TW200835759A - Cationic electrodeposition coating composition and application thereof - Google Patents

Abstract

The present invention relates to a cationic electrodeposition coating composition, which provides an uncured electrodeposited film having storage elasticity modulus (G') at 140 DEG C within a range of from 80 to 500 dyn/cm2 and loss elasticity modulus (G") at 80 DEG C within a range of from 10 to 150 dyn/cm2, and which is superior in smoothness and edge coatability; and a method for establishing both of smoothness and edge coatability therewith; as well as; a cationic electrodeposition coating composition comprising crosslinked resin particles having an average particle size within a range of from 1.0 to 3.0 μm and thermal softening temperature within a range of from 120 to 180 DEG C ; and a method for producing a cationic electrodeposition film having established smoothness and edge coatability, wherein the cationic electrodeposition film is prepared by applying a voltage to an article immersed in a cationic electrodeposition coating composition, and wherein the cationic electrodeposition coating composition comprises crosslinked resin particles having an average particle size within a range of from 1.0 to 3.0 μm and thermal softening temperature within a range of from 120 to 180 DEG C . The present invention can provide a method for establishing both of surface smoothness and edge coatability of the cationic electrodeposition coating composition, and cationic electrodeposition coating composition which can provide an electrodeposition film having excellent surface conditions.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic 5-electrodeposition coating composition having excellent smoothness and edge coating power, and a method of using the composition to simultaneously satisfy smoothness and edge coating force.

Furthermore, the present invention relates to a cationic electrodeposition coating composition having excellent smoothness and edge coating power, particularly a cationic electrodeposition coating composition comprising specific crosslinked resin particles, and the use of the composition simultaneously 10 A method that meets the smoothness and edge coating power. I: Prior Art 3 Background of the Invention Electrodeposition coating is a coating method which is carried out by dipping an object to be coated in an electrodeposition coating composition and applying a voltage. Since the electric 15 deposition coating method can automatically and continuously apply an object to be coated having a precise complicated shape, it has been widely and practically used as a method of mainly coating a large-sized object having a complicated shape, in particular It is for example a car body. Since the electrodeposited coating is on the object, it is naturally desirable that the coated surface be smooth. Further, the perforated portions of the metal and the like have sharp edges and the anti-corrosion performance is deteriorated unless the coated film is properly coated on the edge portion. Therefore, surface smoothness and edge coating force have both the performance required for the electrodeposition coating. On the other hand, surface smoothness is obtained by baking to fluidization to reduce the viscosity of the uncured coating film: the edge coating force is maintained so as not to lower the uncured coating film. Point 5 200835759 degrees to get. That is, the edge coating force is required to suppress the coating film from sinking when the coating film is cured, and the coating film also remains at the sharp edge. That is, surface smoothness and edge coating force are conflicting effects. The technique of coating the film viscosity of the electrodeposited film is described in Japanese Patent Laid-Open Publication No. 2002-285077 (Patent Document No.) and describes an electrodeposition coating composition for electric wires, in which a coating film is used. Curing spears. The medium minimum coating viscosity is between 30 and 150 PaS (Section 3 of the patent specification). Patent Document 1 describes that by adjusting the viscosity of the coating film in the curing process of the coating film, the edge coating force and the like can be changed without melting under the condition of melting. Japanese Laid-Open Patent Publication No. 6-6579 (Patent Document 2) discloses a method of coating a surface of an uncured coating film formed by coating a cationic electrodeposition coating composition with a chipping resistant primer. Further performing the middle door coating and the page coating 'and simultaneously curing the three layers, wherein the minimum viscosity is 1〇4 to 1〇8 q when curing the coating film of the cationic 15 electrodeposition coating composition. s ° It is revealed that since the three coating layers are only baked immediately, the coating step is shortened, the edge covering property is excellent, and the resulting coating film composed of a plurality of layers has excellent overcoat characteristics and chipping resistance. This publication discloses the overcoat characteristics and edge coverage characteristics of a coating film composed of a plurality of layers, but does not investigate the overcoat characteristics and edge coverage characteristics of the electrode 20 deposited film itself. On the other hand, in the case of __, a coating composition comprising a cationic electrodeposition coating composition of the invention has been conventionally employed, which uses particles described later to control the viscosity of the coating film. Incidentally, it has recently been proposed to reduce the content of ash 6 200835759 in the electrodeposition coating composition. The reduction in the ash content is, for example, a decrease in the amount of the high specific gravity solid component of the inorganic colorant, and no sedimentation is formed in the solid content of the electrodeposition coating composition. The reduction in ash content is used to agitate the electrodeposition bath to reduce the energy and labor required to prevent settling. Therefore, when the content of the inorganic coloring material 5 is lowered to correspond to the above-mentioned requirement for lowering the ash content, the resin content in the coating composition is considerably increased, and the viscosity of the uncured coating film obtained by electrodeposition coating cannot be appropriately Increasing, the underside control at the edge portion does not properly adjust the lower edge coating force. On the other hand, since a solid concentration of about 20% by weight is used in the current cationic electrodeposition coating composition 10, after the number of electrodeposition coatings, water is separately washed in several steps, and adhesion is completely removed in the object. After the unnecessary electrodeposition coating composition (especially the solid content), a baking step is performed. Therefore, the use of a large amount of water, the washing step using water is prolonged, and it has recently been proposed to reduce the washing water and shorten the washing with water. As a method of shortening the washing step using water, it is required to further reduce the solid concentration of 20% by weight of the coating composition, the so-called low solid content. However, when this low solid content is simply carried out, sedimentation of the solid content of the electrodeposition coating composition easily occurs because the viscosity of the coating composition is lowered. When the content of the inorganic colorant is further lowered as described, the sedimentation of the contents of the solid interior 20 is more likely to occur. Therefore, it is difficult to carry out the mixing of the electrodeposition bath to prevent sedimentation and to reduce the energy load. That is, even if the energy saving and shortening steps of the low solid content are confirmed, it is still desired to control the viscoelastic cationic electrodeposition coating composition to easily perform edge coating force, excellent surface smoothness and prevention. 7 200835759 The method of obtaining this coating composition, i.e., the coating composition having improved thixotropic properties, has several techniques for adding crosslinked resin particles to a cationic electrodeposition coating composition. Japanese Patent Application Publication No. 2005-23232 (Patent Document 3) discloses the addition of a micro-resin particle having a particle size of 〇5 t0 m to an internal cross-linking to a cationic electrodeposition coating composition (Patent Document 3, Patent Application) Item 6 of the scope). The resin particles having such a small size are added to the electrodeposition coating composition, and there has been conventionally improved thixotropy. Japanese Laid-Open Patent Publication No. 2002-212488 (Patent Document 4) discloses a cationic electrodeposition coating composition comprising emulsion polymerization by a mixture of α, cold-ethylene unsaturated monomers. The crosslinked resin particles which use an ammonium acrylate resin as an emulsifier so as to improve the corrosion resistance of the edge portion of the article. The resin particles obtained herein are small particles having a particle size of from 〇·〇5 to 3.3//m. However, when the crosslinked resin particles having an average particle size of 丨.0#111 or less are added to the electrodeposition coating composition, the smoothness of the resulting coating film is lowered. Patent Document 1: Japanese Patent Application Publication No. 2002-285077. Patent Document 2: Japanese Patent Application Publication No. 6-65791. Patent Document 3: Japanese Patent Application Publication No. 2005-23232. 20

Patent Document 4: Japanese Patent Application Publication No. 2002-212488. tDeclaration content; J Summary of the invention 颞8 200835759 The nature and edge coating described herein is an object of the present invention to provide a method for simultaneously meeting the conflicting surface smoothness of the cationic electrodeposition coating composition. . Further, it is an object of the present invention to provide a solid concentration method for reducing the cationic concentration in a solid coating method, preventing sedimentation of a coating composition which is reduced by a gray matter, and at the same time conforming to the above Shuli

Ionous electrodeposition coatings conflict surface smoothness and edge, positive performance in the composition. &,,, Coating Method Accordingly, the present invention provides a cationic electrodeposition coating composition which provides an uncured electric sink having a rich modulus of elasticity (G') at 14 Gt of 80 to 500 Within the range of dyn/cm2, and at 8 (rc = the amount of loss of elasticity (〇'') is in the range of 1 〇 to 150 dyn/cm 2 , and it has excellent smoothness and edge coating power. The cationic electrodeposition coating composition preferably comprises a cationic epoxy resin, a blocked isocyanate curing agent, and, if necessary, resin particles (preferably crosslinked resin particles) and/or colorants (more The present invention further provides a method for producing a cationic electrodeposited film having an established smoothness and edge 20 coating force, wherein the cationic electrodeposited film is impregnated in a cationic state. The article in the electrodeposition coating composition is prepared by applying a voltage, the method comprising the steps of: adjusting a storage elastic modulus of the uncured electrodeposited film of the cationic electrodeposition coating composition at 14 ° C ( G,) is at 80 to 500 dyn/cm2 9 200835759 The loss elastic modulus (G,,) of the uncured electrodeposited film at 8 〇Χ and the immersion ion-coated coating composition in the range of 10 to 150 dyn/cm 2 is within the range of 10 to 150 dyn/cm 2 . 5 Adjusting the storage elastic modulus and loss elastic modulus, #佳为为添加% resin particles or inorganic colorants. The average particle size of the crosslinked resin particles is in the range of 1·〇 to 3·〇Μηι The content of the crosslinked resin particles, which is 3 to 15% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition. 1〇Inorganic colorant is added to the cationic electricity Depositing a coating composition, wherein the content of the organic colorant is preferably from 1 G to 20% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition to adjust the storage elastic modulus and Loss modulus of elasticity. - Adjusted storage elastic transfer i and loss (4), inorganic colorant and >, range #乂>^ crosslinked resin particles in the particle size of 1.G to 3 m Adding to the cationic electrodeposition coating composition, wherein the inorganic The cerium content of the material is preferably 〇5 to 1% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition. The inorganic colorant and the crosslinked resin particles are all added to the cationic electrodeposition. • In the example in which the 2G coating composition is used to adjust the storage elastic modulus and the loss elastic modulus, the content of the crosslinked resin particles is preferably the weight of the resin solid content relative to the cationic electrodeposited coating composition. 3 to 15% by weight. The method of simultaneously establishing the surface smoothness of the cationic electrodeposition coating composition having a low solid content and a low ash content and the edge coating strength of 200835759 has been studied. The inventors of the present invention have found that the easy and easy addition of specific crosslinked resin particles to the cationic electrodeposition coating composition can solve the problem and achieve the present invention. Accordingly, the present invention provides a cationic electrodeposition coating composition, 5 comprising crosslinked resin particles having an average particle size in the range of 1.0 to 3.0/m and a thermosoftening temperature of 12 to 18 ( Within the scope of rc, the composition has excellent smoothness and edge coating power.

The content of the parent resin particles is preferably from 3 to 15% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition. The smectic electrodeposition coating composition is preferably a cationic electrodeposition coating composition having a low solids content and a low ash content, the composition containing no inorganic colorant, or the inorganic colorant content relative to the cation The weight of the resin solid content of the electrodeposition coating composition does not exceed 7% by weight. The solid concentration of the cationic electrodeposition coating composition of the present invention is preferably 15 in the range of 〇·5 to 9% by weight. In the present invention, the crosslinked resin particles may be preferably a compound having two or more unsaturated double bonds and (b) a compound in the molecule by a known method such as suspension polymerization or ritual polymerization. Preparation of acrylic acid. Clothing 20

The present invention further provides a chemical electrodeposition film of a cationic electrodeposition coating composition which is in the range of 8 〇 to 5 〇〇 dyn/cm at 14 (the storage elastic modulus U, 里 W) And the loss elasticity at 80 t is in the range of 10 to 150 dyn/cm 2 . The present invention further provides a cured cationic electrodeposited film having an Ra value (not as a smoothness index of a coating film) of not more than 11 200835759 over 0·25//, which is cured by curing the cationic electrodeposition Obtained by coating the composition. The present invention further provides a method of producing a cationic electrodeposited film having an established smoothness and edge coating power, wherein the cationic electrodeposited film is formed by impregnating a cationic electrodeposition coating composition. The article is prepared by applying a voltage, and wherein the cationic electrodeposition coating composition comprises crosslinked resin particles, the average particle size of the crosslinked resin particles being in the range of 1·0 to 3.0/m and the heat softening temperature It is in the range of 120 to 180 ° C. 10 The present invention further provides a method of producing a cationic electrodeposited film having improved smoothness and edge coating force from a cationic electrodeposition coating composition having a low ash content and a low solid content, comprising the steps of: adjusting uncured The storage elastic modulus (G,) of the electrodeposited film at 140 ° C is in the range of 80 to 500 dyn / cm 2 , and 15 the loss elastic modulus of the uncured electrodeposited film at 80 C (g,, Is in the range of 10 to 150 dyn/cm 2 , wherein the cationic electrodeposition coating composition contains crosslinked resin particles, the average particle size of the crosslinked resin particles is in the range, and the heat softening temperature is The content of the crosslinked resin particles in the no to the 18th generation is 3 to 15% by weight based on the weight of the resin_content of the cationic electrodeposition coating composition. EFFECT OF THE INVENTION According to the present invention, both smoothness and edge coating force can be adjusted by 0 12 2008 35759 5 10 15 20 during dynamic coating of the uncured electrodeposition coating during electrodeposition coating. The elastic modulus G" and the library elastic modulus G are established. In the conventional technique, the material viscosity coefficient η in the (4) state transition measurement is arranged to ensure the smoothness of the lowest fuse degree, but the scale solution is The compatibility of the above smoothness with the edge coating force is only impossible by the viscosity. It is found that the dynamic viscosity of the uncured coating film of the coating composition on the rider f has been found. In the control smoothness, the loss elasticity is made. · (Subtraction) is important in the specific range (4): Furthermore, it has been found that in controlling the edge coating force, the control store = G' (elastic term) In the specific range, it is important. In addition, in this =, it has been issued, and the loss of control __, at the same time, the age-dependent modulus G is controlled, and the mosquitoes are re-made in the mosquito range, so that Both the smoothness of the electrodeposited film and the edge coating force. By G" and the parameters of the vertical (Iv) a material not in a particular range of parameters _, smoothness, and edge coatability of the resulting electrodeposition _ _ is established simultaneously. According to the present invention, the simultaneously established surface smoothness and edge coating force can be evaluated only by controlling the loss elastic modulus and age-type wire of the uncured electrodeposited film coated by electrodeposition. A method can be provided which can be used to enable the deposition of the coating layer or the effectiveness of the coating. Furthermore, 'in accordance with the present invention, by adding crosslinked resin particles to the cationic electrodeposition coating residual wire', the "heteroping granule size is in the range of U" to 3 angstroms m and the thermal softening temperature is 12 It is possible to achieve the surface smoothness and edge coating force of the (10) t's _'. In a low ash form of cationic electrodeposition coating composition, due to 13 200835759 5

10 15

The increase in the bond for coating the film towel cannot be achieved by adding a money coloring material, and it is expected that the coating power of the edge is deteriorated, but the edge coating force can also be added to the cationic property by adding 4 inch 疋 parent-linked resin particles according to the present invention. The electrodeposition coating composition is modified to improve 'and it can be a pole material or improve the coating film efficacy of the low ash shape cationic electrodeposition coating composition. Herein, the cationic electrodeposition coating composition of the low ash form means that the solid color of the cationic electrodeposition coating composition is completely free of inorganic coloring matter, or even if it contains an inorganic coloring material, it is relative to The solid content of the composition is up to 7% by weight (i.e., a cationic electrodeposition coating fine composition having a low ash content. Further, in the present invention, a cationic electrodeposition coating composition of a low @(四) type is provided. The material has superior ability to prevent sedimentation and is capable of establishing surface smoothness and edge coating force as described above. The low solid form cationic electrodeposition coating composition herein means cationic electrodeposition. The coating composition has a solid content concentration of 2 〇/6 低 lower than the manufacturer and especially Q in the range of Q5 to 9% by weight (that is, a cationic electrodeposition coating composition having a low solid content). In the study of this month, the surface smoothness and edge coating force were simultaneously established with the dynamic viscoelastic measurement side of the electrodeposited film obtained by electrodepositable coating. In particular, #在下Loss The modulus of elasticity G" and the storage elastic modulus G under the voyage, when it falls within a certain range, that is, the loss elastic modulus G at 8 °C, is M15Gdyn/em2, and the storage impurities in the assignment Modulus M 8 W dy-2, surface smoothness and edge coverage are established, but in the present invention, it has been found that the average particle size is in the range of h0 to 3.0 ΑΠ! and 14 200835759 ",, the softening of the cross-linked resin particles of 12 ° C or higher is added to the cationic coating, which is a solution. The simple description of the figure is shown in Figure 1. A graph of the behavior of the dynamic viscoelasticity of the coating composition in terms of the loss of the S-modulus (G,,) value; Figure 2 is a graph showing the storage elastic modulus (G,) of the dynamic viscoelasticity of the five coating compositions. A graph of the behavior of the values; Figure 3 is a graph showing the behavior of the complex viscosity coefficient (η) values of the dynamic viscoelasticity of the five coating compositions; Figure 4 is a graph showing the number of coating compositions at 80. (: a graph of the relationship between the storage elastic modulus (G,) and the electrodeposition structure; the fourth diagram shows the composition of several coatings a graph showing the relationship between the complex viscosity coefficient (η*) and the electrodeposited structure at 80 ° C; Figure 4C is a graph showing the loss of elastic 15 modulus (G" at 80 ° C in several coating compositions and A graph of the relationship between electrodeposited structures; ® Figure 5A is a graph showing the relationship between storage modulus (G') and electrodeposition structure at 140 ° C in several coating compositions; Figure 5B shows A graph of the relationship between the complex viscosity coefficient Of) and the electrodeposited structure at 140 ° C in several coating compositions; • 20 Figure 5C shows the loss of elastic modulus at 140 ° C in several coating compositions (G") a graph of the relationship between the electrodeposition structure and FIG. 6A is a graph showing the relationship between the storage modulus (G') and the edge coating force at 8 〇 X in several coating compositions. The figure is a graph showing the relationship between the complex viscosity 15 200835759 coefficient (rf) and the edge coating force at 80 ° C in several coating compositions; Figure 6C shows the 80 ° in several coating compositions. a graph of the relationship between loss elastic modulus (G") and edge coating force at C; Figure 7A shows several coating compositions at i4 〇 °C A graph showing the relationship between the elastic modulus 5 (G,) and the edge coating force; Figure 7B is a graph showing the complex viscosity coefficient (η*) and edge coating force at i4〇°c in several coating compositions. Figure 7C is a graph showing the relationship between the loss elastic modulus (G" at 140 ° C and the edge coating force in several coating compositions; 10 Figure 8 shows the explanation A graph of the relationship between the temperature of the heat softening temperature and the storage elastic modulus G'; Fig. 9 is a schematic view schematically showing a portion 3 micrometers apart from the edge of the cutter blade. [Λ] 15 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Dynamic viscoelasticity is the modulus of elasticity observed when a (periodic) strain or force (stress) is applied to a linear viscoelastic body, and the number of vibrations and temperature. And set. The following description of dynamic viscoelasticity is described in Rheology (Edited by Japan Rheology Academy), 2nd Edition: Polymer liquid rheology, pages 31-39; And described in polymer chemistry (p〇lymer Chemistry), Introduction (Introduction) (Seizo Okamura, Akio Nakajima, Shigeharu Onogi, Yasunori Nishijima, Toshinobu Higashimura and Norio Ise), 4th edition: each of the polymer materials 16 200835759 Various performances of polymer substances, Viscoelasticities, pages 149 to 155. The stress and strain at an angular velocity [ω (2π x frequency F)] are given by the following formula: Strain γ(1)=Y〇e1G)t (dyn/cm2) Stress σ(1)=a0e1((Dt + s)(dyn/cm2) Where Y(t) is the strain at time (1), cj(t) is the stress at time (1), γ〇 is the strain at t=0, is the stress at t=0, and δ represents the relative The complex elastic modulus G* is represented by the following equation: ^ ^ (^〇/y〇)el6 = (a〇/y〇)(cos5 - i sin5) Generally used for viscosity control of coating compositions The complex viscosity coefficient [η* sGVco (poor)] of the factor is obtained by quantifying the viscoelasticity of the combined properties of the viscosity and elasticity of the coating composition. That is, in the present invention, the viscosity and elasticity are individually controlled. The tube, as well as the smoothness and edge coating force, are simultaneously established by individual control. Smoothness must be ensured to control the fluidity of the coating composition during the baking process. The dot characteristics are related to the fluidity, and thus The relationship between stress and strain is represented by the following formula: Loss modulus of elasticity (viscosity) G" = G* sin3 (dyn/cm2) On the other hand, it must be The edge coating force is controlled to control the force for maintaining the positioning in the baking seed production, and the force is related to the impurity characteristic. The relationship between the stress and the strain is represented by the following formula: · Storage elastic modulus (elasticity) G' = G* cos8 (dyn/cm2) 17 200835759 5

10 15

^Including the cationic t-sinking I (four) _ coating composition =,, the viscosity term in the initial stage of the baking process, the uncured coating film W and the composition is roughly affected by the loss elastic modulus G". Γ By condensing and pseudo-crosslinking, the uncured coating film reaches the condensed Wei, in the continuous state at the two ends.) Next, the elastic term predominates, and the slab roughly stores the elastic modulus G, (four) ringing. A temperature f at this temperature, in the baking process as a loss of viscoelastic behavior between the Ή Ή 里 里 里 ” ” 黏 黏 黏 黏 黏 储存 储存 储存 储存 储存 储存 储存 储存 储存 储存 损失 损失 损失 损失 损失 损失 损失 损失 损失G,,) < (store elasticity modulus G,). That is, 1 means that at this point, the viscosity term dominates and the elasticity term dominates. In the present invention, it has been found that by controlling the specific temperature (the loss bomb of 8) is not higher than the pivot point and controlling the storage elastic modulus G at a specific temperature (1), the smoothness can be achieved by not lowering the gel point. The edge coating force is simultaneously established, and this (4) is achieved by this. In the present invention, the present invention is described by explaining the method which has been achieved by the present invention. First, the preliminary experiment described below was carried out. Several coating compositions were observed. The viscoelastic behavior of the object, especially the conventional coating composition for adding the coloring material, the coating composition without the coloring material, and the coating composition including the crosslinked resin particles. According to the rise in temperature, the coating composition is 20 The viscosity begins to drop to 4 〇 to 8 (rc, between about 8 〇 to about ◦ ◦, the viscosity is slightly increased, and when it exceeds 1 〇〇. 〇, the viscosity is greatly reduced to maneuver. After the flow, The curing reaction begins to increase the viscosity again, the viscosity gradually rises to nearly 150 ° C, and then, the viscosity suddenly rises to full solidification. In order to study and confirm the dynamic viscoelasticity of the coating composition, use 18 200835759 UBM The limited liability company (U-Corporation) Rheosol-G3000 measures five coating compositions' and measures the temperature at a 〇·5 degree strain, a frequency of 0.02 Hz, and a temperature rise rate of 2 ° C/min. The strain value γ(1) with the stress value P(t) and the relative ratio δ between the stress and the strain. The storage elastic modulus (G'), the loss elastic modulus (G,,) and the complex viscosity coefficient ( η*) is calculated from the relationship between the obtained stress value d(t), the strain value 丫(1), and the relative ratio § according to the above formula, and is displayed in the first to third figures, respectively. The coating composition of the drawing to Fig. 3 is as follows: "STD" is PN-310 (cationic electrodeposition coating composition: manufactured by Nippon Paint Co., Ltd.); a colorless material, which is a coating composition having no coloring component in PN-310 (PWC = 0%); "Resin Particle 1" is a coating composition in which 15% by weight of crosslinked resin particles are used (having an average particle size of 1 to 3//m) adding "colorless material"; "resin particle 2" is a coating composition, Adding 15% by weight of crosslinked resin particles (having an average particle size of 1 〇〇 nm) to ''colorless material'), and "resin particle 3" is a coating composition in which 10% by weight is paid Co-resin particles (having an average particle size of 1 Å) are added to the "colorless material" which is different from the "resin particle 2". As shown in Figures 1 to 3, the coating is applied to individual coatings. The composition is not the same as 20, and the behavior is quite different. It is almost divided into three modes (40 to 8 ° C, 80 to 100 ° C and ΙΟΟΌ or higher), but it can be understood that the behavior of dynamic viscoelasticity is coated. The formulation of the composition varies greatly, especially in the presence of, for example, the components of the granules, and it is understood that the patterns described by the five coating compositions are different. Therefore, it is also known that the dynamic viscoelastic behavior 19 200835759 can be optimally adjusted by changing the formulation. In particular, looking at Figures 1 through 3, it can be seen that there is a large difference between individual coating compositions based on behaviors approaching 80 °C and behaviors approaching 14 °C. 5 Furthermore, the following experiments were carried out based on this basis. Preparation of several coating compositions, such as PN-310 (cationic electrodeposition coating composition: manufactured by Nippon Paint Co., Ltd. (Nipp〇n Paint Co., Ltd.); coating composition in which the change The amount of the inorganic coloring component in the PN-310 coating composition; the coating composition in which the inorganic coloring component is removed from the PN-310; and the coating 10 composition in which the crosslinking to be added to the final composition is changed The type and amount of resin particles, as well as the measurement of individual viscosity behaviors. The viscoelastic behavior at 80 C, all g, value and electrodeposited structures (Fig. 4A), η* values and electrodeposited structures (Fig. 4B) and G, values And the electrodeposited structure (Fig. 4C) is shown in Fig. 4, so that the change at different temperatures can be easily understood from the results of 15 such viscoelasticity. Similarly, the three viscoelastic behavior at 140C, all G, value and electrodeposited structures (different 5A), η and electrodeposited structures (Fig.) and g, values, and electrodeposited structures (Fig. 5C) The figure is shown in Figure 5. Furthermore, the electrodeposition structure is represented by the table (4). The evaluation of the electrodeposited structure 20 herein means the appearance of the electrodeposited film described later, that is, the smoothness, and the calculated value of the arithmetic mean roughness (Ra) of the roughness curve. That is, the above smoothness is evaluated by the electrodeposition structure to observe the relationship between the electrodeposited structure and the viscoelastic behavior. As shown in Figures 4 and 5, the behavior of + + and 仃, the electrodeposited junction at 80C 200835759 = the change in viscoelasticity in the coating composition at the re-measurement point and measurement 4 deposition structure The relationship is relevant (see Figure 4C). 10 15 20 Similarly, the behavior of the edge coating force _ the amount of the knot and the three viscoelastic behavior: 糸 6A to 6C and the second to the seventh. Figure. As shown in Figure 2, the relationship between the storage elastic modulus and the force is known (see figure from the figure). That is, the change of the sound and the electrodeposition structure (smoothness) or the edge coating force I herein, the above-mentioned edge coating force can be referred to by the description. Further, the "coating" shown in Fig. 6 and Fig. 7 has the same meaning as the "edge coating force" described herein. Applying the upper (four) fruit, the customs clearance, and the basis of the tree evaluation, the present invention can be applied to the electrodeposited structure (smoothness) and the storage elastic modulus (G, The invention has been applied to the edge coating force. Further, the preferred range of the storage elastic modulus (G,) and the loss elastic modulus A can be selected by referring to the attached figures 4 and 7. That is, referring to FIG. 7A, G at 140t is preferably in the plane of 8〇 to · dyn/Cm2, and with reference to FIG. 4C, G′ under _ may be selected from 10 to 150 dyn/cm 2 . Within the range (smaller electrodeposited structure Ra means better smoothness). The storage amount (G,) is preferably in the range of 90 to dyn/cm and more preferably (10) to lion/(3)^. Furthermore, the loss elastic modulus (G") of the thief is preferably within the range of 10 to 120 dyn/cm2, and more preferably within the range of 1 G to (10) coffee. The field storage elastic enthalpy (G') is lower than The desired lower limit of the storage elastic modulus (G,) is feared that the edge coating force of the electrodeposited film is deteriorated, and when the storage elastic modulus (G') exceeds the desired upper limit, it is likely to be smooth. When the loss is 0, the loss elastic modulus G" is lower than the desired lower limit of the loss elastic modulus G", it is feared that even if the smoothness is improved, the edge coating force of the obtained electrodeposited film is deteriorated, and § mussels are lost. When the elastic modulus G" exceeds the desired upper limit, the smoothness may be lowered. Herein, the storage elastic modulus G, and the loss elastic modulus G, are related to the elastic modulus of the uncured electrodeposited film. "Uncured, meaning a state in which an electrodeposition coating film by electrodeposition coating of a cationic electrodeposition coating composition has not been cured by baking. Cationic electrodeposition coating The coating composition, as described above, contains or contains a crosslinked resin particle and/or an inorganic colorant, but contains an aqueous binder containing a cationic epoxy resin dispersed or dissolved in an aqueous medium and closed. The isocyanate curing agent's dot resin 'neutralizes the acid, and the organic solvent. For the mixed behavior, there is a method of adding the crosslinked resin particles as the first method. The average particle of the crosslinked resin particles The ruler* inch plate is in the range of 1,0 to 3.GMm. When the average impurity size is less than ι·〇_, the proportion of the surface area is increased, and the contact with the cationic electrocoating towel is included. The fat component of the cationic epoxy 2 fat-like cross (four) called plus, to the viscosity of the film coated with money. "Ransheng; therefore, the adjustment of the above-mentioned transfer behavior becomes difficult. Another aspect, when The particle size is greater than 3. 〇 _, the cause of the occurrence The sedimentation of the coating composition without the mixing and the smoothness caused by the aggregation of the particles applied at the horizontal level upon coating were reduced.

Further, it is preferred that the cross-linked tree particles of the secret recipe have an average particle size falling within the range of U 22 200835759 to 3. 〇/zm, and i2 (thermal softening temperature of rc or higher) and preferably Falling in the range of 120 to 180 ° C to simultaneously establish the surface smoothness and edge coating force of the cationic electrodeposition coating composition having low ash content and low solid content. Although it is also carried out in the conventional technique in cationicity It is proposed that the resin particles are added to the electrodeposition coating composition to have almost no average particle size. Since the resin particles are added to control viscosity only in the conventional art, it is required to have less than 1 〇/zm. Resin particles having an average particle size, but in the present invention, from the viewpoint of dynamic viscoelasticity, in particular, the loss elastic modulus (G" at 80 ° C and the storage elastic modulus at 14 {rc] ,), the addition of crosslinked resin particles, which has a larger average particle size than the conventional technique and a thermal softening temperature of 120 C, and preferably falls within the range of (:: to achieve simultaneous establishment) Surface smoothness and edge coating The average particle size of the crosslinked resin particles used in the present invention is as described above in the range of 1.0 to 3.0, but the lower limit is preferably 12 // m and still more preferably i melon. On the other hand, the upper limit is preferably / / m and the further step is preferably 2 2 / / m. As described above, when it is less than 1 force, it is within the average particle size range of the resin particles of the prior art. It is not preferable because the surface smoothness is deteriorated. The crosslinked resin particles having an average particle size of more than 3 〇 _ reduce the smoothness due to electrodeposition of the coating composition without stirring. The sedimentation is due to the aggregation of particles applied at the horizontal plane due to dripping during electrodeposition. In this paper, the average particle size can be measured by the following method. The average particle size of the resin particles is by Niktis〇 C〇.,Ltd. manufactures 23 200835759·R〇TRAC934_A, using granular granules for transmission measurement

the amount. Further, the particle size distribution of the resin particles is: in the form of a J and below the tired frequency W; it is calculated as a medium value. These measurements and calculations apply #ί (7X) _ = 1.33 and the refractive index of the resin content ΐβ59. Chic

10 15

As described above, the crosslinked resin particles used in the present invention have a thermal softening temperature in the range of 12 Torr to mrc (10) for simultaneous establishment of a cationic electrodeposition coating composition of low ash and a (iv) volume. Sexual and edge coating power, but the upper limit is preferably 14 (rc, and more: 16 (rc. When the thermal softening temperature is lower than 12 (rc, storage elastic modulus for baking uncured electrodeposited film is not established) The value 'and the inability to ensure the edge coating force. Another-side, can not be synthesized - material, which cross-linking resin particles;: softening temperature exceeds 180 ° C. ^ Cooked billion temperature hook father to talk about the temperature at which the fat particles begin to soften. AI , measuring the G value of the labeled crosslinked resin particles at individual temperatures. The temperature at which the change in the G' value of the change in the official temperature changes abruptly is called the heat softening temperature. It can be determined by the following. The storage elastic modulus G of the sample obtained by adjusting the concentration of the crosslinked resin particles to 3 〇 % (as a solid content), at a strain of 0.5, a frequency of 0·02 Hz, and 4. (TC/min The temperature rises at a rate of 20, using the Rheosol-G3000 (limited by UBM) It is measured at 90 ° C by a temperature-dependent measurement method manufactured by UBM Corporation, which is a rotary dynamic viscoelasticity measuring device. The measurement results are shown in the graph of Fig. 8. It can be seen from Fig. 8. Although the storage elastic modulus G' of the crosslinked resin particles maintains a constant viscosity in the initial temperature region (about 9 〇 to 14 〇 24 200835759 c in Fig. 8), it is at a temperature (more than 14 在 in Fig. 8). The storage elastic modulus G' decreases at the temperature of the crucible. The tangent of the area of the viscosity and the tangent of the area where the viscosity is lowered are drawn, and the temperature at the intersection is defined as the thermal softening temperature. 5 10 15 20 In order to increase the resin particles The heat softening temperature is required to increase the degree of crosslinking of the resin particles. In the present invention, the resin particles are crosslinked resin particles for the green heat retention softening temperature region. The glass transition temperature is a softening of the resin, but when crosslinked The resin particle towel measures the glass transition temperature (if it reaches several hundred levels (the degree of 〇; therefore, the thermal decomposition of the resin at this temperature is frequent, and the particle size cannot be observed) The softening property of the body. Therefore, the heat softening temperature is applied in the present invention. Further, 'requires cross-linking _ age to have a crosslinked structure. In the case where there is no cross-link 冓, the above 14 (rc: lower storage elastic modulus g) The value of , is small. 41 coffee 2 '(10) its side, because it is impossible to ensure the amount of difficulty in the edge coating composition, the weight of the cationic electrodeposition coating resin content is preferably 3 to 15 faces. The content of the parent (four) fat granules is less than 3% by weight, _ establishes the surface smoothness and the edge _ force is 眺 and when the film is lowered, for example, the anti-heart property, the content of the coating film, the sound protection spoon, in this article, The solid resin component (the resin contained in the cationic electrodeposition coating composition is difficult to handle) has a solid weight. ★The content of cross-linked resin particles in Mingzhong:::::r cationic electrodeposition coating two = the weight of the inner material, preferably, falls within the range of 3 to 15% by weight, with the same as 25 200835759 5 • Surface smoothness and edge coating force are established, but the lower limit thereof is preferably 4% by weight, and more preferably 5% by weight. On the other hand, the upper limit thereof is preferably 10% by weight, and more preferably 8% by weight. It is considered that the average particle size of the crosslinked resin particles is in the range of 1.0 to 3.0 / / 111, which is preferably produced by suspension polymerization. Although the particle size and the heat softening temperature of the crosslinked resin particles are in the above range, they may be produced by other methods such as emulsion polymerization, but suspension polymerization is carried out from the viewpoint that the particle size is within a desired range. It is the preferred form. 10 Crosslinked resin particles include, but are not particularly limited to, for example, resin-containing resin particles having a crosslinked structure mainly obtained using an ethylenically unsaturated monomer; and a resin containing an internally crosslinked urethane resin Granules; fine resin particles containing internally crosslinked melamine resin, and the like. The above-mentioned resin having a crosslinked structure obtained mainly using an ethylenically unsaturated monomer includes, but is not limited to, for example, internally crosslinked resin particles obtained by the following steps: containing a crosslinking monomer as a main component The monomer composition and the ethylenically unsaturated monomer are subjected to suspension polymerization in an aqueous medium to prepare an aqueous suspension, and the above aqueous suspension 20 is replaced by a solvent; the internally crosslinked resin obtained by the NAD method A granule obtained by a monomer composition containing a crosslinking monomer as a main component and an ethylenically unsaturated monomer in a non-aqueous organic solvent in which a monomer is dissolved but does not dissolve a polymer Copolymerization, the non-aqueous organic solvent such as a low SP organic solvent of an aliphatic hydrocarbon, a high SP organic solvent such as an ester, 26 200835759 ketone and an alcohol; or internal crosslinking obtained by a sedimentation-precipitation method or the like Resin particles. The above ethylenically unsaturated monomers include, but are not limited to, alkyl esters such as acrylic acid or methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and butyl methacrylate. Ester and 2-ethyl methacrylate; styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, ethylene, propylene, vinyl acetate, vinyl propionate, • acrylonitrile, Mercapto acrylonitrile, dimethyl acrylonitrile, dimethyl amine ethyl methacrylate and the like. Two or more of the above ethylenically unsaturated monocaps may be used in combination. The above crosslinking monomer includes, but is not particularly limited to, for example, a monomer having two or more ethylenically unsaturated bonds in a molecule, and an ethylenically unsaturated group having two or more individually supported mutually reactive groups. Mission and so on. A monomer having a radically polymerizable two or more ethylenically unsaturated 15 bonds in the molecule can be used for the production of the above-mentioned internally crosslinked fine resin particles, but is not particularly limited to, for example, a polymerizable polyol. Unsaturated monocarboxylic acid esters such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol Dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane 20-alkyl trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, neopentyl Alcohol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol dipropylene vinegar, pentaerythritol triacetate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol tridecyl acrylate Ester, pentaerythritol tetramethacrylate, ethylene glycol dimercaptopropene 27 200835759 dilute acid ester, ethylene glycol diacrylate, ethylene glycol aryloxy dimethyl acrylate, u, : u叁 hydroxyl group Ethylene diacrylate, 丨丄^ Hydroxymethyl bromide triacrylate, hydroxymethyl bromide dimethyl acrylate, u'i hydroxymethyl ethane trimethacrylate, m• hydroxymethyl 5 propane diacrylate And hydrazine hydroxymethylpropane bismuth methacrylate, a polymerizable unsaturated alcohol ester of ceric acid, such as triallyl cyanuric acid vinegar, diallyl isocyanuric acid vinegar, tri-propyl propyl Pyromellitic acid vinegar, dipropyl propyl p-benzoic acid hydrazine and diallyl phthalic acid vinegar; aromatic compounds substituted with two or more vinyl groups, such as divinylbenzene. The combination of the mutually reactive functional groups present in the above-mentioned ethylenically unsaturated group having two or more individually supported mutually reactive groups includes, but not particularly limited to, an ethoxy group and a carboxyl group, an amine group and a carbonyl group, and Alkoxy and carboxylic anhydride groups, amine and gasified carboxylic acid groups, alkyleneimine groups and carbonyl groups, organoalkoxyalkylene groups and carboxyl groups, hydroxyl groups and isocyanate glycidyl acrylate 15 groups, and combinations of similar groups . Among them, a combination of an ethoxy group and a carboxyl group is more preferred. The above resin particles containing an internally crosslinked urethane resin are fine resin particles composed of a polyurethane polymer, which is obtained by the following steps: The polyisocyanate component is reacted with 20 an active hydrogen-containing component having a phenolic hydroxyl group at the last % and a diol or triol having a carboxyl group to form a polycondensate-containing terminal group. A urethane prepolymer having a carboxylate at the pendant group and then reacting the prepolymer with a bonding agent containing active hydrogen. 28 200835759 The polyisocyanate component used in the above prepolymer comprises an aromatic diisocyanate such as diphenylmethane-4,4,diisocyanate, toluene diisocyanate and dimethyl diisocyanate; aliphatic diisocyanate such as Liu Ya Methyl diisoxamic acid _ and 2,2,4·trimethylethane diisocyanate; cycloaliphatic diisocyanate 5, such as cyclohexane diisocyanate, 1-isocyanato-3-isocyanate Methyl ester group - 3,5-trimethylcyclohexane (isophorone diisocyanate), 4,4,-dicyclohexylmethane diisocyanate and methylcyclohexylene diisocyanate; and the like. The above polyisocyanate component is preferably hexamethylene diisocyanate and isophor i diisocyanate. The above-mentioned diol having a terminal group at the terminal includes, but not particularly limited to, a polyether diol, a polyester diol, and a polycarbonate diol having a molecular weight of from 1 Torr to 50 Å. The diol having a hydroxyl group at the terminal includes, and is not particularly limited to, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene adipate, polyhexamethylene adipate, poly Neopentyl adipate, 15*hexine glycol diol 'polymethylpental vinegar diol, polyhexamethylene carbonate vinegar, and the like. The above-mentioned carboxyl group-containing diol includes, but is not particularly limited to, for example, ruthenium methyl hydrazine, a blanket of methyl propionate _, dimethylol lactic acid hydrazine, and the like. Of these, dimethylolpropionate is preferred. 2 〇 The above two 兀* includes, 彳曰I 4 士 ^ 仁 is not particularly limited to, for example, trimethylolpropane, hydroxymethylethane, glycerol

AuMs decanediol and the like. By using triterpene alcohol, the inside of the urethane lipid particles has a crosslinked structure. The above fine resin particles containing an internally crosslinked second &amp;&lt;- cyanoamine resin are not particularly limited to, for example, a trimeric amine obtained by the following procedure. 200835759 Resin particles: in the presence of an emulsifier, Dispersing the triazide resin and the polyol in water and subsequently performing the tripolyamine resin in the particles formed by dispersion corresponds to the multi-component; and the like. The above melamine resin includes 'but is not particularly limited to, for example, di-, 5-tris-, tetra-, penta-, and hexa-methylol melamine resins and alkyl vinegars thereof (alkyl groups are methyl group 6, propyl group, and alkyl group). Propyl, butyl or isobutyl) and the like. The above melamine resin is commercially available, and for example, a resin of CYMEL 303 ^ CYMEL 325 &gt; CYMEL 1156 (manufactured by #^ Mitsui Cytec Industries Inc.) can be mentioned. The above polyols include, but are not particularly limited to, for example, a glycol or a tetrahydric alcohol having an anthracene of 500 to 3000; The above polyol is preferably a poly-propyl ether triol and a polyethyl ether triol. The above-mentioned parent-linked resin particles may be obtained by separating internal cross-linked fine resin particles, which are carried out by, for example, filtration, spray drying, and freeze-drying, and grinding to a suitable particle size using a grinder. For use in powder form, the aqueous dispersion obtained may be used or the medium in the aqueous dispersion may be replaced with a solvent. When the second method adjusts the above-described viscoelastic behavior, there is a method whereby the amount of the inorganic colorant used is 10 to 20 by weight relative to the weight of the solid content of the cationic electrodeposition coating composition 20 Within the range of % (hereinafter occasionally referred to as "PWC"). In the conventional cationic electrodeposition coating composition, the PWC described above exceeds 20% by weight, and is set at 25 wt% or less, so that smoothness and edge coating force cannot be established at the same time, but fall by 10 by use. To 20% by weight &lt; pwc, smoothing 30 200835759 properties and edge coating force can be established at the same time. Herein, PWC means the ratio of all the solid contents contained in the resin component and the color component of the cationic electric/esthetic coating composition. When the PWC of the inorganic colorant is less than 10% by weight, the resin content is too large, and the resin softens due to an increase in temperature, so that the high viscosity of the target 5 cannot be achieved, and the above-described viscosity behavior cannot be adjusted. On the other hand, when the PWC exceeds 20% by weight, the color material becomes too order, the condensing effect due to the resin cannot be obtained, and thus the high viscosity cannot be exhibited; therefore, it is difficult to control the viscoelasticity. Furthermore, as described above, the pwc of the inorganic colorant affects the viscosity behavior, but the particle size affects the degree of viscosity behavior to a lesser extent. The inorganic coloring material, as used herein, is not particularly limited as long as it is a coloring material generally used for electrodeposition coating compositions. Examples of coloring materials include inorganic coloring materials generally used, such as titanium white and iron oxide dyeing colors; filler materials such as kaolin, talc, aluminum silicate, calcium carbonate, mica and clay; for example, zinc phosphate, iron phosphate , aluminum phosphate, calcium phosphate, zinc phosphite 15 , cyanide, zinc oxide, aluminum tripolyphosphate, molybdate acid, aluminum molybdate, calcium molybdate, and aluminum phosphomolybdate, zinc aluminum phosphomolybdate, antimony compound Anti-corrosion coloring materials such as antimony compounds. The third method of adjusting the above-mentioned viscoelastic behavior is a method of using the above-mentioned crosslinked resin particles and inorganic colorant in combination. In this example, the average particle size of the above-mentioned 20-tree dendrimer is in the range of 1 Å to 3 〇^, and the amount used is relative to the weight of the solid content in the coating composition, which is 3 to 15 reset % within the range. On the other hand, the inorganic colorant ΐ (PWC) to be used can be reduced to a range of 〇·5 to 1% by weight based on the weight of the solid content in the coating composition. The lower limit is preferably i% by weight, 31 200835759 and more preferably 2% by weight. On the other hand, the upper limit thereof is preferably 7% by weight, and more preferably 5% by weight. When the amount used exceeds 1% by weight, the amount of the toner exceeds the required amount too much' and the flat appearance may be damaged due to the sedimentation of the toner. Furthermore, when it is less than 5% by weight, it is feared that the leuco characteristics are lowered. 5 By simultaneously using the inorganic colorant and the crosslinked resin particles, the amount of the inorganic colorant can be further reduced, and as a result, the energy and labor for preventing the sedimentation of the solid content of the electrodeposition coating composition can be expected. Further, when the viscoelastic behavior can be adjusted only by using the crosslinked resin particles but without using the inorganic colorant, the energy and manpower 10 for preventing the sedimentation of the solid contents can be greatly reduced. Further, when the inorganic coloring material is not contained or even if the inorganic coloring material is contained, the amount of the inorganic coloring material contained is extremely small, and even if the coating material is washed with water after the electrodeposition coating, the water washing step is greatly shortened; Great for simplifying equipment and reducing resource usage. Next, the composition of 15 for the general cationic electrodeposition coating composition will be described. Electrostatic deposition coating group cationic cationic electrodeposition coating composition aqueous medium; adhesive resin, comprising cationic epoxy resin dispersed in or dissolved in an aqueous medium and a blocked isocyanate curing agent; neutralizing acid; and organic Solvent. The cationic electricity 20 deposition coating composition may further comprise an inorganic colorant. The content of the inorganic colorant is preferably not more than 7% by weight based on the weight of the solid content of the cationic electrodeposition coating composition. As described above, in order to confirm the low fire knife, the composition may be free of inorganic colorants. As described above, in the present invention, in order to provide a low-density ionic-electrodeposition coating composition having a surface smoothness and an edge coating force, 32, 35,759, ash and/or low solid form, cationic electrodeposition The coating composition can be cut to contain specific crosslinked resin particles. A cationic epoxy resin which can be applied to the cationic epoxy resin of the present invention includes an amine modified epoxy resin. The cationic epoxy resin generally opens the epoxy of any of the biguanide type epoxy resins by using an active hydrogen compound which can be incorporated into the cationic group, or by opening a part of the epoxy ring by using other active hydrogen compounds. And then using the active hydrogen compound of the I/v cationic group] to open the remaining epoxy ring.

1〇 Typical examples of Wei-type resin include double-type A-type epoxy resin and double-type F-type epoxy resin. The products available on the market include YD-7011R (manufactured by Tosho Kasic Co., Ltd. (epoxy equivalent: 460 to pin), Epik () te 828 (by Yuk Shdl) Manufactured by Epoxy Co" Ltd., epoxy equivalent: 18〇 to 19〇), Epik〇te 1〇〇1 15 (same manufacturer, epoxy equivalent: 450 to 500), Epikote 1010 (same manufacturer, ring) Oxygen equivalents: 3000 to 4000) and the like, and commercially available products of the latter include Epikote 807 (same manufacturer, epoxy equivalent: 170) and the like. Represented by the following chemical formula and disclosed in JP_A_5_306327 An epoxy resin containing a 20 σ oxazepine ring can be used as a cationic epoxy resin: H2C-CH-CH2-〇-R. 0

-O-CHo-CH &一&lt;/°&quot;°\ /NRN /CH-CH2-0 - R-&quot;CH〇OHo -O-CHo-CH-CH, 33 200835759 where R means by removing a residual group formed by the diglycidyloxy group of the diglycidyl ethoxylate, R, which means a residual group formed by removing one of the isocyanate groups in the diazide vinegar compound, and Means 1 敕. This is an example of a method for introducing an oxazolidone ring into an epoxy resin in the S (4) (four) layer. In the presence of an inert catalyst, heating and maintaining the temperature are used to make the polycyclic ring Blocked polyisoxamic acid blocked with a lower alcohol such as methanol (IV)

The catalyst is reacted, and the lower alcohol which becomes a by-product is distilled off from the system to obtain a product. X 10 The reaction of a bifunctional raw epoxy resin with a monohydric alcohol-blocked diisocyanate such as a bis-formate is known to obtain an epoxy resin containing an oxazolidinone ring. Examples of epoxy resins containing σ oxime-rings and their preparations are known and disclosed in JP-A-200 (M28959, paragraphs 0012 to 〇〇47. These epoxy resins can be modified with suitable resins, For example, a polyester polyvalent I5 alcohol, a polyether polyol, and a monofunctional alkyl phenol. Further, the epoxy resin can extend its chain by utilizing the reaction of an epoxy group with a diol or diweiric acid. The ring of the epoxy resin is opened by the active hydrogen compound, so that after the ring is opened, the amine equivalent is from 〇3 to 4. 〇meq/g, and wherein the proportion of the primary amine group is preferably more than 5 to 50%. 20 Active hydrogen compounds which can introduce cationic groups include acid salts, sulfides and acid mixtures of primary amines, secondary amines and tertiary amines. Primary amines, secondary amines or/and secondary amine salts are used as An active hydrogen compound capable of introducing a cationic group such that a gas-making resin containing a primary amine group, a secondary amine group or/and a tertiary amine group can be prepared. 34 200835759 Specific examples include butylamine, octylamine, diethylamine, Dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methyl-B Alcoholamine, triethylamine hydrochloride, N,N-dimethyl-ethanolamine acetate, a mixture of diethyl disulfide and acetic acid, and a secondary amine which is a blocked primary amine such as amine ethylethanolamine 5 ketimine and diketimine of diethylenetriamine, etc. A combination of one or more amines is available. A blocked isocyanate curing agent is to be applied. The polyisocyanate of the blocked isocyanate curing agent of the present invention means a compound having 2 or more isocyanate groups in one molecule. One of the polyisocyanates includes any form of polyisocyanate such as an aliphatic type or an alicyclic group. Group, aromatic and aromatic-aliphatic, etc. Specific examples of polyisocyanates include aromatic diisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate and Naphthalene diisocyanate; aliphatic 15-membered diisocyanate having 3 to 12 carbon atoms, such as hexamethyl diisocyanate (HDI), 2,2,4·trimethylhexane diisocyanate and leucine diisocyanate; Up to 18 carbon atoms Alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methylcyclohexane Alkyl diisocyanate, isopropylidene 20 dicyclohexyl-4,4'-diisocyanate and 1,3-diisocyanate methylcyclohexane (hydrogenated XDI), hydrogenated TDI and 2,5- or 2,6 - bis(isocyanatomethyl)-bicyclo[2.2_1]octane (also known as norbornane diisocyanate); aliphatic diisocyanate having an aromatic ring, such as di-tolyl diisocyanate (XDI) and Tetramethylxylene diisocyanate (TMXDI); an upgraded product of these isocyanates (amine 35 200835759 formic acid product, carbodiimide, urethodione, urethane) A product of urethoimine, biuret and/or isocyanurate upgrading, and the like. They may be used singly or in combination of two or more thereof. 5 an adduct or prepolymer obtained by reacting a polyisocyanate with a polyvalent alcohol at a NCO/OH ratio of 2 or higher, and can also be used as a blocked isoxanthene sulfonate curing agent, which is more Alcohols such as ethylene glycol, propylene glycol, trimethoprim or hexane triol. The addition of the blocking agent to the polyisocyanate group is stable at room temperature, but when heated to a dissociation temperature or higher, a free isocyanate group may be produced. The blocking agent includes a conventional blocking agent such as ε_caprolactam and butylcellosolve. The cationic electrodeposition coating composition contains crosslinked resin particles as a 15 component, and the crosslinked resin particles can be added to the electrodeposition coating composition at any stage in the preparation process. Preferably, the crosslinked resin particles are directly added to the previously prepared 11⁄4 ionic electrodeposition coating composition. Inorganic colorant The electrodeposition coating composition used in the present invention may contain a conventional inorganic 20 colorant. When it is used in a low ash form, the colorant, especially the content of the inorganic color, may be reduced, or the colorant may not be added. Examples of inorganic pigments = specialized inorganic pigments, such as titanium white and iron oxide dyed pigments; for example, kaolin, talc, shi shi ming, carbonated dance, mica and clay filler pigments; Iron sulphate, phosphoric acid, linalic acid, sulphate, nitriding, 36 200835759 zinc oxide, dimeric acid, zinc molybdate, molybdate, citrate, and filling (four) Ming, zinc citrate Anti-corrosive coloring materials such as Ming, oxidized silk, silver hydroxide, chlorinated carbonate, lanthanum nitrate and barium sulfate. The content of the inorganic colorant is 7% by weight or less, and preferably 5% by weight or less, and more preferably 5% by weight or less based on the weight of the solid tree s s of the cationic electrodeposition coating composition 5. 3 wt% or less. Further, the "% by weight" relative to the weight of the solid resin content is referred to as pwc. When the concentration of the inorganic colorant exceeds 7% by weight, the low ash content cannot be appropriately obtained, and thus the energy load for preventing sedimentation is increased. When the coloring material is used as a component of the electrodeposition coating composition, the coloring materials are generally dispersed in an aqueous medium (that is, a color material dispersed phase) at a high concentration of the preformed paste. It is a powder, and it is difficult to disperse the powder into a uniform state in one step at a low concentration used for the electrodeposition coating composition. This paste is generally called a toner dispersion paste. 15 The pigment dispersion paste can be borrowed Prepared by dispersing a colorant together with a colorant-dispersing resin in an aqueous medium. Generally, the color-dispersing resin includes a cationic or nonionic surfactant having a low molecular weight, and, for example, having a quaternary ammonium group and / or a cationic polycondensate of a modified epoxy resin of a tertiary sulfhydryl group. An aqueous medium, ion-exchanged water, water containing a small amount of alcohol, or the like is used as a water-based medium. In general, a color-dispersing resin is used. The amount is 20 to 1 part by weight based on 100 parts by weight of the coloring matter (as a solid content). After the coloring material dispersion resin is mixed with the coloring material, a conventional dispersing device such as a ball mill and a sand mill is used. Disperse the colorant until the color of the mixture in the mixture is 37 200835759 into a specific uniform particle size to obtain a color dispersion paste. In addition to the fused knife, the cationic electrode of the present invention is used to coat the composition. Containing rhyme compounds 5

10 &gt; organotin compounds such as dibutyltin dilaurate, dibutyltin oxide and dioctyltin oxide, such as Ν.methyl phenanthrene; and the gold terminal =: sulfonium salt, cobalt salt and copper salt. They can be used as a self-curing agent to dissociate the encapsulating agent. The concentration of the catalyst is preferably from 0.1 to 6 parts by weight based on 100 parts by weight of the solid content of the total amount of the cationic epoxy resin and the curing agent in the electrodeposition coating composition. Preparation of composition

g The cationic electrodeposition coating composition of the present invention may be obtained by crosslinking the above cationic epoxy resin and the blocked isocyanate curing agent, and if necessary, crosslinking the resin particles and/or the coloring paste. The material and the catalyst are prepared by dispersing in an aqueous medium. Further, the aqueous medium generally contains an acid for neutralizing the 15 cationic epoxy resin to improve the dispersibility. The neutralizing acid includes an inorganic acid or an organic acid such as hydrochloric acid, nitric acid, phosphoric acid, citric acid, acetic acid, lactic acid, aminosulfonic acid, and N-acetylglycine. As used herein, the aqueous w shell is water or a mixture of water and an organic solvent. It is preferred to use water that has been replaced by a parent. Examples of the organic solvent which can be used include hydrocarbons (e.g., dimethyl 20 stupid or decyl), alcohols (e.g., decyl alcohol, n-butanol, isopropanol, 2-ethylhexanol, ethylene glycol, and propylene glycol), Ethers (eg, ethylene glycol monoethyl ether, ethanol monobutyl ether, ethylene ether monohexyl ether, propylene glycol monoethyl ether, 3-methyl-3-methyl methoxybutanol, diethylene ether single Ethyl ether and diethylene glycol monobutyl ether), ketones (such as mercaptoisobutyl ketone, cyclohexanone, isophorone and acetoacetone), esters (Example 38 200835759 scaly acetate), And mixtures such as ethyl alcohol monoethyl ether acetate and ethylene glycol monobutyl. The cationic electrodeposition coating composition of the present invention may contain crosslinked resin particles. For the added method, the crosslinked resin particles may be added at any stage of the stage of electrodeposition coating of the electroformed article, and it is preferred to directly add the crosslinked resin particles to the previously prepared cationic electrodeposition coating composition to be closed. The amount of isocyanate-based curing agent must be suitable for curing reactions using functional groups containing active chlorine, such as primary 10 amine groups, secondary amine groups or hydroxyl groups in cationic epoxy resins to provide a good cure coat. Floor. Generally speaking, the weight ratio of the solid content in the cationic cyclic oxime resin to the solid content in the blocked isocyanate curing agent is in the range of 9 to 5, and preferably 80/. 20 to 65/35 (epoxy resin / curing agent). The amount of neutralizing acid is an amount suitable for neutralizing at least 2 G% of the cationic epoxy resin cation 15 group, and preferably 30 to 60%. The organic solvent is a main component of a solvent for preparing a resin component such as a cationic epoxy resin and a blocked isocyanic acid curing agent. Complex operations are required to completely remove the solvent. Further, when the organic solvent is contained in the cation-free epoxy resin as the adhesive resin component, the fluidity of the coating film is improved and the smoothness of the coating enthalpy is improved during film formation. The organic solvent generally included in the coating composition includes ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol. Monohexyl ether and the like. 39 200835759 In addition to the above ingredients, the cationic electrodeposition coating composition may contain conventional additives for coating compositions such as plasticizers, surfactants, antioxidants, and ultraviolet absorbers. According to the present invention, in the example of the cationic electrodeposition coating composition having a low solid content, the solid content concentration is set to 20% by weight or less. The conventional content is 20% by weight. In particular, the solid content concentration of the coating composition is preferably in the range of 〇·5 to 9% by weight, and the lower limit thereof is preferably 2% by weight, more preferably 4% by weight. On the other hand, the upper limit thereof is preferably 7% by weight, and more preferably 6% by weight. When the solid content concentration 10 is less than 5% by weight, a suitable coating film cannot be formed, and when it is higher than 9% by weight, in the cationic electrodeposition coating process, for example, a cleaning step and equipment for eliminating the use of water cannot be obtained. Simplify and other effects, which are caused by low solid content. Herein, the solid content concentration means the concentration relative to the total weight of the color component and the resin component (including the 15 crosslinked resin particle component) of the cationic electrodeposition coating composition as a reference for the solid content. Therefore, the low solid content is intended to reduce the conductivity of the cationic electrodeposition coating composition. Therefore, it is preferred to separately add a conductivity control agent. The conductivity control agent to be used in the present invention is not particularly limited as long as it is a material for adjusting the conductivity of the cationic electrodeposition coating composition within a desired range, but preferably has from 200 to 500 mmol/ The conductivity control of the amine group-containing compound of the amine price of l〇〇g. When the amine valence for the cationic electric control and the conductivity control agent of the coating composition is adjusted to the above range, it may be any amine-containing compound, but in general, conductivity control is preferred. Amine modified epoxy resin and amine modified propionate resin. Dan 40 200835759, a conductivity control agent for the cationic electrodeposition coating composition of the present invention, if necessary, can be neutralized with an acid. The acid value is preferably from 250 to 450 mmol/100 g and most preferably from 300 to 400 mmol/100 g. When the amine value is less than 200 mmol/100 g, the addition amount required to adjust the conductivity of the cationic electrode 5 having a low solid content deposition composition to an optimum value is increased, and the corrosion prevention property may be lost. If the amine price exceeds 500 mmol/l〇〇g, it has a sinking

The shortcomings of reduced productivity and the inability to achieve the desired deep plating capability. Furthermore, the compatibility with the steel plate is also reduced. The above conductivity control agent includes an amine group-containing compound having a low molecular weight or a high molecular weight, such as a conventional high molecular weight resin such as an amine-modified epoxy resin and an amine-modified acrylic resin. Examples of the low molecular weight compound containing an amine group include monoethanolamine, diethanolamine, dimethylbutylamine, and the like. 15 20 乂L is a high molecular weight compound containing an amine group, and particularly preferably an L amine modified epoxy resin and an amine modified acrylic resin. The amine wax is obtained by modifying the epoxy group of the epoxy resin with an amine compound. A general epoxy resin can be used as the epoxy dragon, preferably a bisphenol type epoxy resin having a molecular weight of 5 Å, a tert-butyl catechol gas tree &amp; a linear brittle varnish type epoxy Fine and a line type wire Γ Ϊ tree type epoxy resin. Among these epoxy resins, the most desirable ones are varnish-resin type epoxy resins and nail-type secret varnishes, which are commercially available. These epoxy resins are commercially available. Examples of the ring gas, including a linear type varnish resin type epoxy resin 41 manufactured by The Dow Chemical Co., Ltd. (2008), 200835759 DEN-438; manufactured by T〇hto Kasei Co., Ltd. &amp; the age-old line type with varnish resin epoxy resin ydcn·? . These epoxy resins can be modified with, for example, polyester polyols, poly-polyols, and monofunctional burnt agglomerates. Alternatively, the epoxy resin utilizes the reaction of an epoxy 5 group with a diol or a dicarboxylic acid to extend the chain. As the amine-modified acrylic resin, for example, a homopolymer of dimethylaminoethyl methacrylate (which is an amine group-containing monomer) or monomethylaminoethyl methacrylate can be used. a copolymer of an ester and another polymerizable monomer, used in its original form, or a glycidyl group of a homopolymer of methacrylic acid 10 glycidyl ester modified with an amine compound, or glycidyl methacrylate S A glycidyl group of a modified copolymer of a polymerizable monomer. The compound which introduces an amine group into an epoxy resin or an epoxy group-containing acrylic resin includes a primary amine, a secondary amine, a tertiary amine, and the like. Specific examples thereof include butylamine, octylamine, diethylamine, dibutylamine, dimethylbutylamine, monoethyl 15 alcoholamine, diethanolamine, N-methyl-ethanolamine, triethylamine hydrochloride, N, N. a mixture of dimethylethanolamine acetate, diethyldisulfide and acetic acid, and furthermore, a secondary amine which is a blocked primary amine, such as diketimine and diethyl of amine ethylethanolamine Diketimine or the like of diethylhydroamine. A variety of amines can be used. 2) As described above, the number average molecular weight of the amine-modified epoxy resin and the amine-modified acrylic resin is preferably in the range of 500 to 20,000. When the number average molecular weight is less than 500, there is fear of loss of corrosion resistance, and although the cause is unclear, the deep plating ability is lowered and the compatibility with the zinc steel sheet is lowered. When the number average molecular weight exceeds 20,000, it is likely to cause a bad appearance of the finished product. The amine-modified epoxy resin or the amine-modified acrylic resin may also be neutralized first by neutralizing the acid. The acid used for neutralization includes inorganic acids and organic acids, and hydrochloric acid, fore, formic acid, formic acid, acetic acid, acetic acid and lactic acid. The above cationic electrodeposition coating composition is applied to an article by electrodeposition to form an electrodeposited film. Objects include, but are not particularly limited to, examples

Iron plate steel! Lu board and its surface treated objects and molded objects, as long as it is electrically conductive. 10 Electrodeposition coating of a cationic electrodeposition coating composition is carried out by applying a voltage ranging from 50 to 45 GV between the anode and the cathode of the article to be coated. When the applied voltage is less than (4), the Thai deposit does not, and when it exceeds 450 ν' the coating film breaks and looks. Abnormal: during the electrodeposition coating, the liquid coating composition in the bath is generally adjusted to 15 to 45 ° C range. 10 Electrodeposition coating includes a step of impregnating an article in a cationic electrodeposition coating composition, and a step of forming a film between the cathode (4) and the voltage to be coated to form an electrodeposited film. Furthermore, the voltage applied can be varied depending on the electrodeposition conditions, and is generally 2 to 4 minutes. The thickness of the obtained electrodeposited film is generally in the range of 5 to 25 (d). When the film thickness λ!, at 5&quot;m, the anti-corrosion property is sufficient, and when the film thickness exceeds 25/m, the thickness is insufficient to provide the desired coating film efficiency. Further, when the film thickness is 15/m, the sheet resistance of the electrodeposited film is preferably in the range of _ to 1600 kQ/cm2. When the sheet resistance of the coated film is less than 43 200835759 kQ/cm2, it is in a state in which an appropriate resistance cannot be obtained, and it is feared that the deep clock is inferior. Furthermore, when it exceeds 1600 kD/cm2, it is feared that the coating film is poor in appearance. The film resistance of the coated film is more preferably from 1100 to 150 〇 kD/cm 2 . Within the scope. 5 The film resistance of the coated film can be determined by the following formula according to the residual current value (A) at the final coating voltage (V): φ Thin film resistance (FR) = V/A. After electrodeposition coating, the obtained electrodeposited film is washed in its original form or with water, and baked at 120 to 260 ° C, and preferably at 140 to 220 10 C for 10 to 30 minutes. A cured electrodeposited film was obtained. The cured electrodeposited film of the present invention has excellent surface smoothness or an Ra value as an evaluation index of the surface flat lake property, preferably 〇 25 #m or less, and more preferably 0.20 / / m or less. Furthermore, the lower limit is preferably zero. Ra value 疋 According to JIS-B0601, an evaluation type surface roughness measuring machine I5 (manufactured by SURFTEST SJ-201P' Mitsutoyo Corporation) was used. The smaller Ra value provides a better coating film appearance with suppressed undulations. Furthermore, in the present invention, there is provided a method for simultaneously establishing the smoothness and edge coating force of a cationic electrodeposition coating composition, characterized in that 20 is coated by cationic electrodeposition by impregnation of the material. In the composition and the process of forming a cationic electrodeposited film by applying a voltage, the cationic electrodeposition coating composition comprises crosslinked resin particles having an average particle size of 1.0 to 3.0 / / m The range and the heat softening temperature are in the range of 120 to 180 C. Furthermore, in the present invention, even if the cationic 44 200835759 electrodeposition coating composition is in a low solid form and a low ash form, the ability to prevent sedimentation of the solid content in the electrodeposition coating composition can be achieved by the cationic package. In particular, it is improved by adding a specific crosslinked resin particle as an additive to the coating composition, and at the same time, surface smoothness and edge coating force can be established. In the case of 5, the amount used is in the range of 3 to 15% by weight based on the weight of the solid content in the cationic electrodeposition coating composition. EXAMPLES The present invention will be described in further detail based on the following examples. Those skilled in the art will appreciate that the invention is not limited to the embodiments. In this embodiment, 10, unless otherwise stated, "parts" and "%" are based on weight. Production Example 1A: A closed isocyanurate curing agent is equipped with a stirrer, a cooler, In a nitrogen supply tube, a thermometer, and a flask for dropping liquid, 199 parts of a trimer of hexamethylene diisocyanate (CORONATE HX: manufactured by Nippon Polyurethane Industry Co., 15 Ltd.) and 32 parts of methyl group were weighed. Isobutyl ketone and 〇·〇 3 parts of dibutyltin dilaurate' and a dropping funnel were added dropwise 87.0 parts of methyl ethyl _ two in one hour while scrambling and bubbling with nitrogen. The temperature was raised from self-rise to 70 ° C. Next, the reaction was continued for 1 hour, and the reaction was continued until the absorption of the NCO group in the infrared spectrometer disappeared. Next, 2〇〇·74 parts of n-butanol and 39.93 parts were added. Methyl isobutyl ketone to prepare a mixture having a nonvolatile content of 80%. Gas Process Example 2A: An amine modified helium resin emulsion is equipped with a stirrer, a cooler, a nitrogen supply pipe, and In the flask with the dropping solution, weighed 71.34 parts of 2,4-/2,6- Tolyl diisocyanate 45 200835759 (80/20% by weight), 111.98 parts of isopropyl isobutyl ketone and 0.02 parts of dibutyl tin dilaurate, and from a dropping funnel, adding U.24 parts dropwise within 3 minutes Methanol, while _ and _ nitrogen foaming. Due to the heat of the exothermic reaction, the temperature is raised from room temperature to 6 (rc. Next, after the reaction lasts for 3 〇 5 minutes, 'from the dropping funnel' at 30 46.98 parts of ethylene glycol monoethylhexyl group were added dropwise to the ^ knife U. The temperature was raised to % to 75 C due to the heat of the exothermic reaction. After the reaction was continued for 30 minutes, 41.25 parts were added. The addition of a double a and propylene-acrylic acid adduct (5 mol) (BP_5p, Sany〇c〇, manufactured by (5)) was added to the mixture, the temperature was raised to 9 〇t, and the reaction was continued while 10 IR was measured. The spectrum disappeared until the NCO group disappeared. Successively, 475.0 parts of bisphenol a type ternary oxygen tree yttrium (YD-7011R'manufactured by T〇htoKasei Co., Ltd.) having an epoxy equivalent of 475 was added. To dissolve uniformly, and then raise the temperature from 130 ° C to 142 ° C, and by azeotrope with MIBK from the reaction system 15 After the reaction mixture was cooled to 125 ° C, L107 parts of benzyldimethylamine was added, and a reaction to form an oxazolidinone ring by de-methanolation was continued. The reaction was continued until the epoxy equivalent was H40. Next, the mixture was cooled to 10 ° C, and 24.56 parts of N-methylethanolamine, 11.46 parts of diethanolamine, and 26.08 parts of amine ethyl ethyl 20 alkanolamine (ketimine) were added. (78.8% solution of methyl isobutyl ketone), reacted at 110 ° C for 2 hours. Next, 20·74 parts of ethylene glycol mono-2-ethylhexyl ether and 12.85 parts of methyl isobutyl ketone were added to the mixture to be diluted, and the nonvolatile content was adjusted to 82%. The number average molecular weight (measured by the GPC method) was 1380, and the amine equivalent was 94.5 meq/100 g. 46 200835759 Weighing (4)·11 parts of ion-exchanged water and 5.04 parts of acid in another container' slowly add dropwise to the above-mentioned amines which are heated to the heart of the heart (solid content is .0 parts) The base-modified epoxy resin and the % part (solid content: 25. parts) of the blocked isocyanate curing agent 5 of the production example 1 = 'the compound' and the mixed mixture to the uniform dispersion. Next, ion exchange water was added to adjust the solids content to 36%. : The colorant dispersing blush was placed in a flask equipped with a stirrer, a cooler, a nitrogen supply tube, a thermometer, and a dropping liquid, and 382.20 parts of a bisphenol 10 A type epoxy resin having an epoxy equivalent of 188 was weighed ( Trade name: DER-331J) and bismuth bisphenol a, the temperature is raised to 80 ° C to uniformly dissolve the mixture, followed by the addition of 153 parts of 2-ethyl-4·methylimidazole 1 % solution, and reacted at i7 ° C for 2 hours. After cooling the mixture to 140 ° C, 196.50 parts of 2-ethylhexanol semi-blocked isophorone diisocyanate (nonvolatiles containing 15 : 90%) was added to the mixture, and the reaction was carried out until the NCO group Run out. Add 205.00 parts of propylene glycol monobutyl ether, add 408.00 parts of 1-(2-thioethylthio)-2-propanol and 134.00 parts of methyl propionate, and add 144.00 parts of ion exchange. Water, and the reaction mixture at 70 ° C. The reaction is continued until the acid value is 5 or lower. The obtained resin varnish was released to a nonvolatile content of 35% by using 1150.50 parts of ion 20 exchange water. 1Example 4: The tray of the dispersion-dispersed paste was placed in a sand mill, and 120 parts of the color-dispersed resin varnish obtained in Production Example 3, 100.0 parts of kaolin, 92 parts of titanium dioxide, and 8.0 parts were fed. Dibutyltin oxide and 184 parts of ion-exchanged water were dispersed, and the particle size was 10/zm or less until 47 200835759 to obtain a toner dispersion paste (solid content: 48%). Production Example 5A: Production of crosslinked resin particles In a reaction vessel, 120 parts of butylcellosolve was fed, and the mixture was heated to 120 °C. Within 3 hours, a solution was added dropwise, which was a mixture of 2 parts of t-butylperoxyethylhexanoate and 10 parts of butylcellosolve, and a single-hatch mixture. Containing 15 parts of glycidyl methyl acrylate vinegar, 50 parts of 2-ethylhexyl decyl acrylate, 20 parts of 2-hydroxyethyl methacryl 10 acrylate and 15 parts of butyl methacrylate The ester has an SP value of 10.1. After aging for 30 minutes, a solution was added dropwise over 30 minutes, which was 〇β 5 parts of t-butylperoxy-2-ethylhexanoate and 5 parts of butylcellosolve. The mixture, as well as the cooling mixture. Heating and stirring were carried out at 80 ° C by adding 7 parts of N,N-dimethylaminoethanol and 15 parts of 15% 50% lactic acid solution to the mixture for quartification. When the acid mussels are 1 or lower and the viscosity stops increasing, the heating is terminated to obtain an acryl-based resin having an ammonium group. The number of money groups per molecule of the acetonitrile-based resin having an ammonium group was 6.0. Into the reaction vessel, 120 parts of an acrylonitrile-based resin having an ammonium group and 270 parts of deionized water were added, and the mixture was stirred with heating at 75 °C. A 100% neutralized aqueous solution of 1·5 parts of 2,2,-azobis(2-(2-imidazolin-2-yl)propan) and acetic acid was added dropwise over 5 minutes. After 5 minutes of aging, 30 parts of methacrylic acid was added dropwise in 5 minutes. After 5 minutes of aging, a mixture of α, s-ethylene-unsaturated monomer was stirred, 48 200835759

€ 5 contains 170 parts of methyl methacrylate, 4 parts of stupid ethylene, 3 parts of n-butyl methacrylate, 5 parts of glycidyl mercapto acrylate and π parts of neopentyl glycol Dimethacrylate, added to a solution of 17 〇 具有 之 之 之 之 酿 及 及 及 250 250 250 250 250 250 250 250 250 250 , , , , , , , , , 获得 获得 获得 获得 获得 获得 获得Add a pre-emulsion. The dispersion of the crosslinked resin particles 1 was obtained by cooling after aging for 60 knives. The dispersion of the crosslinked resin particles had a nonvolatile content of 35%, a pH of 5 Å, and an average particle size of 1 〇〇 nm. 1Example _6A: Preparation of non-crosslinked gluten granules 10 Two parts of laurel peroxide are dissolved in a solution of 104 parts of ethylene and 20 parts of 2-ethylhexylmethyl A mixture of acrylic vinegar and % by weight of lauryl methacrylate. This was added to 497 parts of an aqueous solution in which 8 parts of polyvinyl alcohol (GOUSENOL GH-17, manufactured by Nippon Synthetic Chemical Industry Co. Ltd.) 15 was dissolved in deionized water while stirring, and at 3,500. The dispersion was produced by a HOMOMIC LINE FLOW 30 type machine (high speed disperser, manufactured by TOKUSYU KIKA KOUGYOU Co. Ltd.) under rpm. 20 Suspension polymerization of the suspension was carried out for 5 hours at a stirring speed of 150 rpm and a reaction temperature of 81 to 83 ° C using a general batch reaction vessel, and after cooling, using a mesh of 200 mesh. Dispersion, obtaining non-crosslinked resin particles. The non-volatile content of the dispersion of the non-crosslinked resin particles was 30% and the average particle size was 3/m. Example 1A 49 200835759 2222 parts of the emulsion obtained in Preparation Example 2A, 417 parts of the colorant dispersion paste obtained in Preparation Example 4A, and 2361 parts of ion-exchanged water were mixed to obtain a cationic electrodeposition coating composition. Wherein the PWC was 16.5%, the content of the crosslinked resin particles was zero% by weight, and the solid content was 205% by weight.

Comparative Example 1A 738 parts of the emulsion obtained in Preparation Example 2A, 4 parts of dibutyltin oxide and 4598 parts of ion-exchanged water were mixed to obtain a cationic electrodeposition coating composition in which PWC was 0%, and crosslinked resin particles were obtained. The content was zero by weight of 10% by weight, and the solid content was 5% by weight.

Comparative Example 2A 702 parts of the emulsion obtained in Preparation Example 2A, 38 parts of the crosslinked resin particles obtained in Preparation Example 5A, 4 parts of dibutyltin oxide and 4596 parts of ion-exchanged water were mixed to obtain a cationic electrodeposition coating. The coating composition, 15 wherein PWC was 0%, the content of the crosslinked resin particles was 5% by weight, and the solid content was 5% by weight.

Comparative Example 3A 665 parts of the emulsion obtained in Preparation Example 2A, 76 parts of the crosslinked resin particles obtained in Preparation Example 5A, 4 parts of dibutyltin oxide and 20 4596 parts of ion-exchanged water were obtained to obtain cationic electrodeposition. The composition was coated in which PWC was 0%, the content of the crosslinked resin particles was 10% by weight, and the solid content was 5% by weight.

Comparative Example 4A A mixture of 665 parts of the emulsion obtained in Preparation Example 2A, 89 parts of the preparation 50 200835759

5 The non-crosslinked resin particles obtained in the preparation of Example 6A, 4 parts of dibutyltin oxide and 4582 parts of ion-exchanged water were used to obtain a cationic electrodeposition coating composition in which PWC was 0%, and the content of the non-crosslinked resin particles was 10% by weight, and a solid content of 5% by weight. Comparative Example 5A 389 parts of the emulsion obtained in Preparation Example 2A, 125 parts of the colorant dispersion paste obtained in Preparation Example 4A, and 3486 parts of ion-exchanged water were mixed to obtain a cationic electrodeposition coating composition, wherein PWC was 25%, the content of the crosslinked resin particles was 0% by weight, and the solid content was 5% by weight. 10 Example 2A 702 parts of the emulsion obtained in Preparation Example 2A, 42 parts of crosslinked resin particles (crosslinked resin particles in which methyl methacrylate is a main component; TAFTTIC^FJOO: Toyobo Co., Ltd.) were mixed. Manufactured), 4 parts of dibutyltin oxide and 4592 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition having a PWC of 0%, a crosslinked resin particle content of 5% by weight, and a solid content of 5 weight%. Example 3A 665 parts of the emulsion obtained in Preparation Example 2A, 84 parts of crosslinked resin particles (crosslinked resin particles in which methyl methacrylate was the main component 20; TAFTIC® F-200 · Toyobo Co·) , manufactured by Ltd., 4 parts of dibutyltin oxide and 4587 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition in which PWC is 0%, crosslinked resin particles are 10% by weight, and solid content It is 5% by weight. Example 4A 51 200835759 Mix 628 parts of the emulsion obtained in Preparation Example 2A, and 127 parts of crosslinked resin particles (crosslinked resin particles in which methyl methacrylate is the main component; TAFTIC^F-200: Toyobo Co. , manufactured by Ltd., 4 parts of dibutyltin oxide and 4581 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition, wherein PWC is 〇%, crosslinked resin particles are 15% by weight, and solid The content is 5% by weight.

Example 5A 628 parts of the emulsion obtained in Preparation Example 2A, 40 parts of the crosslinked resin particles (crosslinked resin particles in which the styrene monomer was mainly 10, CHEMISNOW SX500H · Soken Chemical &amp; Engineering Co Ltd., manufactured, having an average particle size of 4 parts of dibutyltin oxide and 4668 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition, wherein PWC is 〇%, and the content of crosslinked resin particles is 15 parts by weight. %, and the solid content is 5% by weight.

15 Example 6A A mixture of 56 parts of the emulsion obtained in Preparation Example 2A, 54 parts of the preparation example 4A, a pigment dispersion paste of 4 parts, and 4 parts of crosslinked resin particles (Crossing the Moon Tree Granules in which styrene monomer is the main component; Lan SX500H: Soken Chemical &amp; Engineering c., manufactured by Ud, having an average particle size of 3 ) and 4739 parts of ion-exchanged water, obtained by cationic electrodeposition coating composition The content of the towel pWq_, the crosslinked resin particles was 15% by weight, and the solid content was 5% by weight. Regarding the prepared cationic electrodeposition coating composition, the dynamic elastic viscoelasticity of 8 (the loss elastic modulus under rc and the storage bombing amount under 14叱52 200835759, and the level of miscellaneous and miscellaneous) were evaluated by the following method. Coating force. The measurement of the amount of red touch surface of the fascinating ship - the tin plate was immersed in the cationic electrodeposition coating prepared as described above. By applying electricity to the electrodeposited film, it was baked. After baking, the film thickness is 15_, and then the plate is washed with water to remove the excess electrodeposition = $ composition. Then, after the water is recorded, the plate with the uncured coating film is taken out immediately after the drying. To prepare a sample. The dynamic viscoelasticity of the sample is determined by temperature, and is measured by (10)(6)(4)(10)m 10 15 20), which is a rotary dynamic viscoelasticity measuring device (at a strain of 〇5deg and a frequency of 0.02 Hz) ), where the sample is set, and the measured temperature is maintained at the machine. After the measurement was started, when the electrodeposited film was uniformly distributed on the cone plate, the viscosity measurement of the coating film was performed. The evaluation of the appearance of the deposited film was carried out by measuring the arithmetic mean roughness (Ra) on the roughness curve by measuring the slidability of the film. The cold-rolled steel sheet treated with the zinc (di) sulphate was impregnated in the cationic electrodeposition coating composition prepared as described above. The uncured electrodeposited film obtained by applying a voltage is excited. The paste was baked for ig minutes, so that the film thickness after baking was 15 // m. Next, the value of the cured electrodeposited film was measured in accordance with JIS-B0601 using an evaluation type surface roughness measuring machine (SURFTEST SJ 2 〇 lp manufactured by Mitsutoyo C〇rp0rati〇n). The test was repeated 7 times on a sample having a cut-off of 2·5 mm (the number of dispenses was 5), and the Ra value was an average of the measured values without the maximum and minimum values. The results are shown in Table 1. It can be appreciated that a smaller Ra value provides a better appearance of the coated film with suppressed irregularities. 53 200835759 Evaluation method of the edge coating force The zinc oxide-treated cutter blade (LB-50K manufactured by OLFACo) was used as a coating material to be impregnated into the cationic electrodeposition coating composition. A voltage was applied between the anode and the cathode of the above article to obtain a 5 electrodeposited film in which the application voltage in the above electrodeposition conditions was adjusted so that the thickness of the electrodeposited film on the blade was 15 / / m. The electrodeposited film obtained by water washing was washed and then baked at 160 ° C for 10 minutes to obtain a cured electrodeposited film. The cutter blade coated with the electrodeposited film was bent at the center. The thickness of the electrodeposited film applied to the cutter blade was measured by a 10 digital microscope (VH-8000 manufactured by KEYENCE Corporation) at a distance (30 μm) from the (sharp) edge of the cutter blade. Figure 9 outlines the point of the cutter blade at a distance of 30 microns from the edge of the blade. 54 200835759

Evaluation result Melt viscosity ash (colorant) content (%) Resin particle content (%) Resin particle edge coating force (/zm) Smoothness Ra (C/0 = 2.5) Storage elastic modulus G' (dyn/cm2) CL end | ^ U) On 0.19 Κ) bJ U) 〇On b 0.30 t—* Lh On 〇Lh Production Example 5A: Crosslinked average particle size: 0.1 μηι _ J Comparative Example 2Α 00 u&gt; 0.37 ι—^ Ο K ) oo 〇o Production Example 5Α: Crosslinked average particle size: 0.1 μπι ____________________________________ί Comparative Example 3Α 0.20 Ln o 〇— o Production Example 6Α: No cross-linking average particle size: 1 to 5 Comparative Example 4Α 00 b 0.33 t—* U α\ )—i Lh bO κ> Lh o &gt; o 0.18 Η-^ Ui Lh 00 ON 澌&gt; ^ Ui 0.21 00 Lh 00 00 o TAFTIC F-200: Average particle size: 2 μηι Example 2Α O oo 0.21 H-» o &lt;1 H-* H-^ u&gt; o 1—A o TAFTIC F-200: Average particle size: 2 μπι Example 3Α 00 to 0.23 1—* to Lfi H-* K&gt; o HA Ui TAFTIC F-200: Average particle size: 2 μηι Example 4Α oo 0.24 H-^ ON — to K-^ o Ϊ—^ CHEMISNOW SX500H Average particle size: 3 μπι i Example 5Α 00 U) 0.24 U) a\ to CHEMISNOW SX500H Average particle size: 3 μιη Example 6Α 55 200835759 10 15 20 As shown in Table 1, it is understood that there is a dynamic viscosity defined in The electrodeposition coating composition of the loss elastic modulus (G,,) and the storage elastic modulus (G,) in the elastic range provides excellent performance in smoothness and edge coating force. In particular, in Comparative Example 1A, the electrodeposition coating composition having a storage elastic modulus (G') outside the range defined by the present invention did not provide a good edge coating force. In Comparative Example 2A, the electrodeposition coating composition comprising the crosslinked resin particles of Preparation Example 5A and having a loss elastic modulus (G,,) and a storage elastic modulus (G') which are outside the scope of the present invention, Does not provide good smoothness and good edge coating. Similar to Comparative Example 2A, in Comparative Example 3A, the crosslinked resin particles of the preparation examples were contained, wherein the crosslinked resin particles had an average particle size of 1 〇 Q ^ and had a loss elastic modulus (G ) outside the range defined by the present invention. The electrodeposition coating composition does not provide good smoothness. In Comparative Example 4A, an electrodeposition coating composition comprising non-crosslinked resin particles and having a heterogeneous modulus (G,) exceeding the definition of the dry circumference of the present invention provides a non-covering force. In Comparative Example 5A, a coating composition containing no resin resin and having a loss elastic modulus (g,) which exceeded the range defined by the present invention was contained, and it was not possible to provide a turbidity. The electrodeposition coating composition of Example 1A π Preparation 4A, in which all parameters are coated in the range of Γ:: provides excellent smoothness and excellent edge, per-electrodeposition coating composition The package control is within the edge coating force of the hair (G) and 敎 (four) modulus (G) of the hair (4), and provides excellent smoothness and excellentness. 56 200835759 is equipped with a stirrer, 199 parts of hexamethylene diisocyanate trimer (CORONATE HX : Nippon Polyurethane Industry Co) was weighed in a cooler, a nitrogen supply tube, a thermometer, and a flask for dropping liquid.

Ltd.), 32 parts of methyl isobutyl ketone and 0. 03 parts of dibutyl 5 butyl laurate, and from the dropping funnel, 87 parts of methyl b was added dropwise within 1 hour. Ketone oxime, while stirring and foaming with nitrogen. The temperature was initially raised from 50C to 70 °C. Next, the reaction was continued for 1 hour, and the reaction was continued until the absorption of the NC0 group in the infrared spectrometer disappeared. Next, 0.74 parts of n-butanol and 39.93 parts of methyl isobutyl ketone were added to prepare a mixture having a nonvolatile content of 80%. Reproducible Example ^ : The emulsion of the amine-modified cyclohexyl epoxide and the sealed isocyanate curing agent _ j is reported in the cruising with a stirrer, a cooler, a nitrogen supply pipe and a drip leak. 71.34 parts by weight of 2,4-/2,6-streptyldiisocyanate 15 (80/20% by weight), 11 L of 98 parts of methyl isobutyl ketone and 2 parts by weight of dibutyltin dilaurate, and From the dropping funnel, 14.24 parts of methanol was added dropwise over 30 minutes while stirring and bubbling with nitrogen. Due to the heat of the exothermic reaction, the temperature is raised from room temperature to 6 Torr. Hey. Next, after the reaction was continued for 3 minutes, 46.98 parts of ethylenediamine monoethylhexyl ether was added dropwise from the dropping funnel over 3 minutes. The temperature rises to 70 to 75 C due to the heat of the exothermic reaction. After the reaction was continued for 30 minutes, 41.25 parts of bisphenol a and propylene oxide calcined product (5 moi) (BP-5P, manufactured by Sanyo Kasei Co., Ltd.) were added to the mixture to set the temperature. Raise to 9 (TC, and continue the reaction, while measuring the IR spectrum until the NC0 group disappears. 57 200835759 Successively, add 475.0 parts of bisphenol A epoxy resin with an epoxy equivalent of 475 (YD-7011R, Dongdu Huacheng Co., Ltd. (manufactured by TohtoKasei Co., Ltd.) was uniformly dissolved, and then the temperature was raised from 130 ° C to 142 ° C, and water was removed from the reaction system by azeotropy with MIBK. After the mixture was cooled to 125 ° C, 1.107 parts of benzyldimethylamine was added, and a reaction to form a ketone ring by demethylation was continued. The reaction was continued until the epoxy equivalent was 1140. 'Cool the mixture to 10 ° C, and add 24.56 parts of N-methylethanolamine, 11.46 parts of diethanolamine and 26.08 parts of the amine ethyl etheethanolamine ketimine (78.8%) Methyl isobutyl ketone solution), reacted under liot: for 2 hours. Next, 20.74 parts Ethylene glycol mono-2-ethylhexyl ether and 12.85 parts of methyl isobutyl ketone were added to the mixture to be diluted, and the nonvolatile content was adjusted to 82%. The amine modified epoxy resin was obtained, and the amount thereof was obtained. The average molecular weight (measured by the GPC method) was 1380, 15 and the amine equivalent was 94.5 meq/100 g. In another container, 145.11 parts of ion-exchanged water and 5.04 parts of acetic acid were weighed and slowly added dropwise. 320.11 parts (solid content: 75.0 parts) of the above-mentioned amine-modified epoxy resin and 19,038 parts (solid content: 25.0 parts) of the sealed mixture of the blocked isocyanate curing agent of the production example 1B, and the stirring mixture To uniform dispersion. Next, ion-exchanged water was added to adjust the solid content to 36%. Preparation Example 3B: Colorant Dispersion Resin Varnish was manufactured using a stirrer, a cooler, a nitrogen supply tube, a thermometer, and a drip leak. In the flask, weighed 382.20 parts of bisphenol 58 200835759 type A epoxy resin (trade name: DEL331J) and 111.98 parts of bisphenol A, and raised the temperature to 8 (rc to uniformly dissolve the mixture). And then add 153 parts of a 1% solution of hydrazine methylimidazole, and reacting at 170 ° for 2 hours. After cooling the mixture to 140 ° C, 196.50 parts of 5 ethylhexanol semi-closed isophor A keto diisocyanate (nonvolatile content of 90%) was added to the mixture, and the reaction was carried out until the NCO group was consumed. Add 205.00 parts of propylene glycol monobutyl ether, add 408.00 injured 1-(2-ethylethylthio)-2-propanol and 134.00 parts of methyl propyl vinegar 'add 144.00 parts of ion exchange Water, and reacted at 70 ° C to mix 1 〇. The reaction is continued until the acid value is 5 or lower. The obtained resin varnish was diluted to a nonvolatile content of 35% using 1150.50 parts of ion-exchanged water. The toner dispersion paste was pulverized in a sand mill, and 120 parts of the colorant dispersion resin varnish obtained in Production Example 3B, 100.0 parts of kaolin, 92 parts of titanium oxide, 8.0 15 parts of dibutyltin oxide, and 184 were fed. The ion-exchanged water was dispensed, and dispersed until the particle size was 10 / / m or less to obtain a toner dispersion paste (solid content: 48%). : For comparison of crosslinked resin particles _ 诰 In a reaction vessel, 120 parts of ethylene glycol dibutyl ether 20 (butylcellosolve) was fed, and heated to 120 ° C with stirring. A solution was added dropwise over a period of 3 hours, which was a mixture of 2 parts of t-butylperoxy-2-ethylhexanoate and 10 parts of butyl cellosolve, and a monomer. The admixture 'containing 15 parts of glycidyl methyl acrylate, 50 parts of 2-ethylhexyl methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate 59 200835759 vinegar and 15 parts of n-butyl methacrylate. After aging for 3 minutes, a solution was added dropwise over 30 minutes, which was 〇·5 parts of t-butylperoxy-2-ethylhexanoate and 5 parts of ethylene glycol dibutan ( Blend of butylcellosolve), as well as cooling the mixture. Heat and stir at 8 (TC), add 7 parts of N,N-dimethylaminoethanol and 15 parts of 50% lactic acid solution to the mixture. When the acid value is 1 or lower and the viscosity stops increasing The heating is terminated to obtain an acryl-based resin having an ammonium group. The number of ammonium groups per molecule of the acryl-based resin 0 having an ammonium group is 6.0. In the reaction vessel, 12 parts of an acrylonitrile having an ammonium group is added. Base tree 1 rouge and 'partisan water, and add a mixture at 75 ° C. Add 15 parts of 2,2,-azobis (2_(2_imidazolinyl) dropwise in 5 minutes 100% neutralizing aqueous solution of propane) and acetic acid. After aging for 5 minutes, add 30 parts of methyl methacrylate dropwise in 5 minutes. After aging for 5 knives, use α to stir. _ Ethylene-unsaturated monomer mixture, 15 contains 70 parts of methyl methacrylate, 40 parts of styrene, 3 parts of 曱 Φ-based propylene S-n-butyl acrylate, 5 parts of glycidyl methyl Acrylate and 30 parts of neopentyl alcohol monomethacrylate, added to a solution of 170 parts of acryl-based resin with ammonium group A mixture of 25 parts of deionized water was obtained by pre-emulsion, and a pre-emulsion was added dropwise in 4 minutes. • After aging 60, cooling was carried out to obtain a dispersion of crosslinked resin particles 1. Crosslinking The dispersion of the resin particles has a nonvolatile content of 35%, a pH of 5.0, and a flat particle size of 〇1 &quot; m. Here, the average particle size is determined according to the following: Average particle size of the tree The size is measured by the granule particle transmission measurement 200835759 method 'using yQCR〇TRAC934〇upA manufactured by Nikkiso Co Ltd Ltd.'. Further, the particle size distribution of the resin particles is measured by the measuring device, and is calculated from the measured value. The average particle size of the cumulative relative frequency [F(X) = 〇5] was accumulated. In these measurements and measurements, the refractive index of the solvent (water) was 133, 5 and the refractive index of the resin content applied was 1.59.

Preparation Example 6B In a flask equipped with a reflux condenser and a stirrer, 295 parts of mercaptoisobutyl ketone (hereinafter, abbreviated as "MIBK,"), 37.5 parts of methylethanolamine, and 52.5 parts were fed. Diethanolamine, stirring and maintaining the mixture 10 at 10 ° C. Slowly add 205 parts of phenolic novolak resin type epoxy resin (trade name: YDCN-703, Todu 〇Kasei Co" Ltd .) Manufacturing). After the completion of the addition of π, the reaction was carried out for 3 hours. When the molecular weight is measured, the molecular weight is 2,100. When the amine valence (MEQ (B)) of the amine-modified resin was measured, the amine value was 340 mm 〇 l / l 〇〇 g. 15 5 parts by weight of formic acid and 1254.5 parts of deionized water were added to 140 parts of the amine-modified resin solution, and the mixture was stirred for 3 minutes while maintaining at 80 °C. The organic solvent was removed under reduced pressure to obtain a conductivity controlling agent having a solid content of 5.0%.

Example 1B 20 Mix 628 parts of the emulsion obtained in Preparation Example 2B, and 127 parts of crosslinked resin particles (crosslinked resin particles in which methyl methacrylate monomer is a main component; GM-0105 (trade name) : (manufactured by GANZ Chemical Co., Ltd.), 4 parts of dibutyltin oxide and 4581 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition in which PWC is 0%, and resin pellet 61 200835759 is 15 weight. %, and the solid content is 5% by weight.

Paste Example 2B' Mix 628 parts of the emulsion obtained in Preparation 2B, 127 parts of the crosslinked resin particles (crosslinked resin particles, wherein methacrylic acid is the main 5 component; TAFTIC8F-200 · Toyobo Co ·, manufactured by Ltd., 4 parts of dibutyltin oxide and 4581 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition, wherein PWC is 0%, the content of crosslinked resin particles is 15% by weight, and solid The content is 5% by weight.

• Example 3B 10 Mixing 561 parts of the emulsion obtained in Preparation Example 2B, 19 parts of the colorant dispersion paste obtained in Preparation Example 4B, and 114 parts of the crosslinked resin particles (crosslinked resin particles in which mercaptoacrylic acid The methyl ester monomer is the main component; TAFTIC® F-200: manufactured by Toyobo Co., Ltd.), 3 parts of dibutyltin oxide and 4303 parts of ion-exchanged water, and a cationic electrodeposition coating composition 15 is obtained, wherein PWC The content of the crosslinked resin particles was 3% by weight, and the solid content was 5% by weight.

Example 4B 578 parts of the emulsion obtained in Preparation Example 2B, 360 parts of the conductivity control agent obtained in Preparation Example 6B (solid content: 5%), and 127 parts of 20 crosslinked resin particles (crosslinked resin particles) were mixed. , wherein the decyl acrylate monoester is the main component; TAFTIC^F-200: manufactured by Toyobo Co., Ltd.), 4 parts of dibutyltin oxide and 4331 parts of ion-exchanged water to obtain a cationic electrodeposition coating The coating composition in which PWC was 0%, the content of the crosslinked resin particles was 15% by weight, and the solid content was 5% by weight. 62 200835759 5 • Comparative Example IB 2444 parts of the emulsion obtained in Preparation Example 2B, 250 parts of the colorant dispersion paste obtained in Preparation Example 4B, 2346 parts of ion-exchanged water and 10 parts of dibutyltin oxide were obtained. A cationic electrodeposition coating composition in which the solid content was 20% by weight. Comparative Example 2B 738 parts of the emulsion obtained in Preparation Example 2B, 4 parts of dibutyltin oxide and 4598 parts of ion-exchanged water were mixed to obtain a cationic electrodeposition coating composition in which PWC was 0% (excluding ash content). The content of the crosslinked resin 10 particles was 0% by weight, and the solid content was 5% by weight. Comparative Example 3B 702 parts of the emulsion obtained in Preparation Example 2B, 38 parts of the crosslinked resin particles obtained in Preparation Example 5B, 4 parts of dibutyltin oxide and 4596 parts of ion-exchanged water were mixed to obtain a cationic electrodeposition coating. The coating composition, 15 wherein PWC is 0%, the content of the crosslinked resin particles is 5% by weight, and • the solid content is 5% by weight. Comparative Example 4B 665 parts of the emulsion obtained in Preparation Example 2B, 76 parts of the crosslinked resin particles obtained in Preparation Example 5B, 4 parts of dibutyltin oxide and 20 4596 parts of ion-exchanged water were mixed to obtain cationic electrodeposition. The composition was coated, wherein PWC was 0%, the content of the crosslinked resin particles was 10% by weight, and the solid content was 5% by weight. Comparative Example 5B A mixture of 579 parts of the emulsion obtained in Preparation Example 2B and 38 parts of the blended 63 200835759 resin particles (parent resin particles in which the styrene monomer is the main component; CHEMISNOW® SX130M: Soken Chemical &amp; Engineering

Co., Ltd. manufactured) 4 parts of dibutyltin oxide and 4388 parts of ion-exchanged water to obtain a cationic electrodeposition coating composition, wherein pwc is 5, the content of 5 crosslinked resin particles is 15% by weight, and solid The content is 5% by weight. With respect to the prepared cationic electrodeposition coating composition, 8 in dynamic viscoelasticity was evaluated by the following method (loss elastic modulus under rc and storage elastic modulus under 14 Å, and smoothness and edge coating) Covering force

10 It will be difficult to ride in the above-mentioned equipment. The electrode is formed into an electrodeposited film so that the film thickness after baking is #m and then the plate is washed with water to remove excess electrodeposition coating.

The appearance of the electrodeposited film was evaluated. The cold-rolled steel sheet treated with the zinc phosphate treated in the above-mentioned composition was impregnated and electrodeposited. The uncured electrodeposited film obtained by applying a voltage was baked at 160 ° C for 1 minute, so that the baking was aimed at A ^

L5// m. Next, the electrodeposited film was cured, and it was measured using an evaluation type surface roughness measuring machine 64 200835759 (SURFTEST SJ 2 〇 lp manufactured by Mitsutoyo Corporation). Repeated measurement 7 times on samples with a cut width of 2·5 mm (allocation number 5), and the Ra value is measured without maximum and minimum values

The uncured electrodeposited film obtained by immersing the cold-rolled steel sheet treated with zinc phosphate in the horizontal direction and the individual cationic electrodeposition coating composition f obtained in the stomach of the comparative example is baked. membrane

• After baking the uncured electrodeposited film at 160°CT for 10 minutes, the average roughness of the rough-diffraction curve was evaluated by the same surface roughness measuring machine as described above to evaluate the appearance of the electrodeposited film (4). The sedimentation of the right electrodeposition coating composition is poor because the sedimentable component 15 settles in the horizontal plane during electrodeposition coating, compared with the vertical appearance of the electrodeposited film (smoothness in the straight direction), electrodeposition Evaluation of the horizontal (planar) appearance of the film. ^ Smoothness in the horizontal direction) deteriorates. The sedimentation is acceptable or accommodative. 'Conservation can be accepted by the horizontal appearance and the vertical appearance. (〇): The horizontal Ra value is unacceptable (X): the horizontal Ra value

Vertical Ra value = less than 0.05 β 111 Vertical Ra value = not less than 0·05 65 200835759 By adjusting the concentration of crosslinked resin particles to 30% by weight (as solid content) to utilize Rheosol-G3000 (manufactured by UBM Corporati〇n) , • It is a rotary dynamic viscoelasticity measuring device, based on temperature-dependent measurement method, from 9 〇1: measuring the storage elastic modulus G of the sample, the measurement condition is ·· strain Q.5 5 degrees, frequency 〇·02 The Hz &amp; temperature rise rate is 4.0 ° C / min. The measurement results are shown in the graph of Fig. 8. Draw the tangent of the area of constant viscosity and the tangent of the area where the viscosity decreases. The temperature at the intersection is defined as the thermosoftening temperature °, the evaluation method of the shading coating force. 10 As described above, the edge coating force is evaluated. Figure 9 is a view of the point schematically showing the distance from the edge of the cutter blade of 3 〇 micrometers. If the thickness of the film at this point does not exceed 7 8 Am, the edge coating force is acceptable. The grain size of the grain and the earth were measured according to the following, and the average particle size of the particles of the tree and the sapphire particles used in each of the above examples and comparative examples were measured. Average of crosslinked resin particles • The female size is measured by the granular particle transmission method using Nikkiso Co.,

MlCR〇TRAC934〇upA manufactured by Ltd. is used for measurement. Further, the particle size distribution of the resin particles is measured by a measuring device, and the average particle size under the cumulative relative frequency F(x) = 0 is calculated from the measured value. These .2〇 measurements and calculations use a solvent (water) refractive index of 1.33 and a resin content of 1.59. 66 200835759 Table 2 Example 1B Example 2B Example 3B Example 4B Content of inorganic pigment (%) 0 0 3 0 Crosslinked resin particle type Crosslinked resin particles #3 Crosslinked resin particles #4 Crosslinked resin particles # 4 Crosslinked Resin Particles #4 Content (%) 15 15 10 :15 Degree of crosslinking Large thermal softening temperature 120 140 140 140 Particle size (μπι) 2.0 2.0 2.0 2.0 Conductivity control agent - - - 〇Melt viscosity 80° C/G" value 113 107 90 99 140 °C / G' value 125 475 222 188 Evaluation of sedimentation 〇〇〇〇 smoothness Ra (C / 0 = 2.5) 0.21 0.23 0.23 0.22 edge coating force (μπι) 7.8 8.0 7.9 7.8 67 200835759 Comparative Example IB Comparative Example 2B Comparative Example 3B Comparative Example 4B Comparative Example 5B Content of Inorganic Colorant (%) 23 0 0 0 0 Crosslinked Resin Particle Type Crosslinked Resin Particle #1 Crosslinked Resin Particle #1 Crosslinked Resin Particles #2 Content (%) 5 10 15 Degree of crosslinking Large thermal softening temperature 140 140 107 Particle size (μπι) 0.1 0.1 1.5 Conductivity control agent - - - - - Melt viscosity 80 °C / G" value 89 23 156 228 94 1 40 ° C / G, value 155 21 73 110 75 Evaluation of sedimentation X 〇〇〇〇 smoothness Ra (C / 0 = 2.5) 0.18 0.19 0.30 0.37 0.22 edge coating force (μπι) 7.9 3.6 6.0 8.3 5.6 cross-linking The degree is described in terms of the heat softening temperature and based on the measurement of the heat softening temperature. 5 Degree of crosslinking (large): Thermal softening temperature of 140 ° C or higher. 68 200835759 Degree of crosslinking (middle): Thermal softening temperature of 120 ° C or higher and below 140 ° C. Degree of crosslinking (small): Thermal softening temperature of 120 ° C or lower. Crosslinked Resin Particles #1: The crosslinked resin particles obtained in Preparation Example 5B. 5 Crosslinked Resin Particles #2 : CHEMISNOW SX-130M (trade name),

Manufactured by Soken Chemical &amp; Engineering Co., Ltd. Father's Resin Particles #3 · GM-0105 (trade name), manufactured by GANZ Chemical Co., Ltd. Father's Resin Particles #4 · F-200 (trade name), manufactured by Toyobo Co., Ltd. 10 . As shown in Tables 2 and 3 above, it is known that an electrodeposition coating composition having a low ash content and a low solid content contains an average particle size in the range of 10 to 3.0 / / m and a thermosoftening temperature of 120 to 180 ° The crosslinked resin particles in the C range provide both excellent smoothness and edge coating power. The degree of potency was similar to that of Comparative Example 1B, which was a conventional coating composition. In Comparative Example 1B, the electrodeposition coating composition contained a conventional inorganic coloring material free of tree gambling particles, which provided good surface smoothness and good edge coating force. This electrodeposition coating composition has a low degree of sedimentation evaluation because of the high ash content therein. In Comparative Example 2B, the electrodeposition coating composition 20 contained no inorganic coloring matter and contained no resin particles, and provided good smoothness and highly deteriorated edge coating force. With respect to Comparative Examples 3B to 5B, the electrodeposition coating composition contained resin particles. In Comparative Examples 3B and 4B, the particle size was small. In Comparative Example 5B, the heat softening temperature was low. Therefore, Comparative Examples 3B to 5B would provide poor edge coating force and poor surface smoothness. 69 200835759 [Simplified circular description] Figure 1 is a graph showing the behavior of loss elastic-modulus (G") values of dynamic viscoelasticity in five coating compositions; - Figure 2 shows five coatings. A graph of the behavior of the dynamic viscoelastic storage elastic modulus (G') value of the composition; Figure 3 is a graph showing the complex viscosity coefficient (the behavior of the r〇 value of the dynamic viscoelasticity of the five coating compositions) Figure 4A is a graph showing the relationship between storage elastic modulus (G') and electrodeposition structure at 80 ° C in several coating compositions; 10 Figure 4B shows several coating compositions Graph of the relationship between complex viscosity coefficient (if) and electrodeposition structure at 80 ° C; Figure 4C shows the loss of elastic modulus (G" at 80 ° C in several coating compositions and electrodeposition structure A graph of the relationship; Figure 5A is a graph showing the relationship between the storage elastic modulus 15 (G') and the electrodeposition structure at 140 ° C in several coating compositions; ^ Figure 5B shows several a graph of the relationship between the complex viscosity coefficient (rf) and the electrodeposited structure at 140 ° C in the coating composition; Figure 5C shows several A graph of the relationship between loss of modulus of elasticity (G") and electrodeposition structure at 140 ° C in the coating composition; 20 Figure 6A shows the storage of elasticity at 80 ° C in several coating compositions. A graph of the relationship between the amount (G') and the edge coating force; and Fig. 6B is a graph showing the relationship between the complex viscosity coefficient (if) and the edge coating force at 80 ° C in several coating compositions. Figure 6C is a graph showing the relationship between loss of elasticity 70 200835759 modulus (G") and edge coating force at 80 ° C in several coating compositions; Figure 7A shows several coating compositions A graph showing the relationship between the elastic modulus (G') and the edge coating force at 140 ° C; Figure 7B is a graph showing the complex viscosity 5 coefficient at 140 ° C in several coating compositions (&lt;) a graph showing the relationship between the edge coating force; Figure 7C is a graph showing the relationship between the loss elastic modulus (G" at 140 ° C and the edge coating force in several coating compositions; A graph illustrating the relationship between the temperature of the thermal softening temperature and the storage elastic modulus G' is shown for display; 10 Figure 9 is an outline showing the edge of the cutter blade From a schematic view of a portion of the main member 30 microns [REFERENCE NUMERALS: None

71

Claims (1)

200835759 X. Patent application scope: i. A cationic electrodeposition coating composition which provides an uncured electrodeposited film having a storage elastic modulus (G,) of from 8 Å to 500 at 1401. In the range of dyn/cm2, and at 80T:, the loss of the modulo i (G'') is in the range of 10 to 150 dyn/cm2, and the composition has excellent smoothness and edge coating power. 2. A cationic electrodeposition coating composition as claimed in claim 1 which comprises a cationic epoxy resin, a blocked isocyanate curing agent&apos; and, if necessary, a crosslinked resin particle and/or an inorganic colorant. 1〇3· A method of producing a cationic electrodeposited film having an established smoothness and edge coating force, wherein the cationic electrodeposited film is impregnated in a cationic electrodeposition coating composition The article is prepared by applying a voltage. The method comprises the steps of: adjusting the uncured electrodeposited coating of the cationic electrodeposition coating composition. The storage elastic modulus (G,) of the film at M0 ° C is 80. The loss elastic modulus (G,,) at 8 〇t in the range of 500 dyn/cm and adjusting the cationic electrodeposition coating composition is 10 to 15 〇dyn/cm 2 In the range. 2. The method of claim 3, wherein the crosslinked resin particles are added to the cationic electrodeposition coating composition, and the average particle size of the crosslinked resin particles is in the range of 1.0 to 3.0 So that the storage elastic modulus and the loss elastic modulus can be adjusted. 5. The method of claim 4, wherein the content of the crosslinked resin particles 72 200835759 is from 3 to 15% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition. 6. The method of claim 3, wherein an inorganic colorant system is added to the cationic electrodeposition coating composition, wherein the inorganic colorant contains 5 parts relative to the cationic electrodeposition coating composition The resin solid content has a weight of 10 to 20% by weight to adjust the storage elastic modulus and the loss elastic modulus. 7. The method of claim 3, wherein the crosslinked resin particles and the inorganic colorant are added to the cationic electrodeposition coating composition, and the crosslinked 10 resin particles have a particle size ranging from 1.0 to 3.0/ Within the range of zm, wherein the content of the inorganic colorant is from 0.5 to 10% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition to adjust the storage elastic modulus and the loss elastic modulus. 8. The method of claim 7, wherein the content of the crosslinked resin particles is from 3 to 15% by weight based on the weight of the resin solid content of the cationic electrodeposition coating composition. 73