JP5241360B2 - Pigment dispersion paste and electrodeposition paint - Google Patents

Description

  The present invention relates to a pigment dispersion paste excellent in redispersibility of a pigment that enables energy saving and equipment saving of a painting facility, and an electrodeposition coating using the pigment dispersion paste.

  Electrodeposition paints are widely used as undercoat paints for metal products such as automobile bodies because they have excellent paint workability and good rust prevention. The pigment-dispersed paste used in this electrodeposition coating is usually stored in a tank after production or stored in a warehouse in a drum can. However, if it is not stirred regularly, the pigment may settle and hinder use. is there. In particular, when transporting to overseas painting facilities, the pigment dispersion paste contained in the drum can is exposed to a non-stirring state for a long period of time, and thus improving the storage stability of the pigment dispersion paste is an urgent task. Yes.

  On the other hand, in order to prevent sedimentation of pigments, electrodeposition paints usually circulate and agitate with a pump during breaks, at night, and on holidays. However, the installation and maintenance of such equipment is enormous. Therefore, there is a need for an electrodeposition paint that can be applied to energy saving and equipment saving of painting equipment.

  In order to meet such demands, an invention relating to an electrodeposition paint using titanium oxide coated with zirconium as a white pigment and precipitated barium sulfate has been disclosed (see Patent Document 1).

  In addition, an electrodeposition coating material has been proposed in which carbon black having a low specific gravity is used as a pigment and liquid tin catalyst is used as a curing catalyst and the pigment does not settle substantially during stationary storage (see Patent Document 2). However, this electrodeposition paint has a problem with storage stability of the emulsion and paint stability of the electrodeposition paint because the liquid tin catalyst is blended in the emulsion, and also uses carbon black as a pigment. There is a problem that the color is limited to black.

In addition, it contains 0.1 to 20 parts by mass of a cellulose composite per 100 parts by mass of the solid content of the base resin, the curing agent, and the base resin and the curing agent, thereby enabling energy saving and equipment saving of the coating equipment. An electrodeposition paint is disclosed (see Patent Document 3). However, Patent Document 3 discloses that when applied to an electrodeposition paint that obtains a white paint film containing titanium white having a high specific gravity or an electrodeposition paint that obtains a tea paint film using iron oxide, In particular, since the redispersibility of the paint is insufficient when it is restarted after stirring and circulation of the electrodeposition paint for a long period of time such as consecutive holidays, the paint is insufficiently dispersed. As a result, there was a need for improvement.
JP 2000-281943 A JP 2004-123942 A JP 2006-111699 A

  An object of the present invention is to provide a pigment-dispersed paste for an electrodeposition paint having excellent storage stability. Furthermore, a cationic electrodeposition paint is manufactured using the pigment dispersion paste, and even if the stirring and circulation of the electrodeposition paint is stopped during breaks, holidays, and nights, it is excellent in redispersibility and paint stability, and in a wide range of paint colors. It is to provide an applicable electrodeposition paint.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed an electrodeposition coating material containing a pigment dispersion resin (A), a color pigment (B), an extender pigment (C), and a cellulose composite (D). It is a pigment dispersion paste, and the total solid content of the resin (A) is 100 parts by mass,
(1) As the color pigment (B),
(B1) 100 parts by mass of titanium dioxide serving as a substrate is coated with 0.1 to 10.0 parts by mass of Al ₂ O ₃ and not coated with SiO ₂ and / or (b2) 60 parts of iron oxide. -800 parts by mass,
(2) 2 to 200 parts by weight of fine particle barium sulfate having an average primary particle diameter of 0.01 to 0.1 μm as extender pigment (C), and (3) 1 to 50 parts by weight of cellulose composite (D) The present inventors have found that the above object can be achieved by a cationic electrodeposition paint using a pigment dispersion paste for electrodeposition paints characterized by containing a part. The present invention has been completed.

  The pigment dispersion paste of the present invention is excellent in storage stability, so it is possible to save the labor and cost of stirring during storage, and the pigment redispersion even when stored in a tank or drum without stirring. Because of its excellent properties, it is possible to provide a coated article with excellent finish.

  The cationic electrodeposition paint of the present invention is excellent in the redispersibility of the paint when the paint is stirred and circulated in the painting line for a long time on holiday or at night and then restarted. Energy saving operation and equipment saving such as stopping and reducing the number of units are possible.

The reason why the cationic electrodeposition coating composition of the present invention is excellent in the above-described performance can be considered as follows. That is, conventionally, in the pigment dispersion paste, when formulating titanium dioxide or aluminum silicate containing _{(Al 2 O 3 · SiO 2} ) and SiO _2, next to a portion of the SiO ₂ is SiOH, firmly bond of SiO-Si And the redispersibility of the pigment sedimented aggregate is significantly deteriorated. Therefore, it is necessary to remove these pigment components from the pigment dispersion paste, but when the titanium dioxide containing SiO ₂ or aluminum silicate (Al ₂ O ₃ · SiO ₂ ) is removed, the pigment dispersion paste settles. There was a problem that it was easy to do.

  However, in the pigment dispersion paste of the present invention, (1) by adding the cellulose composite (D), the pigment dispersion paste forms a pseudo network (an effect of controlling rheology), and thus it is difficult to settle. (2) By blending fine barium sulfate having an average primary particle diameter of 0.01 to 0.1 μm, the precipitated pigment component does not aggregate and a hard cake layer is not formed. (3) Furthermore, since the pigment dispersion resin has a novolak epoxy structure, the hydroxyl group is oriented on the pigment surface and the hydrophilicity of the pigment dispersion paste is improved, so that the redispersibility is excellent. Thereby, the cake layer of the settled pigment component is easily loosened, and the dispersion of the pigment component in water is promoted.

  Hereinafter, the pigment dispersion paste of the present invention and the electrodeposition paint using the pigment dispersion paste will be described in detail.

The pigment dispersion paste of the present invention is a pigment dispersion paste for electrodeposition paints comprising a pigment dispersion resin (A), a color pigment (B), an extender pigment (C) and a cellulose composite (D), For a total of 100 parts by mass of the solid content of A),
(1) As the color pigment (B),
(B1) 100 parts by mass of titanium dioxide serving as a substrate is coated with 0.1 to 10.0 parts by mass of Al ₂ O ₃ and not coated with SiO ₂ and / or (b2) 60 parts of iron oxide. -800 parts by mass,
(2) 2 to 200 parts by weight of fine particle barium sulfate having an average primary particle diameter of 0.01 to 0.1 μm as extender pigment (C), and (3) 1 to 50 parts by weight of cellulose composite (D) A pigment-dispersed paste for electrodeposition paints, characterized by comprising a part.
Pigment dispersing resin (A):
As the pigment dispersion resin (A) used in the pigment dispersion paste of the present invention, those usually used for the preparation of electrodeposition paints can be used. For example, amino group-containing epoxy resins such as tertiary amine type, quaternary Examples thereof include ammonium salt type epoxy resins and quaternary ammonium salt type acrylic resins. These resins can be used alone or in combination of two or more resins. Among these pigment-dispersing resins (A), the novolak epoxy resin-based pigment dispersing resin (A1) shown below is particularly preferable from the viewpoint of the stability and anticorrosive properties of the pigment-dispersed paste.

Novolac epoxy resin pigment dispersion resin (A1):
The novolac epoxy resin-based pigment dispersion resin (A1) (hereinafter sometimes referred to as “pigment dispersion resin (A1)”) is a glycidyl etherified product (a1) or a cyclic ester compound (a2) of a novolac type phenol resin. The amine compound (a3) and the phenol compound (a4) are mixed with the component (a1) 30 to 70 based on the total solid mass of the component (a1), the component (a2), the component (a3) and the component (a4). It is a resin obtained by reacting at a ratio of mass%, component (a2) 5 to 45 mass%, component (a3) 5 to 15 mass% and component (a4) 1 to 30 mass%.

Glycidyl etherified product of novolac type phenol resin (a1)
As the glycidyl etherified product (a1) of the novolak type phenol resin, a compound represented by the following formula (1) can be preferably used.

（上式中、Ｒ^１およびＲ^２は同一もしくは相異なり、各々水素原子、炭素数１〜８のアルキル基、アリール基、アラルキル基またはハロゲン原子を表わし、Ｒ^３は水素原子、炭素数１〜１０のアルキル基、アリール基、アラルキル基、アリル基またはハロゲン原子を表わし、Ｒ^４およびＲ^６は同一もしくは相異なり、各々水素原子、炭素数１〜４のアルキル基またはグリシジルオキシフェニル基を表わし、Ｒ^５は水素原子、炭素数１〜１０のアルキル基、アリール基、アラルキル基、アリル基またはハロゲン原子を表わし、そしてｎは１〜３８の整数である）
上記一般式（１）において、「アルキル基」は、直鎖状もしくは分枝鎖状であり、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、イソアミル、ヘキシル、ヘプチル、オクチル、２−エチルヘキシル、ノニル、デシル基などが挙げられる。

(In the above formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group or a halogen atom, and R ³ represents a hydrogen atom, 1 to carbon atoms. 10 represents an alkyl group, an aryl group, an aralkyl group, an allyl group, or a halogen atom, and R ⁴ and R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a glycidyloxyphenyl group, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom, and n is an integer of 1 to 38)
In the general formula (1), the “alkyl group” is linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl. Hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl group and the like.

  The “aryl group” may be either monocyclic or polycyclic, and examples thereof include phenyl and naphthyl groups. Particularly, the phenyl group is preferable, and the “aralkyl group” is an aryl-substituted alkyl group. And includes, for example, benzyl, phenethyl and the like, and benzyl is preferred.

  “Halogen atom” includes fluorine, chlorine, bromine and iodine atoms.

The “glycidyloxyphenyl group” represented by R ⁴ or R ⁶ is a group represented by the following formula (2).

（上式中、Ｗは水素原子または炭素数１〜１０のアルキル基を表わす）
前記一般式（１）において、Ｒ^１およびＲ^２としては水素原子、メチル基、塩素原子および臭素原子が好適であり、特に水素原子、メチル基および臭素原子が好ましい。

(In the above formula, W represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)
In the general formula (1), R ¹ and R ² are preferably a hydrogen atom, a methyl group, a chlorine atom and a bromine atom, and particularly preferably a hydrogen atom, a methyl group and a bromine atom.

Further, as R ³ and R ⁵ , a methyl group, a tert-butyl group, a nonyl group, a phenyl group, a chlorine atom and a bromine atom are preferable, and a methyl group, a tert-butyl group, a phenyl group and a bromine atom are particularly preferable. is there. Furthermore, R ⁴ and R ⁶ are preferably hydrogen atoms, and n is particularly preferably 1-8.

  The number average molecular weight of the novolac epoxy resin pigment dispersing resin (A1) is generally preferably in the range of about 400 to about 8,000, particularly 600 to 2,000. The novolac epoxy resin pigment dispersion resin (A1) preferably has 3.5 to 10 glycidyl groups per molecule, and the novolac epoxy resin pigment dispersion resin (A1). The epoxy equivalent is preferably in the range of about 180 to about 2,000, especially 200 to 600.

  Here, the “number average molecular weight” is determined according to the method described in JIS K 0124-83 as “TSK GEL4000HXL”, “TSK G3000HXL”, “TSK G2500HXL”, “TSK G2000HXL” (manufactured by Tosoh Corporation). And the standard curve of standard polystyrene with a chromatogram obtained with an RI refractometer at 40 ° C. and a flow rate of 1.0 ml / min using tetrahydrofuran for GPC as an eluent.

  The novolac epoxy resin pigment dispersion resin (A1) is, for example, the following formula (3):

（上式中、Ｒ^１、Ｒ^２およびＲ^３は前記と同義である）
で示されるフェノール化合物（ａ１１）と、下記式（４）
Ｒ^４−ＣＨＯ 式（４）
（上式中、Ｒ^４は、炭素数１〜４のアルキル基またはグリシジルオキシフェニル基を表わす）
で示されるアルデヒド化合物（ａ１２）および／または下記式（５）
Ｒ^４−ＣＯ−Ｒ^６ 式（５）
（上式中、Ｒ^４およびＲ^６は、炭素数１〜４のアルキル基またはグリシジルオキシフェニル基を表わす）
で示されるケトン化合物（ａ１３）を縮重合反応させることにより得られるノボラック型フェノール樹脂（ａ１４）に、さらにエピハロヒドリン（ａ１５）を反応させてグリシジルエーテル基を導入することにより製造することができる。

(Wherein R ¹ , R ² and R ³ are as defined above)
And a phenol compound (a11) represented by the following formula (4):
R ⁴ —CHO Formula (4)
(In the above formula, R ⁴ represents an alkyl group having 1 to 4 carbon atoms or a glycidyloxyphenyl group)
The aldehyde compound (a12) and / or the following formula (5)
R ⁴ —CO—R ⁶ formula (5)
(In the above formula, R ⁴ and R ⁶ represent an alkyl group having 1 to 4 carbon atoms or a glycidyloxyphenyl group)
Can be produced by further reacting an epihalohydrin (a15) with a novolac-type phenol resin (a14) obtained by subjecting the ketone compound (a13) represented by the following polycondensation reaction to a glycidyl ether group.

  In addition, during or after the reaction for obtaining the novolac-type phenol resin (a14), the following formula (6)

（上式中、Ｒ^１、Ｒ^２およびＲ^３は前記と同義である）で示されるフェノール化合物（ａ１６）を末端封止剤として併用してもよい。

A phenol compound (a16) represented by the formula (wherein R ¹ , R ² and R ³ are as defined above) may be used in combination as an end-capping agent.

Specific examples of the group R ⁷ in the formula (6) include methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, nonyl group, ethylene group, propylene group, phenyl Group, benzyl group, chlorine atom, bromine atom and iodine atom, etc., preferably methyl group, tert-butyl group, nonyl group, phenyl group, chlorine atom and bromine atom, especially methyl group, tert-butyl group A phenyl group and a bromine atom are preferred.

  Examples of the phenol compound (a11) represented by the formula (3) include phenol, p-propenylphenol, o-benzylphenol, 6-n-amyl-n-cresol, o-cresol, p-cresol, o- Ethylphenol, o-phenylphenol, p-phenylphenol, p-tert-pentylphenol, p-tert-butylphenol, o-chlorophenol, p-chlorophenol, 4-chloro-3,5-xylenol, o-allylphenol , Nonylphenol, o-bromophenol, p-cumylphenol and the like.

  Examples of the aldehyde compound (a12) represented by the formula (4) include acetaldehyde and formaldehyde. Alternatively, m- (or p-) hydroxybenzaldehyde may be used as the aldehyde compound (a12), and this hydroxybenzaldehyde may be glycidyl etherified with epihalohydrin (a15) after the reaction with the phenol compound (a11) component.

  In addition, the benzene nucleus of the hydroxybenzaldehyde may be substituted with an alkyl group having 1 to 10 carbon atoms.

  Examples of the ketone compound (a13) represented by the formula (5) include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  Furthermore, examples of the epihalohydrin (a15) include epichlorohydrin and epibromohydrin. A novolak-type phenol resin (a14) is obtained by subjecting the component (a11) to the condensation polymerization reaction of the component (a12) and / or the component (a13). This polycondensation reaction can be carried out according to a known method for producing a novolak type phenol resin.

  In the production of the novolak type phenol resin (a14), if necessary, during or after the polycondensation reaction between the component (a11) and the component (a12) and / or the component (a13), The phenol compound (a16) shown can be reacted as a terminal blocking agent.

  Specific examples of the phenol compound (a16) represented by the formula (6) include 2-tert-butyl-4-methylphenol, 2,4-xylenol, 2,6-xylenol, and 2,4-dichloro. Examples include phenol, 2,4-dibromophenol, dichloroxylenol, dibromoxylenol, 2,4,5-trichlorophenol, and 6-phenyl-2-chlorophenol.

  The polycondensation reaction of the component (a16) with the component (a11), the component (a12) and / or the component (a13) can be carried out in the same manner as described above.

  The glycidyl etherified product (a1) of the novolac type phenol resin can be obtained by reacting the phenolic hydroxyl group in the novolac type phenol resin (a14) with the epihalohydrin (a15) to glycidyl ether. Specifically, for example, a novolac-type phenol resin (a14) is dissolved in epihalohydrin (a15) to form a solution, and an aqueous solution of an alkali metal hydroxide is continuously added to the solution. It is obtained by distilling off the epihalohydrin (a15) of the reaction. The component (a15) can be separated from this distilled liquid and reused. This reaction is preferably carried out in the presence of an ether solvent such as dioxane or diethoxyethane.

  The glycidyl etherified product (a1) of the novolak type phenol resin can be produced as described above, but a commercially available product may be used. As glycidyl etherified products, DEN-438 and DEN-439 (made by Dow Chemical Japan Co., Ltd., trade name); as polyglycidyl etherified products of cresol type novolak resin, EPICRON N-695 (produced by Dainippon Ink Co., Ltd., products) Name), CNE195LB (Changchun Japan Co., Ltd.), EOCN-102S, EOCN-1020 and EOCN104S (Nippon Kayaku Co., Ltd., trade name); BREN-S as a polyglycidyl etherified product of bromo-modified phenol type novolac resin (Nippon Kayaku Co., Ltd., trade name); long Examples of the polyglycidyl etherified product of the chain alkyl-modified phenol type novolak resin include ESMB-260 (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

Cyclic ester compound (a2)
The cyclic ester compound (a2) has the following formula (7)

（上式中、Ｒ^８は水素原子またはＣＨ_３を表し、ｎは３〜６の整数である）
で示されるものであってよく、具体的には、例えば、δ−バレロラクトン、ε−カプロラクトン、ζ−エナラクトン、η−カプリロラクトン、γ−バレロラクトン、δ−カプロラクトン、ε−エナラクトン、ξ−カプリロラクトンが挙げられ、特に好ましくはε−カプロラクトンである。環状エステル化合物（ａ２）のラクトンに基因するメチレン鎖部分は、ノボラックエポキシ樹脂系の顔料分散用樹脂（Ａ１）に貯蔵安定性を付与する。

(In the above formula, R ⁸ represents a hydrogen atom or CH ₃ , and n is an integer of 3 to 6)
Specifically, for example, δ-valerolactone, ε-caprolactone, ζ-enalactone, η-caprolactone, γ-valerolactone, δ-caprolactone, ε-enalactone, ξ- Caprolactone is exemplified, and ε-caprolactone is particularly preferable. The methylene chain portion derived from the lactone of the cyclic ester compound (a2) imparts storage stability to the novolak epoxy resin pigment dispersion resin (A1).

Amine compound (a3)
The amine compound (a3) may be a primary or secondary amine compound having at least one primary hydroxyl group in one molecule. This is useful for introducing a primary hydroxyl group and a basic group into the pigment dispersing resin (A).

  A cationic resin is formed by a reaction between the amino group of the amine compound (a3) and the glycidyl group of the glycidyl etherified product (a1) of the novolak type phenol resin represented by the formula (1), and the primary resin in the cationic resin is produced. Hydroxyl group and basic group are produced by reaction with conventional bisphenol A type epoxy resin, but water dispersibility is remarkably superior to those groups, and pigment dispersion paste and cation using the pigment dispersion paste are used. Contributes to improving the stability of electrodeposition paints. Furthermore, in the formed coating film, it contributes also to the improvement of anticorrosion property, especially corrosion resistance.

Specific examples of the amine compound (a3) include the compounds exemplified below.
(1) Primary alkanolamines such as monoethanolamine, monopropanolamine, monobutanolamine (2) N-methylethanolamine, N-ethylethanolamine, diethanolamine, di-n- (or iso) -propanolamine, Secondary alkanolamines such as dibutanolamine (3) Adducts (secondary alkanolamines) of the above primary alkanolamines with α, β-unsaturated carbonyl compounds, such as monoethanolamine and N, N- Adducts with dimethylaminopropylacrylamide, adducts of monoethanolamine and hydroxyethyl (meth) acrylate, adducts of monoethanolamine and hydroxypropyl (meth) acrylate, monoethanolamine and hydroxybutyl (meth) acrylate (4) Primary and secondary alkanolamines such as hydroxyethylaminoethylamine (5) One or more selected from hydroxyamine, hydroxyethylhydrazine and hydroxybutylhydrazine and ketone compounds such as dimethyl ketone , Methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, dipropyl ketone and other condensates (secondary alkanolamine)
(6) An amine compound in which a primary hydroxyl group, a secondary amino group, and an amide group coexist in one molecule represented by the following formula (8).

（上式中、ｎは１〜６の整数であり、Ｒ^９は水酸基および／または重合性不飽和基を含有してもよい炭素数４〜３６の炭化水素鎖を表わす）
前記式（８）で示されるアミン化合物は、例えば、Ｎ−ヒドロキシアルキルアルキレンジアミンと炭素数５〜３７のモノカルボン酸とを脱水縮合反応させることによって得られる。かかるジアミンとしては、例えば、ヒドロキシエチルアミノエチルアミン、Ｎ−ヒドロキシエチルプロピレンジアミン、Ｎ−ヒドロキシエチルブチレンジアミン、Ｎ−ヒドロキシエチルペンチレンジアミン、Ｎ−ヒドロキシエチルヘキシレンジアミンなどの第１級水酸基を含有する第１、２ジアミンが好適であり、またモノカルボン酸としては、例えば、椰子油脂肪酸、ひまし油脂肪酸、米ぬか油脂肪酸、大豆油脂肪酸、トール油脂肪酸、脱水ひまし油脂肪酸、サフラワー油脂肪酸、あまに油脂肪酸および桐油脂肪酸などの混合脂肪酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リシノール酸、リノール酸、リノレイン酸、エレオステアリン酸、１２−ヒドロキシステアリン酸、ベヘン酸などが挙げられる。

(In the above formula, n is an integer of 1 to 6, and R ⁹ represents a hydrocarbon chain having 4 to 36 carbon atoms which may contain a hydroxyl group and / or a polymerizable unsaturated group)
The amine compound represented by the formula (8) can be obtained, for example, by subjecting N-hydroxyalkylalkylenediamine and a monocarboxylic acid having 5 to 37 carbon atoms to a dehydration condensation reaction. Examples of such diamines include primary hydroxyl groups such as hydroxyethylaminoethylamine, N-hydroxyethylpropylenediamine, N-hydroxyethylbutylenediamine, N-hydroxyethylpentylenediamine, N-hydroxyethylhexylenediamine, and the like. First and second diamines are preferred, and examples of monocarboxylic acids include coconut oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil Mixed fatty acids such as fatty acids and tung oil fatty acids, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, 12-hydroxystearic acid, Behe Such as acid, and the like.

  The reaction of the diamine with the monocarboxylic acid to obtain the amine compound represented by the above formula (8) is usually performed by mixing both components in an approximately equimolar ratio and using an organic solvent such as toluene or methyl isobutyl ketone. It can be carried out by removing a specified amount of reaction product water, and an amine compound can be obtained by removing the residual organic solvent by a reduced pressure method or the like.

  The amine compound thus obtained generally has an amine value (secondary amine) in the range of 88 to 350 mgKOH / g, particularly 120 to 230 mgKOH / g, and a hydroxyl value (preferably a primary hydroxyl group) of 44. It is preferable to be within the range of -350 mgKOH / g, particularly 60-230 mgKOH / g.

  Of the compounds (1) to (6) as the amine compound (a3), primary alkanols and secondary amines (2), (3) and (6) are preferred. In particular, it is preferable to use an amine compound represented by the formula (8) (particularly hydroxyethylaminoethyl fatty acid amide) and diethanolamine in order to improve finish and anticorrosion properties.

Phenol compound (a4)
As the phenol compound (a4), one having at least one, preferably 1 to 5, phenolic hydroxyl groups in one molecule can be used. Specifically, for example, 2,2-bis (p-hydroxyphenyl) propane, 4,4′-dihydroxybenzophenone, 1,1-bis (p-hydroxyphenyl) ethane, 1,1-bis (p-hydroxy) Phenyl) isobutane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, Examples thereof include polyhydric phenol compounds such as 1,1,2,2-tetra (p-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenyl sulfone, phenol novolac, and cresol novolac.

  Furthermore, monophenol compounds such as phenol, nonylphenol, α- or β-naphthol, p-tert-octylphenol, o- or p-phenylphenol can also be used.

  In order to form a coating film having more excellent anticorrosion properties, as the phenol compound (a4), in particular, bisphenol A [2,2-bis (p-hydroxyphenyl) propane] or bisphenol F [bis (p-hydroxyphenyl) is used. It is preferable to use a reaction product of bisphenols such as) methane] and epichlorohydrin.

  Among these reaction products, in particular, the number average molecular weight is at least 300, preferably in the range of about 800 to about 3,000, and an average of 2 or less per molecule, preferably about 0.00. Those represented by the following formulas containing 8 to 1.2 phenolic hydroxyl groups are suitable.

（上式中、ｎは平均して０〜７の数であり、Ｒ^１０は活性水素化合物の残基を表わす）
上記式において、Ｒ^１０の前駆体である活性水素含有化合物としては、例えば、第２級アミンのようなアミン類；ノニルフェノールのようなフェノール類；脂肪酸のような有機酸；チオール類；アルキルアルコール、カービトールのようなアルコール類；無機酸などの化合物が挙げられる。これらのうちで特に好ましいものは、第１級水酸基を有する第２級アミンであるジアルカノールアミンや、ノニルフェノール、フェニルフェノール、フェノールのようなモノフェノールである。特に、第１級水酸基含有アミンを用いると硬化性が向上し、またモノフェノールを用いると安定性がよくなる。

(In the above formula, n is an average number of 0 to 7, and R ¹⁰ represents a residue of an active hydrogen compound)
In the above formula, the active hydrogen-containing compound which is a precursor of R ¹⁰ includes, for example, amines such as secondary amines; phenols such as nonylphenol; organic acids such as fatty acids; thiols; Examples include alcohols such as carbitol; compounds such as inorganic acids. Of these, dialkanolamine which is a secondary amine having a primary hydroxyl group, and monophenol such as nonylphenol, phenylphenol and phenol are particularly preferred. In particular, when a primary hydroxyl group-containing amine is used, curability is improved, and when monophenol is used, stability is improved.

  Further, as the phenol compound, for example, 1 mol of a bisphenol A diglycidyl ether type polyepoxide having a molecular weight of 340 or more, preferably 380 to 2,000, and a molecular weight of 200 or more, preferably 200 to 2,000. Reaction of 1 mol of bisphenol A polyphenol within the range of 1 and 1 mol of a compound having active hydrogen in the presence of a catalyst or a solvent, if necessary, at a temperature of 30 to 300 ° C., preferably 70 to 180 ° C. Let

  In addition, as the phenol compound (a4), polyols such as dimer diol, ethylene glycol, propylene glycol and butylene glycol; polyether glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyester polyols such as polycaprolactone; Polycarboxylic acids; polyisocyanates; monoisocyanates; oxides of unsaturated compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide; allyl glycidyl ether, polypropylene glycol diglycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl Has hydroxyl groups such as ether, butyl glycidyl ether, and phenyl glycidyl ether. Glycidyl esters of organic acids such as fatty acids; that glycidyl ether compounds alicyclic oxirane-containing compounds and the like may also be used those obtained by reacting bisphenol A. Further, a compound obtained by graft polymerization of δ-4-caprolactone, an acrylic monomer or the like to this compound can also be used.

  The resin for pigment dispersion (A1) is, for example, a method in which a glycidyl etherified product (a1), a cyclic ester compound (a2), an amine compound (a3) and a phenol compound (a4) of a novolak type phenol resin are reacted simultaneously, It is obtained by a method in which a cyclic ester compound (a2) and an amine compound (a3) are reacted with a glycidyl etherified product (a1) of a phenol resin, and then a phenol compound (a4) is reacted.

  The reaction temperature in the reaction of the glycidyl etherified product (a1), cyclic ester compound (a2), amine compound (a3) and phenol compound (a4) of the novolak type phenol resin is usually 50 to 300 ° C. in the presence of an organic solvent, The inside of the range of 70-200 degreeC is especially preferable.

  The obtained pigment dispersion resin (A1) has a number average molecular weight of generally 1,000 to 20,000, particularly 1,500 to 10,000, and a hydroxyl value of 10 to 1000 mgKOH / g, particularly 50 to. 300 mgKOH / g and an amine value in the range of 10 to 300 mgKOH / g, particularly 30 to 100 mgKOH / g are also preferred for coating performance and paint stability.

  The ratio of the novolac epoxy resin-based pigment dispersion resin (A1) is 10 to 100% by mass, preferably 20 to 90% by mass, more preferably 40%, based on the solid content of the pigment dispersion resin (A) used. -70 mass% is preferable from the surface of the stability of a pigment dispersion paste. By using the pigment dispersion resin (A1) described above as the pigment dispersion resin of the pigment dispersion paste, the cake layer of the precipitated pigment component is easily loosened, and the dispersion of the pigment component in water is promoted.

The color pigment (B) used in the pigment dispersion paste is 0.1 to 10.0 parts by mass of Al ₂ O ₃ in 100 parts by mass of titanium dioxide serving as a base with respect to the solid content of the pigment dispersion resin (A). 60 to 800 parts by mass of titanium dioxide (b1) and / or iron oxide (b2) that are coated and not coated with SiO ₂ are contained.

For example, as commercial products of titanium dioxide (b1), JR-600A (A1 ₂ O ₃ 2.5% coating), JR-603 (A1 ₂ O ₃ 5%, ZrO 0.5% coating), JR-600E (A1 ₂ O ₃ 3.8% coating). Examples of commercially available iron oxide (b2) include Toda Color 130R and Toda Color 140ED (manufactured by Toda Kogyo Co., Ltd.).

  As other color pigments (B), those commonly used for electrodeposition paints can be used as well, and examples of the color pigments include carbon black, perylene black phthalocyanine blue, and phthalocyanine green.

  The extender pigment (C) used in the pigment dispersion paste of the present invention contains fine particle barium sulfate (c1) having an average primary particle diameter of 0.01 to 0.1 μm, particularly 0.02 to 0.07 μm. It is characterized by that. Examples of commercially available fine particle barium sulfate (c1) include Varifine BF-20 and Varifine BF-40 (above, trade name, manufactured by Sakai Chemical Industry Co., Ltd.).

The mixing ratio of the fine barium sulfate (c1) is 2 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 10 parts by weight of the fine particle barium sulfate (c1) with respect to 100 parts by weight of the pigment dispersion resin (A). 100 parts by mass is also preferred for obtaining a pigment dispersion paste having excellent pigment redispersibility. As other extender pigments (C), mica, talc and the like can be used. More preferably, it is preferable not to contain aluminum silicate (Al ₂ O ₃ .SiO ₂ ) in the pigment dispersion paste in order to obtain a pigment dispersion paste having excellent pigment redispersibility.

  This pigment dispersion paste contains 1 to 50 parts by mass, preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass of the cellulose composite (D) with respect to 100 parts by mass of the pigment dispersion resin (A). It is characterized by that.

  The cellulose composite (D) is a composite comprising fine cellulose and water-soluble gums and / or hydrophilic substances, and is a composite comprising fine cellulose, water-soluble gums and hydrophilic substances; fine cellulose and water soluble A composite composed of a functional gum; and a composite composed of fine cellulose and a hydrophilic substance. For example, a water-soluble gum and / or a hydrophilic substance is added to fine cellulose obtained by grinding cellulose. Can be dispersed and made into a homogeneous slurry, which is then dried.

  The fine cellulose is, for example, cellulose having an average degree of polymerization of 30 to 375 by depolymerizing cellulose-based materials such as wood pulp and refined linter by acid hydrolysis, alkaline oxidative decomposition, enzymatic decomposition, steam explosion decomposition and the like. And then grinding, for example by wet grinding with mechanical shear.

The wet grinding can be performed using a medium mill, for example, a wet vibration mill, a wet planetary vibration mill, a wet ball mill, a wet roll mill, a wet ball mill, a wet bead mill, a wet paint shaker, or a machine such as a high-pressure homogenizer. it can. As the high-pressure homogenizer, a type in which the slurry is guided to a fine orifice at a high pressure of about 500 Kg / cm ² or more and collides with each other at a high flow rate is effective.

  The optimum grinding concentration in these mills varies depending on the model, but in general, a solid content concentration in the range of 5 to 15% for a medium mill and 5 to 20% for a high-pressure homogenizer is suitable. A medium mill is suitable for efficiently grinding cellulose.

  By the above grinding, fine cellulose having an average particle size of 10 μm or less, preferably 8 μm or less, more preferably 5 μm or less can be obtained. In addition, an average particle diameter is a value when it measures using the laser diffraction type particle size distribution analyzer LA-920 (made by Horiba Ltd.). The resulting fine cellulose is mixed with water-soluble gums and / or hydrophilic substances to form a composite. Thereby, it can prevent that the cellulose particle refined | miniaturized at the time of drying reaggregates.

  As the water-soluble gums, water-soluble gums having high water swellability and good compatibility with water in cellulose are preferable. For example, locust bean gum, guar gum, tamarind gum, quince seed gum, karaya gum, gum arabic , Tragacanth gum, ghatti gum, arabinogalactan, agar, carrageenan, alginic acid and its salts, ferceleran, pectin, quince, xanthan gum, curdlan, pullulan, dextran, gellan gum, gelatin, cellulose derivatives such as cellulose glycolate, etc. be able to. Among these, sodium cellulose glycolate has both swellability and hydrophilicity, so that it can be used alone without using a hydrophilic substance.

  On the other hand, examples of hydrophilic substances include water, starch hydrolysates, dextrins, glucose, fructose, xylose, sucrose, lactose, maltose, isomerized sugar, coupling sugar, palatinose, neosugar, mannitol, and reduced starch saccharification. Examples thereof include monosaccharides such as koji, maltose, lactulose, polydextrose, fructooligosaccharide and galactooligosaccharide, water-soluble saccharides including oligosaccharide, sugar alcohols such as xylitol, maltitol, mannitol and sorbitol, sorbose and the like. The hydrophilic substance promotes dispersion of cellulose in water, and has a remarkable effect on dispersibility or dispersion stability by combining with water-soluble gums.

  The proportion of fine cellulose in the cellulose composite (D) is generally 0.1 to 99 mass%, preferably 1 to 95 mass%, more preferably 10 to 85 mass%, based on the solid content of the cellulose composite. It is suitable from the surface of coating stability that it exists in the range. The ratio of the water-soluble gum and the hydrophilic substance used in combination is usually 95/5 to 5/95, preferably 80/20 to 20 / in terms of the mass ratio of the water-soluble gum / hydrophilic substance. It can be in the range of 80.

  The cellulose composite (D) can be produced by mixing and dispersing finely divided cellulose with water-soluble gums and / or hydrophilic substances, followed by drying. In particular, the water-soluble gums are It is important to dissolve sufficiently and mix uniformly. In order to promote dissolution and complexing, heat treatment may be performed.

  Although drying can also be performed by freeze-drying, spray drying, etc., the method of drying in a film form is excellent, for example. Examples of the method of drying in a film form include, for example, a slurry obtained by uniformly mixing finely divided cellulose together with water-soluble gums and / or hydrophilic substances, such as glass, stainless steel, aluminum, nickel / chromium plated steel plates, and the like. The method of apply | coating on a material and drying is mentioned. The substrate may be heated in advance, or may be heated with infrared rays, hot air, high frequency, or the like after application. The drying temperature is preferably 200 ° C. or less, and the coating film thickness is preferably 10 mm or less as the thickness of the slurry. Industrially, dry powder can be obtained using a dryer such as a steel belt dryer, drum dryer, or disk dryer. When the dry powder thus obtained is observed with an electron microscope, the finely divided cellulose is arranged in a mesh pattern on the surface, and numerous voids are observed between the finely divided celluloses.

  Commercially available products of the cellulose composite (D) obtained as described above include Avicel RC-N81, Avicel RC-N30, Avicel RC-591, Avicel CL-611, Theolas Cream FP-03 (above, Asahi Kasei Chemicals ( Product name) and the like.

  In general, the cellulose composite (D) is preferably blended into the pigment dispersion paste and introduced into the electrodeposition paint, but can be blended into the electrodeposition paint at any stage of the preparation of the electrodeposition paint. Alternatively, it can also be directly blended into a previously prepared electrodeposition paint containing a base resin and a curing agent, for example, in the form of a dispersion formed by mixing water and a cellulose composite.

  Such a cellulose composite (D) has the ability to stably disperse without settling in water, and when applied to an electrodeposition coating, the above-mentioned pigment dispersion resin (A) and colored pigment (B ) And extender pigment (C) in combination, and excellent paint redispersibility and finish when the paint is stirred and circulated for a long time on holiday or at night Can be obtained.

  Examples of the anticorrosive pigment appropriately blended in the pigment dispersion paste of the present invention include aluminum phosphomolybdate, aluminum tripolyphosphate, bismuth oxide, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate, bismuth silicate, and hydrotalcite. And zinc compounds.

  Furthermore, the curing catalyst appropriately blended in the pigment dispersion paste of the present invention is effective for promoting the crosslinking reaction of the coating film. For example, dioctyl tin oxide, dibutyl tin oxide, tin octoate, dibutyl tin dilaurate and dibutyl tin And dibenzoate.

The blending ratio of the pigment dispersion resin (A) used for preparing the pigment dispersion paste is 0.1 to 20 parts by mass, particularly 3 to 15 in total per 100 parts by mass of the solid content of the base resin and the curing agent. It is desirable to be within the range of 5 parts by mass, more particularly 5-12 parts by mass.
The pigment dispersion paste is produced by a pigment dispersion resin (A), a color pigment (B), an extender pigment (C) and a cellulose composite (D), and optionally a rust preventive pigment, a curing catalyst, a neutralizing agent, It can be carried out by blending a surfactant, water and the like and dispersing the pigment to prepare a pigment dispersion paste. The pigment dispersion can be performed using a dispersing machine such as a ball mill, a pebble mill, a sand mill, or a shaker. Examples of the neutralizing agent include acetic acid, formic acid, lactic acid, propionic acid and the like. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether.

  The pigment dispersion paste thus obtained is appropriately blended with a surfactant, a neutralizing agent, etc., and dispersed using a conventional dispersing machine such as a ball mill, pebble mill, sand mill, shaker, etc. Can be made to be 15 μm or less, preferably 8 μm or less. Among these, a ball mill is preferable from the viewpoint of workability, and a dispersion time by the ball mill is preferably 1 to 96 hours, and more preferably 10 to 48 hours from the viewpoint of pigment particle size and production man-hour.

  In this specification, the particle diameter (tube) of the pigment component is dispersed based on the degree of dispersion according to the JIS K-5400-4.7.1 (1990) distribution diagram method, and the distribution density of the particles using a tube gauge. Is a reading of the scale where dense particles began to appear.

[About electrodeposition paint]
The pigment dispersion paste provided by the present invention can be mixed with an emulsion containing a base resin and a curing agent to produce an electrodeposition paint.

  The electrodeposition paint may be either an anionic type or a cationic type, but in general, a cationic type is preferred from the viewpoint of corrosion resistance. Further, as the base resin, for example, any resin for paint such as epoxy resin, acrylic resin, polybutadiene resin, alkyd resin, polyester resin, etc. can be used. The polyamine resin represented by is preferable.

  An amine-added epoxy resin is obtained by adding an amine compound to an epoxy resin, and as an epoxy resin used at that time, in particular, from the viewpoint of anticorrosiveness of a coating film, a polyphenol compound and an epihalohydrin, for example, Epoxy resins obtained by reaction with epichlorohydrin are preferred.

  As the polyphenol compound that can be used for the formation of the epoxy resin, the same as those conventionally used can be used, for example, bis (4-hydroxyphenyl) -2,2-propane (bisphenol A), 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl) methane (bisphenol F), bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis ( 4-hydroxy-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra (4-hydroxyphenyl) -1,1,2,2-ethane, 4,4-dihydroxydiphenyl Examples include sulfone (bisphenol S), phenol novolac, cresol novolac, etc. That.

  Moreover, as an epoxy resin obtained by reaction of a polyphenol compound and epichlorohydrin, what is shown by the following formula induced | guided | derived from bisphenol A is suitable especially.

エポキシ樹脂は、一般に１８０〜２，５００、好ましくは２００〜２，０００、さらに好ましくは４００〜１，５００の範囲内のエポキシ当量を有することができ、また、一般に少なくとも２００、特に４００〜４，０００、さらに特に８００〜２，５００の範囲内の数平均分子量を有するものが適している。

The epoxy resin can generally have an epoxy equivalent weight in the range of 180 to 2,500, preferably 200 to 2,000, more preferably 400 to 1,500, and is generally at least 200, in particular 400 to 4, Those having a number average molecular weight in the range of 000, more particularly in the range of 800 to 2,500 are suitable.

  Examples of such commercially available epoxy resins include those sold by Japan Epoxy Resins Co., Ltd. under the trade names jER828EL, 1002, 1004, and 1007.

  The amine compound is a cationic component that cationizes the epoxy resin by introducing an amino group into the epoxy resin, and contains at least one active hydrogen that reacts with the epoxy group, for example, a primary amino group An amine compound having the following formula is used.

  Examples of the amine compound having a primary amino group include ketiminates such as monoethanolamine, propanolamine, hydroxyethylaminoethylenediamine, hydroxyethylaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Can be mentioned.

  The amine compound having the primary amino group can be used in combination with other amine compounds, and as the amine compound that can be used in combination, a secondary amine is particularly preferable. For example, diethylamine, diisopropylamine, diethanolamine, di (2 -Hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol and the like.

  The above epoxy resin can be modified by reacting with xylene formaldehyde resin, caprolactone polyol compound or the like.

  The xylene formaldehyde resin can be produced, for example, by subjecting xylene, formaldehyde, and optionally phenols to a condensation reaction in the presence of an acidic catalyst. As said formaldehyde, the compound etc. which generate | occur | produce formaldehyde, such as formalin, paraformaldehyde, and trioxane which are industrially easy to acquire, can be illustrated. The xylene formaldehyde resin can generally have a viscosity in the range of 20 to 50,000 centipoise (25 ° C.), preferably 30 to 15,000 centipoise (25 ° C.), and generally 100 to 50,000, especially It preferably has a hydroxyl equivalent weight within the range of 200 to 10,000.

  On the other hand, the caprolactone polyol compound can be obtained by adding caprolactone to a compound containing a plurality of active hydrogen groups, for example, ethylene glycol, propylene glycol, trimethylolpropane and the like.

  In general, modification of an epoxy resin with a xylene formaldehyde resin or a polycaprolactone polyol compound is preferably performed by reacting an amine compound and a modifier simultaneously with an epoxy group of the epoxy resin.

  The use ratio of the above modifier is not strictly limited and can be appropriately changed according to the application of the coating composition, etc., but generally 5 to 50 mass based on the solid content mass of the epoxy resin. %, Preferably in the range of 10 to 30% by mass.

  Conventionally known curing agents such as blocked polyisocyanate compounds and amino resins can be used as the curing agent to be blended in the cationic electrodeposition coating, and blocked polyisocyanate compounds are particularly preferred.

  Examples of the polyisocyanate compound include aromatic, alicyclic or aliphatic such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and isophorone diisocyanate. Polyisocyanate compounds and excess isocyanate compounds include terminal isocyanate-containing compounds obtained by reacting low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, and castor oil. .

  Examples of the blocking agent include lactam compounds such as ε-caprolactam and γ-butyrolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol; n-butanol, Examples thereof include aliphatic alcohols such as 2-ethylhexanol; aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; ether alcohol compounds such as ethylene glycol monobutyl ether. Of these, oxime-based and lactam-based blocking agents are blocking agents that dissociate at relatively low temperatures, and are particularly suitable from the viewpoint of low-temperature curability.

  The use amount of the base resin and the curing agent is 60 to 90%, preferably 70 to 85%, and the curing agent is 40 to 10%, preferably 30 to 15%, based on the total mass of both. % Range.

  The above-mentioned base resin and curing agent can usually be made into an emulsion by neutralizing the resin with a water-soluble organic acid such as formic acid, acetic acid, or lactic acid to make it water-soluble or water-dispersed.

The electrodeposition paint can be prepared by adding a pigment dispersion paste to an emulsion and, if necessary, blending additives such as an organic solvent, a surfactant, a surface conditioner, a repellency inhibitor, etc. To obtain a bath of cationic electrodeposition paint by diluting with deionized water or the like so that the solid content concentration is in the range of 5 to 25% by mass and adjusting the pH in the range of 5.0 to 7.0. Can do. The electrodeposition coating is usually performed at a bath temperature of 15 to 35 ° C. and an applied voltage of 100 to 400 V, an interelectrode distance of 0.3 to 2 m, preferably 0.5 to 1.5 m, and an electrode ratio (anode / cathode) of 1/8 to It can be carried out under the conditions of 2/1, preferably 1/5 to 1/2.
The film thickness of the electrodeposition coating film is not particularly limited, but generally it is preferably within the range of 10 to 40 μm based on the cured coating film. Moreover, generally the baking conditions of a coating film are suitable for 5-90 minutes within the range of 100-200 degreeC.

  The electrodeposition paint of the present invention, compared with conventionally known electrodeposition paints, is particularly redispersible and stable when the paint is stirred and circulated in the painting line for a long time on holiday or at night. Because of its superiority, it can save energy and operate equipment.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited thereby. “Parts” and “%” indicate “parts by mass” and “% by mass”.

Production Example 1 Pigment Dispersion Resin No. Production Example of 1 Solution 1010 parts of jER828EL (made by Japan Epoxy Resin Co., Ltd., trade name, epoxy resin), 390 parts of bisphenol A, 240 parts of polycaprolactone diol (number average molecular weight of about 1200) and 0.2 part of dimethylbenzylamine In addition, the reaction was continued at 130 ° C. until the epoxy equivalent reached about 1,090.

  Next, 134 parts of dimethylethanolamine and 90 parts of acetic acid were added and reacted at 120 ° C. for 4 hours, and then the solid content was adjusted by adding ethylene glycol monobutyl ether to form an ammonium salt resin pigment having a solid content of 60%. Resin for dispersion No. One solution was obtained. Resin for pigment dispersion No. 1 had an ammonium salt number of 44 mgKOH / g and a number average molecular weight of 3,000.

Production Example 2 Pigment Dispersion Resin No. Example of manufacturing two solutions
Into a flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 450 parts of nonylphenol and 960 parts of CNE195LB (Note 1) are charged, gradually heated while mixing and stirring, and reacted at 160 ° C. Thereafter, 430 parts of ε-caprolactone is charged, and the temperature is raised to 170 ° C. for reaction. Further, 105 parts of diethanolamine and 124 parts of N-methylethanolamine were reacted, and after confirming that the epoxy value became 0, ethylene glycol monobutyl ether was added to adjust the solid content, and a pigment dispersion resin having a solid content of 60% No. Two solutions were obtained.

The pigment dispersion resin No. The hydroxyl value of 2 was 150 mgKOH / g, the amine value was 70 mgKOH / g, and the number average molecular weight was 2200.
(Note 1) CNE195LB: manufactured by Changchun Japan Co., Ltd., trade name, cresol type novolac epoxy Production Example 3 Pigment Dispersion Paste No. Production of Pigment Dispersion Resin No. 60 having a solid content of 60% 1 10.0 parts (solid content 6.0 parts), JR-600E (note 2) 20 parts, Varifine BF-20 (note 10) 3.0 parts, Avicel RC-N81 (note 12) 3.0 Part, KW-140E (Note 14) 1.0 part, bismuth hydroxide 2.0 part, dioctyltin oxide 1 part, deionized water 23.4 parts, and after dispersing for 20 hours in a ball mill, taken out, solid content 55% pigment dispersion paste no. 1 was obtained.

Production Examples 4 to 14 Pigment dispersion paste No. 2-No. Production of Pigment Dispersion Paste No. 12 except that the blending contents are as shown in Table 1. In the same manner as in No. 1, pigment dispersion paste No. 1 2-No. 12 was obtained.

（注２）ＪＲ−６００Ｅ：テイカ株式会社製、ＴｉＯ_２に対してＡ１_２Ｏ_３を３．８％コーティングしたチタン白
（注３）ＪＲ−６０３：テイカ株式会社製、ＴｉＯ_２に対してＡ１_２Ｏ_３５％とＺｒＯ０．５％をコーティングしたチタン白
（注４）ＪＲ−９０３：テイカ株式会社製、ＴｉＯ_２に対してＡ１_２Ｏ_３３％とＺｒＯ１％コーティングしたチタン白
（注５）タイペークＣＲ−９７：石原産業社製、ＴｉＯ_２に対してＡ１_２Ｏ_３４％とＺｒＯ１％コーティングしたチタン白
（注６）タイペークＣＲ−９３：石原産業社製、ＴｉＯ_２に対してＡ１_２Ｏ_３３％とＳｉＯ_２５％コーティングしたチタン白
（注７）ＪＲ−８００：テイカ株式会社製、ＴｉＯ_２に対してＡ１_２Ｏ_３３％とＳｉＯ_２４％コーティングしたチタン白
（注８）トダカラーＫＮ−Ｏ：戸田工業社製、商品名、酸化第ニ鉄
（注９）カーボンＭＡ−７：三菱化学社製、商品名、カーボンブラック
（注１０）バリファインＢＦ−２０：堺化学社製、商品名、平均粒子径０．０３μｍの微粒子硫酸バリウム
（注１１）ハイドライトＰＸＮ：ジョージアカオリン社製、商品名、アルニミウムシリケート
（注１２）アビセルＲＣ−Ｎ８１：旭化成ケミカルズ（株）製、商品名、セルロース複合体（結晶セルロース、カラヤガム、デキストリン）
（注１３）アビセルＲＣ−Ｎ３０：旭化成ケミカルズ（株）製、商品名、セルロース複合体（結晶セルロース、キサンタンガム、デキストリン）
（注１４）ＫＷ−１４０Ｅ：テイカ社製、商品名、トリポリリン酸二水素アルミニウム
実施例１〜７、比較例１〜５
製造例３〜１４で得た顔料分散ペーストＮｏ．１〜Ｎｏ．１２を各１００ｇ採り、蓋のついたガラス容器に４０℃で４週間貯蔵した。貯蔵後の状態を下記の基準（注１５参照）で評価した。その結果を表２に示す。

(Note 2) JR-600E: manufactured by Teika Co., Ltd., titanium white coated with 3.8% A1 ₂ O ₃ on TiO ₂ (Note 3) JR-603: manufactured by Teika Co., Ltd., A1 with respect to TiO _{2 2} O ₃ 5% and coated titanium white ZrO0.5% (Note 4) JR-903: Tayca Co., _A1 2 _O 3 with respect to TiO ₂ 3% and ZrO1% coated titanium white (Note 5) Tipaque CR-97: manufactured by Ishihara Sangyo Kaisha, Ltd., _A1 2 _O 3 4% with respect to TiO ₂ and ZrO1% coated titanium white (Note 6) TIPAQUE CR-93: manufactured by Ishihara Sangyo Kaisha, Ltd., with respect to TiO _{2 A1} 2 O ₃ 3% and _SiO 2 5% coated titanium white (Note 7) JR-800: Tayca Co., _A1 2 _O 3 3% with respect to TiO ₂ and _SiO 2 4% coated Ji White (Note 8) Toda Color KN-O: Toda Kogyo Co., Ltd., trade name, ferric oxide (Note 9) Carbon MA-7: Mitsubishi Chemical Co., Ltd., trade name, Carbon Black (Note 10) Varifine BF- 20: Made by Sakai Chemical Co., Ltd., trade name, fine particle barium sulfate with an average particle size of 0.03 μm (Note 11) Hydrite PXN: Made by Georgia Kaolin, trade name, Aluminium silicate (Note 12) Avicel RC-N81: Asahi Kasei Chemicals Product name, cellulose composite (Crystalline cellulose, Karaya gum, dextrin)
(Note 13) Avicel RC-N30: manufactured by Asahi Kasei Chemicals Corporation, trade name, cellulose composite (crystalline cellulose, xanthan gum, dextrin)
(Note 14) KW-140E: manufactured by Teika, trade name, aluminum dihydrogen tripolyphosphate Examples 1-7, Comparative Examples 1-5
Pigment dispersion paste No. 1 obtained in Production Examples 3-14. 1-No. 100 g of each 12 was taken and stored in a glass container with a lid at 40 ° C. for 4 weeks. The state after storage was evaluated according to the following criteria (see Note 15). The results are shown in Table 2.

（注１５）顔料分散ペーストの安定性：貯蔵後の顔料分散ペーストの状態を観察した。

(Note 15) Stability of pigment dispersion paste: The state of the pigment dispersion paste after storage was observed.

  ◎ indicates that there is no problem because it immediately returns to the state before storage after stirring.

  In the case of ◯, the pigment settles and a cake layer is seen, but if it is stirred for about 30 minutes, it returns to the state before storage.

  For Δ, a pigment layer settles and a cake layer is observed. If the mixture is stirred for about 1 to 2 hours, the sedimented cake layer disappears, but pigment aggregation remains in the pigment-dispersed paste.

  In x, the pigment settles and a cake layer is observed, and the cake layer that has settled does not disappear even after stirring for 2 hours or more.

Production Example 15 Cationic Resin No. Production Example of 1 Solution In a separable flask having an internal volume of 2 liters equipped with a thermometer, a reflux condenser, and a stirrer, 1010 parts of jER828EL (trade name, epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.) and bisphenol A 390 And 0.2 part of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent was 800.
Next, 160 parts of diethanolamine and 65 parts of ketimine compound of diethylenetriamine were added and reacted at 120 ° C. for 4 hours, 355 parts of ethylene glycol monobutyl ether was added, and cationic resin no. One solution was obtained. Cationic resin no. 1 had an amine value of 67 mgKOH / g and a number average molecular weight of 2,000.

Production Example 16 Cationic Resin No. Example of manufacturing two solutions
A separable flask similar to Production Example 15 was charged with 480 parts of 50% formalin, 110 parts of phenol, 202 parts of 98% industrial sulfuric acid and 424 parts of metaxylene, and reacted at 84 to 88 ° C. for 4 hours.

After completion of the reaction, the xylene solution phase in which the resin is dissolved and the sulfuric acid aqueous phase are separated from each other, and then the xylene solution phase is washed with water three times and treated for 20 minutes at 20-30 mmHg / 120-130 ° C. Then, unreacted meta-xylene was distilled off to obtain 480 parts of phenol-modified xylene formaldehyde resin having a viscosity of 1050 centipoise (25 ° C.).
To another flask, 1000 parts of jER828EL (manufactured by Japan Epoxy Resin, trade name, epoxy resin, epoxy equivalent 190, molecular weight 350), 400 parts of bisphenol A and 0.2 part of dimethylbenzylamine are added, and epoxy equivalent at 130 ° C. The reaction was continued until 750.

  Next, after adding 300 parts of the xylene formaldehyde resin, 137 parts of diethanolamine and 95 parts of ketimine compound of diethylenetriamine, the mixture was reacted at 120 ° C. for 4 hours, and then added with 403 parts of methyl isobutyl ketone to contain xylene formaldehyde resin-modified amino groups. An epoxy resin solution having a resin solid content of 80% by mass, a cationic resin No. Two solutions were obtained. Cationic resin no. 2 had an amine value of 57 mgKOH / g and a number average molecular weight of 2,000.

Production Example 17 Production Example of Blocked Polyisocyanate Curing Agent Solution In a reaction vessel, 270 parts of Cosmonate M-200 (Note 19) and 130 parts of methyl isobutyl ketone were added and heated to 70 ° C. 240 parts of ethylene glycol monobutyl ether was added dropwise thereto over 1 hour, and then the temperature was raised to 100 ° C. While maintaining this temperature, sampling was performed over time, and after confirming that the absorption of unreacted isocyanate groups could not be determined by infrared absorption spectrum measurement, the temperature was lowered and the blocked polyisocyanate having a resin solid content of 80% A curing agent solution was obtained.

Production Example 18 Emulsion No. Production of Cationic Resin No. 1 obtained in Production Example 15 After mixing 17.5 with 87.5 parts (solid content 70 parts), the blocked polyisocyanate curing agent obtained in Production Example 17 with 33.3 parts (solid content 30 parts) and 10% acetic acid 15 parts, and stirring uniformly , 158.2 parts of deionized water was added dropwise with vigorous stirring over about 15 minutes, and emulsion No. 34 having a solid content of 34% was added. 1 was obtained.

Production Example 19 Emulsion No. Production of Cationic Resin No. 1 obtained in Production Example 16 After mixing 87.5 parts (solid content 70 parts) 2 and the blocked polyisocyanate curing agent obtained in Production Example 17 with 33.3 parts (solid content 30 parts) and 15 parts of 10% acetic acid, the mixture was stirred uniformly. , 158.2 parts of deionized water was added dropwise with vigorous stirring over about 15 minutes, and emulsion No. 34 having a solid content of 34% was added. 2 was obtained.

Example 8
Emulsion no. 1 to 294 parts (100 parts solids), pigment dispersion paste No. No. 1 was added 60.9 parts (solid content 33.5 parts) and deionized water 312.6 parts and mixed uniformly to give a cationic electrodeposition paint No. 1 having a solid content of 20%. 1 was obtained.

Examples 9-16, Comparative Examples 6-12
In the same manner as in Example 1, the cationic electrodeposition paint no. 2-No. 16 was obtained.

試験板の作成
実施例８〜１６及び比較例６〜１２で得たカチオン電着塗料中に、パルボンド＃３０２０（日本パーカライジング社製、リン酸亜鉛処理剤）で化成処理した０．８×１５０×７０ｍｍの冷延ダル鋼板を浸漬し、それをカソードとして浴温２８℃及び印加電圧２５０Ｖの条件で電着塗装し、膜厚２０μｍの電着塗膜を形成せしめ、水洗後、１７０℃−２０分の焼付けを行なって試験板を得た。塗料試験及び試験板の性能試験結果を下記の表５及び表６に示す。

Preparation of test plates 0.8 × 150 × treated with Palbond # 3020 (manufactured by Nihon Parkerizing Co., Ltd., zinc phosphate treating agent) in the cationic electrodeposition paints obtained in Examples 8 to 16 and Comparative Examples 6 to 12 A 70 mm cold-rolled dull steel plate is dipped, electrodeposited with a bath temperature of 28 ° C. and an applied voltage of 250 V as a cathode, to form an electrodeposition coating film with a thickness of 20 μm, and after washing with water, 170 ° C.-20 minutes The test plate was obtained by baking. The coating test and the performance test result of the test plate are shown in Tables 5 and 6 below.

（注１６）再分散性：各電着塗料３Ｌ抜き取ってから４８時間静止した後、２時間攪拌し、４００メッシュ濾過網にて全量濾過して残渣量（ｍｇ／Ｌ）を測定した。

(Note 16) Redispersibility: After 3 L of each electrodeposition paint was taken out, it was allowed to stand for 48 hours, stirred for 2 hours, and filtered through a 400 mesh filter to measure the amount of residue (mg / L).

◎: Residue amount less than 5 mg / L ○: Residue amount is 5 mg / L or more and less than 10 mg / L △: Residue amount is 10 mg / L or more and less than 25 mg / L ×: Residue amount 25 mg / L or more.
(Note 17) L-shaped finish: Each electrodeposition paint was coated with a test plate bent into an L-shape as an object to be coated. And the horizontal plane (L plane) was evaluated.

◯ indicates that neither lump, repellency, or gloss reduction is observed on the L-shaped surface. △ indicates that either Lump-side or repellency is observed on the L-shaped surface. Noticeable (Note 18) Anticorrosion:
The electrodeposited coating film of each test plate was cut with a knife so as to reach the substrate, and this was subjected to a salt spray resistance test for 840 hours according to JISZ-2371. Evaluation based on the criteria.

◎ indicates that the maximum width of rust and blisters is less than 2 mm (one side) from the cut part.
○: The maximum width of rust and blisters is 2mm or more and less than 3mm from the cut part (one side)
△ indicates that the maximum width of rust and blisters is 3 mm or more and less than 4 mm (one side) from the cut part,
X indicates that the maximum width of rust and blisters is 4 mm or more (one side) from the cut part.
(Note 19) Impact resistance: Using a DuPont impact tester, the test was conducted under the conditions of 1/2 inch diameter of hitting point, height of falling weight 30 cm, measurement atmosphere −20 ° C. The surface) was evaluated visually.
○: No abnormality △: Some small cracks are seen ×: Large cracks are seen

The cationic electrodeposition paint of the present invention can omit stirring during storage of the pigment dispersion paste, and can save energy and equipment in the coating line.

Claims (5)

At least one pigment dispersing resin (A), coloring pigment (B), extender pigment (C) and cellulose composite (D) selected from the group consisting of an amino group-containing epoxy resin and a quaternary ammonium salt type epoxy resin A pigment dispersion paste for an electrodeposition coating, comprising 100 parts by mass of the total solids of the resin (A),
(1) As the color pigment (B),
(B1) 100 parts by mass of titanium dioxide serving as a substrate is coated with 0.1 to 10.0 parts by mass of Al ₂ O ₃ and not coated with SiO ₂ and / or (b2) 60 parts of iron oxide. -800 parts by mass,
(2) 2 to 200 parts by weight of fine particle barium sulfate having an average primary particle diameter of 0.01 to 0.1 μm as extender pigment (C), and (3) 1 to 50 parts by weight of cellulose composite (D) A pigment dispersion paste for electrodeposition paints, characterized by comprising a part. The resin for pigment dispersion (A) is a glycidyl etherified product (a1), a cyclic ester compound (a2), an amine compound (a3), and a phenol compound (a4) of a novolak-type phenol resin, as component (a1) and component (a2). , Based on the total solid mass of component (a3) and component (a4), component (a1) 30 to 70% by mass, component (a2) 5 to 45% by mass, component (a3) 5 to 15% by mass and The pigment dispersion paste for electrodeposition paints according to claim 1, which is a novolac epoxy resin pigment dispersion resin obtained by reacting at a ratio of 1 to 30% by mass of component (a4). The pigment dispersion paste for electrodeposition paints according to claim 1 or 2, wherein the extender pigment (C) does not contain aluminum silicate (Al ₂ O ₃ · SiO ₂ ). The pigment dispersion paste for electrodeposition paints according to any one of claims 1 to 3, and a cationic electrodeposition paint containing an amine-added epoxy resin and a crosslinking agent, wherein the solid content of the amine-added epoxy resin and the crosslinking agent A cationic electrodeposition paint containing 1 to 60 parts by mass of the pigment dispersion paste for electrodeposition paint in terms of solid content with respect to 100 parts by mass in total. An article coated with the cationic electrodeposition paint according to claim 4.