JP5719232B2 - Glittering paint composition, glittering resin film and laminated coating film - Google Patents

Description

  The present invention relates to a glittering coating composition, and a glittering resin film and a laminated coating film obtained using the composition.

  Conventionally, a luster pigment having a titanium oxide layer provided on the surface of a scaly material such as natural mica, synthetic mica, or scaly alumina has been used in many fields. These conventional glitter pigments have a strong glitter feeling and a grain feeling (shiny gloss feeling), and are used as pigments imparting pearl luster.

  However, there is a demand for a design that has a higher-class feel and exhibits a silky shine, a so-called silky feeling. JP-A-2006-257179 (Patent Document 1) discloses a glitter pigment capable of imparting such a silky feeling by treating an organic basic compound with an acid after treating the layered titanate compound with an acid. A glittering pigment aqueous medium dispersion containing titanic acid flakes (titania nanosheets) swollen or peeled off is disclosed.

  Further, titanic acid flakes useful as additives such as paints and methods for producing the same are disclosed in JP-A-9-67124 (Patent Document 2), JP-A 2000-344520 (Patent Document 3), and JP-A-2004-255684. No. (Patent Document 4), International Publication No. WO1999 / 011574 (Patent Document 5), and further having a base layer containing titanic acid flakes (flaky titanic acid pigment) and excellent chipping resistance A multilayer coating film is disclosed in JP 2006-305515 A (Patent Document 6).

  However, conventional resin films containing titanic acid flakes as described in Patent Documents 1 to 6 exhibit high gloss and a good silky feeling, but sufficient adhesion cannot be obtained due to the occurrence of peeling or the like. There was a problem.

JP 2006-257179 A JP-A-9-67124 JP 2000-344520 A JP 2004-255684 A International Publication No. WO1999 / 011574 JP 2006-305515 A

  The present invention has been made in view of the above-described problems of the prior art, and exhibits a high glossiness and a good silky feeling, and the occurrence of peeling and the like is sufficiently suppressed so that the glossy resin film has excellent adhesion. It is an object of the present invention to provide a glittering paint composition capable of forming a film, and a glittering resin film and a laminated coating film having good silky feeling and excellent adhesion obtained by using the composition.

  As a result of intensive studies to achieve the above object, the present inventors have determined that an amino group-containing acrylic resin having a specific range of amine values as a matrix resin when a resin film containing titanic acid flakes is used. By using it, it was found that the obtained resin film had excellent silkiness and excellent adhesion, and the present invention was completed.

That is, the glittering paint composition of the present invention is obtained by subjecting an amino group-containing acrylic resin having an amine value of 0.05 to 0.3 mmol / g-solid and base treatment after acid treatment to the layered titanate. And a titanic acid flake having an average thickness of 0.5 to 300 nm .

In addition, the glittering resin film of the present invention is obtained by subjecting an amino group-containing acrylic resin having an amine value of 0.05 to 0.3 mmol / g-solid and base treatment after acid treatment to the layered titanate. A single layer is peeled off and has an average thickness of 0.5 to 300 nm and contains titanic acid flakes dispersed in the resin.

  Furthermore, the laminated coating film of the present invention is a laminated coating film comprising at least a base layer and a clear layer laminated on an object to be coated, wherein the glitter of the present invention is provided between the base layer and the clear layer. It is characterized in that a conductive resin film is disposed.

The titanic acid flakes used in the present invention are preferably those having an average thickness of 0.5 to 100 nm and an average major axis of 5 to 50 μm.

  Moreover, in this invention, it is preferable that the compounding quantity of the said titanic acid flake is 7-20 mass parts with respect to 100 mass parts of solid content of the said amino group containing acrylic resin.

  The reason why a glittering resin film having both excellent design and high adhesiveness can be obtained by the present invention is not necessarily clear, but the present inventors speculate as follows. That is, first, the titanic acid flakes used as the glitter pigment in the present invention have a higher refractive index than the acrylic resin used together. Therefore, since the resulting glittering resin film contains two components having different refractive indexes, the so-called good silky sensation, which is a silky and deep and dense sparkle, is obtained. In addition, since the amino group contained in the acrylic resin used in the present invention has a higher affinity with titania than other polar groups, the interlayer of the titanic acid flakes is intercalated with the amino group-containing acrylic resin. The present inventors presume that this is reinforced, thereby increasing the adhesion. Furthermore, according to the knowledge of the present inventors, if the amine value of the acrylic resin used is too high, aggregation of titanic acid flakes occurs and the silky feeling decreases, but in the present invention, an amino acid having a specific range of amine values. Since the group-containing acrylic resin is used, the occurrence of aggregation of titanic acid flakes is sufficiently prevented, and since the titanic acid flakes are uniformly dispersed in the acrylic resin as a matrix, a good silky feeling is maintained, resulting in excellent The present inventors speculate that a glittering resin film having both excellent design and high adhesiveness can be obtained.

  According to the present invention, a glittering paint composition capable of forming a glittering resin film having high glitter and exhibiting a good silky feeling and sufficiently suppressing occurrence of peeling and having excellent adhesion, and It is possible to provide a glittering resin film and a laminated coating film having a good silky feeling and excellent adhesion obtained using the same.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the glittering paint composition of the present invention will be described. The glitter coating composition of the present invention comprises an amino group-containing acrylic resin having an amine value of 0.05 to 0.3 mmol / g-solid, and titanic acid flakes as a glitter pigment. Is.

  The titanate flakes used in the present invention are flaky titanium oxides, and so-called titania nanosheets are preferably used. Such a titanic acid flake is preferably one having an average thickness of 0.5 to 300 nm, more preferably 0.5 to 100 nm. Those having an average thickness of less than the lower limit generally tend to be difficult to produce. On the other hand, particles having an average thickness exceeding the upper limit tend to have a noticeable particle feeling and impair the silky feeling. .

  Moreover, as a titanic acid flake used by this invention, a thing with an average major axis of 5-50 micrometers is preferable, and a thing with 15-50 micrometers is more preferable. When the average major axis is less than the lower limit, sufficient silky feeling tends to be difficult to obtain, and when the average major axis exceeds the upper limit, it generally tends to be difficult to produce. Here, the average major axis means the average grain size in the plane direction perpendicular to the thickness direction of the titanate flakes. Further, such an average major axis and the aforementioned average thickness can be measured by observation with a scanning electron microscope (SEM) or the like.

  Furthermore, the average aspect ratio (ratio of the average major axis to the average thickness) of the titanate flakes used in the present invention is preferably 1000 to 10,000. If the average aspect ratio is less than the lower limit, a sufficient silky feeling tends to be difficult to obtain. On the other hand, if it exceeds the upper limit, it tends to be difficult to uniformly disperse the titanate flakes in the resin film.

  The titanate flakes used in the present invention can be obtained by a conventionally known method, for example, the method described in Patent Documents 1 to 6 described above, and is obtained by first subjecting a layered titanate to acid treatment as described below. By subjecting the layered titanic acid to a base treatment and peeling off a single layer, the titanic acid flakes used in the present invention can be suitably obtained.

As the layered titanate used here, a layered titanate of a lipidocrosite type (for example, Cs _x Ti _{2-x / 4} O ₄ (where 0.5 ≦ x ≦ 1), A _x Ti _{2-x / 3} Li _{x / 3} O ₄ (where A = K, Rb, Cs; 0.5 ≦ x ≦ 1) and the like. Specific examples of the lipidocrosite-type layered titanate include K _0.8 Ti _1.73 Li _0.27 O ₄ , Rb _0.75 Ti _1.75 Li _0.25 O ₄ , Cs _{0.7 Examples} thereof include Ti _1.77 Li _0.23 O ₄ and Cs _0.7 Ti _1.825 O ₄ .

The lipidocrocite-type layered titanate includes, for example, K ₂ CO ₃ , Rb ₂ CO ₃ , or Cs ₂ CO ₃ , anatase-type TiO _2, and other metals such as Li ₂ CO ₃ as necessary. It can be prepared by mixing carbonate with a predetermined molar ratio and calcining the mixture at a high temperature of 600 to 1200 ° C. for 6 to 24 hours in the air.

  When the aspect ratio of the obtained titanate flakes is to be increased, when preparing the layered titanate, a large layered titanate is prepared using a molten salt such as KCl, which will be described later. A method of sequentially performing acid treatment and base treatment is effective.

  The thus prepared lipidocrosite-type layered titanate is composed of a host layer, a metal ion layer, and an octahedron in which six oxygen atoms are coordinated to titanium and linked in a two-dimensional direction. Have a crystal structure in which are alternately stacked. The host layer is negatively charged as a whole layer because part of the titanium site is vacant. The negative charge is compensated by the metal ion layer, so that the entire lipidocrocite-type layered titanate is electrically neutral.

First, the layered titanate is mixed with an acid and stirred. Since the metal ion layer exhibits high ion exchange properties, metal ions other than Ti are exchanged at high levels, preferably all with hydrogen ions, while maintaining the layered structure by this acid treatment, and hydrogen-type layered titanic acid ( For _{example, H x Ti 2-x /} 4 O 4 · nH 2 O ( provided _{that, 0.5 ≦ x ≦ 1),} H x + x / 3 Ti 2-x / 3 O 4 · nH 2 O ( where 0.5 ≦ x ≦ 1)) is formed. Thereafter, the obtained hydrogen-type layered titanic acid is washed. In order to exchange metal ions other than Ti with hydrogen ions at a higher level, it is preferable to repeat the acid treatment and the washing treatment a plurality of times.

  The treatment time with the acid is preferably about 1 to 5 days. Even if the treatment time with the acid is shorter than the above lower limit or longer than the above upper limit, even if the base treatment described later is applied, the layered titanic acid tends to be hardly peeled to a single layer.

  Examples of the acid include strong acids such as hydrochloric acid, nitric acid, and sulfuric acid. The acid concentration is preferably 0.1 to 10N. The layered titanate is preferably mixed in an amount of 1 to 50 g per 1 L of the acid having the above concentration. The acid treatment temperature is preferably 0 to 50 ° C. By setting these conditions within the above range, the metal ions tend to be exchanged with hydrogen ions at a higher level in the acid treatment time.

  Next, the hydrogen-type layered titanic acid is mixed with a basic substance and stirred. The hydrogen-type layered titanic acid is a kind of solid acid, and when mixed with a basic substance, the basic substance is taken in between the layers as a guest. At this time, when the mixture is vigorously stirred, the layered titanic acid is separated into a single layer (nanosheet), and a dispersion containing a single layer of titanic acid flakes is obtained.

  The base treatment time is preferably about 1 to 5 days. When the time of the base treatment is shorter than the above lower limit, the layered titanic acid tends to be hardly peeled up to a single layer. On the other hand, if it is longer than the above upper limit, the titanate flakes are destroyed and the aspect ratio tends to be small.

  Examples of the basic substance include tetrabutylammonium hydroxide (TBAOH), tetrabutylammonium chloride (TBAC), tetraoctylammonium chloride (TOAC), tetradodecylammonium chloride (TDAC), and tetrastearylammonium chloride (TSAC). Examples include tetraalkylammonium salts. The basic substance is usually used after being dissolved in a solvent such as water. The concentration of the basic substance in this solution is preferably 0.1 to 3 mol / L. The hydrogen-type layered titanic acid needs to be mixed so that the molar ratio of the basic substance (layered titanic acid / basic substance) is 1/5 to 2/1. It is particularly preferred to mix so that the ratio is about 2/1. The temperature for the base treatment is preferably 0 to 50 ° C. By setting these conditions within the above range, it tends to be able to form a nanosheet at a higher level in the base treatment time.

  Next, the acrylic resin used in the present invention will be described. That is, in the present invention, it is necessary to use an amino group-containing acrylic resin having an amine value of 0.05 to 0.3 mmol / g-solid as the matrix resin when the resin film containing titanic acid flakes is used. It is more preferable to use an amino group-containing acrylic resin having an amine value of 0.1 to 0.3 mmol / g-solid. If the amine value is less than the lower limit, sufficient adhesion cannot be obtained and the silky feeling is also lowered. On the other hand, if the amine value exceeds the upper limit, the titanate flakes aggregate and the resin film It cannot be uniformly dispersed therein, and the silky feeling is lowered.

The amine value referred to here is the number of mmoles of amino group-containing monomer equivalent to hydrochloric acid required to neutralize 1 g of resin solids, and can be determined as follows. That is, the amine value is measured by adding tetrahydrofuran to a sample and dissolving it, and then titrating with a 0.1 mol / L hydrochloric acid solution to the equivalent point by potentiometric titration. The equivalence point is the maximum inflection point on the titration curve. Then, the amine value is determined from the titration amount of the hydrochloric acid solution based on the following calculation formula.
Amine value (mmol / g-solid) = hydrochloric acid titration (mL) / resin solid content (g) x 0.1.

  The amino group-containing acrylic resin used in the present invention is not particularly limited as long as its amine value is within the above range, and the number average molecular weight is preferably about 6000 to 30000.

  The production method of the amino group-containing acrylic resin used in the present invention is not particularly limited, and can be obtained by copolymerizing an acrylic monomer having an amino group and another unsaturated monomer by a known polymerization method. At that time, the blending amount of the acrylic monomer having an amino group to be copolymerized is adjusted so that the amine value of the resulting amino group-containing acrylic resin is within the above range.

  Examples of the acrylic monomer having an amino group include dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminomethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, and other dialkylaminoalkyl methacrylates; dimethylaminomethyl acrylate, Dialkylaminoalkyl acrylates such as dimethylaminoethyl acrylate, diethylaminomethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate; dimethylaminomethyl methacrylamide, dimethylaminoethyl methacrylamide, dimethylaminopropyl Dialkylaminoalkyl methacrylamides such as chloramide, diethylaminomethyl methacrylamide, diethylaminoethyl methacrylamide, diethylaminopropyl methacrylamide; dimethylaminomethylacrylamide, dimethylaminoethylacrylamide, dimethylaminopropylacrylamide, diethylaminomethylacrylamide, diethylaminoethylacrylamide, diethylaminopropylacrylamide And dialkylaminoalkylacrylamide. These can be used alone or in combination of two or more.

  Examples of the other unsaturated monomer copolymerized with the acrylic monomer having an amino group include, for example, acrylonitrile, styrene and styrene derivatives, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, hydroxyethyl acrylate, methacrylic acid, Examples thereof include vinyl monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and hydroxyethyl methacrylate. These can be used alone or in combination of two or more.

  Examples of the polymerization method for synthesizing the amino group-containing acrylic resin used in the present invention include known polymerization methods such as a solution polymerization method, an emulsion polymerization method and a bulk polymerization method. Among these, the solution polymerization method is simple and preferable. When the amino group-containing acrylic resin is produced by a solution polymerization method, a mixture of monomers is copolymerized in the presence of a solvent and a polymerization initiator. The polymerization may be performed at a temperature at which the monomer can be polymerized, but usually 80 to 140 ° C. is appropriate. As the solvent, any organic solvent that can dissolve the acrylic resin to be formed can be used without particular limitation. Examples of such organic solvents include hydrocarbon solvents such as toluene; ester solvents such as ethyl acetate, butyl acetate and ethylene glycol monoalkyl ether acetate; ether solvents such as dioxane and ethylene glycol monoalkyl ether; methyl ethyl ketone. Ketone solvents such as: various alcohol solvents.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile. Azo polymerization initiators such as benzoyl peroxide, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate And organic peroxide polymerization initiators such as tert-butylperoxyisopropyl monocarbonate and 2,2-bis (4,4-ditert-butylperoxycyclohexyl) propane.

  The glittering paint composition of the present invention contains the amino group-containing acrylic resin and the titanic acid flakes, and preferably further contains a solvent capable of dissolving the amino group-containing acrylic resin. Such a solvent is not particularly limited, and examples thereof include water and various organic solvents similar to the solvent used in the preparation of the alkyl resin described above. These solvents can be used alone or in admixture of two or more. The concentration (solid content concentration) of the amino group-containing acrylic resin in the glittering paint composition of the present invention is not particularly limited, and is usually preferably 3 to 20% by mass, and preferably 5 to 15% by mass. More preferred.

  The blending amount of the titanic acid flakes in the glittering paint composition of the present invention is preferably 7 to 20 parts by mass, and 10 to 20 parts by mass with respect to 100 parts by mass of the solid content of the amino group-containing acrylic resin. More preferably. When the blending amount of the titanic acid flakes is less than the lower limit, sufficient silky feeling tends to be difficult to obtain, and when it exceeds the upper limit, the adhesion tends to decrease.

  Further, in the glittering paint composition of the present invention, the above-mentioned blended so as to be 30 to 90% (more preferably 40 to 80%) of the amino group amount necessary for producing the titanic acid flakes to be used. It is preferable to adjust the amount of amino groups in the amino group-containing acrylic resin. If the amount of the amino group is less than the lower limit, sufficient adhesion cannot be obtained and the silky feeling tends to be reduced. On the other hand, if the amount exceeds the upper limit, the titanic acid flakes aggregate and uniformly in the resin film. It cannot be dispersed and the silky feeling tends to decrease. In addition, the amount of amino groups required to produce the titanic acid flakes to be used can be determined as follows. That is, the amino group amount (mol) necessary for producing the titanic acid flakes can be obtained by dividing the amount (mol) of titanic acid used by 2.

  The glittering paint composition of the present invention can be suitably obtained by dispersing the titanic acid flakes in the amino group-containing acrylic resin solution. Examples of the dispersing method include a ball mill, a disper mill, and a three roll. And the like. Further, in the glittering paint composition of the present invention, general paint additives such as a thickener, an ultraviolet absorber, an antioxidant, a leveling agent, a surface conditioner, an anti-sagging agent, an antifoaming agent and an activator An agent may be added.

  Next, the glitter resin film of the present invention will be described. That is, the glitter resin film of the present invention comprises the amino group-containing acrylic resin and the titanic acid flakes dispersed in the resin. The coating composition can be formed, for example, by coating on a substrate and drying (preheating) and baking (baking and curing) the coating film. The film thickness (film thickness after baking) of the glitter resin film is not particularly limited, but is preferably 5 to 100 μm, and more preferably 10 to 40 μm. If the film thickness is less than the above lower limit, the amount of titanate flakes is small and it tends to be difficult to obtain a silky feeling. On the other hand, when the film thickness exceeds the above upper limit, a coating film defect such as aside occurs, and the appearance tends to deteriorate.

  The method for applying the glitter coating composition is not particularly limited, and various conventionally known coating methods may be used, but a coating method that applies a shearing force such as spray coating or doctor blade coating is preferable. Accordingly, the titanic acid flakes can be more reliably oriented and dispersed in parallel to the film surface, and there is a tendency to obtain a glittering resin film having a more silky design.

  The blending amount of the titanic acid flakes in the glittering resin film of the present invention is preferably 7 to 20 parts by mass, and 10 to 20 parts by mass with respect to 100 parts by mass of the solid content of the amino group-containing acrylic resin. More preferably. When the blending amount of the titanic acid flakes is less than the lower limit, sufficient silky feeling tends to be difficult to obtain, and when it exceeds the upper limit, the adhesion tends to decrease.

  Next, the laminated coating film of the present invention will be described. That is, the multilayer coating film of the present invention is a multilayer coating film comprising at least a base layer and a clear layer laminated on an object to be coated, and the brightness of the present invention is between the base layer and the clear layer. It is characterized in that a conductive resin film is disposed. When the laminated coating film of the present invention is formed as a vehicle exterior, the glitter resin film of the present invention is laminated on at least an electrodeposition layer, an intermediate coating layer and a base layer on an object to be coated such as a steel plate. Furthermore, it is preferable that at least a clear layer is laminated thereon.

  Such an electrodeposition layer (electrodeposition coating film) is not particularly limited, and can be obtained, for example, by coating a surface of an object to be coated such as a steel plate with a cationic electrodeposition paint as an undercoat paint. Here, as the cationic electrodeposition coating, a known one is preferably obtained by blending an aqueous salt solution or aqueous dispersion of a cationic polymer compound with a crosslinking agent, a pigment or various additives as necessary. Can be used. Examples of the cationic polymer compound include those obtained by introducing a cationic group such as an amino group into an acrylic resin or epoxy resin having a crosslinkable functional group, which is neutralized with an organic acid or an inorganic acid. Can be water-soluble or water-dispersed. As a crosslinking agent for curing these polymer compounds, a block polyisocyanate compound, an alicyclic epoxy resin, or the like can be used. The thickness of the electrodeposition layer (thickness after baking) is not particularly limited, but is usually preferably about 10 to 40 μm.

  Further, the intermediate coating composition for forming the intermediate coating layer (intermediate coating film) is not particularly limited. For example, basically, a thermosetting resin composition composed of a base resin and a crosslinking agent is preferably used. Examples of such base resins include acrylic resins, polyester resins, alkyd resins having two or more crosslinkable functional groups such as hydroxyl group, epoxy group, isocyanate group, and carboxyl group in one molecule, and crosslinking. Examples of the agent include amino resins such as melamine resins and urea resins, polyisocyanate compounds that may be blocked, carboxyl group-containing compounds, and the like. The film thickness of the intermediate coating layer (film thickness after baking) is not particularly limited, but is usually preferably about 10 to 30 μm.

  Furthermore, the base paint for forming the base layer (base coating film) is not particularly limited, and for example, a known solvent-based colored base paint or aqueous colored base paint is preferably used. Examples of such an aqueous colored base paint include a pigment, a resin that can be dissolved or dispersed in water, a crosslinking agent as necessary, and water as a solvent. Examples of the resin that can be dissolved or dispersed in water include a resin containing a hydrophilic group such as a carboxyl group and a crosslinkable functional group such as a hydroxyl group in one molecule, specifically, an acrylic resin or a polyester resin. And polyurethane resin. Examples of the crosslinking agent include hydrophobic or hydrophilic alkyl ether melamine resins and blocked isocyanate compounds. On the other hand, examples of the solvent-based coloring base paint include those containing a pigment, a resin similar to the above, and a crosslinking agent and a solvent as necessary. The thickness of the base layer (the thickness after baking) is not particularly limited, but is usually preferably about 5 to 20 μm.

  Also, the clear paint that forms the clear layer (clear coating film) is not particularly limited, and includes, for example, a thermosetting resin and an organic solvent that can form a transparent coating film, and an ultraviolet absorber if necessary. What is being done is mentioned. Examples of the thermosetting resin include resins such as an acrylic resin, a polyester resin, an alkyd resin, a fluororesin, a urethane resin, and a silicon-containing resin having a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, and an epoxy group. Melamine resins, urea resins, (block) polyisocyanate compounds, epoxy resin compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilane group-containing compounds or resins, which can react with these crosslinkable functional groups What consists of a crosslinking agent is mentioned. The film thickness of the clear layer (film thickness after baking) is not particularly limited, but is usually preferably about 20 to 50 μm.

  In the laminated coating film of the present invention, the glitter resin film of the present invention is disposed between the base layer and the clear layer. The method for forming the glitter resin film is as described above. is there. In the present invention, the conditions for drying (preheating) and baking (baking and curing) the coating film are not particularly limited. For example, the drying process is performed at 60 to 90 ° C. for about 1 to 5 minutes. As conditions, 140 to 220 degreeC and about 10 to 40 minutes are employ | adopted suitably.

  The glittering resin film and laminated coating film of the present invention obtained by using the glittering paint composition of the present invention described above exhibit a so-called silky feeling that the titanic acid flakes dispersed in the film shine like silk. The silky feeling can be evaluated by flip-flop properties (FF properties) described in Examples described later. In addition, the glitter resin film and the laminated coating film of the present invention are excellent in adhesion because occurrence of peeling is sufficiently suppressed, and such adhesion is a cross-cut peel test described in the examples described later. It is possible to evaluate by.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, evaluation of silky feeling and adhesion was performed according to the following methods, respectively.

<Silky feeling evaluation test>
Using the multi-angle spectrocolorimeter (manufactured by X-Rite, portable multi-angle spectrocolorimeter MA68II) with respect to the obtained laminated coating film, the incident angle is 45 ° and the light receiving angle is 15 to 110 °. The brightness (L ^* value) was measured, and the difference between the maximum value and the minimum value was evaluated as a flip-flop value (FF value). A higher FF value indicates better silky feeling.

<Adhesion test>
The adhesion of the obtained laminated coating film was evaluated by a cross-cut peel test described in JIS D0202-19889. In addition, it was set as the crosscut (2 mm square, 100 squares), and the cello tape (trademark) CT-24 (Nichiban Co., Ltd. product, width 24mm) was used as a tape.

Example 1
<Manufacture of titanic acid flakes>
K ₂ CO ₃ (6.138 g), Li ₂ CO ₃ (1.094 g), anatase TiO ₂ (15.374 g), and KCl (20.002 g) as a flux were mixed thoroughly using a mortar for 10 minutes. . This mixture was kept in the atmosphere at 820 ° C. for 1 hour to melt KCl, and then baked at 1000 ° C. for 8 hours. Thereafter, the reaction product was gradually cooled to obtain a layered titanate. When this layered titanate was subjected to X-ray diffraction measurement using an X-ray diffractometer (RINT2100, manufactured by Rigaku Corporation), it was found to be K _0.8 Ti _1.73 Li _0.27 O _4. confirmed. Moreover, when the shape of this layered titanate was observed using a scanning electron microscope (S3600N, manufactured by Hitachi High-Technologies Corporation), it was confirmed that the particles had a mean particle size of 30 μm.

Next, 15 g of the layered titanate and 1 L of 0.5N hydrochloric acid were mixed and stirred with a stirrer at room temperature for 1 day. By this acid treatment, K ⁺ and Li ^{+ of} K _0.8 Ti _1.73 Li _0.27 O ₄ are replaced with H ₃ O ⁺ while maintaining the layered structure, and layered titanic acid (H _0.7 Ti _1.825 O ₄ · H ₂ O) was obtained. Thereafter, the layered titanic acid was washed with water and filtered.

Next, the layered titanic acid and a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 0.3 mol / L are molar ratio (H _0.7 Ti _1.825 O _{4 .H 2} O: TMAH) = 4: The mixture was mixed to 1 (titanic acid concentration: 15 wt%) and stirred with a stirrer at room temperature for 1 day to obtain an aqueous dispersion of titanic acid flakes.

  Next, this aqueous dispersion was filtered, and the obtained titanic acid flakes were washed with water. When the shape of the titanic acid flakes was observed using an atomic force microscope (D3100 + NanoScope IIIa manufactured by VEECO, tapping mode, using a super sharp tip), a single layer peeled titanic acid having an average thickness of 1 nm and an average major axis of 30 μm It was confirmed that it was a flake (titania nanosheet).

<Production of amino group-containing acrylic resin>
Acrylic resin reaction vessel equipped with a stirrer, thermometer, reflux condenser, etc. was charged with 157.7 g (1.33 mol) of ethylene glycol monobutyl ether, heated and stirred under N ₂ atmosphere, and reached 72 ° C. , 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid and 6.3 g (0.04 mol) of dimethylaminopropylacrylamide (DMAPAA), and 2,2′-azobis- A solution containing 3.99 g (0.016 mol) of 2,4-dimethylvaleronitrile and 15 g of ethylene glycol monobutyl ether was added dropwise over 90 minutes. After completion of the dropwise addition, the mixture was stirred at 72 ° C. for 30 minutes, then 1 g of 2,2′-azobis-2,4-dimethylvaleronitrile ethylene glycol monobutyl ether solution (1 wt%) was added dropwise, and stirring was continued at 72 ° C. for 2 hours. And then cooled. The polymerization rate was 100% within the error range. The resulting reaction solution is diluted by adding water so that the solid content (nonvolatile content) concentration is 15 wt%, and further neutralized with 13 g (0.15 mol) of dimethylethanolamine to obtain an amino group-containing acrylic resin solution. Got.

  Then, the amine value of the synthesized resin was measured as follows. That is, the solvent was removed by heating at 105 ° C. for 3 hours, and 5 g of the dried resin was placed in a 100 mL beaker and dissolved in 50 mL of tetrahydrofuran. Subsequently, it titrated with 0.1 mol / L hydrochloric acid solution using the potentiometric automatic titrator, and the amine titer was calculated | required from hydrochloric acid titer 15mL of an equivalence point. The resulting amino group-containing acrylic resin had an amine value of 0.3 mmol / g-solid and a number average molecular weight (Mn) of 24,000.

<Preparation of glitter paint composition>
1 g of 15 wt% aqueous dispersion of titanic acid flakes and 10 g of amino group-containing acrylic resin solution are mixed so that the blending amount of titanic acid flakes is 10 parts by mass with respect to 100 parts by mass of the solid content of the amino group-containing acrylic resin. And stirring with a stirrer at 25 ° C. for 1 day, and then isocyanate (made by DIC) so that the blending ratio (acrylic resin / isocyanate, mass ratio) of acrylic resin (solid content) and isocyanate (solid content) is 80/20. , Trade name: DNW5000) 0.4 g was mixed to obtain a glittering paint composition. In the resulting glittering paint composition, the amount of amino groups in the amino group-containing acrylic resin corresponds to 80% of the amount of amino groups necessary for preparing the blended titanic acid flakes.

<Preparation of laminated coating film>
Cationic electrodeposition paint (trade name: Electron GT-10, manufactured by Kansai Paint Co., Ltd.) is electrodeposited onto the galvanized steel sheet that has been subjected to the zinc phosphate chemical conversion treatment so that the cured film thickness is 15 μm. Heat-cured for a minute, and then air-coated with an automotive intermediate coating (trade name: Amirac TP-65, manufactured by Kansai Paint Co., Ltd.) to a cured film thickness of 35 μm, and heat-cured at 140 ° C. for 30 minutes. It was. A colored base paint (trade name: TP-58 (white), manufactured by Kansai Paint Co., Ltd.) was laminated thereon so as to have a cured film thickness of 30 μm to prepare a white coated plate. The glitter coating composition was applied to this white coated plate by a doctor blade method so that the cured film thickness was 15 μm, and heated at 80 ° C. for 3 minutes. Then, an isocyanate curable two-component clear coating (trade name: R-298 Clear, manufactured by Nippon Bee Chemical Co., Ltd.) is laminated on the uncured coating surface by a doctor blade method so that the cured film thickness becomes 35 μm. A laminated coating film was prepared by baking at 30 ° C. for 30 minutes.

  Subsequently, the design property of the obtained laminated coating film was evaluated by the silky feeling evaluation test, and the adhesion property was evaluated by the adhesion test. The obtained results are shown in Table 1.

(Example 2)
Implemented except that 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid, and 4.7 g (0.03 mol) of dimethylaminopropylacrylamide (DMAPAA) were used as monomers. In the same manner as in Example 1, an amino group-containing acrylic resin solution was obtained. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The obtained amino group-containing acrylic resin had an amine value of 0.2 mmol / g-solid and a number average molecular weight (Mn) of 28,000.

  Next, a glittering coating composition was prepared in the same manner as in Example 1 except that this amino group-containing acrylic resin solution was used, and a laminated coating film was formed in the same manner as in Example 1 using this. Obtained. In the resulting glittering coating composition, the amount of amino groups in the amino group-containing acrylic resin corresponds to 60% of the amount of amino groups necessary for preparing the blended titanic acid flakes. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Example 3)
The layered titanic acid and an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.6 mol / L are in a molar ratio (H _0.7 Ti _1.825 O _{4 .H 2} O: TMAH) = 2: 1. Thus, an aqueous dispersion of titanic acid flakes was obtained in the same manner as in Example 1 except that mixing was performed (the titanic acid concentration was 15 wt%). The titanic acid flakes were titanic acid flakes (titania nanosheets) having an average thickness of 1 nm and an average major axis of 30 μm.

  Other than using 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid, and 3.1 g (0.02 mol) of dimethylaminopropylacrylamide (DMAPAA) as monomers. Obtained an amino group-containing acrylic resin solution in the same manner as in Example 1. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The resulting amino group-containing acrylic resin had an amine value of 0.1 mmol / g-solid and a number average molecular weight (Mn) of 15000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that an aqueous dispersion of these titanic acid flakes and an amino group-containing acrylic resin solution were used. 1 was used to obtain a laminated coating film. In the obtained glittering paint composition, the amount of amino groups in the amino group-containing acrylic resin corresponds to 40% of the amount of amino groups necessary for preparing the blended titanic acid flakes. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Comparative Example 1)
An acrylic resin solution was obtained in the same manner as in Example 1 except that only 144.7 g (1.45 mol) of ethyl acrylate and 10.4 g (0.145 mol) of acrylic acid were used as monomers. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The obtained acrylic resin had an amine value of 0 mmol / g-solid and a number average molecular weight (Mn) of 18000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that this acrylic resin solution and the aqueous dispersion of titanic acid flakes obtained in Example 3 were used. A laminated coating film was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Comparative Example 2)
Implemented except that 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid, and 0.6 g (0.004 mol) of dimethylaminopropylacrylamide (DMAPAA) were used as monomers. In the same manner as in Example 1, an amino group-containing acrylic resin solution was obtained. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The obtained amino group-containing acrylic resin had an amine value of 0.03 mmol / g-solid and a number average molecular weight (Mn) of 18000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that this amino group-containing acrylic resin solution and the aqueous dispersion of titanic acid flakes obtained in Example 3 were used. Using this, a laminated coating film was obtained in the same manner as in Example 1. In the resulting glittering coating composition, the amount of amino groups in the amino group-containing acrylic resin corresponds to 8% of the amount of amino groups necessary for preparing the blended titanic acid flakes. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Comparative Example 3)
Implemented except that 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid, and 9.4 g (0.06 mol) of dimethylaminopropylacrylamide (DMAPAA) were used as monomers. In the same manner as in Example 1, an amino group-containing acrylic resin solution was obtained. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The resulting amino group-containing acrylic resin had an amine value of 0.4 mmol / g-solid and a number average molecular weight (Mn) of 18000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that this amino group-containing acrylic resin solution and the aqueous dispersion of titanic acid flakes obtained in Example 3 were used. Using this, a laminated coating film was obtained in the same manner as in Example 1. In the resulting glittering paint composition, the amount of amino groups in the amino group-containing acrylic resin corresponds to 100% of the amount of amino groups necessary for preparing the blended titanic acid flakes. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Comparative Example 4)
A carboxyl group-containing acrylic resin solution was obtained in the same manner as in Example 1 except that 144.7 g (1.45 mol) of ethyl acrylate and 11.8 g (0.165 mol) of acrylic acid were used as monomers. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The obtained carboxyl group-containing acrylic resin had an amine value of 0 mmol / g-solid and a number average molecular weight (Mn) of 16000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that this carboxyl group-containing acrylic resin solution and the aqueous dispersion of titanic acid flakes obtained in Example 3 were used. Using this, a laminated coating film was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Comparative Example 5)
As Example 1, except that 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid, and 2.2 g (0.02 mol) of hydroxyethyl acrylate were used as monomers. Thus, a solution of a hydroxyl group-containing acrylic resin was obtained. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The obtained hydroxyl group-containing acrylic resin had an amine value of 0 mmol / g-solid and a number average molecular weight (Mn) of 17,000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that this hydroxyl group-containing acrylic resin solution and the aqueous dispersion of titanic acid flakes obtained in Example 3 were used. Using this, a laminated coating film was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

(Comparative Example 6)
As Example 1, except that 144.7 g (1.45 mol) of ethyl acrylate, 10.4 g (0.145 mol) of acrylic acid, and 2.0 g (0.02 mol) of styrene were used as monomers. A solution of styryl group-containing acrylic resin was obtained. The polymerization rate was 100% within the error range. Further, the amine value was measured in the same manner as in Example 1. The obtained styryl group-containing acrylic resin had an amine value of 0 mmol / g-solid and a number average molecular weight (Mn) of 16000.

  Next, a glittering paint composition was prepared in the same manner as in Example 1 except that this styryl group-containing acrylic resin solution and the aqueous dispersion of titanic acid flakes obtained in Example 3 were used. Using this, a laminated coating film was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating the designability and adhesion of the obtained multilayer coating film.

  As is apparent from the results shown in Table 1, a laminated coating film obtained using the glittering paint composition of the present invention containing an amino group-containing acrylic resin having an amine value in a predetermined range and titanic acid flakes. (Examples 1 to 3) had high glitter and a good silky feeling, and the occurrence of peeling and the like was sufficiently suppressed and the adhesiveness was excellent.

  On the other hand, when an acrylic resin having an amine value of zero is used (Comparative Example 1) or when an amino group-containing acrylic resin having an amine value lower than the predetermined range is used (Comparative Example 2), silky feeling and adhesion All of the properties were inferior. Further, when an amino group-containing acrylic resin having an amine value higher than the predetermined range was used (Comparative Example 3), the titanic acid flakes aggregated and the silky feeling was extremely inferior.

  Furthermore, when the acrylic resin (amine value is zero) containing functional groups other than amino groups (Comparative Examples 4 to 6), both silky feeling and adhesion were inferior.

  As described above, according to the glittering paint composition of the present invention, the glittering property of the present invention is excellent in adhesiveness because it exhibits high glitter and exhibits a good silky feeling, and the occurrence of peeling and the like is sufficiently suppressed. It becomes possible to obtain the resin film and the laminated coating film of the present invention provided with the resin film. Therefore, the glittering paint composition of the present invention is capable of forming a glittering resin film and a laminated coating film having a deep, calm and dense shine like silk and having excellent adhesion. It is very useful as a paint for homes.

Claims (7)

An amino group-containing acrylic resin having an amine value of 0.05 to 0.3 mmol / g-solid, and a layered titanate subjected to acid treatment and then subjected to base treatment to peel off a single layer and have an average thickness A glittering paint composition comprising a titanic acid flake having a thickness of 0.5 to 300 nm . 2. The glittering paint composition according to claim 1, wherein the titanic acid flakes have an average thickness of 0.5 to 100 nm and an average major axis of 5 to 50 μm.   3. The glittering paint composition according to claim 1, wherein the blended amount of the titanic acid flakes is 7 to 20 parts by mass with respect to 100 parts by mass of the solid content of the amino group-containing acrylic resin. An amino group-containing acrylic resin having an amine value of 0.05 to 0.3 mmol / g-solid, and a layered titanate subjected to acid treatment and then subjected to base treatment to peel off a single layer and have an average thickness A glittering resin film having a thickness of 0.5 to 300 nm and containing titanic acid flakes dispersed in the resin. The glittering resin film according to claim 4, wherein an average thickness of the titanic acid flakes is 0.5 to 100 nm and an average major axis is 5 to 50 μm.   The glittering resin film according to claim 4 or 5, wherein a blending amount of the titanic acid flakes is 7 to 20 parts by mass with respect to 100 parts by mass of the solid content of the amino group-containing acrylic resin.   It is a laminated coating film provided with the base layer and clear layer which were laminated | stacked on the to-be-coated article, Comprising: Between the said base layer and the said clear layer, It is any one of Claims 4-6 A laminated coating film comprising a glittering resin film.