JP2008111048A - Near-infrared-shielding coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared-shielding coating composition exhibiting transparency and hard coating properties. <P>SOLUTION: The near-infrared-shielding coating composition exhibiting transparency and hard coating properties comprises a polymer substance comprising a reaction product obtained by causing (a) an amino group-containing silane compound represented by the following formula: R<SB>4-n</SB>-Si-(OR')<SB>n</SB>(wherein R is an amino group-containing organic group; R' is a methyl group, an ethyl group or a propyl group; and n is an integer selected from among 1-3) to react with (b) at least one boron compound selected from the group consisting of H<SB>3</SB>BO<SB>3</SB>and B<SB>2</SB>O<SB>3</SB>at a ratio of at least 0.02 mol of the component (b) to 1 mol of the component (a), and (c) a conductive metal oxide and/or a near infrared-absorbing pigment. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a near-infrared shielding coating composition having transparency and hard coat properties.

  Conventionally, various inorganic coating compositions having transparency and hard coat properties are known. The silicon-based material containing the organosilane compound and the boron compound is either obtained by hydrolyzing both compounds in water or polymerized, or is a compound that does not react and does not polymerize. It was. This hydrolysis reaction is usually carried out by a sol-gel method, but has a drawback that it requires a complicated process and takes a long time for production.

For example, Non-Patent Document 1 discloses silicon ethoxide (Si (OC ₂ H ₅ ) ₄ ) as one of metal alkoxides and trimethoxy boron (B (OCH ₃ ) ₃ ) as another metal alkoxide that is an additional raw material. Is used as a raw material and dissolved in an alcohol solvent and water to control the pH of the solution and the catalyst used, and a method for producing glass by a sol-gel method is described. In this method, a metal alkoxide is hydrolyzed / condensed to form a sol, gelled while controlling the reaction conditions, and then dried and sintered to obtain a glass.

In Non-Patent Document 2, silicon ethoxide (Si (OC ₂ H ₅ ) ₄ ) is reacted with water and hydrolyzed as one of metal alkoxides to form a sol, and then the amount of water, the type of catalyst, A method for producing an organic-inorganic composite through a gel state while controlling pH, process conditions and the like is disclosed.

  Patent Document 1 discloses a curable resin (A) containing a hydrolyzable silyl group, a Lewis acid (B) such as boron trifluoride or its amine complex, and an aminosilane compound having an amino group in the molecule. A curable resin composition having a high curing rate and containing (C) and a mercaptosilane compound (D) containing a hydrolyzable silyl group and a mercapto group is described.

  Patent Document 2 describes a room temperature curable composition containing a substance obtained by mixing and reacting a glycidoxypropyl group-containing alkoxysilane and an aminopropyl group-containing alkoxysilane. However, in order to obtain a coating solution for film formation, it is necessary to contain a diluting solvent, a curing catalyst, and an ultraviolet absorber in the room temperature curable composition.

Patent Document 3 discloses a specific skeleton obtained by mixing a mixture of dichlorodiphenylsilane as an organohalogen silane and boron trichloride at a temperature of 0 ° C. or less in a toluene solvent and co-ammonolysis with ammonia gas. A method for producing a boron-containing organosilazane polymer having a structure is described.
JP 2005-54174 A JP 2000-319512 A JP-A-7-11001 Japanese Patent Laid-Open No. 9-145917 JP-A-8-295826 Glass Engineering Handbook, published by Asakura Shoten, first edition, pp. 47-49, July 5, 1999 Glass Engineering Handbook, published by Asakura Shoten, first edition, pages 432-438, 1999

  Moreover, sunlight rays consist of ultraviolet rays, visible rays, and near infrared rays (heat rays), and the energy ratio thereof is 5% for ultraviolet rays, 45% for visible rays, and 50% for near infrared rays. Therefore, if ultraviolet rays and near-infrared rays are cut off, a material that cuts off solar energy by 55% without any loss of transparency can be produced. In addition, if the near-infrared rays are cut off, a material that cuts off solar energy by 50% can be made without losing transparency.

  In addition, near infrared rays are emitted from plasma display (PDP) type displays that have been mass-produced in recent years, causing various problems, and development of near-infrared absorbing dyes has been actively conducted.

  In order to solve such a problem, a coating composition having near-infrared shielding and absorption characteristics is desired.

  In a material with high heat ray blocking properties, a plasma consisting of positive ions and free electrons is confined in an electron conductor, and free electrons are said to be plasma vibration, and electromagnetic waves having a high frequency due to the plasma frequency are transmitted through the plasma. However, low electromagnetic waves cannot be transmitted through the plasma and are absorbed or reflected. In order for a substance to be transparent to visible light and to absorb or reflect near-infrared rays, the plasma frequency is about 800- Must be near 1000 nm.

  A material having high conductivity such as a general metal has a high free electron density and a high plasma frequency, and is therefore opaque to both near infrared rays and visible rays. On the other hand, insulators such as ceramics and resins are transparent to visible light and near infrared light because there are no free electrons. Conductive metal oxides such as ITO (Indium Tin Oxide) and ATO (Antimony Tin Oxide) have suitable conductivity and the plasma frequency is in the near infrared region, so that it is transparent to visible light and near It is opaque to infrared rays.

  Further, in Patent Document 4, a plasma display panel (PDP) generates a discharge between electrodes arranged in parallel on a front glass substrate, and excites ultraviolet rays from a rare gas such as xenon or neon enclosed therein to fluoresce. Although a display device that emits light by irradiating the body is described, it may be accompanied by light emission in the near-infrared region, which may cause malfunctions in devices such as a remote control and a wireless microphone. Therefore, there is a need for an optical filter that blocks near infrared rays of 800 to 1000 nm so as not to leak outside.

  One method for blocking near infrared rays is to use a near infrared absorbing dye. Examples of the dye having absorption in the near infrared region include azo, aluminum, anthraquinone, cyanine, diimonium, dithiol metal complex, squarylium, naphthalocyanine, and phthalocyanine.

  In the form of ultrafine particles, these conductive metal oxides and near-infrared absorbing dyes are usually used as coating compositions by being dispersed or dissolved in a resin binder that is transparent and excellent in haze characteristics. However, the resin binder has various problems to be solved, such as light deterioration, lack of hard coat properties as a coating film, insufficient optical properties, and restrictions on processing conditions during film formation. is doing.

  A coating agent containing a metal alkoxide such as tetraethoxysilane (TEOS) and an aminosilane compound has been known for a long time. However, such a coating agent is inferior in film property and difficult to form into a film. Moreover, the film strength (hardness) was insufficient depending on the application.

  For example, Patent Document 5 describes a resin composition for coatings comprising a metal alkoxide such as tetraethoxysilane (TEOS) or a condensate thereof and an aminosilane compound. However, even when such a metal alkoxide condensate is used, the film property is improved, but there is room for improvement in hardness.

  The present invention does not require complicated steps such as hydrolysis required in the sol-gel method, can be manufactured without requiring a long time, and has high weather resistance, excellent optical characteristics and hard coat characteristics. A near-infrared shielding coating composition is provided.

The present invention solves the above problems,
(A) Silane compound containing an amino group represented by the following formula: R _4-n —Si— (OR ′) _n
(Wherein R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3); and (b) H ₃ BO _At least one boron compound selected from the group consisting of ₃ and B ₂ O ₃ :
(A) a polymer substance containing a reaction product obtained by reacting (b) component at a ratio of 0.02 mol or more with respect to 1 mol of component;
(C) It is related with the near-infrared shielding coating composition which has a transparency and a hard-coat characteristic containing a conductive metal oxide and / or a near-infrared absorption pigment | dye.

  According to the present invention, it does not require complicated steps such as hydrolysis required in the sol-gel method, can be manufactured without requiring a long time, and has high weather resistance, excellent optical properties and hard coat properties. A near-infrared shielding coating composition having the following can be produced. The resulting coating composition can be applied to glass, ceramics and transparent plastics.

(Detailed explanation)
When the component (a) (silane compound containing an amino group) and the component (b) (boron compound) are mixed, they react to form a transparent and viscous liquid in several minutes to several tens of minutes and solidify. This is presumably because the boron compound acts as a crosslinking agent via the amino group in the component (a), polymerizes these components, resulting in a viscous liquid and solidifies. . In addition, (a) component is a liquid. In the present invention, water is not used in the reaction between the component (a) and the component (b).

The component (a) is a silane compound containing an amino group represented by the following formula.
R4 _-n- Si- (OR ') _n
(In the formula, R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3).

  Here, R represents an amino group-containing organic group. For example, monoaminomethyl, diaminomethyl, triaminomethyl, monoaminoethyl, diaminoethyl, triaminoethyl, tetraaminoethyl, monoaminopropyl, diaminopropyl, Examples include triaminopropyl, tetraaminopropyl, monoaminobutyl, diaminobutyl, triaminobutyl, tetraaminobutyl, and organic groups having an alkyl group or aryl group having more carbon atoms than these. It is not limited. γ-aminopropyl and aminoethylaminopropyl are particularly preferred, and γ-aminopropyl is most preferred.

  R 'in component (a) represents a methyl group, an ethyl group or a propyl group. Among these, a methyl group and an ethyl group are preferable.

In the component (a), n represents an integer selected from 1 to 3. Among them, n is preferably 2 to 3, and n is particularly preferably 3.
That is, as the component (a), γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are particularly preferable.

The component (b) is at least one boron compound selected from the group consisting of H ₃ BO ₃ and B ₂ O ₃ . The component (b) is preferably H ₃ BO ₃ .

The amount of both components used in the reaction between component (a) and component (b) is a ratio of 0.02 mol or more of component (b) to 1 mol of component (a), preferably 0.02 mol. A ratio of ˜8 mol, more preferably a ratio of 0.02 mol to 5 mol.
If the amount of the component (b) is less than 0.02 mol with respect to 1 mol of the component (a), the time required for solidification may become long or may not be sufficiently solidified. Moreover, when (b) component exceeds 8 mol, (b) component may remain without melt | dissolving in (a) component.

  The mixing conditions (temperature, mixing time, mixing method, etc.) of the polymeric substance (a) component and the (b) component of the present invention can be appropriately selected. Under normal room temperature conditions, it becomes a transparent and viscous liquid in several minutes to several tens of minutes, and then solidifies. The time for solidification and the viscosity and rigidity of the reaction product obtained also differ depending on the proportion of the boron compound.

  The boron compound (b) is preferably a boron compound alcohol solution dissolved in an alcohol having 1 to 7 carbon atoms. Examples of the alcohol having 1 to 7 carbon atoms include methyl alcohol, ethyl alcohol, various propyl alcohols, various butyl alcohols, and glycerin, and methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferable. By using the alcohol solution, the time for dissolving the component (b) in the component (a) can be shortened. In view of handling, the concentration of the boron compound in the alcohol is preferably high.

  The reaction product is preferably a reaction product obtained by reacting the component (a) and the component (b) without passing through a step of hydrolysis by adding water.

  The component (c) is a conductive metal oxide and / or a near infrared absorbing dye. The component (c) is a near-infrared ray blocking material, and the near-infrared ray can be blocked by adding the component (c).

  Although it does not specifically limit as a conductive metal oxide of (c) component, For example, the oxide of the at least 1 sort (s) of metal selected from Au, Ag, Ni, Cu, In, Sn, and Sb is mentioned. Preferably, it is at least one oxide selected from the group consisting of ITO (indium tin oxide) and ATO (antimony tin oxide).

  Moreover, in order for a substance to be transparent with respect to light, in addition to not having reflection and absorption with respect to visible light, it is necessary to have as little scattering as possible. Therefore, in order to reduce scattering, ultrafine particles having a wavelength half of the light, that is, an average particle diameter smaller than 200 nm are particularly preferable.

  The transparency of the film obtained from the coating composition is judged by the haze value (the ratio of the scattered light component in the total transmitted light). However, when the haze value exceeds 2%, it feels cloudy, so it is transparent. The haze value is preferably 2% or less. In order to achieve such a haze value of 2% or less, when using particles having a refractive index of about 2, such as ultrafine particles of ITO (indium tin oxide) or ATO (antimony tin oxide), the average particle diameter It is preferable to use a material in which is dispersed to 100 nm or less. However, if the average particle size is too small, the transparency increases, but the near-infrared shielding property may decrease. Therefore, in order to obtain a certain level of near-infrared shielding property, It is not preferable to disperse the fine particles too much to make the dispersed particle size too small to 10 nm or less. Therefore, in consideration of the balance between transparency and near-infrared ray blocking property, it is preferable to adjust the average particle size within an appropriate range.

  (C) Although the usage-amount of the conductive metal oxide of a component is not specifically limited, With respect to 100 weight part of polymeric materials containing the reaction product obtained by making (a) component and (b) component react, Preferably it is 0.5-50 weight part, More preferably, it is 1-20 weight part, More preferably, it is 2-10 weight part.

  The near-infrared absorbing dye of component (c) is not particularly limited as long as it has a near-infrared absorbing ability. For example, azo-based, aluminum-based, anthraquinone-based, cyanine-based, diimonium-based, diol metal complex-based, nosquarylium Mention may be made of at least one near-infrared-absorbing dye selected from phthalocyanine-based near-infrared absorbing dyes. Among these, diimonium-based and phthalocyanine-based near-infrared absorbing dyes are preferable. As such a near-infrared absorbing dye, [bis (4-t-butyl-1,2-dithiophenolate) copper-tetra-n-butylammonium] (BBT manufactured by Sumitomo Seika Co., Ltd.), 1,1,5, 5-tetrakis [4- (diethylamino) phenyl] -1,4-pentadiene-3-ylium-P-toluenesulfonate (Karenz IR-T manufactured by Showa Denko KK), phthalocyanine compound (TKR-2040 manufactured by Yamamoto Kasei Co., Ltd.), etc. Can be mentioned.

  When the near-infrared absorbing dye of component (c) is a dye that dissolves in a solvent such as a lower alcohol or ether, it can be contained in the coating composition of the present invention in the form of a solution dissolved in such a solvent. In the case of a dye that does not dissolve in such a solvent, it may be contained in the coating composition of the present invention as it is in the form of particles or the like. When the near-infrared absorbing pigment of component (c) is contained in the form of such particles, it is preferable to use those having an average particle size similar to that of the conductive metal oxide of component (c).

  (C) Although the usage-amount of the near-infrared absorption pigment | dye of a component is not specifically limited, When using with the form of the solution dissolved in the above solvents, (a) component and (b) component are made to react. Preferably, it is 0.01 parts by weight or more, more preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 25 parts by weight, with respect to 100 parts by weight of the polymer substance containing the reaction product obtained by Particularly preferred is 0.5 to 15 parts by weight. The amount used when the near-infrared absorbing dye of component (c) is used in the form of a solid such as particles includes a high amount of reaction product obtained by reacting component (a) with component (b). Preferably it is 0.1-50 weight part with respect to 100 weight part of molecular substances, More preferably, it is 0.5-25 weight part, More preferably, it is 1-15 weight part.

  (C) The conductive metal oxide and the near-infrared absorbing dye can be used in combination.

  The coating composition of this invention can further contain the condensate of a metal alkoxide and / or a metal alkoxide as (d) component. That is, component (d) can be added during or after the reaction of component (a) and component (b). When the component (d) is added, the content of the metal salt in the resulting reaction product can be increased, the electrical characteristics and chemical characteristics can be further improved, and the component (d) is not used. Since it is in the same viscous liquid state as, it can be processed into fibers or films.

  Examples of the metal of the metal alkoxide as component (d) include Si, Ta, Nb, Ti, Zr, Al, Ge, B, Na, Ga, Ce, V, Ta, P, and Sb. It is not limited to these. Si, Ti and Zr are preferred, and since the metal alkoxide of component (d) is preferably a liquid, Si and Ti are particularly preferred. Examples of the alkoxide (alkoxy group) of the metal alkoxide of component (d) include methoxy, ethoxy, propoxy, butoxy, and alkoxy groups having more carbon atoms. Methoxy, ethoxy, propoxy, and butoxy are preferred, and methoxy and ethoxy are more preferred.

Specific examples of the component (d) metal alkoxide include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, tetra Methoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, methyltrimethoxytitanium, ethyltriethoxytitanium, propyltripropoxytitanium, butyltributoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium , Methyltrimethoxyzirconium, ethyltriethoxyzirconium, propyltripropoxyzirconium, and butyl And the like butoxy zirconium.
Among them, preferred are tetraethoxysilane, tetramethoxysilane, ethyltriethoxysilane, and methyltrimethoxysilane.
(D) The usage-amount of the metal alkoxide of a component has a preferable ratio of 10 mol or less with respect to 1 mol of (a) component. More preferably, it is a ratio of 0.1 mol to 5 mol. If the amount of the component (d) is less than 0.1 mol with respect to 1 mol of the component (a), it may be difficult to obtain the effect of adding the component (d) as described above. Beyond the mole, it may become cloudy.

（式中、Ｒ^１は、アルキル基を表わし、その一部は水素であってもよく、Ｒ^１は、夫々独立に同一であっても異なっていてもよく、ｍは２〜２０から選択される整数を表わし、Ｍは、Ｓｉ、Ｔｉ及びＺｒからなる群から選択される少なくとも１種の金属を表わす。） Examples of the metal alkoxide condensate of component (d) include metal alkoxide condensates (d) represented by at least one formula selected from the group consisting of the following formulas (d1) and (d2). it can.

(In the formula, R ¹ represents an alkyl group, part of which may be hydrogen, R ¹ may be the same or different independently, and m is selected from 2 to 20) M represents at least one metal selected from the group consisting of Si, Ti and Zr.)

  That is, the component (d) can be added during or after the reaction between the component (a) and the component (b). By adding the component (d), the hardness can be increased, the electrical characteristics and chemical characteristics can be further improved, and since it becomes a viscous liquid state, it can be processed into a fiber or film form. it can.

  The amount of the condensate of the metal alkoxide that is the component (d) is preferably 2 to 50 mol in terms of the weight of the metal alkoxide monomer with respect to 1 mol of the component (a), and is 4 mol or more. Is more preferable. That is, when the amount of component (d) added is too large, the hardness tends to decrease. On the other hand, when the amount is too small, the Si content decreases, so that the hardness may decrease depending on the application. Durability issues may occur. Moreover, when there is too much addition amount of (d) component, there exists a tendency for the hardening time for obtaining the polymer composition of this invention to become long.

(D) R ¹ in the component represents an alkyl group, part of which may be hydrogen, and R ¹ may be independently the same or different, but R ¹ is a methyl group , An ethyl group, a propyl group, a butyl group, and an alkyl group having a carbon number higher than that, preferably a methyl group or an ethyl group.

  In the component (d), m represents an integer selected from 2 to 20, preferably 3 to 10, and most preferably 5.

  M in the component (d) represents at least one metal selected from the group consisting of Si, Ti and Zr, preferably Si or Ti, and most preferably Si.

  As the metal alkoxide monomer unit constituting the component (d), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, Tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, methyltrimethoxytitanium, ethyltriethoxytitanium, propyltripropoxytitanium, butyltributoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxy Zirconium, methyltrimethoxyzirconium, ethyltriethoxyzirconium, propyltripropoxyzirconium And a butyl tributoxyzirconium can be exemplified.

  When the component (d) is represented by the formula (d1), it is preferably a tetraethoxysilane condensate (pentamer) or a tetramethoxysilane condensate (pentamer), and the formula (d2 ) Is preferably a condensate of ethyltriethoxysilane (pentamer) or a condensate of methyltrimethoxysilane (pentamer).

  As described above, the coating composition of the present invention can contain a metal alkoxide (monomer) and / or a metal alkoxide condensate as the component (d), but the viscosity of the metal alkoxide monomer is the same as that of the condensate. Compared with the metal alkoxide monomer, there is an advantage that the adhesion of the resulting coating composition to the substrate may be improved. If the amount is more than the same amount as the product, the film properties when the coating film is thickened may deteriorate.

  The coating composition of the present invention may further contain a diol compound and / or a synthetic resin (component (e)) instead of the component (d) or in addition to the component (d). That is, the component (e) can be added during the reaction between the component (a) and the component (b) or after the reaction, instead of the component (d) or in addition to the component (d). By adding the component (e), it is possible to impart crack prevention properties to the resulting reaction product, and the coating composition containing the component (e) can be used as a resin hard coat agent.

  (E) Although it does not specifically limit as a synthetic resin of a component, A thermosetting resin, a thermoplastic resin, an ultraviolet curable resin etc. can be mentioned, Specifically, an acrylic resin, an epoxy resin, a polyester resin, Examples thereof include amino resins, urethane resins, and furan resins, and synthetic resins having various degrees of polymerization (molecular weight) can be used. Among these, epoxy resin, dipentaerythritol hexaacrylate, epoxy acrylate, vinyl ester resin, and the like are preferable.

  Although it does not specifically limit as a diol type compound of (e) component, Polycaptolactone diol, 1, 6 hexanediol, polycarbonate diol, and polyester diol can be mentioned. Among them, polyester diol is particularly preferable.

  (E) The usage-amount of a component has a preferable ratio of 50 weight% or less with respect to the whole composition. More preferably, the ratio is 1 to 40% by weight. If the component (e) is less than 1% by weight, the effect of adding the component (e) as described above may be difficult to obtain, and if the component (e) exceeds 40% by weight, a resin curing agent may be added. It may be necessary to add, and high hardness may not be obtained.

  When the coating composition of the present invention contains the component (e) and the metal alkoxide condensate as the component (d), the content of the metal alkoxide condensate as the component (d) may be reduced. preferable. That is, when the component (e) is contained and the content of the component (d) is large, the curing time for obtaining the coating composition of the present invention tends to be long, and the moisture curing time is long. May occur. In this case, specifically, the addition amount of the component (d) is preferably 2 to 20 mol in terms of the weight of the metal alkoxide monomer with respect to 1 mol of the component (a).

  In addition to the components listed above, the coating composition of the present invention can be used as a colorant, an antifungal agent, a photocatalytic material, an antirust agent, an anticorrosive agent, an antialgae agent, a water repellent agent, and an electroconductive material. Materials, etc. can be included.

  By including the polymer composition of the present invention as a main component, a coating agent or an adhesive can be obtained.

A functional material can be obtained by applying the coating composition of the present invention to an inorganic substrate or an organic substrate. Examples of the inorganic base material or organic base material include wood, stone materials, plastics, textile products, and the like. Thus, since the coating composition of the present invention can be applied even with a viscosity of 1 poise or less, it can be modified while making use of the material of the base material by impregnating the base material. .
Furthermore, even if it contains a photocatalyst and is used as a binder, it is less likely to decompose over time than a normal organic binder. Moreover, heat resistance and electrical insulation can be provided to the base material surface by apply | coating to a base material.

  The use as a coating composition of the present invention is useful for a hard coat of an optical display material and an apparatus. For example, for liquid crystal (specifically, AG / AR film, TAC film, polarizing film, separate film, transparent electrode, color filter, alignment film, retardation film, prism sheet, diffuser plate, light guide plate, reflector plate, etc.) The present invention is useful for the hard coating of PC and PP coating, and also for the plasma display.

  Since the coating composition of the present invention has an inorganic substance (Si) as a skeleton, even if it is used as an adhesive for a photocatalyst, it tends to be less likely to be decomposed or deteriorated than an organic (carbon skeleton) adhesive. .

Examples will be described below.
The sample was prepared in the molar ratio or weight ratio shown in each example of Table 1, but after the boron compound (component (b)) was sufficiently reacted with the silane compound (component (a)) Components ((c) component, (d) component, (e) component, etc.) were added.

Example 1
As component (a), 10 parts by weight of H ₃ BO ₃ powder is added as component (b) to 40 parts by weight of γ-aminopropyltriethoxysilane liquid, and after stirring for 5 minutes, tetraethoxysilane is used as component (d). 140 parts by weight, and further stirred for 5 minutes and allowed to stand, then, 20 parts by weight of bisphenol A resin (CY232 manufactured by Nagase Chemtech Co., Ltd.) as component (e) and antimony tin oxide ultrafine particles as component (c) 4 parts by weight (Altorich ATO reagent) was added and mixed to prepare the coating composition of Example 1.
Example 2
As the component (c), a coating composition of Example 2 was prepared in the same manner as in Example 1 except that 8 parts by weight of antimony tin oxide ultrafine particles (Alto Rich ATO reagent) was added.
Example 3
As the component (d), a coating composition of Example 3 was prepared in the same manner as Example 2 except that 100 parts by weight of tetraethoxysilane pentamer was added.
Example 4
As the component (c), 1,1,5,5-tetrakis [4- (diethylamino) phenyl] -1,4-pentadiene-3-ylium-P-toluenesulfonate (Showa Denko) A coating composition of Example 4 was prepared in the same manner as in Example 1 except that 0.4 part by weight of Karenz IR-T) was added.
Example 5
As the component (c), 1,1,5,5-tetrakis [4- (diethylamino) phenyl] -1,4-pentadiene-3-ylium-P-toluenesulfonate (Showa Denko) A coating composition of Example 5 was prepared in the same manner as Example 1, except that 2 parts by weight of Karenz IR-T) was added.
Example 6
As the component (d), a coating composition of Example 6 was prepared in the same manner as Example 5 except that 100 parts by weight of tetraethoxysilane pentamer was added.

Comparative Example 1
(C) The coating composition of the comparative example 1 was prepared like Example 1 except not adding the antimony tin oxide ultrafine particle (ATO reagent by Aldrich) as a component.
Comparative Example 2
An epoxy resin composition was obtained by kneading 10 parts by weight of a curing agent (HY956 manufactured by Nagase Chemtech) with 30 parts by weight of an epoxy resin (Detanite CY-232 manufactured by Nagase Chemtech). 8 parts by weight of antimony tin oxide ultrafine particles (Aldrich ATO reagent) was added to parts by weight and cured at 110 ° C. for 1 hour to prepare a coating composition of Comparative Example 2.
Comparative Example 3
An epoxy resin composition was obtained by kneading 10 parts by weight of a curing agent (HY956 manufactured by Nagase Chemtech) with 30 parts by weight of an epoxy resin (Detanite CY-232 manufactured by Nagase Chemtech). 2 parts of 1,1,5,5-tetrakis [4- (diethylamino) phenyl] -1,4-pentadiene-3-ylium-P-toluenesulfonate (Karenz IR-T manufactured by Showa Denko KK) with respect to parts by weight A coating composition of Comparative Example 2 was prepared by adding parts by weight and curing at 110 ° C. for 1 hour.

Evaluation results The coating compositions obtained in each Example and Comparative Example were applied to a glass plate with a roller so that the coating amount was about 40 g / m ² , a test piece was prepared, and the pencil hardness and near-infrared region were applied. The film transmittance and near-infrared shielding properties were evaluated.
The pencil hardness was measured according to JIS K5400 8.4.2. Moreover, the transmittance | permeability in a near-infrared region measured the transmittance | permeability of the light with a wavelength of 800-1500 nm with the spectrophotometer, and calculated | required the minimum value of the transmittance | permeability.
The evaluation results are shown in Table 1.
Further, the transmittance in the near-infrared region is smaller in the second and third embodiments than in the second comparative example and in the fifth and sixth embodiments compared with the third comparative example. This is probably because a dense coating film was obtained.

  The coating composition of the present invention has high weather resistance, excellent optical properties and hard coat properties, and can be applied to glass, ceramics and transparent plastics.

Claims (14)

(A) Silane compound containing an amino group represented by the following formula: R _4-n —Si— (OR ′) _n
(Wherein R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3); and (b) H ₃ BO _At least one boron compound selected from the group consisting of ₃ and B ₂ O ₃ :
(A) a polymer substance containing a reaction product obtained by reacting (b) component at a ratio of 0.02 mol or more with respect to 1 mol of component;
(C) A near-infrared shielding coating composition having transparency and hard coat properties, comprising a conductive metal oxide and / or a near-infrared absorbing dye.   The coating composition according to claim 1, wherein the boron compound (b) is a boron compound alcohol solution dissolved in an alcohol having 1 to 7 carbon atoms.   The silane compound as the component (a) is at least one silane compound selected from the group consisting of γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. The coating composition according to claim 1 or 2. The coating composition according to claim 1, wherein the boron compound as the component (b) is H ₃ BO ₃ .   The said reaction product contains the reaction product obtained by making it react by the ratio of said (b) component 0.02-5 mol with respect to 1 mol of said (a) component, Any one of Claims 1-4. The coating composition according to Item.   The said reaction product is a reaction product obtained by making (a) component and (b) component react, without passing through the hydrolysis process which adds water, The any one of Claims 1-5. Coating composition.   The coating composition according to claim 1, further comprising (d) a metal alkoxide and / or a condensate of metal alkoxide.   The coating composition according to claim 7, comprising a metal alkoxide as component (d).   The coating composition according to claim 8, wherein the metal in component (d) is at least one element selected from the group consisting of Si, Ti and Zr.   The coating composition according to claim 9, wherein tetramethoxysilane and / or tetraethoxysilane are present as a metal alkoxide of component (d) at a ratio of 10 mol or less with respect to 1 mol of component (a). The coating composition of Claim 7 containing the condensate of the metal alkoxide represented by at least 1 sort (s) selected from the group which consists of the following formula | equation (d1) and (d2) as (d) component.

(In the formula, R ¹ represents an alkyl group, part of which may be hydrogen, R ¹ may be the same or different independently, and m is selected from 2 to 20) M represents at least one metal selected from the group consisting of Si, Ti and Zr.)   The coating composition according to claim 11, wherein the metal alkoxide condensate (d) is contained in an amount of 2 to 50 mol in terms of the weight of the metal alkoxide monomer with respect to 1 mol of the component (a).   The condensate (d) of the metal alkoxide is represented by the formula (d1), and is a condensate of tetraethoxysilane or tetramethoxysilane, according to any one of claims 11 to 13. Coating composition.   The coating composition according to claim 1, further comprising (e) a diol compound and / or a synthetic resin.