JPH09263717A - Water-base coating material containing near-infrared absorber dispersed therein and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base coating material contg. a near-infrared absorber dispersed therein and having a high durability by pulverizing a specific naphthalocyanine compd. to a specified average particle size and dispersing the resultant powder in a water-base coating material. SOLUTION: At least one naphthalocyanine compd. represented by formula I (wherein A<1> to A<24> are each H or a halogen; and M is two hydrogen atoms, a divalent metal atom, a substd. tri- or tetravalent metal atom, or an oxymetal) is pulverized to an average particle size of 1μm or lower, pref. 0.5μm or lower, still pref. 0.2μm or lower and then used. M in formula I is e.g. two hydrogen atoms, Cu, Pd, Pb, AlCl, InCl, TiO, or VO. Though varied depending on the attempted near-infrared absorbance, the thickness of a coating film, etc., the amt. of the compd. dispersed is usually 0.001-20% based on the nonvolatile content of the coating material. Examples of the water-base coating material are water-base acrylic resin, water-base urethane resin, and water-base polyester resin coating materials, though there is no specific limitation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a near-infrared absorbing agent-dispersed aqueous coating material, a near-infrared absorbing filter and a heat ray absorbing window glass obtained by using the same. By coating the near-infrared absorbing agent-dispersed aqueous coating material on plastic or glass, a near-infrared absorbing filter can be easily produced. Further, since it is water-based without using an organic solvent, it is excellent in safety and environmental hygiene. In particular, heat-absorbing glass can be easily produced by applying it to window glass, and by using it for windows of buildings, cars, trains, ships, aircraft, etc., heat rays from the outside can be blocked and the temperature inside and inside the vehicle can be reduced. The rise can be suppressed. Therefore, there is also an energy saving effect by reducing the cooling cost in the summer.

[0002]

2. Description of the Related Art As a paint that absorbs near-infrared rays, an organic solvent type in which a near-infrared absorbing dye is dissolved is known. However, since an organic solvent is used, it is safe and environmentally friendly. Due to problems, water-based paints are desired. Conventionally, it is known that finely divided phthalocyanine pigments such as phthalocyanine green and phthalocyanine blue are dispersed in a water-based paint, but they have large absorption in the visible region and lack transparency when used as a window material. . Further, JP-A-61-151193 introduces a naphthalocyanine pigment, but there is no description that it is used for a water-soluble paint.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a near-infrared absorber-dispersed water-based paint which has high durability at low cost and easily. Further, it is to provide a near-infrared absorbing filter using the same and a heat ray absorbing window glass in which the filter is applied to the window glass.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the naphthalocyanine pigment is atomized and dispersed in an aqueous paint to easily and easily obtain the desired near infrared rays. They have found that an absorbent-dispersed water-based paint can be produced, and completed the present invention. That is, the present invention provides a near-infrared absorber obtained by pulverizing at least one kind of naphthalocyanine compound represented by the following general formula (1) (Chemical Formula 2) into an average particle size of 1 micron or less and dispersing it in an aqueous paint. Dispersed water-based paint The present invention also relates to a near-infrared absorbing filter obtained by using the near-infrared absorber-dispersed aqueous coating material and a heat ray absorbing window glass obtained by applying the near-infrared absorber-dispersed aqueous coating material to a window glass.

[0005]

Embedded image [In the formula, A ^{1 to} A ²⁴ each independently represent a hydrogen atom or a halogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal. Represents]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The near-infrared absorber-dispersed water-based coating composition of the present invention is prepared by pulverizing at least one naphthalocyanine compound represented by the general formula (1) to an average particle size of 1 micron or less. It is obtained by dispersing it in In the naphthalocyanine compound represented by the general formula (1), A ^{1 to} A
Examples of the halogen atom represented by ²⁴ are fluorine, chlorine, bromine, and iodine, which may be mixed.

Examples of the divalent metal atom represented by M include Cu (II), Zn (II), Fe (II) and Co (I
I), Ni (II), Ru (II), Rh (II), Pd (I
I), Pt (II), Mn (II), Mg (II), Ti (I
I), Be (II), Ca (II), Ba (II), Cd (I
I), Hg (II), Pb (II), Sn (II) and the like. Examples of mono-substituted trivalent metal atoms include AlC
l, AlBr, AlF, AlI, GaCl, GaF, G
aI, GaBr, InCl, InBr, InI, In
F, TlCl, TlBr, TlI, TlF, FeCl,
_{RuCl, Al-C 6 H 5} , Al-C 6 H 4 (C
_{H 3), In-C 6} H 5, In-C 6 H 4 (CH 3),
_{In-C 6 H 5, Mn} (OH), Mn (OC 6 H 5),
Mn [OSi (CH _{3) 3],} and the like.

An example of a disubstituted tetravalent metal atom is Cr.
Cl ₂ , SiCl ₂ , SiBr ₂ , SiF ₂ , Si
I ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , Ge
I ₂ , GeF ₂ , SnCl ₂ , SnBr ₂ , SnF ₂ ,
TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ ,
Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , S
n (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR
₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof], Si (OR ′) ₂ , S
n (OR ') ₂ , Ge (OR') ₂ , Ti (O
R ′) ₂ , Cr (OR ′) ₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof], Sn
(SR ") ₂ , Ge (SR") ₂ (R "is an alkyl group,
A phenyl group, a naphthyl group, and derivatives thereof] and the like. Examples of oxymetal include VO and Mn
O, TiO, etc. are mentioned. More preferable M is two hydrogen atoms, Cu, Pd, Pb, AlCl, and I.
nCl, TiO or VO, with VO being particularly preferred. The near-infrared absorber-dispersed water-based coating composition of the present invention is obtained by atomizing the naphthalocyanine compound into particles having an average particle size of 1 micron or less, more preferably 0.5 micron or less, and even more preferably 0.2 micron or less. Therefore, it can be easily manufactured. The smaller the particle size, the better the dispersibility and the more excellent the transparency after coating. The method of atomizing the naphthalocyanine compound is not particularly limited, and either dry method or wet method may be used, and methods such as a sand mill method, a ball mill method, and a spike mill method are used. When mixing, existing additives such as an ultraviolet absorber, a light stabilizer and an antioxidant may be added, if necessary.

The amount of the naphthalocyanine compound added varies depending on the desired near infrared absorption amount, the film thickness when the paint is applied, and the like, but is usually 0.001-2 with respect to the nonvolatile content of the paint.
0%. As the water-based paint used in the present application, water-based acrylic resin paints, water-based urethane resin paints, water-based polyesters described in "Latest water-based coating technology (CMC)", "Technical trends of water-based coatings (Nippon Paint Shimbun)", etc. Examples thereof include resin paints, but are not particularly limited.

The near-infrared absorbing filter of the present invention comprises a near-infrared absorbing agent-dispersed aqueous coating material obtained by the above method, which is applied on a transparent resin film, transparent resin, transparent glass or the like, as a bar coder, a blade coater or a spin coater. It is manufactured by coating with a reverse coater, a die coater, or a spray. The near-infrared absorbing filter thus obtained can also be used as a heat ray absorbing coating material for agriculture. The heat ray absorbing window glass of the present invention is produced by coating the window glass with the above-mentioned near-infrared ray absorbing agent-dispersed aqueous paint.

[0011]

EXAMPLES The present invention will be described in more detail with reference to examples. In addition, a part represents a weight part here. Example 1 A naphthalocyanine dye represented by the formula (2)
It was atomized to an average particle size of 0.2 μm or less and dispersed in water at 30% by weight. The dispersion aqueous solution (10 parts) and a water-based urethane paint (P960) (50 parts) manufactured by Mitsui Toatsu Chemicals, Inc. were mixed to prepare a near-infrared absorber-dispersed water-based paint. This coating material was applied onto a float glass having a thickness of 3 mm with a roll coater and dried to prepare a heat ray absorbing glass. According to JIS-R-3106, when the visible light transmittance (Tv) and the solar radiation transmittance (Te) of the glass were measured with a spectrophotometer (UV-3100) manufactured by Shimadzu Corporation, Tv = 71.4%, Te = 59.6%, which well absorbed heat rays.

[0012]

Embedded image In addition, when Tv and Te of the float glass having a thickness of 3 mm and not coated with the coating material were measured, Tv = 89.4.
%, Te = 85.3%.

Example 2 The naphthalocyanine dye represented by the formula (3) (formula 4) was atomized to an average particle size of 0.2 μm or less and dispersed in water at 30% by weight. The dispersed aqueous solution (10 parts) and a water-based urethane paint (UD-736) (50) manufactured by Mitsui Toatsu Chemicals, Inc.
Part) was mixed to prepare a near-infrared absorber-dispersed water-based paint. This coating material was applied onto a float glass having a thickness of 3 mm with a roll coater and dried to prepare a heat ray absorbing glass. When Tv and Te were measured in the same manner as in Example 1, Tv = 72.6% and Te = 59.2%, and the heat ray was well absorbed.

[0014]

Embedded image

Example 3 The naphthalocyanine dye represented by the formula (4) (formula 5) was atomized to an average particle size of 0.2 μm or less and dispersed in water at 30% by weight. The dispersion aqueous solution (10 parts) and a water-based acrylic paint (SKK-2013) (5) manufactured by Mitsui Toatsu Chemicals, Inc.
0 part) was mixed to prepare a near-infrared absorber-dispersed water-based paint. Apply this paint on a float glass with a thickness of 3 mm.
It was applied with a roll coater and dried to produce a heat ray absorbing glass. When Tv and Te were measured in the same manner as in Example 1, Tv = 67.4% and Te = 53.5%, and the heat ray was well absorbed.

[0016]

Embedded image The heat ray absorbing glass was subjected to a light resistance test with a carbon arc lamp (63 ° C.) for 1000 hours, but no decrease in absorption rate due to deterioration of the dye was observed.

Examples 4 to 10 Heat ray absorbing glass was prepared in the same manner as in Example 1 except that the kind of naphthalocyanine was changed, and Tv and Te were measured. The results are shown in Table-1 (Table 1 and Table 2). A decrease in Te was observed in all of the glasses, confirming the heat ray shielding effect.

[0018]

[Table 1]

[0019]

[Table 2]

Comparative Example 1 A glass was produced in exactly the same manner as in Example 1 except that phthalocyanine green was used instead of naphthalocyanine. When Tv and Te were measured in the same manner as in Example 1, Tv = 69.6% and Te = 70.5%, the heat ray cut rate was small, and the visible ray transmittance was also low. It was insufficient for glass.

[0021]

INDUSTRIAL APPLICABILITY The present invention provides a near-infrared absorbing / dispersing aqueous coating material having high durability in a simple manner, and the obtained near-infrared absorbing / dispersing aqueous coating material can be applied to a heat ray absorbing window glass or the like. It is possible and extremely valuable in practical use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09B 47/00 C09B 47/00 C09K 3/00 105 C09K 3/00 105 (72) Inventor Matsu ▲ Saki ▼ ▲ Yorai ▼ Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Shuhei Imon 2-1, Tango-dori, Minami-ku, Aichi Prefecture Nagoya Mitsui Toatsu Chemical Co., Ltd. (72 ) Inventor Masataka Iwata 2-1, Tango-dori, Minami-ku, Aichi Prefecture, Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Keisuke Soma, 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. A near-infrared absorber dispersion in which at least one naphthalocyanine compound represented by the following general formula (1) (Chemical formula 1) is pulverized to an average particle size of 1 micron or less and dispersed in an aqueous paint. Water-based paint. Embedded image [In the formula, A ^{1 to} A ²⁴ each independently represent a hydrogen atom or a halogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal. Represents] 2. M is two hydrogen atoms, Cu, Pd, P
The near-infrared absorber-dispersed aqueous coating material according to claim 1, which is b, AlCl, InCl, TiO or VO. 3. The near-infrared absorber-dispersed water-based paint according to claim 2, wherein M is VO. 4. A near-infrared absorption filter obtained by using the near-infrared absorber-dispersed aqueous coating material according to claim 1. 5. A heat-ray-absorbing window glass obtained by applying the near-infrared absorber-dispersed water-based coating composition according to claim 1 to the window glass.