the general formula (2) has 1 mol part of a non-reducing di- or trisaccharide (a1) and 2 to 4 carbon atoms. Step (1) of obtaining compound (a12) from chemical reaction (1) with 20 to 100 parts by mole of alkylene oxide (a2);
A step (3) of obtaining a compound (a124) from a chemical reaction (3) of 1 mol part of the compound (a12) and 0.5 to 0.67 mol part of a diglycidyl ether having 10 to 50 carbon atoms (a4); and It can be produced by a method (2) or the like including a step (4) for obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (4) between the compound (a124) and 1 to 3 mole parts of an epihalohydrin (a3).

  Examples of the diglycidyl ether (a4) having 10 to 50 carbon atoms include tetramethylene diglycidyl ether, glycerin diglycidyl ether, 2,2-dimethylpropylene diglycidyl ether, hexamethylene diglycidyl ether, trimethylolpropane diglycidyl ether, penta Examples include erythritol diglycidyl ether and polyoxyalkylene (glycol / alkylene oxide adduct, etc., having 4 to 44 carbon atoms, alkylene having 2 to 4 carbon atoms) diglycidyl ether.

  In the step (3), the amount (mole part) of the diglycidyl ether having 10 to 50 carbon atoms (a4) is used relative to 1 part by mole of the compound (a12) {non-reducing disaccharide or trisaccharide (a1)}. 0.5 to 0.67 is preferable, more preferably 0.5 to 0.65, particularly preferably 0.55 to 0.65, and most preferably 0.55 to 0.63. Within this range, the water resistance of the coating film is further improved.

  In the step (4), the usage amount (mol part) of the epihalohydrin (a3) is preferably 1 to 3 with respect to 1 mol part of the compound (a124) {non-reducing di- or trisaccharide (a1)} More preferably, it is 1-2.5, Most preferably, it is 1.5-2.5, Most preferably, it is 1.7-2.3. Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

Among the polyoxyalkylene compounds (Y), the polyoxyalkylene compound (Y3) represented by the general formula (3) has 1 mol part of a non-reducing di- or trisaccharide (a1) and 2 to 4 carbon atoms. Step (1) of obtaining compound (a12) from chemical reaction (1) with 20 to 100 parts by mole of alkylene oxide (a2);
A step (5) of obtaining a compound (a52) from a chemical reaction (5) of 1 mol part of a glycol having 2 to 15 carbon atoms (a5) and 10 to 40 mol parts of an alkylene oxide having 2 to 4 carbon atoms (a2);
Chemical reaction (1) of 1 mol part of compound (a12), 0.5 to 0.67 mol part of compound (a52) and 1 to 1.33 mol part of diglycidyl ether (a4) having 10 to 50 carbon atoms A step (6) of obtaining a compound (a12524) from the above (6); and a step (7) of obtaining a polyoxyalkylene compound (Y3) from a chemical reaction (7) of 1 to 3 mole parts of the compound (a12524) and epihalohydrin (a3). It can be produced by the method (3) or the like.

  The glycol (a5) includes an aliphatic diol having 2 to 9 carbon atoms and an aromatic diol having 6 to 15 carbon atoms.

  Examples of the aliphatic diol having 2 to 9 carbon atoms include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexamethylene glycol, cyclohexylene glycol, hydroxymethylcyclohexylmethyl alcohol, methylcyclohexylene glycol and trimethylcyclohexyl. Examples include silylene glycol.

  Examples of the aromatic diol having 6 to 15 carbon atoms include hydroquinone, resorcinol, dihydroxytoluene, dihydroxyethylbenzene, dihydroxytetramethylbenzene, xylylene glycol, dihydroxynaphthalene, dihydroxybiphenyl, dihydroxydimethylbiphenyl, dihydroxyanthracene, dihydroxyphenanthrene, Examples thereof include bisphenol F and bisphenol A.

  Of these glycols (a5), ethylene glycol, propylene glycol, hexamethylene glycol and -bisphenol A are preferable, and propylene glycol is more preferable.

  In the step (5), the amount (mole part) of the alkylene oxide (a2) used is preferably 10 to 40, more preferably 14 to 40, particularly preferably 14 to 1 part by mole of the glycol (a5). 36, most preferably 20-30. Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

  In the step (6), the amount of the compound (a52) used (mole parts) is 0.5 to 0.00 with respect to 1 mol part of the compound (a12) {non-reducing di- or trisaccharide (a1)}. 67 is preferable, more preferably 0.5 to 0.65, particularly preferably 0.55 to 0.65, and most preferably 0.55 to 0.63. Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

  In the step (6), the amount (mole part) of the diglycidyl ether having 10 to 50 carbon atoms (a4) is used relative to 1 part by mole of the compound (a12) {non-reducing disaccharide or trisaccharide (a1)}. 1 to 1.33 is preferable, more preferably 1 to 1.3, particularly preferably 1.05 to 1.3, and most preferably 1.05 to 1.25. Within this range, the water resistance of the coating film is further improved.

  For the addition reaction between the non-reducing di- or trisaccharide (a1) or glycol (a5) and the alkylene oxide (a2), a known method (JP 2004-224945 A) or the like can be applied, and anionic polymerization , Cationic polymerization or coordinated anionic polymerization may be used. These polymerization forms may be used alone or in combination according to the degree of polymerization.

  For the addition reaction of alkylene oxide (a2), a known reaction catalyst (JP 2004-224945 A) can be used. In addition, when using the amide demonstrated below as a reaction solvent, it is not necessary to use a reaction catalyst.

  When a reaction catalyst is used, the amount used (% by weight) is 0.01 to based on the total weight of the non-reducing disaccharide or trisaccharide (a1) or glycol (a5) and the alkylene oxide (a2). 1 is preferable, 0.03 to 0.8 is more preferable, and 0.05 to 0.6 is particularly preferable. When it is within this range, the economy (required production time, catalyst cost, etc.), the purity of the product (monodispersity, etc.), etc. are further improved.

  When the reaction catalyst is used, it is preferable to finally remove the reaction catalyst from the reaction product. As the removal method, an alkali adsorbent such as a synthetic aluminosilicate {for example, trade name: Kyoward 700, Kyowa Chemical Industry ( Manufactured by the same 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, etc.), a method using an ion exchange resin (special And a method of filtering a carbonate formed by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000).

  As the end point of removal of the reaction catalyst, the CPR (Controlled Polymerization Rate) value described in JIS K1557-4: 2007 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2. It is as follows.

  A known reaction vessel (JP 2004-224945 A) or the like can be used for the reaction. As the reaction atmosphere, it is preferable that the inside of the reaction apparatus is evacuated or dried in an inert gas atmosphere (such as argon, nitrogen and carbon dioxide) 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, hereinafter the same) 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 determined when the decrease in the reaction pressure becomes 0.001 MPa or less. The required reaction time is usually 4 to 12 hours.

  A reaction solvent can be used in the step of the addition reaction of alkylene oxide (a2). As the reaction solvent, those having no active hydrogen are preferable, and more preferable is a product formed by reaction with non-reducing di- or trisaccharide (a1) or glycol (a5), alkylene oxide (a2) and (a2). Those that dissolve the product are 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 non-reducing di- or trisaccharide (a1) or glycol (a5) and alkylene oxide (a2), 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 based on the weight of the non-reducing di- or trisaccharide (a1) or glycol (a5) and the alkylene oxide (a2). Preferably it is 0.05 or less, Most preferably, it is 0.01 or less. The residual amount of the reaction solvent can be determined by gas chromatography using an internal standard substance.

  Examples of the method for removing the reaction solvent include the method described in JP-A-2005-132916.

  The reaction between the compound (a12), the compound (a124) or the compound (a12524) and the epihalohydrin (a3) is carried out by a dehydrohalogenation reaction with a basic substance (Williamson synthesis reaction: a hydrogen halide generated sequentially during the reaction as a base The reaction is driven by neutralizing with a chemical substance).

  As reaction conditions, for example, the reaction temperature is set to 40 to 80 ° C. with stirring in a nitrogen atmosphere.

  Examples of basic substances that can be used in this reaction include alkali metal or alkaline earth metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide). , Calcium hydroxide and barium hydroxide, etc.), alkali metal alcoholates (C 1-2: sodium methylate and potassium ethylate, etc.), alkali metal or alkaline earth metal carbonates (sodium carbonate, potassium carbonate and carbonic acid) Barium etc.). Of these, alkali metal hydroxides are preferred, sodium hydroxide and potassium hydroxide are more preferred, and sodium hydroxide is particularly preferred.

  In this case, the amount of the basic substance used is preferably such that the base equivalent (eq.) Of the basic substance / halogen equivalent (eq.) Ratio of the halogenated hydrocarbon is 0.9 to 1.1. The amount is more preferably 0.95 to 1.05.

  After completion of the reaction, it is preferable to remove the formed neutralized salt and the basic substance (if remaining). (1) When the basic substance remains, first use an acidic substance. Neutralize. Next, a method for removing neutralized salts, etc. by filtration, (2) a method for removing first produced neutralized salts, etc. by filtration, and then a method for removing remaining basic substances using an adsorbent, etc., (3) by an organic solvent An extraction method or the like can be applied.

  Among the methods of (1), in order to neutralize the remaining basic substances, mineral acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), organic acids (formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, terephthalic acid) Oxalic acid, malonic acid, adipic acid, succinic acid, lactic acid, etc.) can be used. Neutralized salts with these are removed by filtration.

  Of the methods (2), the method using an adsorbent or the like can be removed in the same manner as the removal of the reaction catalyst for the addition reaction of alkylene oxide (a2).

  The extraction method of (3) is to add water and an organic solvent (having very low solubility in water such as hexane, toluene, xylene, etc.) to the reaction product and shake the reaction product to remove the organic solvent. In this method, a neutralized salt and a basic substance are separated into an aqueous layer by extraction into a layer. The organic solvent layer is preferably further washed with deionized water or the like. A suitable volume ratio of reaction product: water: organic solvent is approximately 1: 1: 1. At this time, if 1 to 5% by weight of sodium chloride is added to water, the separation between the aqueous phase and the organic phase may be improved. In the case of (3), it is preferable to finally remove the neutralized salt and the basic substance by using the method of (2) together.

  As the end point of the removal of the basic substance, the CPR (Controlled Polymerization Rate) value described in JIS K1557-4: 2007 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, most preferably 2 or less.

  Further, it is preferable to remove moisture. In this case, dehydration is performed at 100 to 130 ° C. under reduced pressure {gauge pressure (hereinafter the same) −0.05 to −0.098 MPa} for 1 to 2 hours. The water content in the product is preferably 0.1% by weight or less, more preferably 0.05% by weight or less.

  Moisture can be measured by a known method. For example, Karl Fischer method (JIS K0113: 2005, coulometric titration method) or weight loss by thermal drying (for example, 0.5 g of a sample is dried at 130 ° C. for 1 hour). , Weight change before and after that).

  As the reaction vessel, it is preferable to use a reaction vessel capable of heating, cooling, stirring and dropping (press-fitting). 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 epihalohydrin (a3) into the reaction system. Moreover, as reaction temperature (degreeC), 40-80 are preferable, More preferably, it is 50-70.

  The end point of the reaction can be confirmed by the following method. That is, when the pH of the reaction solution is measured and becomes 7 to 9, the reaction is terminated. The required reaction time is usually 4-8 hours.

  The polyoxyalkylene compound (Y) produced by the above method may have a distribution in the number of oxyalkylene groups, q, etc. In this case, strictly speaking, it becomes a mixture of a plurality of types of polyoxyalkylene compounds. A polyoxyalkylene compound represented by any one of the general formulas (1) to (3) is contained in the mixture. Even in this case, the manufacturing method is not limited.

  Among the polyoxyalkylene compounds (Y) represented by any one of the general formulas (1) to (3), the polyoxyalkylene compound (Y1) represented by the general formula (1) is shown in Table 1. Preferred examples include compounds produced using raw materials {non-reducing di- or trisaccharide (a1), alkylene oxide (a2) and epihalohydrin (a3)}.

  Q1 represents sucrose, Q2 represents trehalose, Q3 represents meletitose, P represents propylene oxide, E represents ethylene oxide, B represents butylene oxide, and these subscripts are non-reducing di- or trisaccharides, respectively. The number of moles per mole, / represents a block shape, • represents a random shape, ECH represents epichlorohydrin, and the subscript represents the number of moles per mole of non-reducing di- or trisaccharide.

  Among the polyoxyalkylene compounds (Y) represented by any one of the general formulas (1) to (3), the polyoxyalkylene compound (Y2) represented by the general formula (2) is shown in Table 2. Preferred examples include compounds produced using raw materials {non-reducing di- or trisaccharide (a1), alkylene oxide (a2), epihalohydrin (a3) and diglycidyl ether (a4)}.

  Q1, Q2, Q3, P, E, B, /,..., ECH, and suffixes are the same as those in Table 1. Α is diglycidyl ether of polyoxyethylene (1.5 mol), polyoxypropylene (15 mol), polyoxyethylene (1.5 mol) glycol (ethylene oxide adduct of polyoxypropylene glycol; pluronic type). , Β is 1,6-hexanediol diglycidyl ether, γ is polyoxypropylene glycol (3 mol) diglycidyl ether, δ is polyoxypropylene glycol (7 mol) diglycidyl ether, and the subscript is non-reducing. It represents the number of moles per mole of the sex di- or trisaccharide.

  Among the polyoxyalkylene compounds (Y) represented by any one of the general formulas (1) to (3), the polyoxyalkylene compound (Y3) represented by the general formula (3) is shown in Table 3. Preferred examples include compounds produced using raw materials {non-reducing disaccharides or trisaccharides (a1), alkylene oxides (a2), epihalohydrins (a3), diglycidyl ethers (a4) and glycols (a5)}.

Q1, Q2, Q3, P, E, B, /,..., ECH, α, β, γ, δ and their subscripts are the same as those in Tables 1 and 2.
Further, DEG represents diethylene glycol, DPG represents dipropylene glycol, HG represents hexamethylene glycol, and BPA represents bisphenol A, and these subscripts represent the number of moles relative to 1 mol of the non-reducing di- or trisaccharide, respectively.
However, the subscript described in the column of alkylene oxide (a2) is the same as in Tables 1 and 2, but the subscript described in alkylene oxide (a2) ′ represents the number of moles relative to 1 mol of glycol.

  Of these, No. 3, 4, 6, 7, 11, 14, 15, 16, 21, 24, 25, 30, 32, 36 or 40 are preferred, and more preferably It is a polyoxyalkylene compound represented by 7, 15, 30 or 36.

  The epoxy equivalent (g / eq.) Of the polyoxyalkylene compound (Y) is preferably 2,000 to 10,000, more preferably 2,500 to 9,000, particularly preferably 3,000 to 8,000, Most preferably, it is 3,000-7,000. Within this range, the hydrophilicity (drying unevenness) and water resistance (rust resistance) of the coating film are further improved.

  The resin modifier of the present invention can be applied to both aqueous and non-aqueous resins. Among these, it is suitable for water-based resins, further suitable for water-based epoxy resins, water-based urethane resins, water-based polyester resins, and the like, and particularly suitable for resins for cationic electrodeposition paints and resins for baking paints. The number average molecular weight of these aqueous resins is preferably about 500 to 10,000.

  The method of modifying the resin using the resin modifier of the present invention is not limited as long as it is contained in an aqueous resin or non-aqueous resin, but it is preferably contained from the stage of synthesizing the resin, and the reaction component (simple It is preferable to use as one of (mer).

  The use amount (% by weight) of the resin modifier of the present invention is preferably 5 to 40, more preferably 7 to 38, particularly preferably 7 to 35, based on the weight of the resin and the resin modifier. Especially preferably, it is 10-33, Most preferably, it is 10-30. Within this range, the dryness unevenness of the coating produced using the modified resin composition comprising the resin modifier of the present invention is further improved, and the water resistance of the coating film (the inherent property of the resin) It is difficult to adversely affect the water resistance).

  The resin modifier of the present invention is suitable for paints. Among the paints, it is suitable for water-based paints, and further suitable for cationic electrodeposition paints and baking paints.

  When the resin modifier of the present invention is applied to a paint, the content (% by weight) of the resin modifier of the present invention is preferably 0.5 to 5 based on the weight of the paint and the resin modifier, More preferably, it is 1-3.

  The modified resin composition comprising the resin modifier of the present invention and a resin is suitable for a paint. Among the paints, it is suitable for water-based paints and further suitable for cationic electrodeposition paints.

  The coating material using the resin modifier of the present invention can be applied to an object to be coated by an ordinary method, and is electrodeposition coating, brush coating, roller coating, air spray coating, airless coating, roll coater coating and flow coater. A painting method such as painting can be applied.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Parts and% represent parts by weight and% by weight, 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 purified granulated sugar {manufactured by Taiyo Co., Ltd., hereinafter the same}, DMF {Mitsubishi After supplying 1000 parts by Gas Chemical Co., Ltd., the same applies hereinafter, the operation of pressurizing with nitrogen gas to 0.4 MPa with a gauge pressure and discharging to 0.02 MPa was repeated three times (hereinafter, , Referred to as nitrogen substitution). Thereafter, the temperature was raised to 100 ° C. with stirring, and at this temperature, 176 parts (4 mol parts) of EO was added dropwise over 2 hours, and 1740 parts (30 mol parts) of PO were further added dropwise over 8 hours. Stirring was continued for 3 hours to react the remaining PO. Next, DMF was removed under reduced pressure at 120 ° C. to obtain an adduct (B1) of sucrose / EO 4 mol / PO 30 mol.

  In a pressure-resistant reaction vessel similar to the above, sucrose / EO 4 mol / PO 30 mol adduct (B1) 2258 parts (1 mol part) and potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. The amount is expressed as a net equivalent amount excluding. same as below. } 8 parts were added and nitrogen substitution was repeated 3 times, and further dehydrated at 120 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, PO2088 parts (36 mol parts) were added dropwise over 6 hours at 100 ° C. with reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Next, after adding 50 parts of deionized water at 90 ° C., 150 parts of Kyoward 700 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 an adduct (S1) of sucrose / EO 4 mol / PO 66 mol.

<Production Example 2>
Into a pressure-resistant reaction vessel similar to Production Example 1, 342 parts (1 mol part) of purified granulated sugar (manufactured by Taikaku Co., Ltd., the same shall apply hereinafter) and 1000 parts of DMF were added, followed by nitrogen substitution. Thereafter, the temperature was raised to 100 ° C. with stirring, and at this temperature, 88 parts (2 mole parts) of EO was added dropwise over 1 hour, and 1740 parts (30 mole parts) of PO were further added dropwise over 8 hours. Stirring was continued for 3 hours to react the remaining PO. Subsequently, DMF was removed under reduced pressure at 120 ° C. to obtain an adduct (B2) of sucrose / EO 2 mol / PO 30 mol.

  In a pressure-resistant reaction vessel similar to Production Example 1, 2170 parts (1 mole part) of sucrose / EO2 mole / PO30 mole adduct (B2) and 10 parts of potassium hydroxide were added, and nitrogen substitution was repeated three times. And dehydrated under reduced pressure of 0.6 to 1.3 kPa. Next, PO 3364 parts (58 mole parts) were added dropwise over 9 hours at 100 ° C. under reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Next, Kyoward treatment and dehydration were performed to obtain an adduct (S2) of sucrose / EO2 mol / PO88 mol.

<Production Example 3>
Into a pressure-resistant reaction vessel similar to Production Example 1, 342 parts (1 mole part) of purified granulated sugar and 1000 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. while stirring, and 1740 parts (30 mole parts) of PO was added dropwise at this temperature over 8 hours, and stirring was further continued for 3 hours at the same temperature to react with the remaining PO. Next, DMF was removed under reduced pressure at 120 ° C. to obtain a sucrose / PO 30 molar adduct (S3).

<Production Example 4>
In a pressure-resistant reaction vessel similar to Production Example 1, 2082 parts (1 mole part) of sucrose / PO 30 mole adduct (1 mole part) and 9.0 parts of potassium hydroxide were added, and the nitrogen substitution was repeated three times. And dehydrated under reduced pressure of 0.6 to 1.3 kPa. Subsequently, 2900 parts (50 mol parts) of PO was added dropwise at 100 ° C. over 8 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Next, Kyoward treatment and dehydration were performed to obtain a sucrose / PO 80 mol adduct (S4).

<Production Example 5>
Into a pressure-resistant reaction vessel similar to Production Example 1, 342 parts (1 mole part) of trehalose {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1000 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1160 parts (20 mole parts) of PO was dropped at this temperature over 6 hours, and stirring was further continued for 3 hours at the same temperature to react with the remaining PO. Next, DMF was removed under reduced pressure at 120 ° C. to obtain a trehalose / PO20 molar adduct (S5).

<Production Example 6>
1502 parts (1 mol part) of trehalose / PO 20 mol adduct (S5) and 5.0 parts of potassium hydroxide were added to the same pressure resistant reactor as in Production Example 1, and the nitrogen substitution was repeated three times. And dehydrated under reduced pressure of 0.6 to 1.3 kPa. Next, PO2320 parts (40 mol parts) were added dropwise at 100 ° C. over 8 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Next, Kyoward treatment and dehydration were performed to obtain a trehalose / PO60 molar adduct (S6).

<Production Example 7>
Into a pressure-resistant reaction vessel similar to Production Example 1, 504 parts (1 mole part) of meretitol {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1500 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 2320 parts (40 mole parts) of PO was added dropwise at this temperature over 10 hours, and stirring was further continued for 3 hours at the same temperature to react with the remaining PO. Subsequently, DMF was removed under reduced pressure at 120 ° C. to obtain an adduct of meretitol / PO 40 mol (S7).

<Production Example 8>
Into a pressure-resistant reaction vessel similar to Production Example 1, 504 parts (1 mole part) of meretito and 1500 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. with stirring, and at this temperature, 176 parts (4 mole parts) of EO was added dropwise over 2 hours, and 1740 parts (30 mole parts) of PO were added dropwise over 8 hours, followed by the same temperature. Stirring was continued for 3 hours to react the remaining PO. Next, DMF was removed under reduced pressure at 120 ° C. to obtain an adduct (B3) of meretitol / EO 4 mol / PO 30 mol.

  To a pressure resistant reactor similar to Production Example 1, 2420 parts (1 part by mole) of meretito / EO4 mole / PO30 mole adduct (B3) and 10.0 parts of potassium hydroxide were added, and the nitrogen substitution was repeated three times. Dehydration was performed at 120 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, PO3828 parts (66 mol parts) were added dropwise over 10 hours at 100 ° C. with reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Subsequently, Kyoward treatment and dehydration were carried out to obtain an adduct (S8) of meletitose / EO4 mol / PO96 mol.

<Production Example 9>
After charging diethylene glycol {special grade reagent, Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “DEG”} 106 parts (1 mole part) and 2 parts of potassium hydroxide into the same pressure resistant reactor as in Production Example 1 And replaced with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 1160 parts (20 mole parts) of PO was dropped and reacted at the same temperature. Next, Kyoward treatment gave DEG / PO 20 molar adduct (U1).

<Production Example 10>
In the same pressure resistant reaction vessel as in Production Example 1, 134 parts (1 mole part) of dipropylene glycol {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “DPG”} and 5 parts of potassium hydroxide were charged. Thereafter, the atmosphere was replaced with nitrogen. Thereafter, the temperature was raised to 100 ° C. while stirring, and then, 2204 parts (38 parts by mole) of PO2 were dropped and reacted at the same temperature. Further, 88 parts (2 mole parts) of EO were dropped and reacted at the same temperature. Next, Kyoward treatment was performed to obtain a DPG / PO 38 mol / EO 2 mol adduct (U2).

<Production Example 11>
In the same pressure resistant reactor as in Production Example 1, hexamethylene glycol {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “HG”} 118 parts (1 mole part) and 1.5 parts of potassium hydroxide were added. After the addition, the atmosphere was replaced with nitrogen. Thereafter, the temperature was raised to 100 ° C. while 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 an HG / PO 10 molar adduct (U3).

<Production Example 12>
698 parts (1 mol part) of HG / PO 10 mol adduct (U3) and 2.5 parts of potassium hydroxide were charged into a pressure resistant reaction vessel similar to Production Example 1, and then purged with nitrogen and dehydrated. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 986 parts (17 mole parts) of (PO) were dropped and reacted at the same temperature. Further, 132 parts (3 mole parts) of EO was dropped and reacted at the same temperature. Next, Kyoward treatment was performed to obtain HG / PO27 mol / EO3 mol adduct (U4).

<Production Example 13>
In 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) was dropped at the same temperature to cause reaction. Furthermore, 132 parts (3 parts by mole) of (EO) were added dropwise and reacted to obtain a DPG / PO13 mole / EO3 mole adduct (EO 1.5 mole-PO15 mole-EO 1.5 mole pluronic glycol).

  Next, in a pressure-resistant reaction vessel similar to the above, this pluronic glycol and sodium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., pure component converted amount excluding moisture, hereinafter the same} 80 parts (2 moles) Part) and an aqueous solution of sodium hydroxide consisting of 100 parts of water, dehydrated at 120 ° C. under reduced pressure for 3 hours, and sealed under reduced pressure, and 185 parts (2 mole parts) of epichlorohydrin {manufactured by Kashima Chemical Co., Ltd.} Was added dropwise at 60 ° C. for 3 hours with stirring. Further, after stirring for 4 hours at the same temperature, Kyoward treatment and dehydration (however, the temperature was set to 80 ° C., the same applies to the case of epichlorohydrin adduct) and pluronic glycol (EO 1.5 mol-PO15 mol-EO1). .5 mol) diglycidyl ether (L1) was obtained. The epoxy equivalent was 570 (g / eq).

<Example 1>
In a pressure-resistant reaction vessel similar to Production Example 1, 5534 parts (1 mole part) of sucrose / EO2 mole / PO88 mole adduct (S2), 80 parts of sodium hydroxide (2 mole part) and 100 parts of water are hydroxylated. An aqueous sodium solution was added and dehydrated at 120 ° C. under reduced pressure for 3 hours, and then 185 parts (2 mol parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours while sealed under reduced pressure. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y11) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (1) was 2830.

<Example 2>
Sodium hydroxide consisting of 4982 parts (1 mole part) of sucrose / PO 80 mole adduct (S4), 92 parts (2.3 mole parts) of sodium hydroxide and 120 parts of water in a pressure resistant reaction vessel similar to Production Example 1. The aqueous solution was charged and dehydrated at 120 ° C. for 3 hours under reduced pressure, and then 213 parts (2.3 mol parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours under sealed conditions. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y12) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (2) was 2280.

<Example 3>
“Sucrose / EO 2 mol / PO 88 mol adduct (S2) 5534 parts (1 mol part)” and “trehalose / PO 60 mol adduct (S6) 3822 parts (1 mol part)”, “sodium hydroxide 80 Part (2 mole parts) and 100 parts of water "aqueous solution of sodium hydroxide" was changed to "sodium hydroxide solution of 40 parts (1 mole part) of sodium hydroxide and 50 parts of water" and "185 parts of epichlorohydrin" The resin modifier (Y13) of the present invention was obtained in the same manner as in Example 1 except that (2 mol parts) was changed to “92.5 parts (1 mol parts) of epichlorohydrin”. The epoxy equivalent (g / eq.) Of the resin modifier (3) was 4,000.

<Example 4>
Except for changing to "Sucrose / EO2 mol / PO88 mol adduct (S2) 5534 parts (1 mol part)" and "Meletitose / EO4 mol / PO96 mol adduct (S8) 6248 parts (1 mol part)" In the same manner as in Example 1, a resin modifier (Y14) of the present invention was obtained. The epoxy equivalent (g / eq.) Of the resin modifier (4) was 3,300.

<Example 5>
Sodium hydroxide consisting of 6246 parts (3 mol parts) of sucrose / PO 30 mol adduct (S3), 60 parts (1.5 mol parts) of sodium hydroxide and 80 parts of water in a pressure resistant reaction vessel similar to Production Example 1. An aqueous solution was added, dehydrated at 120 ° C. under reduced pressure for 3 hours, cooled to about 25 ° C., and polyoxypropylene glycol (7 mol) diglycidyl ether {Gliciere PP-300P, manufactured by Sanyo Chemical Industries, An epoxy equivalent of 290 g / eq, “Glicier” is a registered trademark of the company} 1160 parts (2 mole parts) was added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Further, 139 parts (1.5 mole parts) of epichlorohydrin was added dropwise at 60 ° C. with stirring for 3 hours. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y21) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y21) was 5,200.

<Example 6>
In a pressure resistant reactor similar to Production Example 1, sucrose / EO 4 mol / PO 66 mol adduct (S1) 8692 parts (2 mol parts), sodium hydroxide 80 parts (2 mol parts) and water 100 parts of water Sodium aqueous solution was added and dehydrated at 120 ° C. under reduced pressure for 3 hours, and then cooled to about 25 ° C., 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} 310 parts (1 mole part) was added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Further, 185 parts (2 mole parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours with stirring. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y22) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y22) was 4,800.

<Example 7>
In a pressure resistant reaction vessel similar to Production Example 1, trehalose / PO 20 mol adduct (S5) 4506 parts (3 mol parts), sodium hydroxide aqueous solution consisting of 80 parts (2 mol parts) sodium hydroxide and 100 parts water and The mixture was dehydrated at 120 ° C. under reduced pressure for 3 hours, and then cooled to about 25 ° C., and 1160 parts (2 mol parts) of Glicier PP-300P was added, followed by replacement with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Further, 185 parts (2 mole parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours with stirring. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y23) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y23) was 3,100.

<Example 8>
Sodium hydroxide consisting of 8472 parts (3 parts by mole) of meretitol / PO40 mole adduct (S7), 48 parts (1.2 parts by weight) of sodium hydroxide and 60 parts of water in the same pressure resistant reactor as in Production Example 1. An aqueous solution was added, dehydrated at 120 ° C. under reduced pressure for 3 hours, cooled to about 25 ° C., and the pluronic glycol (EO 1.5 mol—PO 15 mol—EO 1.5 mol) diglycidyl obtained in Production Example 13 2280 parts (2 mole parts) of ether (L1) was added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Furthermore, 111 parts (1.5 mole parts) of epichlorohydrin was added dropwise at 60 ° C. with stirring for 3 hours. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y24) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y24) was 9,300.

<Example 9>
In a pressure-resistant reaction vessel similar to Production Example 1, 6246 parts (3 mol parts) of sucrose / PO 30 mol adduct (S3) and 3632 parts of HG / PO 27 mol / EO3 mol adduct (U4) obtained in Production Example 12 ( 2 mol parts) and sodium hydroxide aqueous solution consisting of 60 parts (1.5 mol parts) of sodium hydroxide and 80 parts of water, dehydrated at 120 ° C. for 3 hours under reduced pressure, and then cooled to about 25 ° C. Then, 1240 parts (4 mole parts) of Epiol P-200 was added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Further, 139 parts (1.5 mole parts) of epichlorohydrin was added dropwise at 60 ° C. with stirring for 3 hours. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y31) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y31) was 7,800.

<Example 10>
In a pressure-resistant reaction vessel similar to Production Example 1, sucrose / EO 4 mol / PO 66 mol adduct (S1) 8692 parts (2 mol parts) and HG / PO 10 mol adduct (U3) 698 parts obtained in Production Example 11 ( 1 mol part), sodium hydroxide aqueous solution consisting of 80 parts of sodium hydroxide (2 mol parts) and 100 parts of water, dehydrated under reduced pressure at 120 ° C. for 3 hours, cooled to about 25 ° C., 1,6HD-DEP (D) {Hexamethylene glycol diglycidyl ether, Yokkaichi Gosei Co., Ltd., epoxy equivalent 116 g / eq} 464 parts (2 mole parts) was added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Further, 185 parts (2 mole parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours with stirring. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y32) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y32) was 5,200.

<Example 11>
In a pressure-resistant reaction vessel similar to Production Example 1, 3004 parts (2 mol parts) of trehalose / PO 20 mol adduct (S5) and 2426 parts of DPG / PO 38 mol / EO 2 mol adduct (U2) obtained in Production Example 10 ( 1 mol part), sodium hydroxide aqueous solution consisting of 48 parts (1.2 mol parts) of sodium hydroxide and 100 parts of water, dehydrated under reduced pressure at 120 ° C. for 3 hours, and then cooled to about 25 ° C. Then, 2280 parts (2 mole parts) of pluronic glycol (EO 1.5 mole-PO 15 mole-EO 1.5 mole) diglycidyl ether obtained in Production Example 13 was added, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Furthermore, 111 parts (1.2 mol parts) of epichlorohydrin was added dropwise at 60 ° C. with stirring for 3 hours. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y33) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y33) was 6,800.

<Example 12>
In a pressure-resistant reaction vessel similar to Production Example 1, 5648 parts (2 mole parts) of meletitose / PO 40 mole adduct (S7) and 1266 parts (1 mole part) of DEG / PO 20 mole adduct (U1) obtained in Production Example 9 ) And sodium hydroxide aqueous solution consisting of 80 parts (2 mole parts) of sodium hydroxide and 100 parts of water, dehydrated at 120 ° C. for 3 hours under reduced pressure, cooled to about 25 ° C., and Epiol P— Then, 310 parts (2 mole parts) of 200 were added and replaced with nitrogen. Thereafter, the mixture was reacted at 100 ° C. for 6 hours with stirring. Further, 185 parts (2 mole parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours with stirring. Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a resin modifier (Y34) of the present invention. The epoxy equivalent (g / eq.) Of the resin modifier (Y34) was 3,700.

<Comparative Example 1>
In a pressure-resistant reaction vessel similar to Production Example 1, from 624.6 parts (0.3 mole parts) of sucrose / PO 30 mole adduct (S3), 16 parts of sodium hydroxide (0.4 mole parts) and 22 parts of water Then, after dehydrating at 120 ° C. for 3 hours under reduced pressure, dichloromethane (reagent special grade, manufactured by Sigma Aldrich Japan Co., Ltd.) 17 parts (0.2 mole part) was added at 100 ° C. It was added dropwise over a period of time, and stirring was further continued at 100 ° C. for 2 hours. It was confirmed that the pressure of the reaction system had completely reached equilibrium.
Next, 1000 mL of ion-exchanged water was added, and the mixture was stirred for 1 hour at 60 ° C. and then transferred to a separatory funnel. After standing for 1 day, the produced precipitate was subjected to No. A crude reaction liquid was obtained by filtration using two filter papers. 500 parts of the crude reaction liquid was subjected to Kyoward treatment and dehydration to obtain a polyether (HP1) composed of (S3) 3 mol / dichloromethane 2 mol.

  In a pressure-resistant reaction vessel similar to Production Example 1, 6270 parts (1 mole part) of polyether (HP1) consisting of 3 moles of (S3) / 2 moles of dichloromethane, 60 parts of sodium hydroxide (1.5 mole parts) and water A sodium hydroxide aqueous solution consisting of 80 parts was charged and dehydrated at 120 ° C. for 3 hours under reduced pressure. Then, 139 parts (1.5 mol parts) of epichlorohydrin was added dropwise at 60 ° C. for 3 hours under sealed conditions. . Further, the mixture was stirred at the same temperature for 4 hours, then subjected to Kyoward treatment and dehydration to obtain a comparative resin modifier (H1). The epoxy equivalent of the comparative resin modifier (H1) was 4,500.

<Comparative example 2>
In the same pressure-resistant reaction vessel as in Production Example 1, 267 parts (1 mole part) of oleylamine {Naimine O-205, manufactured by Nippon Oil & Fats Co., Ltd.} and 0.5 part of potassium hydroxide were charged and nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. while stirring, and 440 parts (10 mole parts) of EO was added dropwise at the same temperature over 4 hours, followed by stirring for 1 hour at the same temperature to react with the remaining EO. Next, Kyoward treatment and dehydration were performed to obtain a comparative resin modifier (H2).

<Comparative Example 3>
Wandamine AI100 {Lion Corporation 1- (2-hydroxyethyl) -2-alkyl-2-imidazoline active ingredient 20% aqueous solution} was used as a comparative resin modifier (H3).

  Using the resin modifiers obtained in Examples and Comparative Examples, after preparing a cationic electrodeposition coating as follows, the hydrophilicity (dry unevenness resistance) and water resistance (rust resistance) were evaluated. The results are shown in Table 5.

(1) Preparation of Resin Emulsion Epicoat 1004 {manufactured by Shell Chemical Co., Ltd., bisphenol A type epoxy resin (epoxy equivalent: 950)} and evaluation sample {resin modifiers obtained in Examples and Comparative Examples} are shown in Table 4. These were used with the indicated blending amounts {the ratio of (epoxy equivalent / amine equivalent) was 1.0 or more (1.1 to 1.2) and the blending amount was determined to be substantially constant} and methyl isobutyl 240 parts of ketone (MIBK), 55 parts of N-methylethanolamine, and 80 parts of MIBK solution (ketimine solution) containing 75% of MIBK diketimine compound of diethylenetriamine were stirred and mixed at 80 ° C. for 6 hours to obtain an epoxy resin. Solutions (1) to (15) were obtained. Moreover, the liquid for epoxy resins (blank) was obtained like the above except having changed "Epicoat 1004" and "evaluation sample" into "Epicoat 1004 only".

      Hexamethylene diisocyanate (HDI) {manufactured by Takeda Pharmaceutical Co., Ltd., trade name: Takenate 700} 850 parts, MIBK 600 parts, dibutyltin dilaurate {manufactured by Wako Pure Chemical Industries, Ltd.} 1 part and 225 parts of trimethylolpropane After reacting at 70 ° C. for 6 hours, 430 parts of methyl ethyl ketoxime was added to the reaction product at the same temperature, 35 parts of n-butanol was further added, and the mixture was stirred at the same temperature for 3 hours to completely block polyisocyanate. A resin solution was obtained.

      The total amount of the epoxy resin solution obtained above (total amount in Table 4) and 600 parts of the completely blocked polyisocyanate resin solution were mixed at 20 to 30 ° C., and then 100 parts of ethylene glycol monobutyl ether and 6% acetic acid were added thereto. 550 parts of an aqueous solution was added for neutralization, and 2200 parts of deionized water (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) were added and mixed uniformly to obtain an emulsified mixed solution. Thereafter, low-boiling substances are distilled off from the emulsified mixed solution at 50 to 60 ° C. under reduced pressure (−0.05 to −0.098 MPa) to obtain about 35% resin emulsions (1) to (15 ) And (blank).

(2) Preparation of cationic electrodeposition coating material 20 parts of about 35% resin emulsion (1-15, blank), titanium dioxide {Ishihara Sangyo Co., Ltd. product, trade name: Taipei R-930}, kaolin {Tsuchiya Kaolin Co., Ltd., product name: Ultra white 90} 15 parts, aluminum phosphomolybdate {special grade made by Wako Pure Chemical Industries, Ltd.} 3.5 parts, carbon black {special grade grade made by Wako Pure Chemical Industries, Ltd.} 1 part , Sannonic SS-70 {Sanyo Chemical Industries, Nonionic Surfactant} 0.5 parts and deionized water 30 parts Excel Auto Homogenizer equipped with impeller blades (manufactured by Nippon Seiki Co., Ltd., Model ED) And dispersed to a maximum particle size of 10 μm or less (measured in accordance with JIS K5600-2-5: 1999) (3000 rpm × 30 minutes) and pigment paste (1 to 5, blank) was obtained.

      400 parts of resin emulsion (1-15, blank) and 500 parts of deionized water are uniformly mixed at about 25 ° C., and 100 parts of pigment paste (1-15, blank) is added thereto, and mixed uniformly at about 25 ° C. Thus, a cationic electrodeposition paint (1 to 15, blank) was obtained.

      Also, 400 parts of a resin emulsion (blank) and 500 parts of deionized water are uniformly mixed at about 25 ° C., and 100 parts of pigment paste (blank) and 25 parts of a resin modifier (H2) are added thereto. The mixture was uniformly mixed at 25 ° C. to obtain a cationic electrodeposition paint (14 ′).

      Further, 400 parts of resin emulsion (blank) and 400 parts of deionized water are uniformly mixed at about 25 ° C., and 100 parts of pigment paste (blank) and 125 parts of resin modifier (H3) are added thereto. The mixture was uniformly mixed at 25 ° C. to obtain a cationic electrodeposition paint (15).

<Hydrophilicity (drying unevenness resistance) -1>
The hydrophilicity (drying unevenness resistance) was evaluated as follows based on the method described in JP-A-4-370165.
1000 parts of cationic electrodeposition paint was put into a stainless beaker, the zinc phosphate-treated iron plate (coating plate) was used as the cathode, the stainless beaker was used as the anode, the paint bath temperature was 28 ° C., and the voltage was applied to 230 V. Over a period of time, cationic electrodeposition was applied to the zinc phosphate-treated iron plate so that the wet film thickness was 28 μm.
Next, the coated zinc phosphate-treated iron plate is lifted from the paint bath, washed with shower water with about 1 L of tap water, and then stood at an angle of 65 degrees with respect to a horizontal plane at 25 ° C. and 50% relative humidity for 30 minutes. I put it. Next, it was baked at a temperature of 170 ° C. for 20 minutes to obtain a coated plate. The number of dry unevenness marks on the coated surface of this coated plate was counted and designated hydrophilic (dry unevenness resistance) -1.

<Hydrophilicity (drying unevenness resistance) -2>
Similar to hydrophilic (drying unevenness resistance) -1, after cationic electrodeposition coating, the coated zinc phosphate-treated iron plate was pulled up from the paint bath and washed with about 1 L of tap water. Next, after sealingly immersing in an aqueous solution adjusted to pH 4 with acetic acid at 50 ° C. for 2 weeks, it was lifted and washed with about 1 L of tap water. After that, it was stood at an angle of 65 degrees with respect to the horizontal plane for 30 minutes under the conditions of 25 ° C. and 50% relative humidity. Next, it was baked at a temperature of 170 ° C. for 20 minutes to obtain a coated plate. The number of dry unevenness marks on the painted surface of this coated plate was counted, and this was designated as dry unevenness resistance-2.

<Water resistance (rust prevention)>
The water resistance (rust resistance) was evaluated as follows based on the method described in JP-A-4-370165.
The coated plate obtained with hydrophilic property (drying unevenness property) -1 was subjected to a salt spray test for 500 hours in accordance with JIS Z2371, and the number of generated rusts was counted to make it water resistant (rust-proof).

  The cationic electrodeposition paints (Examples 1 to 12) using the resin modifier of the present invention were remarkably good in dry unevenness (hydrophilicity) as compared with the blank and Comparative Examples 1 to 3. Moreover, the resin modifier of this invention did not cause the fall of rust prevention property (water resistance). In addition, from the result of hydrophilicity (drying unevenness resistance) -2, the resin modifier of the present invention has almost no dry unevenness even when treated in an aqueous solution of pH 4, compared with the resin modifier of the comparative example. Excellent hydrolysis resistance.

  The resin modifier of the present invention can be applied to both water-based paints and non-water-based paints, but among these, it is suitable for water-based paints, and particularly useful for cationic electrodeposition paints.

Claims (7)

A resin modifier comprising a polyoxyalkylene compound (Y) represented by any one of the general formulas (1) to (3) as an essential component.

(G-) _t S (1)

(G-) _t-1 SL {-S (-G) _t-2 -L} _q- S (-G) _t-1 (2)

(G-) _t-1 SL {-ULS (-G) _t-2 -L} _q -ULS (-G) _t-1 (3)

However, S is group represented by General formula (4), t is an integer of 2-4, L is the reaction residue of C10-50 diglycidyl ether, U is represented by General formula (5) Group, q represents 0 or 1, and G represents a glycidyl group or a hydrogen atom, but in each general formula, at least one G is a glycidyl group.

Q {-(OA-) _n } _t (4)

Z {-(OA-) _m O-} ₂ (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, Z is an alkylene group or arylene having 2 to 15 carbon atoms Group, O represents an oxygen atom, n represents an integer of 5 to 30, t represents an integer of 2 to 4, m represents an integer of 5 to 20, and OA contained in the group (S) represented by the general formula (4) Is an integer of 20 to 100, and when a plurality of S, L, U, (OA) n, (OA) m, Q, Z, q, n, m, and t are contained in one molecule, a plurality of Each of the pieces may be the same or different. The resin modifier according to claim 1, wherein the residue (Q) obtained by removing a hydrogen atom from t hydroxyl groups of a non-reducing di- or trisaccharide is a reaction residue of sucrose. The polyoxyalkylene compound (Y) is 2,000 to 10,000 g / eq. The resin modifier of Claim 1 or 2 which has the epoxy equivalent of. A resin and the resin modifier according to any one of claims 1 to 3 are contained, and 5 to 40% by weight of a resin modifier is contained based on the weight of the resin and the resin modifier. A modified resin composition characterized by the above. A paint comprising the modified resin composition according to claim 4. It contains the resin modifier according to any one of claims 1 to 3, and contains 0.5 to 5% by weight of resin modifier based on the weight of the paint and resin modifier. A coating composition characterized by comprising: A method for producing the resin modifier according to any one of claims 1 to 3,
Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing di- or trisaccharide (a1) and 20 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms And a method (1) comprising a step (2) of obtaining a polyoxyalkylene compound (Y1) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 3 mol parts of an epihalohydrin (a3);

Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing di- or trisaccharide (a1) and 20 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
A step (3) of obtaining a compound (a124) from a chemical reaction (3) of 1 mol part of the compound (a12) and 0.5 to 0.67 mol part of a diglycidyl ether having 10 to 50 carbon atoms (a4); and A method (2) comprising a step (4) of obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (4) of the compound (a124) and 1 to 3 mole parts of an epihalohydrin (a3); or

Step (1) for obtaining a compound (a12) from a chemical reaction (1) between 1 mol part of a non-reducing di- or trisaccharide (a1) and 20 to 100 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
A step (5) of obtaining a compound (a52) from a chemical reaction (5) of 1 mol part of a glycol having 2 to 15 carbon atoms (a5) and 10 to 40 mol parts of an alkylene oxide having 2 to 4 carbon atoms (a2);
Chemical reaction (1) of 1 mol part of compound (a12), 0.5 to 0.67 mol part of compound (a52) and 1 to 1.33 mol part of diglycidyl ether (a4) having 10 to 50 carbon atoms A step (6) of obtaining a compound (a12524) from the above (6); and a step (7) of obtaining a polyoxyalkylene compound (Y3) from a chemical reaction (7) of 1 to 3 mole parts of the compound (a12524) and epihalohydrin (a3). A production method comprising the method (3).