JP4639285B2 - Resin modifier, modified resin composition containing the same, and cationic electrodeposition coating - Google Patents

Description

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

  Addition of hydroxyalkyl imidazoline compounds (Patent Document 1) and ethylene oxide of alkylamines and alkylamides as paint additives to impart hydrophilicity to the coating after cationic electrodeposition and prevent water droplets from remaining on the coating A body (Patent Document 2) and the like are known.

JP-A-4-370165 JP 2002-226778 A

  In the paint additives described in Patent Documents 1 and 2, 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, and the paint additive is washed away during washing with water. There is a problem that it is easy to be removed 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. That is, an object of the present invention is to provide a resin modifier that can impart hydrophilicity (drying unevenness) to a coating film without impairing the water resistance of the coating film.

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 gist of the feature of the resin modifier of the present invention is that the epoxy compound represented by the general formula (1) is an essential component.
However, R is at least 1 sort (s) chosen from the group which consists of an alkyl group, an alkenyl group, and an acyl group, The carbon number of R is 8-18, N is a nitrogen atom, X represents a glycidyl group or a hydrogen atom, At least one of the two X is a glycidyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, M is an organic group having 1 to 3 carbon atoms, q is an integer of 0 to 4, m is 1 to The integer of 20 and n represent the integer of 1-10, and the total number of AO is 20-100.

In addition, the resin modifier of the present invention is characterized by an aliphatic monoamine (a1) having 8 to 18 carbon atoms and / or an aliphatic monoamide (a2) having 8 to 18 carbon atoms,
An alkylene oxide (a3) having 2 to 4 carbon atoms;
Epihalohydrin (a5);
The gist is that an epoxy compound having a structure that can be produced by a chemical reaction with a dihalogenated hydrocarbon having 1 to 3 carbon atoms (a4) as an essential component is necessary.

  The resin modifier of the present invention can impart hydrophilicity (drying unevenness) to the coating without impairing the water resistance (rust resistance) of the coating. That is, the paint comprising the resin modifier of the present invention is remarkably excellent in water resistance and hydrophilicity of the formed coating film. For example, when applied to a cationic electrodeposition coating material, the water resistance of the coating film is lowered. Water droplets are less likely to remain, and it is possible to effectively prevent a deficit of water marks (a phenomenon in which a portion where water droplets existed is slightly recessed compared to a portion where water droplets did not exist).

The general formula (1) will be described.
Among R, as the alkyl group, n-octyl, 2-ethylhexyl, 1-methylheptyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, Examples include n-hexadecyl, n-heptadecyl, n-octadecyl and 16-methylheptadecyl.
Examples of the alkenyl group include undecenyl, 2-ethylhexenyl, n-tetradecenyl, n-hexadecenyl, n-heptadecenyl and octadecenyl.

  Examples of the acyl group include n-octyroyl, 2-ethylhexylyl, 1-methylheptiloyl, n-nonylyl, n-decylyl, n-undecylyl, n-dodecylyl, n-tridecylyl, n-tetradecylyl, n -Pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, 16-methylheptadecyl, octadecenyloyl, etc. are mentioned.

Of these, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-decyloyl, n-undecylyl, n-dodecylyl, n-tridecylyl and octadecenyl are preferable from the viewpoint of balance between hydrophilicity and water resistance. Preferred are n-dodecyl, n-tridecyl, n-dodecyl, n-tridecyl and octadecenyl, and particularly preferred are n-dodecyl, n-dodecyl and octadecenyl.
A plurality of R may be all the same or a part or all of them may be different.

Examples of the organic group (M) having 1 to 3 carbon atoms include alkylene and alkenylene.
Examples of alkylene include methylene, ethylene, propylene, iso-propylene, and the like, and substituted alkylene {hydroxypropylene (—CH ₂ —CH (OH) —CH ₂ ) in which a part of the hydrogen atoms of these groups is replaced with a hydroxyl group or the like. -) Etc.} can also be used.
Examples of alkenylene include ethenylene and propenylene.
Of these, methylene, ethylene and hydroxypropylene are preferable, more preferably methylene and hydroxypropylene, and particularly preferably methylene.
The plurality of M may all be the same, or some or all of them may be different.

  Examples of the oxyalkylene group AO having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Of these, oxyethylene, oxypropylene, and a mixture thereof are preferable from the viewpoint of hydrophilicity and water resistance, and more preferably a mixture of oxyethylene and oxypropylene. The plurality of (AO) n and (AO) m may be the same or different.

  When plural kinds of oxyalkylene groups are contained in OA, there is no limitation on the bonding form (block form, random form and combinations thereof) and content ratio of these oxyalkylene groups, but block form or block form and random form It is preferable to include the combination. In this case, it is preferable to contain oxyethylene in order to further improve the hydrophilicity. In this case, the content ratio (mol%) of oxyethylene is preferably 10 to 60, more preferably 13 to 57, particularly preferably 17 to 53, and most preferably 20 based on the total number of moles of oxyalkylene groups. ~ 50.

n is preferably an integer of 1 to 10, more preferably an integer of 2 to 8, particularly preferably an integer of 3 to 7. Moreover, m is preferably an integer of 1 to 20, more preferably an integer of 2 to 18, and particularly preferably an integer of 3 to 16. Within this range, the balance between hydrophilicity (drying unevenness) and water resistance of the coating film containing the resin modifier of the present invention is further improved. The plurality of n and m may all be the same, or some or all of them may be different.
Moreover, q is preferably an integer of 0 to 4, more preferably an integer of 1 to 3, particularly preferably 2 or 3. Within this range, the water resistance of the paint comprising the resin modifier of the present invention is further improved.

  The total number of AO is preferably an integer of 20 to 100, more preferably an integer of 25 to 95, and particularly preferably an integer of 30 to 90. Within this range, the balance between water resistance and hydrophilicity is further improved.

  Examples of the epoxy compound represented by the general formula (1) include compounds represented by the following chemical formulas. Here, po represents an oxypropylene group, eo represents an oxyethylene group, bo represents an oxybutylene group, me represents a methylene group, et represents an ethylene group, and gy represents a glycidyl group.

  Among these, an epoxy compound represented by formula (3), (4), (7), (9), (10) or (12) is preferred, and more preferably represented by formula (3) or (10). Epoxy compound.

  Examples of the epoxy compound represented by the general formula (1) include an aliphatic monoamine (a1) having 8 to 18 carbon atoms and / or an aliphatic monoamide (a2) having 8 to 18 carbon atoms and an alkylene having 2 to 4 carbon atoms. The epoxy compound etc. which have the structure which can be manufactured by the chemical reaction with an oxide (a3), an epihalohydrin (a5), and a C1-C3 dihalogenated hydrocarbon (a4) as needed are contained. That is, the epoxy compound having a structure that can be produced by this chemical reaction may cause distribution in the number of oxyalkylene groups, q, etc. In this case, strictly speaking, it becomes a mixture of a plurality of types of epoxy compounds. The epoxy compound represented by the general formula (1) is included therein. Even in this case, the manufacturing method is not limited.

  And as a total usage-amount (mol part) of alkylene oxide (a3), 20-100 are preferable with respect to 1 mol part of aliphatic monoamine (a1) and aliphatic monoamide (a2), More preferably, it is 23-97. Particularly preferred is 27 to 93, and most preferred is 30 to 80. Within this range, the balance between the dry resistance and water resistance of the coating film containing the resin modifier of the present invention is further improved.

  The amount of use of the epihalohydrin (a5) (mole part) is preferably 0.3 to 1.5, more preferably 0.33, relative to 1 mol part of the aliphatic monoamine (a1) and aliphatic monoamide (a2). To 1.47, particularly preferably 0.37 to 1.43, and most preferably 0.4 to 1.4. Within this range, the dry unevenness and water resistance of the coating film are further improved.

  When using a C1-C3 dihalogenated hydrocarbon (a4), as this usage-amount (mol part), it is set to 0.1 with respect to 1 mol part of aliphatic monoamine (a1) and aliphatic monoamide (a2). 1-0.9 are preferable, More preferably, it is 0.15-0.85, Most preferably, it is 0.2-0.8, Most preferably, it is 0.25-0.75. Within this range, the dry unevenness and water resistance of the coating film are further improved.

  When the aliphatic monoamine (a1) and the aliphatic monoamide (a2) are used, their use molar ratio (a1 / a2) is preferably from 0.1 to 0.9, more preferably from 0.2 to 0.8. Particularly preferred is 0.3 to 0.7, and most preferred is 0.4 to 0.6. Within this range, the balance between hydrophilicity and water resistance is further improved.

  Examples of the aliphatic monoamine (a1) include n-octylamine, 2-ethylhexylamine, 1-methylheptylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, Examples include n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, 16-methylheptadecylamine, undecenylamine, and octadecenylamine.

  Examples of the aliphatic monoamide (a2) include n-octylamide, 2-ethylhexylamide, 1-methylheptylamide, n-nonylamide, n-decylamide, n-undecylamide, n-dodecylamide, n-tridecylamide, Examples include n-tetradecylamide, n-pentadecylamide, n-pentadecylamide, n-heptadecylamide, n-octadecylamide, 16-methylheptadecylamide, and octadecenylamide. In addition, diamides of diamines such as ethylenediamine and fatty acids, such as ethylenebisstearylamide, can be used.

As alkylene oxide (a3), C2-C4 alkylene oxide etc. can be used, and ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), these mixtures, etc. are mentioned. Among these, from the viewpoint of water resistance and dry unevenness, EO, combined use of EO and PO or BO, and PO are preferable, more preferably combined use of EO and PO or BO, particularly preferably EO and PO and It is a combined use.
Moreover, when using multiple types of alkylene oxide, there is no limitation on the form of reaction (block shape, random shape and combinations thereof) and the use ratio, but it is preferable to include a block shape or a combination of block shape and random shape. . In this case, it is preferable to contain EO, and the use ratio (mol%) of EO is preferably 10 to 60, more preferably 13 to 57, particularly preferably 17 based on the total number of moles of alkylene oxide. ~ 53, most preferably 20-50. Within this range, the balance between hydrophilicity and water resistance is further improved.

As the dihalogenated hydrocarbon (a4), an aliphatic dihalogenated hydrocarbon can be used, and a dihalogenated alkane having 1 to 3 carbon atoms and a dihalogenated alkene having 2 to 3 carbon atoms are used.
Dihalogenated alkanes include dichloromethane, dibromomethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1-dibromoethane, 1,2-dibromoethane, 1,3-dichloropropane, 1,2-dichloropropane. 1,3-dibromopropane, 1,2-dibromopropane, 1-bromo-3-chloropropane, 1-methyl-1,2-dichloroethane, 1-methyl-1,2-dibromoethane and the like.
Dihalogenated alkenes include 1,2-dichloroethylene, 1,2-dibromoethylene, 1,3-dichloropropylene, 2,3-dichloro-1-propylene, 1,3-dibromopropylene and 2,3-dibromo-1 -Propylene etc. are mentioned.
Of these, dihalogenated alkanes are preferred from the viewpoints of dryness unevenness and water resistance of the coating film, more preferably dichloromethane, dichloroethane, 1,3-dichloropropane and 1-methyl-1,2-dichloroethane, low Particularly preferred from the viewpoint of viscosity increase are dichloromethane and dichloroethane. These may be used alone or in combination.

  Examples of epihalohydrin include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferred from the viewpoint of economy.

The epoxy compound can be produced by the following method or the like.
(1) An aliphatic adamine (a1) and / or an aliphatic monoamide (a2) is reacted with an alkylene oxide (a3) to obtain an alkylene adduct (a13 and / or a23). Next, the alkylene adduct (a13 and / or a23) and the dihalogenated hydrocarbon (a4) are reacted to obtain an alkylene adduct conjugate. Then, this alkylene adduct conjugate and epihalohydrin (a5) are reacted to obtain an epoxy compound.
The alkylene adduct conjugate and the alkylene oxide (a3) can also be reacted before the alkylene adduct conjugate and the epihalohydrin (a5) are reacted.
(2) The aliphatic monoamine (a1) and / or the aliphatic amide (a2) and the alkylene oxide (a3) are reacted to obtain an alkylene adduct (a13 and / or a23). Next, this alkylene adduct (a13 and / or a23) and epihalohydrin (a5) are reacted to obtain an epoxy compound at once.
In addition, it is preferable to use an aliphatic monoamide (a2) from a viewpoint of cost, and it is preferable to use an aliphatic monoamine (a1) from a viewpoint of hydrophilicity. Moreover, when aliphatic monoamine (a1) and aliphatic monoamide (a2) are used, it becomes easier to balance hydrophilicity, water resistance, and resin strength.

  For the addition reaction between the aliphatic monoamine (a1) and / or the aliphatic monoamide (a2) and the alkylene oxide (a3), a known method (Japanese Patent Application Laid-Open No. 2004-224945) and the like can be applied. You may implement by any forms, such as superposition | polymerization or coordination anionic polymerization. These polymerization forms may be used alone or in combination according to the degree of polymerization.

For the addition reaction of alkylene oxide (a3), a known reaction catalyst (Japanese Patent Application Laid-Open No. 2004-224945) can be used.
When a reaction catalyst is used, the amount used (% by weight) is preferably 0.01 to 1 based on the total weight of the aliphatic monoamine (a1) and the aliphatic monoamide (a2) and the alkylene oxide (a3). More preferably, it is 0.03-0.8, Most preferably, it is 0.05-0.6. 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 a reaction catalyst is used, it is preferable to remove the reaction catalyst from the reaction product. As the removal method, an alkali adsorbent such as 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 produced by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000).
As the end point of the removal of the reaction catalyst, the CPR (Controlled Polymerization Rate) value described in JIS K1557-1970 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. is there.
A known reaction vessel (JP 2004-224945 A) or the like can be used for the reaction.

  In the reaction with the dihalogenated hydrocarbon (a4), a dehydrohalogenation reaction with a basic substance (Williamson synthesis reaction: the reaction is driven by neutralizing the hydrogen halide sequentially generated during the reaction with a basic substance. ) Etc. can be applied. 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 barium carbonate) 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 the base equivalent (eq.) Of the basic substance based on the halogen equivalent (eq.) Of the dihalogenated hydrocarbon {(base equivalent of basic substance / halogenated carbonization). Ratio of hydrogen halogen equivalent)}, an amount of 1.0 to 1.5 is preferable, 1.05 to 1.4 is more preferable, and 1.1 to 1.3 is particularly preferable.
Moreover, 50-150 are preferable, as for reaction temperature (degreeC), More preferably, it is 60-130, Most preferably, it is 80-120. Within this range, the economy and the purity of the product are further improved.
After completion of the reaction, it is preferable to remove the produced neutralized salt and the remaining basic substance. As the method, (1) the produced neutralized salt is first removed by filtration, and then the remaining basic substance, etc. For example, (2) an extraction method using an organic solvent, and (3) a salting out method using sodium chloride.

The method (1) can be removed in the same manner as the removal of the reaction catalyst used in the addition reaction of the alkylene oxide (a3).
In the extraction method (2), water and an organic solvent (having very low solubility in water such as hexane, toluene, xylene, etc.) are added to the reaction product, and the reaction product is shaken by shaking. And the basic substance is separated into an aqueous layer. The organic solvent layer is further washed with deionized water or the like. A suitable volume ratio of reaction product: water: organic solvent is approximately 1: 1: 1.
In the salting-out method of (3), the reaction product is shaken by adding approximately the same volume of water and a suitable amount (3 to 10% by weight of sodium chloride) of sodium chloride to the reaction product and shaking. In this method, the basic substance is separated from the aqueous layer by precipitation from the aqueous layer.
In the case of (2) or (3), it is preferable to finally remove the basic substance by using an alkali adsorbent such as synthetic aluminosilicate (for example, Kyoward 700).
As the end point of the removal of the basic substance, the CPR (Controlled Polymerization Rate) value described in JIS K1557-1970 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. It is.
Further, it is preferable to remove moisture. In this case, dehydration is performed at 100 to 130 ° C. for 1 to 2 hours under reduced pressure {gauge pressure (hereinafter the same) MPa: −0.05 to −0.098}. The water content in the product is preferably 0.5% by weight or less, more preferably 0.05% by weight or less.
The water content can be measured by a known method. For example, Karl Fischer method (JIS K0113-1997, coulometric titration method) or weight loss by heat 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 pressure-resistant reaction vessel capable of heating, cooling, stirring and dropping (press-fitting). The reaction atmosphere is preferably an inert gas atmosphere (such as argon, nitrogen and carbon dioxide) in which the inside of the reaction apparatus is vacuumed or dried before introducing (a4) into the reaction system. Moreover, as reaction temperature (degreeC), 60-160 are preferable, More preferably, it is 80-130. The reaction pressure (gauge pressure: MPa) is preferably 0.5 or less, more preferably 0.3 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 1 to 6 hours.

The reaction with epihalohydrin (a5) includes (1) an epoxy ring-opening reaction between the hydroxyl group of the reaction product and the epoxy group of (a5), and then (2) an epoxy ring regeneration reaction by dehydrohalogenation. Applicable.
Examples of the catalyst used in the epoxy ring-opening reaction of (1) include alkali metal or alkaline earth metal hydroxides (potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (potassium methylate and Cesium ethylate), alkali metal or alkaline earth metal carbonates (potassium carbonate, cesium carbonate, barium carbonate, etc.), tertiary amines having 3 to 24 carbon atoms (trimethylamine, trioctylamine, triethylenediamine, and tetramethylethylenediamine) Etc.), Lewis acids (stannic chloride, titanium chloride, aluminum trichloride, boron trifluoride, etc.) and the like are used. Of these, alkali metal hydroxides and tertiary amine compounds are preferable, and potassium hydroxide, trimethylamine, and stannic chloride are more preferable.
The end point of the reaction can be performed by confirming the disappearance of the epoxy group. As a method for quantifying the epoxy group, a cetyltrimethylammonium bromide (CTAB) method (JIS K7236) in which hydrogen halide (HB) is generated from perchloric acid and a quaternary ammonium salt (CTAB) and this is reacted with an epoxy group. 2001, ISO 3001: 1999).

  For the epoxy ring regeneration reaction by dehydrohalogenation in (2), alkali metal or alkaline earth metal hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide) Basic substances such as calcium hydroxide and barium hydroxide are used as the catalyst. Of these, alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.

  For the reaction with epihalohydrin (a5), a vessel with heating, cooling, stirring, and a reflux tube can be used. 40-150 are preferable and, as for reaction temperature (degreeC), More preferably, it is 60-100. The reaction atmosphere is preferably a dry inert gas atmosphere. The reaction end point can be determined by confirming the disappearance of the epoxy group.

The epoxy equivalent (g / eq.) Of the resin modifier of the present invention is preferably 500 to 5000, more preferably 700 to 4700, particularly preferably 850 to 4300, and most preferably 1000 to 4000. Within this range, the dry unevenness and water resistance of the coating film are further improved.
The epoxy equivalent (g / eq.) Is measured according to JIS K7236: 2001.

The resin modifier of the present invention can be applied to both aqueous resins and non-aqueous resins. Of these, the resin modifier is suitable for aqueous resins, more suitable for aqueous epoxy resins, particularly cationic electrodeposition. Suitable for paint.
Although the resin modifier of this invention should just be contained in aqueous resin or non-aqueous resin, it is preferable to use it as one of the reaction components in the step which synthesize | combines resin.
The amount (% by weight) of the resin modifier of the present invention is preferably 1 to 50 based on the weight of the resin (when used in the resin synthesis stage, the weight of the monomer constituting the resin), and Preferably it is 2-48, Especially preferably, it is 3-45, More preferably, it is 4-43, Most preferably, it is 5-40. Within this range, the dryness unevenness of the paint produced using the resin comprising the resin modifier of the present invention is further improved, and the water resistance of the coating film (such as the inherent water resistance of the resin) ) Is not adversely affected.

  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 in more detail, this invention is not limited to this. Parts and% represent parts by weight and% by weight, respectively.
<Example 1>
In a pressure-resistant reaction vessel capable of heating, stirring, cooling, dropping, pressurizing and depressurizing, dodecylamine {manufactured by NOF Corporation, product name: Amine BB} 185 parts (1 mol part), potassium hydroxide {reagent special grade Wako Pure Chemical Industries, Ltd.} 0.5 parts was added, and the operation of pressurizing with nitrogen gas until the gauge pressure became 0.4 MPa and discharging until 0.02 MPa was repeated three times ( Pressurized nitrogen substitution). Next, the temperature was raised to 100 ° C. while stirring, and dehydration was performed under a reduced pressure of −0.05 to −0.098 MPa. Next, 176 parts (4 mole parts) of EO was added dropwise at 130 to 150 ° C. over 2 hours, and then stirring was continued at the same temperature for 0.5 hours to react with the remaining EO, so that dodecylamine / EO 4 mole adduct was obtained. (S1) was obtained.

  Sodium hydroxide (purity: 50%) 360 parts (4.5 moles) was added to 1083 parts (3 moles) of dodecylamine / EO4 mole adduct (S1) at 50 ° C. or lower, and the mixture was stirred up. After heating to 130 ° C., dehydration was performed under a reduced pressure of −0.05 to −0.098 MPa. Subsequently, the pressure reduction was stopped, and 170 parts (2 mole parts) of dichloromethane {special reagent grade, manufactured by Sigma Co., Ltd.} was introduced over 2 hours at 100 to 120 ° C. with stirring. Stirring was continued for another 2 hours at the same temperature. Subsequently, 580 parts (10 mol parts) of PO was added dropwise at 100 ° C. over 5 hours, and then stirring was continued for 2 hours at the same temperature to react with the remaining PO and cooled to 40 ° C. The obtained reaction mixture is taken into a separating funnel, 500 parts of ion-exchanged water and 500 parts of n-hexane {special grade reagent, manufactured by Sigma Co., Ltd.} are added and shaken, and then left to stand for separation. A hexane layer was obtained. From this n-hexane layer, n-hexane was distilled off at 100 ° C. under reduced pressure of −0.05 to −0.098 MPa to obtain a trimer of dodecylamine / EO4 mol adduct / PO10 mol adduct ( S2: Theoretical molecular weight 1691) was obtained.

(S2) 169.1 parts (0.1 mole part), epichlorohydrin {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.} 23.3 parts (.0.2) in a reaction vessel equipped with a reflux tube capable of heating, cooling and stirring. 25 parts by mole) and 0.2 part of stannic chloride {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} were added and stirred at 80 ° C. for 3 hours. After confirming the disappearance of the epoxy group, 100 parts (0.25 mol part) of a 10% by weight aqueous sodium hydroxide solution was added and stirred vigorously at 60 ° C. for 6 hours. After standing and cooling, the supernatant was removed by decantation. Next, 100 parts of tap water was charged, stirred vigorously and allowed to stand, and water washing for removing the supernatant was repeated 3 times (hereinafter abbreviated as water washing treatment), and the pH of the supernatant was confirmed to be 7. Thereafter, it was dehydrated at 80 ° C. under a reduced pressure of −0.05 to −0.098 MPa for 1 hour to obtain an epoxy compound (E1) of 1 mol / epichlorohydrin 2 mol (S2).
This (E1) was directly used as the resin modifier (1) of the present invention. The epoxy equivalent (g / eq.) Of (E1) was 932.
(E1) corresponds to the general formula (3). In addition, the structure of (E1) was estimated about the (S1), (S2), and (E1) by analysis, such as GPC, IR, and < ¹ > H-NMR (hereinafter the same).

<Example 2>
In a reaction vessel equipped with a reflux tube that can be heated, cooled, and stirred, dodecylamine / EO 4 mol adduct trimer / PO 10 mol adduct (S2) 338.2 parts (0.2 mol parts), 10 wt% water While adding 160 parts (0.4 mole part) of an aqueous sodium oxide solution and stirring vigorously at 60 ° C., 27.8 parts (0.3 mole part) of epichlorohydrin was added dropwise over 6 hours. The mixture was further vigorously stirred at 80 ° C. for 2 hours and then washed with water, dehydrated at the same temperature under reduced pressure of −0.05 to −0.098 MPa (S2) 2 mol / epichlorohydrin 3 mol (E2 ) This (E2) was directly used as the resin modifier (2) of the present invention. The epoxy equivalent of (E2) was 1920. (E2) corresponds to the general formula (4).

<Example 3>
281 parts (1 mole part) of oleylamide {Nippon Kasei Co., Ltd., product name: Diamit O-200} and 2 parts of potassium hydroxide were charged into the same pressure resistant reactor as in Production Example 1, and nitrogen substitution was performed. . Next, the temperature was raised to 120 ° C. while stirring, and dehydration was performed under a reduced pressure of −0.05 to −0.098 MPa. Next, a mixture of PO 232 parts (4 mol parts) / EO 176 parts (4 mol parts) was added dropwise at 100 to 120 ° C. over 5 hours, and then stirring was continued for 2 hours at the same temperature to leave the remaining PO and EO. Reaction was performed to obtain an oleylamide / (PO4 mol, EO4 mol) adduct (S3).

  Oleylamide / (PO4 mol, EO4 mol) adduct (S3) 275.6 parts (0.4 mol parts) at 50 ° C. or less, 28 parts of sodium hydroxide (purity: 50%) (0.35 mol) The mixture was heated to 130 ° C. while stirring and then dehydrated under reduced pressure of −0.05 to −0.098 MPa. Subsequently, the pressure reduction was stopped, and 29.7 parts (0.3 mole parts) of 1,2-dichloroethane {reagent special grade, manufactured by Sigma Co., Ltd.} were introduced over 7 hours at 100 to 120 ° C. with stirring. The mixture was further stirred at the same temperature for 2 hours and then cooled to 40 ° C. The obtained reaction mixture is taken into a separating funnel, 500 parts of ion-exchanged water and 500 parts of n-hexane {special grade reagent, manufactured by Sigma Co., Ltd.} are added and shaken, and then left to stand for separation. A hexane layer was obtained. From this n-hexane layer, n-hexane was distilled off at 100 ° C. under a reduced pressure of −0.05 to −0.098 MPa to obtain 4 amounts of {oleylamide / (PO4 mol, EO4 mol) adduct}. A body (S4: Theoretical molecular weight 2840) was obtained.

A reaction vessel equipped with a reflux tube capable of heating, cooling and stirring was charged with 284 parts (0.1 mole part), 23.3 parts (0.25 mole part) epichlorohydrin and 0.2 part stannic chloride. , And stirred at 80 ° C. for 3 hours. After confirming the disappearance of the epoxy group, 100 parts (0.25 mol part) of a 10% by weight aqueous sodium hydroxide solution was added and stirred vigorously at 60 ° C. for 6 hours. After standing and cooling, the supernatant was removed by decantation. Subsequently, it was washed with water, and it was confirmed that the pH of the supernatant liquid became 7. Thereafter, dehydration was performed at 80 ° C. under a reduced pressure of −0.05 to −0.098 MPa for 1 hour (S4) to obtain an epoxy compound (E3) of 1 mol / epichlorohydrin 2 mol. This (E3) was directly used as the resin modifier (3) of the present invention.
The epoxy equivalent of (E3) was 1610. (E3) corresponds to the general formula (10).

<Example 4>
A mixed saturated fatty acid amide {manufactured by Nippon Kasei Co., Ltd., product name: Amide AP-1, average molecular weight: 288}, 185 parts (1 mole part) and 1 part of potassium hydroxide are charged into a pressure resistant reactor similar to Production Example 1. Then, after carrying out pressurized nitrogen substitution, the temperature was raised to 120 ° C. while stirring, and dehydration was performed under a reduced pressure of −0.05 to −0.098 MPa. Subsequently, 348 parts (6 mole parts) of PO was added dropwise at 110 to 120 ° C. over 4 hours, and then stirring was continued at the same temperature for 25 hours to react the remaining PO. Further, 88 parts (2 parts by mole) of EO was added dropwise at 120 to 130 ° C. over 2 hours, and then stirring was continued at the same temperature for 0.5 hours to react with remaining PO to react with amide AP-1 / PO 6 mole / An EO2 molar adduct (S5) was obtained.

  36 parts (0.45 mole part) of sodium hydroxide (purity: 50%) was added to 243.6 parts (0.3 mole part) of Amide AP-1 / PO6 mole / EO2 mole adduct (S5) and stirred. The temperature was raised to 130 ° C. while dehydrating under a reduced pressure of −0.05 to −0.098 MPa. Subsequently, the pressure reduction was stopped, and 17 parts (0.2 mol part) of methyl dichloride was introduced over 2 hours at 100 to 120 ° C. with stirring. Stirring was continued for another 2 hours at the same temperature. The obtained reaction mixture is taken into a separating funnel, 500 parts of ion-exchanged water and 500 parts of n-hexane {special grade reagent, manufactured by Sigma Co., Ltd.} are added and shaken, and then left to stand for separation. A hexane layer was obtained. From this n-hexane layer, n-hexane was distilled off under reduced pressure of 100 ° C. and −0.05 to −0.098 MPa to obtain 3 amounts of (amide AP-1 / PO6 mol / EO2 mol adduct). A body (S6: Theoretical molecular weight 2460) was obtained.

    246 parts (0.1 mole part) (S6), 23.3 parts (0.25 mole part) epichlorohydrin and 0.2 part stannic chloride are charged into a reaction vessel equipped with a reflux tube capable of heating, cooling and stirring. , And stirred at 80 ° C. for 3 hours. After confirming the disappearance of the epoxy group, 100 parts (0.25 mol part) of a 10% by weight aqueous sodium hydroxide solution was added and stirred vigorously at 60 ° C. for 6 hours. After standing and cooling, the supernatant was removed by decantation. Subsequently, it was washed with water, and it was confirmed that the pH of the supernatant liquid became 7. Thereafter, dehydration was performed at 80 ° C. under a reduced pressure of −0.05 to −0.098 MPa for 1 hour (S6) to obtain an epoxy compound (E4) of 1 mol / epichlorohydrin 2 mol. This (E4) was directly used as the resin modifier (4) of the present invention. The epoxy equivalent of (E4) was 1420. (E4) corresponds to the general formula (9).

<Comparative Example 1>
In the same pressure resistant reactor as in Example 1, oleylamine {manufactured by NOF Corporation, product name: Naimine O-205,} 267 parts (1 mole part) and 0.5 parts of potassium hydroxide were charged and nitrogen substitution was carried out. . Then, the temperature was raised to 100 ° C. while stirring, and a mixture of 440 parts (10 parts by mole) and 116 parts (2 parts by mole) of EO was added dropwise at the same temperature over 4 hours, and stirring was continued for 1 hour at the same temperature. The remaining EO was reacted. Next, Kyoward treatment was performed to obtain an oleylamine / (EO10 · PO2) molar adduct (S7). This (S7) was directly used as a comparative resin modifier (5).

<Comparative Example 2>
The dodecylamine / EO4 molar adduct trimer / PO10 molar adduct (S2) obtained in Example 1 was used as a comparative resin modifier (6).

<Comparative Example 3>
A 20% aqueous solution of 1- (2-hydroxyethyl) -2-alkyl-2-imidazoline {manufactured by Lion Corporation, product name: Wandamine AI100} was used as a comparative resin modifier (7).

  As described below, after preparing cationic electrodeposition paints (1) to (8) comprising a resin emulsion, a pigment paste, and deionized water, the dry unevenness and water resistance were evaluated.

(1) Resin emulsion Epicoat 1004 {manufactured by Shell Chemical Co., Ltd., bisphenol A type epoxy resin (epoxy equivalent: 950)} 750 parts, evaluation sample {resin modifiers (1) to (6)} 300 parts, methyl isobutyl A mixture of 240 parts of ketone (MIBK), 55 parts of N-methylethanolamine, and 80 parts of MIBK solution containing 75% of MIBK diketiminate of diethylenetriamine was stirred and mixed at 80 ° C. for 6 hours to obtain an epoxy resin solution (1) to (6) was obtained.
An epoxy resin solution (blank) was obtained in the same manner as above except that “750 parts of Epicoat 1004” and “300 parts of evaluation sample” were changed to “950 parts of Epicoat 1004”.

  On the other hand, 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 60 to 70 ° C., 430 parts of methyl ethyl ketoxime was added at the same temperature, and 35 parts of n-butanol was further added to obtain a completely blocked polyisocyanate resin solution.

  After mixing 1320 parts of epoxy resin solution {(1) to (6) or (blank)} and 570 parts of fully blocked polyisocyanate resin solution, 100 parts of ethylene glycol monobutyl ether and 550 parts of 6% acetic acid aqueous solution were added thereto. In addition, the mixture was neutralized, and further deionized {Wako Pure Chemical Industries, Ltd., reagent grade) 2200 parts of water was added and mixed uniformly to obtain an emulsified mixture. Subsequently, low boiling point substances were distilled off from this mixed solution under reduced pressure of −0.05 to −0.098 MPa at 50 to 60 ° C. to obtain 35% resin emulsion {(1) to (6), (blank) }.

(2) Pigment paste 35 parts of a 35% resin emulsion, titanium dioxide {Ishihara Sangyo Co., Ltd. product, trade name: Taipei R-930} 30 parts, kaolin {Tsuchiya Kaolin Co., Ltd. product name: Ultra White 90} 15 parts, aluminum phosphomolybdate {reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) 3.5 parts, carbon black {reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.} 1 part, Sannonic SS-70 {Sanyo Chemical Industries, Ltd. Made in 0.5 parts and 30 parts of deionized water with an Excel auto homogenizer (model ED, manufactured by Nippon Seiki Co., Ltd.) equipped with impeller blades, particle size of 10 microns or less (in accordance with JIS K5600-2-5: 1999) To obtain a pigment paste (3000 rpm × 30 minutes).

Resin emulsion {(1)-(6), (blank)} 400 parts and 500 parts of deionized water are uniformly mixed at about 25 ° C., and 100 parts of pigment paste is added thereto, and then uniformly mixed at about 25 ° C. Thus, a cationic electrodeposition coating material {(1) to (6), (blank)} was obtained.
Further, 1000 parts of cationic electrodeposition paint (blank) and 30 parts of resin modifier (7) were uniformly mixed to obtain a cationic electrodeposition paint (7). Further, 400 parts of resin emulsion (blank) / 400 parts of deionized water / 100 parts of pigment paste / 100 parts of resin modifier (7) were uniformly mixed to obtain a cationic electrodeposition paint (8).

<Drying resistance>
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 painted surface of this coated plate was visually evaluated according to the following criteria, and the results are shown in Table 1.
○: Good with no unevenness of dryness (water mark defect) △: There are 2 or 3 points of dry unevenness ×: Many dry unevennesses are bad

<Water resistance test method>
The water resistance test was evaluated as follows based on the method described in JP-A-4-370165.
The coated plate obtained by the dry unevenness resistance test was subjected to a salt spray test for 500 hours according to JIS Z2371, and the state of rust generation was evaluated according to the following criteria. The results are shown in Table 1.
○: Good without rusting △: Spot rust and paint film swell 2 or 3 points ×: Many point rust and paint film swells are bad

Note 1: Content = Content of resin modifier in cationic electrodeposition paint (%)
Note 2: N content = resin component in cationic electrodeposition paint {Epicoat 1004, evaluation sample {resin modifiers (1) to (6), (7) not included}}, N-methylethanolamine, diethylenetriamine Content of nitrogen atom based on the weight of MIBK diketiminate, hexamethylene diisocyanate (HDI) and trimethylolpropane}

From Table 1, the cationic electrodeposition paint using the resin modifiers of Examples 1 to 4 has better water resistance than the blank and the resin modifiers of Comparative Examples 1 to 3, The dryness unevenness could be remarkably improved without deteriorating the original characteristics (water resistance) of the cationic electrodeposition paint.
In addition, since the N content in the cationic electrodeposition coating containing the resin modifier of the present invention is higher than that of a blank or the like, the throwing power of the coating during cationic electrodeposition is improved. I can guess.

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 (6)

A resin modifier comprising an epoxy compound represented by the general formula (1) as an essential component.
However, R is at least 1 sort (s) chosen from the group which consists of an alkyl group, an alkenyl group, and an acyl group, The carbon number of R is 8-18, N is a nitrogen atom, X represents a glycidyl group or a hydrogen atom, At least one of the two X is a glycidyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, M is an organic group having 1 to 3 carbon atoms, q is an integer of 0 to 4, m is 1 to The integer of 20 and n represent the integer of 1-10, and the total number of AO is 20-100. The resin modifier according to claim 1, wherein the total content of oxyethylene groups is 10 to 60 mol% based on the total number of moles of oxyalkylene groups (AO) having 2 to 4 carbon atoms. An aliphatic monoamine (a1) having 8 to 18 carbon atoms and / or an aliphatic monoamide (a2) having 8 to 18 carbon atoms;
An alkylene oxide (a3) having 2 to 4 carbon atoms;
Epihalohydrin (a5);
An epoxy resin having a structure that can be produced by a chemical reaction with a dihalogenated hydrocarbon having 1 to 3 carbon atoms (a4) as an essential component if necessary. The resin modifier according to any one of claims 1 to 3, wherein an epoxy equivalent is 500 to 5000 (g / eq.). A modified resin composition comprising a resin and the resin modifier according to any one of claims 1 to 4 and containing 1 to 50% by weight of the resin modifier based on the weight of the resin. A cationic electrodeposition paint comprising the modified resin composition according to claim 5.