JP2022028241A - Composition for infrared reflectors, and composition for infrared low radiation materials - Google Patents

Abstract

To provide an infrared reflector that has high heat resistance and also has high thermal conductivity, or a composition that can form an infrared low radiation material.SOLUTION: A composition contains an infrared reflection filler and a polysiloxane copolymer composed of a basket-formed silsesquioxane repeating unit represented by formula (A) and an open-chain siloxane repeating unit. R0 is a C6-20 aryl or a C5-6 cycloalkyl, and R1 is hydrogen, vinyl, allyl, hydroxy group, C6-20 aryl, C5-6 cycloalkyl, C7-40 arylalkyl, or C1-40 alkyl.SELECTED DRAWING: None

Description

The present invention relates to a composition for an infrared reflector and an infrared low emissivity material using a siloxane polymer having a silanol group and a crosslinked product.

In order to realize a low environmental load, the importance of heat insulation of houses, offices, factories, automobiles, etc., which have been kept warm by using air conditioners, is increasing. For example, the power consumption of air conditioners can be reduced by suppressing the rise in indoor temperature in the summer due to the incident of sunlight from windows in the office, and by suppressing the radiation of heat rays (= infrared rays) that cause radiative cooling of the outer wall in the winter. (See, for example, Non-Patent Document 1).

Furthermore, in recent years, infrared radiation control has become important from the viewpoint of reducing the deterioration of the working environment due to infrared radiation emitted from solder reflow furnaces and the loss of emitted energy. In addition, since infrared radiation is proportional to the fourth power of temperature, the higher the temperature, the greater the effect. Therefore, a material with high heat resistance is required because it is often used in equipment that becomes hot.

As a relationship between a solid and light, the relationship "transmittance + absorption rate + reflectance = 1" generally holds. The light absorbed by the substance becomes heat. In addition, the heat generated by the absorption of light diffuses inside the substance, and at the same time, it is released into the air by convection and radiated to the surroundings as far infrared rays. Therefore, if it is desired to control infrared rays without raising the temperature of the coating film, it is better that the infrared ray absorption rate is low. However, if you are on the windowsill and want to lower the sensible temperature of a person who is directly exposed to sunlight, it is better to shield near infrared rays including the absorption wavelength of water. In this case, an infrared absorber can be added and used.

In general, a polymer containing silsesquioxane having a cage-shaped structure has attracted attention from various fields because it has a unique structure and is expected to have a unique effect. As a polymer containing such a silsesquioxane skeleton, a silicon-based polymer having a silsesquioxane skeleton in the main chain is known (see, for example, Patent Document 1). Further, a silicone film having excellent heat resistance has been developed by introducing a crosslinkable functional group into a silicon compound having a silsesquioxane skeleton having a cage structure in the main chain to form a crosslinkable polymer (for example, Patent Document). 2). In addition, a light-reflecting adhesive made by curing polysilsesquioxane and epoxy, which has an open structure instead of a cage type, has also been developed. Thermal decomposition and infrared absorption occurred, and the advantages of silsesquioxane could not be fully utilized (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2009-298908 Japanese Unexamined Patent Publication No. 2010-116464 Japanese Unexamined Patent Publication No. 2011-88847

New Development of Transparent Conductor II, Chapter 20 Application of Transparent Conductor to Window Glass, CMC Publishing, Yutaka Sawada, 2002

As described above, materials aiming at low environmental load using these infrared control are often used in harsh environments, and materials having high resistance to temperature, ultraviolet rays, etc. are required. For that purpose, it is important to develop not only an infrared reflective filler but also a binder polymer having high heat resistance and little absorption in the infrared region for a coating material that controls infrared rays and controls the internal temperature.
Therefore, it is an object of the present invention to provide a composition having high infrared reflectance, high light resistance, low infrared emissivity and high heat resistance by combining an infrared reflective filler and the above silicone polymer. do.

In the compounding of an organic material and an inorganic material, the present inventors react a silsesquioxane compound having a cage-type structure with high heat resistance and chemical stability with a compound containing a chain siloxane structure to form a main chain. By combining a siloxane polymer containing a hydroxy group and a heat ray reflective filler, the weather resistance and heat resistance (1% or 5% weight loss temperature) are extremely high at 350 ° C or higher, and the coating material has high heat ray reflectivity and low heat release. And found that a cured film can be formed, and completed the present invention.

式（Ａ）および（Ｂ）中、
Ｒ^０は独立して、炭素数６～２０のアリールまたは炭素数５～６のシクロアルキルであり、炭素数６～２０のアリールおよび炭素数５～６のシクロアルキルにおいて、少なくとも1つの水素がハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく；
Ｒ^１は独立して、水素、ビニル、アリル、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、または炭素数１～４０のアルキルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキルおよび炭素数７～４０のアリールアルキル中のアリールは、少なくとも１つの水素原子が独立してハロゲン原子または炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよく；
Ｒ^２は独立して、水素、ビニル、アリル、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、または炭素数１～４０のアルキルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、および炭素数７～４０のアリールアルキル中のアリールにおいて、少なくとも１つの水素がハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、炭素数７～４０のアリールアルキル中のアルキレンにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよく；
ｘおよびｙは独立して、１以上である。
式（Ａ）および式（Ｂ）において、Ｒ^０が独立して、フェニルまたはシクロヘキシルであり、Ｒ^１およびＲ^２が独立して、メチルまたはフェニルである化合物は、耐熱性が高いという点で、より好ましい。 The composition for an infrared reflector or the composition for an infrared low emissivity material according to the first aspect of the present invention is
With infrared reflective filler;
A polysiloxane copolymer consisting of a cage-type silsesquioxane repeating unit represented by the formula (A) and a chain siloxane repeating unit represented by the formula (B);
including.

In formulas (A) and (B),
^R0 is independently an aryl with 6 to 20 carbon atoms or a cycloalkyl with 5 to 6 carbon atoms, and in the aryl with 6 to 20 carbon atoms and the cycloalkyl with 5 to 6 carbon atoms, at least one hydrogen is a halogen. Alternatively, it may be replaced with an alkyl having 1 to 20 carbon atoms;
R ¹ is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. There are aryls having 6 to 20 carbon atoms, cycloalkyls having 5 to 6 carbon atoms, and arylalkyls having 7 to 40 carbon atoms in which at least one hydrogen atom independently has a halogen atom or 1 to 20 carbon atoms. The alkylene in the arylalkyl having 7 to 40 carbon atoms may be replaced with an alkyl, and at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O-, -CH. = CH- or cycloalkylene with 5 to 20 carbon atoms may be replaced, and in alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with halogen, and at least one -CH _2- may be replaced. , -O- or may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
^R2 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, and an aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms, or in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
x and y are independently 1 or more.
In formulas (A) and (B), compounds in which R ⁰ is independently phenyl or cyclohexyl and R ¹ and R ² are independently methyl or phenyl have high heat resistance. More preferred.

With this configuration, the absorption rate of the polysiloxane copolymer, which is a polymer component, in the infrared region can be lowered and the heat resistance can be increased. By dispersing the infrared reflecting filler having a high infrared reflectance, high heat ray reflection can be achieved. It can have rate, low heat ray reflectance, and high heat resistance.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the second aspect of the present invention is the composition for an infrared reflector or the composition for an infrared low emissivity material according to the first aspect of the present invention. The infrared reflective filler is a metal oxide.
With this configuration, infrared rays can be reflected by the metal oxide while being hardly absorbed by the polysiloxane copolymer, and a composite material having high infrared reflectance and low emissivity can be obtained.

The composition for infrared reflective material or the composition for infrared low-emissivity material according to the third aspect of the present invention is the composition for infrared reflective material or the composition for infrared low-emissivity material according to the first aspect of the present invention. The infrared reflective filler comprises at least one of tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, phosphorus-doped tin oxide, indium tin oxide, and zinc oxide, aluminum-doped zinc oxide, and gallium-doped zinc oxide.
With this configuration, it is possible to obtain a composite material that is highly transparent to visible light and is suitable for a heat ray reflecting window material that reflects infrared rays.

The composition for infrared reflective material or the composition for infrared low emissivity material according to the fourth aspect of the present invention is the composition for infrared reflective material or the composition for infrared low emissivity material according to the first aspect of the present invention. , The near-infrared absorber further comprises an inorganic filler consisting of tungsten oxide, lanthanum borohydride, molybdenum oxide, and at least one of a composite oxide containing these, or an organic dye.
With this configuration, the amount of near-infrared rays that raise the temperature of human skin and make it feel hot can be reduced among the light incident on the window, so it is possible to add the effect of lowering the human sensible temperature. can.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the fifth aspect of the present invention is the composition for an infrared reflector or the composition for an infrared low emissivity material according to the first aspect of the present invention. , The infrared reflective filler is a metal powder.
With this configuration, when the object to be coated is a non-transparent metal or plastic, it is possible to obtain a coating film having a higher reflectance even if the film thickness is thinner than that of the infrared reflective filler (transparent conductive filler). In particular, when a highly heat-resistant resin is used at a high temperature, the effect of heat insulation due to the formation of the coating film of the present invention is great.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the sixth aspect of the present invention is the composition for an infrared reflector or the composition for an infrared low emissivity material according to the fifth aspect of the present invention. , The infrared reflective filler consists of silver, aluminum, tin, titanium, nickel, chromium, and at least one of the alloys containing these.
With this configuration, the infrared reflective material or the infrared low-emissivity material can obtain high reflectance without the infrared reflective filler (metal filler) absorbing light of a specific wavelength, and can be combined with the polysiloxane copolymer. A composite material having a high infrared reflectance and a low emissivity can be obtained after the composite of the above.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the seventh aspect of the present invention is the composition for an infrared reflector or the composition for an infrared low emissivity material according to the sixth aspect of the present invention. , The infrared reflective filler is in the form of an amorphous powder, a spherical shape, a scaly shape, or a flake shape.
With this configuration, when the reflectance per unit volume is not as high as that of metal such as the infrared reflective filler (transparent conductive filler) of the filler in the spherical or amorphous powder form, the filling amount of the infrared reflective filler in the coating film is high. By doing so, the reflectance of the coating film can be increased, while in the case of scales or flakes, the scales are usually oriented in the direction parallel to the surface of the coating film, so that it is less in the case of a thin but highly reflective metal filler. Infrared light can be efficiently reflected by the filler. The shape of these particles is appropriately selected depending on the purpose of use and the place of use.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the eighth aspect of the present invention is the composition for an infrared reflector or the composition for an infrared low emissivity material according to the first to seventh aspects of the present invention. In the composition, the weight average molecular weight of the polysiloxane copolymer is in the range of 2,000 to 10,000,000.
With such a configuration, it is possible to contain a more preferable compound in that it is hard to be peeled off from the base material and has high durability.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the ninth aspect of the present invention is the composition for an infrared reflector or the composition for an infrared low emissivity material according to the first to eighth aspects of the present invention. In the composition, the glass transition temperature of the polysiloxane copolymer is 0 ° C. or higher.
With such a configuration, it is possible to contain a more preferable compound in that there is little fluctuation in physical properties such as elastic modulus in a temperature range where heat ray reflection is required, and it is resistant to temperature cycles and the like.

The composition for an infrared reflector or the composition for an infrared low emissivity material according to the tenth aspect of the present invention has a crosslink density n of a polysiloxane copolymer obtained from a calculation formula represented by the formula (α). It is 150 mol / m ³ or more.
n = E'/ 3RT ... (α)
In formula (α), n: crosslink density (mol / m ³ ), E': storage elastic modulus (Pa), R: gas constant ((Pa · m ³ ) / K · mol), T: temperature (K). ..
With such a configuration, a more preferable compound can be contained in terms of high mechanical strength.

The composition for an infrared reflecting material or the composition for an infrared low emissivity material according to the eleventh aspect of the present invention is the composition for an infrared reflecting material according to any one of 1 to 4 and 7 to 9 of the present invention. It is an infrared reflective transparent coating material made of objects. When configured in this way, it is necessary to pass transparent and visible light, such as windows of buildings, windows of mobile machines such as automobiles, viewing windows for checking the inside of production equipment, and for agriculture. It can be applied to houses, engineering filters, etc. to form a film.

The composition for infrared reflective material or the composition for infrared low emissivity material according to the twelfth aspect of the present invention is the composition for infrared reflective material according to any one of the first to eleventh aspects of the present invention. Or in an infrared low emissivity material, apply a coating material of the eleventh mode, apply it to hardened glass, transparent heat resistant resin or translucent ceramics, and harden it, an infrared reflective window agent, a translucent cover, or an infrared cut. It is a filter. Generally, the emissivity of the resin is about 0.8-0.9, and with such a configuration, the emissivity of the resin surface having high infrared radioactivity can be lowered.

The infrared reflective material or infrared low emissivity material according to the thirteenth aspect of the present invention is the infrared reflective material or infrared low emissivity material according to any one of the first to twelfth aspects of the present invention, and has a heat resistant temperature of 150. It is applied to a structural material made of engineering plastic with a temperature of ℃ or higher, and by reflecting infrared rays emitted from the outside of the structural material, the temperature rise is suppressed, and the emissivity of infrared rays emitted from the inside to the outside is lowered to retain heat. A sheet, structural material, mechanical part, or electronic device to which the above is applied.

In the infrared reflecting material or the infrared low-radiating material formed from the composition for the infrared reflecting material or the composition for the infrared low-radiating material of the present invention, the binder to be combined with the infrared-reflecting filler has little infrared absorption and very high heat resistance. Since it is a high polysiloxane copolymer, we have invented a heat-curable coating material and a cured product thereof, which have a very high reflecting ability in the infrared to far-infrared region of the composite material and a small radiation.

FIG. 3 is a conceptual diagram in which infrared light is transmitted through a polysiloxane copolymer and infrared light is reflected by an infrared reflective filler in the infrared reflector or infrared low radiation material of the present invention. It is a conceptual diagram of the infrared radiation capacity evaluation apparatus used for evaluating the performance as an infrared low emissivity material of this invention. It is a conceptual diagram of the infrared reflection ability evaluation apparatus used for evaluating the performance as an infrared reflector of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each figure, parts that are the same as or correspond to each other are designated by the same or similar reference numerals, and duplicated description will be omitted. Further, the present invention is not limited to the following embodiments.

The terms used in the present invention will be described. The compound represented by the formula (1) may be referred to as a compound (1). Compounds represented by other formulas may also be abbreviated in the same manner. The expression "at least one A may be replaced by B or C" is at least one A in addition to the case where at least one A is replaced by B and the case where at least one A is replaced by C. Means that at the same time that is replaced by B, at least one of the other A's may be replaced by C. In the chemical formulas described herein, Me is methyl and Ph is phenyl. In the examples, the display data of the electronic balance is shown using g (gram) which is a mass unit. Weight% and weight ratio are data based on such numerical values.

[Composition for infrared reflective material or composition for infrared low emissivity material]
The composition for an infrared reflector or the composition for an infrared low-emissivity material of the present invention is composed of an infrared-reflecting filler having an infrared-reflecting ability and a polysiloxane copolymer, and the infrared-reflecting material or the infrared low-emissivity material can be obtained by heat curing or the like. It is a composition that can be formed. FIG. 1 is a schematic view of a heat ray reflective coating film dispersed in a binder polymer. Infrared light incident on the surface of the binder polymer passes through the binder polymer layer, is reflected by the infrared reflective filler, passes through the binder polymer layer again, and is emitted to the outside from the surface of the binder polymer. That is, it passes through the binder polymer layer twice, and if infrared light is absorbed during this time, the absorbed light energy is converted into heat energy, which raises the temperature of the coating film and finally comes into contact with the binder polymer. Raises the temperature of the atmospheric layer. Therefore, if the infrared absorption of this binder polymer can be reduced and the thickness of the resin layer can be reduced, infrared rays (= heat rays) can be efficiently reflected without raising the temperature of the coating film. The polysiloxane copolymer used in the present invention not only has low infrared absorption, but also has high durability such as heat resistance, and it is not necessary to increase the amount of the binder in anticipation of deterioration. A high-performance infrared reflector or an infrared low-emissivity material can be realized.

Further, when the infrared reflective material or the low infrared radiation material of the present invention is applied to the surface of a part or structure having a high emissivity such as a resin or an oxidized metal, the temperature is lowered by the radiation of infrared rays (radiative cooling). Phenomenon) can be suppressed. This is the opposite phenomenon to the heat-dissipating paint (for example, Japanese Patent Application Laid-Open No. 2003-360605, Japanese Patent Application Laid-Open No. 2013-100454), which has been developed in recent years.

<Polysiloxane copolymer>
The polysiloxane copolymer contains a cage-type silsesquioxane repeating unit represented by the formula (A) and a chain siloxane repeating unit represented by the formula (B).

Cage-shaped silsesquioxane repeating unit represented by the formula (A)

In formula (A), ^R0 is independently an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and in an aryl having 6 to 20 carbon atoms and a cycloalkyl having 5 to 6 carbon atoms. At least one hydrogen may be replaced with a halogen or an alkyl having 1 to 20 carbon atoms;
^R1 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, and an aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms, or in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
x is 1 or more.

(R ⁰ in equation (A))
^R0 is independently an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms.
Examples of the aryl having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferred, with phenyl, naphthyl and anthryl being more preferred.
Examples of the cycloalkyl having 5 to 6 carbon atoms include cyclopentyl and cyclohexyl.
^R0 is preferably phenyl or cyclohexyl.

(R ¹ in equation (A))
^R1 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or alkyl with 1 to 40 carbon atoms. be.
Examples of the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are the same as those described in ^R0 .
Examples of the arylalkyl having 7 to 40 carbon atoms include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl and 4-phenylbutyl. , 5-Phenylpentyl.
Examples of alkyl having 1 to 40 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, and iso-. Examples include pentyl, tert-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl and octadecyl.
R ¹ is preferably selected from phenyl, cyclohexyl, and alkyl having 1-5 carbon atoms, preferably phenyl or methyl.

(X in formula (A))
x is 1 or more, and the total number of cage-type silsesquioxane repeating units represented by the formula (A) contained in the polysiloxane copolymer is, for example, 1 to 500.

Chained siloxane repeating unit represented by the formula (B)

In formula (B), R ² is independently hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or carbon number of carbon atoms. In the aryls of 1 to 40 alkyl, 6 to 20 carbon atoms, 5 to 6 carbon atoms cycloalkyl and 7 to 40 carbon atoms arylalkyl, at least one hydrogen is halogen or 1 to 1 to carbon atoms. It may be replaced with 20 alkyl, or at least one hydrogen may be replaced with halogen in the alkylene in the arylalkyl having 7 to 40 carbon atoms, and at least one -CH _2- may be replaced with -O-,-. It may be replaced with CH = CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- May be replaced with —O— or a cycloalkylene with 5 to 20 carbon atoms;
y is 1 or more.

(Y in equation (B))
y represents a real number of 1 or more, and the total number of chain siloxane repeating units represented by the formula (B) contained in the polysiloxane copolymer (y1 + y2 described later) is, for example, 1 to 3000.

The polysiloxane copolymer is bonded to the surface of a substance selected from an inorganic substance and an organic substance via a chain siloxane represented by the formula (B). Here, the bond is preferably a chemical bond. For example, a functional group such as a hydroxyl group may be imparted to the surface of the substance, and a chemical bond may be formed by a chemical reaction between the functional group and the terminal hydroxyl group of the chain siloxane represented by the formula (B). The chain siloxane represented by the formula (B) may be directly bonded to the surface of the substance, or may be bonded via a spacer or the like.

"The polysiloxane copolymer binds to the surface of a substance selected from an inorganic substance and an organic substance via a chain siloxane represented by the formula (B)" means that the chain represented by the formula (B). The siloxane (linker moiety) first binds to the surface of the substance, and then the cage-type silsesquioxane repeating unit represented by the formula (A) and the chain siloxane repeating unit represented by the formula (B) are optional. Means that they are combined in any proportion and in any order.
[Substances selected from inorganic and organic substances] _{-By 1- (} A _x By 2)
The number of repetitions y1 in the chain siloxane (linker portion) represented by the formula (B) bonded to the surface of the substance is, for example, 1 to 1000.
In (A _x By 2), the number x of the cage-type _{silsesquioxane} repeating units represented by the continuous formula (A) is, for example, 1 to 5, and the chain shape represented by the continuous formula (B). The siloxane repeating unit y2 is, for example, 1 to 30.

式（Ｃ）中、Ｒ^４は独立して、水素、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、炭素数１～４０のアルキル、炭素数１～４０のアルコキシ、ビニル、またはアリルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、および前記炭素数７～４０のアリールアルキル中のアリールにおいて、少なくとも１つの水素がハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、炭素数７～４０のアリールアルキル中のアルキレンにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルにおいて、少なくとも１つの水素が、ハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルコキシにおいて、少なくとも１つの水素が独立してハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよい。 In the present invention, the terminal different from the terminal bonded to the substance selected from the inorganic substance and the organic substance of the polysiloxane copolymer is not particularly limited and may be a hydroxyl group, but the group of the following formula (C) may be used. You may have.

In formula (C), ^R4 is independently hydrogen, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, and alkyl having 1 to 40 carbon atoms. , An alkoxy, vinyl, or allyl having 1 to 40 carbon atoms, and at least 1 in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the aryl alkyl having 7 to 40 carbon atoms. One hydrogen may be replaced with a halogen or an alkyl having 1 to 20 carbon atoms, and at least one hydrogen may be replaced with a halogen in the alkylene in the arylalkyl having 7 to 40 carbon atoms, and at least one -CH. _2- may be replaced with -O-, -CH = CH-, or a cycloalkylene having 5 to 20 carbon atoms, in which at least one hydrogen is replaced with a halogen in an alkyl having 1 to 40 carbon atoms. Also, at least one -CH _2- may be replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms, and in an alkoxy having 1 to 40 carbon atoms, at least one hydrogen is independently halogen. It may be replaced, and at least one -CH _2- may be replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms.

Examples of the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are the same as those described in ^R0 .
Examples of the arylalkyl having 7 to 40 carbon atoms and the alkyl having 1 to 40 carbon atoms are the same as those described in ^R1 .
The alkoxy having 1 to 40 carbon atoms is not particularly limited, but is preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, and propoxy.
^R4 is preferably hydrogen, methylphenyl, vinyl, allyl, or a hydroxyl group.

In the polysiloxane copolymer contained in the composition of the present invention, the ratio (x: y) of the repeating unit represented by the formula (A) to the repeating unit represented by the formula (B) is not particularly limited. For example, 1: 1 to 1:30.
In the polysiloxane copolymer of the present invention, the mass% occupied by the repeating units represented by the formulas (A) and (B) is usually 10% or more, preferably 30% or more, more preferably 50%. As mentioned above, it is particularly preferably 70% or more, usually less than 100%, preferably 99% or less. That is, a unit other than the repeating unit represented by the formula (1) may be included as long as the effect of the present invention is not significantly impaired. Examples of such a unit include-(CH ₂ -CH ₂ )-,-(CH = CH)-,-(O-SiMe ₂ -C ₆ H ₄ -SiMe ₂ )-.

The weight average molecular weight (Mw) of the polysiloxane copolymer in the present invention is not particularly limited, but is preferably 2,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, more preferably. Is 500,000 or less, more preferably 200,000 or less. The weight average molecular weight is determined by calculating a chromatogram obtained by gel permeation chromatography (GPC) from a calibration curve obtained with a molecular weight standard sample, as described in Examples described later.
The polydispersity is, for example, 1 to 4.

These polysiloxane copolymers can be produced, for example, by the following steps.
(I) Equilibrium polymerization of chain or cyclic siloxanes on the surface of a substance selected from inorganic and organic substances, followed by
(Ii) Step of equilibrium polymerization of cage-type silsesquioxane

For example, by reacting an inorganic oxide (silica) whose surface is a hydroxyl group with a chain or cyclic siloxane, an acid catalyst, or a solvent, the chain siloxane is grafted on the silica surface. Next, by adding terminal silanol-type cage-type silsesquioxane to the solution being polymerized, equilibrium polymerization with the grafted siloxane polymer is carried out, and cage-type silsesquioxane is incorporated in the middle of the chain siloxane, and the molecular necklace. Polymer-grafted silica is obtained.

Examples of the chain or cyclic siloxane include compounds represented by the formula (b) or the formula (c). Either or both of these can be used. It is preferable that a reactive functional group such as a hydroxyl group is present on the surface of a substance selected from an inorganic substance and an organic substance, and a surface treatment may be performed to introduce such a reactive functional group.

R ^{2 in the formula (b) and the formula (c) is a group defined in the same manner as R 2 in} the formula (B), and so is the preferred example. n is an integer of 2 to 30.

Examples of the compound represented by the formula (b) include 2,2,4,4,6,6-hexamethylcyclotrisiloxane and 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane. , 2,2,4,4,6,6-hexaethylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-triethyl-2,4 , 6-Tripropylcyclotrisiloxane, 2,2,4,4,6,6-hexapropylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (1-methylethyl) cyclotri Siloxane, 2,4,6-triethyl-2,4,6-tris (1-methylethyl) cyclotrisiloxane 2,2,4,4,6,6-hexakis (1-methylethyl) cyclotrisiloxane, 2, , 4,6-Tributyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tributyl-2,4,6-triethylcyclotrisiloxane, 2,2,4,4,6,6-hexa Butylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (1,1-dimethylethyl) cyclotrisiloxane, 2,46-triethyl-2,4,6-tris (1,1-tris) Dimethylethyl) cyclotrisiloxane, 2,4,6-tris (1,1-dimethylethyl) -2,4,6-tripropylcyclotrisiloxane, 2,2,4,4,66-hexakis (1,1) -Dimethylethyl) cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (trifluoromethyl) cyclotrisiloxane, 2,2,4,4,6,6-hexakis (trifluoromethyl) Cyclotrisiloxane, 2,2,4,4,6,6-hexakis (1,1,2,2,2-pentafluoroethyl) cyclotrisiloxane, 2,4,6-trimethyl-2,4,6- Tris (3,3,3-trifluoropropyl) cyclotrisiloxane, 2,2,4,4,6,6-hexakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 2,4,6- Trimethyl-2,4,6-triphenylcyclotrisiloxane, 2,2,4,4,6,6-hexaphenylcyclotrisiloxane, 2,4,6-tricyclohexyl-2,4,6-trimethylcyclo Trisiloxane, 2,2,4,4,6,6-hexacyclohexylcyclotrisiloxane, 2,2,4,4,6,6-hexavinylcyclotrisiloxane, 2 , 4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane, 2,4,6,8-tetraethyl -2,4,6,8-Tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octaethylcyclotrisiloxane, 2,4,6,8-tetramethyl-2, 4,6,8-Tetrapropylcyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8, 8-octapropylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (1-methylethyl) cyclotetrasiloxane, 2,4,6,8-tetraethyl-2, 4,6,8-Tetraxane (1-methylethyl) cyclotetrasiloxane 2,2,4,4,6,6,8,8-octakis (1-methylethyl) cyclotetrasiloxane, 2,4,6,8 -Tetrabutyl-2,4,6,8-Tetramethylcyclotetrasiloxane, 2,4,6,8-Tetrabutyl-2,4,6,8-Tetraethylcyclotetrasiloxane, 2,2,4,4,6 6,8,8-Octabutylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (1,1-dimethylethyl) cyclotetrasiloxane, 2,4,6 8-Tetraethyl-2,4,6,8-tetrakis (1,1-dimethylethyl) cyclotetrasiloxane, 2,4,6,8-tetrakis (1,1-dimethylethyl) -2,4,6,8 -Tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis (1,1-dimethylethyl) cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4 , 6,8-Tetrakiss (trifluoromethyl) cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis (trifluoromethyl) cyclotetrasiloxane, 2,2,4,4,6 , 6,8,8-octakis (1,1,2,2,2-pentafluoroethyl) cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (3, 3,3-Trifluoropropyl) cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis (3,3,3-trifluoropropyl) cyclotetrasiloxane, 2,4,6 8-Tetramethyl-2, 4,6,8-Tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octaphenylcyclotetrasiloxane, 2,4,6,8-tetracyclohexyl-2,4 6,8-Tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octacyclohexylcyclotetrasiloxane, 2,2,4,4,6,6,8-octa Vinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,6-dietinyl-2,4,4,6,8,8-hexamethyl Cyclotetrasiloxane, 2,2,4,4,6,6,8,8,10,10-decamethylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8, 10-Pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaethylcyclotrisiloxane, 2,4,6,8.10-pentamethyl-2,4 6,8-Pentapropylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8,10-pentapropylcyclopentasiloxane, 2,2,4,4,6,6 8,8,10,10-decapropylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentakis (1-methylethyl) cyclopentasiloxane, 2,4 , 6,8,10-Pentaethyl-2,4,6,8,10-pentakis (1-methylethyl) cyclopentasiloxane 2,2,4,4,6,6,8,8,10,10-decakis (1-Methylethyl) Cyclopentasiloxane, 2,4,6,8,10-Pentabutyl-2,4,6,8,10-Pentamethylcyclopentasiloxane, 2,4,6,8,10-Pentabutyl- 2,4,6,8,10-pentaethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decabutylcyclopentasiloxane, 2,4,6,8, 10,10-Pentamethyl-2,4,6,8,10,10-pentakis (1,1-dimethylethyl) cyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8 , 10-Pentakis (1,1-dimethylethyl) cyclopentasiloxane, 2,4,6,8,10-pentakis (1,1-dimethylethyl) -2,4,6,8,10-pentapropylcyclopenta Siloxane, 2,2,4,4,6 , 6,8,8,10,10-decakis (1,1-dimethylethyl) cyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8-pentakis (trifluoromethyl) Cyclopentasiloxane, 2,2,4,4,6,6,8,8,10.10-decakis (trifluoromethyl) cyclopentasiloxane, 2,2,4,4,6,6,8,8, 10,10-decakis (1,1,2,2,2-pentafluoroethyl) cyclopentasiloxane, 2,4,6,8,10,10-pentamethyl-2,4,6,8-pentakis (3, 3,3-Trifluoropropyl) cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 2, 4,6,8,10-Pentamethyl-2,4,6,8-pentaphenylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaphenylcyclopentasiloxane, 2,4,6,8,10-pentacyclohexyl-2,4,6,8,10-pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10- Decacyclohexylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decavinylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6 , 8,10-Pentavinylcyclopentasiloxane, among which low molecular weight cyclic siloxanes in which ^R2 is an alkyl having 1 to 40 carbon atoms are preferable, hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D3). Cyclic siloxanes such as D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are more preferred, and octamethylcyclotetrasiloxane is particularly preferred from the standpoint of availability, cost, and handling.

Examples of the compound represented by the formula (c) include, for example.
1,1,3,3-Tetramethyl-1,3-disiloxanediol, 1,1,3,3,5,5-hexamethyl-1,5-trisiloxanediol, 1,1,3,3,5 , 5,7,7-Octamethyl-1,7-tetrasiloxanediol, 1,1,3,3,5,5,7,7,9,9-decamethyl-1,9-pentasiloxanediol, 1,1 , 3,3-Tetraphenyl-1,3-disiloxanediol, 1,1,3,3,5,5-hexaphenyl-1,5-trisiloxanediol, DMS-S12 (trade name, manufactured by Gelest), DMS-S14 (trade name, manufactured by Gelest), DMS-S15 (trade name, manufactured by Gelest)
1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,5,5,5-octamethyltrisiloxane, 1,1,1,3,3,5 5,7,7-Decamethyltetrasiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1 , 5-Divinyl-1,1,3,3,5,5-heptamethyltrisiloxane, 1,5-diallyl-1,1,3,3,5,5-heptamethyltrisiloxane, DMS-V00 (Product name, manufactured by Gelest), DMS-V03 (Product name, manufactured by Gelest), DMS-V05 (Product name, manufactured by Gelest)
1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11- Dodecamethylhexasiloxane, 1,3-dimethyl-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,3-cyclohexyl-1,3-dimethyldisiloxane, 1,1, 1,3,3-Tetracyclohexamethyldisiloxane, 1,3-diethyl-1,3-dimethyldisiloxane, 1,1,3,3-tetraethyldisiloxane, 1,3-dimethyl-1,3-dipropyl Disiloxane, 1,3-diethyl-1,3-dipropyldisiloxane, 1,1,3,3-tetrapropyldisiloxane, 1,3-dimethyl-1,3-bis (1-methylethyl) disiloxane 1,1,3-diethyl-1,3-bis (1-methylethyl) disiloxane, 1,1,3,3-tetrakis (1-methylethyl) disiloxane, 1,1,3,3-tetrakis (1) , 1-dimethylethyl) disiloxane, 1,3-bis (1,1-dimethylethyl) -1,3-dimethyldisiloxane, DMS-Hm15 (trade name, manufactured by Gelest), DMS-Hm25 (trade name, Gelest) , DMS-H03 (trade name, manufactured by Gelest), DMS-H11 (trade name, manufactured by Gelest), FM 1105 (trade name, manufactured by JNC Co., Ltd.), FM 1111 (trade name, manufactured by JNC Co., Ltd.) , 1,3-Difluoro-1,1,3,3-tetramethyldisiloxane, 1,5-difluoro-1,1,3,3,5,5-hexamethyldisiloxane, 1,1,3,3 -Tetramethyl-1,3-bis (trifluoromethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (trifluoromethyl) disiloxane, 1,3-dimethoxy- 1,1,3,3-Tetramethyldisiloxane, 1,5-dimethoxy-1,1,1,3,3,5,5-hexamethyltrisiloxane, 1,3-diethoxy-1,1,3,3- Tetramethyldisiloxane, 1,5-diethoxy-1,1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3-tetramethyl-1,3-dipropoxydisiloxane 1,1, 1,3,3,5,5-hexamethyl-1,5-di Propoxytrisiloxane 1,1,3,5,7,7-hexamethoxy-1,3,5,7-tetramethyltetrasiloxane, 3,3,11,11-tetramethoxy-6,6,8,8 -Tetramethyl-2,7,12-Trioxa-3,6,8,11-Tetrasilatridecan, 4,4,12,12-Tetraethoxy-7,7,9,9-Tetramethyl-3,8, 13-Trioxa-4,7,9,12-Tetrasilapentadecane, 1,3-dietinyl-1,1,1,3,3-tetramethyldisiloxane, 1,5-dietinyl l-1,1,3,3, 5,5-Hexamethyltrisiloxane, FM 2205 (trade name, manufactured by JNC Co., Ltd.), 1,1,3,3-tetramethyl-1,3-di-2-propane-1-yldisiloxane, 1, 1,3,3,5,5-hexamethyl-1,5-di-2-propane-1-yltrisiloxane, FM-4411 (trade name, manufactured by JNC Co., Ltd.), FM-4421 (trade name, JNC) (Product name, manufactured by JNC Co., Ltd.), FM-4425 (trade name, manufactured by JNC Co., Ltd.), DMS-C15 (trade name, manufactured by Gelest), DMS-C16 (trade name, manufactured by Gelest), DMS-C21 (trade name, manufactured by Gelest). ), DMS-CA21 (trade name, manufactured by Gelest).

式（ａ）におけるＲ^０は、式（Ａ）におけるＲ^０と同様に定義される基であり、好ましい例も同様である。
式（ａ）におけるＲ^１は、式（Ａ）におけるＲ^１と同様に定義される基であり、好ましい例も同様である。
式（ａ）で表される化合物は、例えば、特開２００６－０２２２０７号公報の記載を参照して合成することができ、以下に示される化合物が好ましい。この化合物において、Ｐｈはフェニルを示し、Ｃ－Ｈｅｘはシクロヘキシルを示す。 Examples of the cage-type silsesquioxane include a compound represented by the formula (a).

R ^{0 in the formula (a) is a group defined in the same manner as R 0 in} the formula (A), and so is a preferable example.
R ^{1 in the formula (a) is a group defined in the same manner as R 1 in} the formula (A), and so is a preferred example.
The compound represented by the formula (a) can be synthesized, for example, with reference to the description in JP-A-2006-022207, and the compounds shown below are preferable. In this compound, Ph represents phenyl and C-Hex represents cyclohexyl.

Further, in the polysiloxane copolymer obtained in the above step (ii), a compound represented by the formula (d) is added to a terminal different from the end bonded to the surface of a substance selected from the inorganic substance and the organic substance of the polysiloxane. By reacting, a terminal different from the end bonded to the surface of the substance of the polysiloxane copolymer may be modified.

式（ｄ）中、Ｒ^３は、式（Ｃ）におけるＲ^２で説明したとおりであり、好ましい基も同様である。
Ｒ^４は独立して、水素、ビニル基、アリル基、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、または炭素数１～４０のアルキルであり、炭素数６～２０のアリール、前記炭素数５～６のシクロアルキルおよび前記炭素数７～４０のアリールアルキル中のアリールは、少なくとも１つの水素が独立してハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、少なくとも１つの水素が独立してハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が独立して－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよい。
ｎは１～３０の整数である。
式（ｄ）で表される化合物としては、例えば、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、ヘキサフェニルジシロキサン、オクタフェニルトリシロキサン、デカフェニルテトラシロキサン、Ｇｅｌｅｓｔ製 ＤＭＡ－Ｔ０７Ｒが挙げられる。 <Compound represented by the formula (d)>

In formula (d), R ³ is as described in R ² in formula (C), and so is the preferred group.
^R4 is independently hydrogen, vinyl group, allyl group, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or 1 to 40 carbon atoms. The aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms and the arylalkyl having 7 to 40 carbon atoms is such that at least one hydrogen is independently halogen or 1 to 1 carbon atoms. The alkylene in the arylalkyl having 7 to 40 carbon atoms may be replaced with 20 alkyl, and at least one hydrogen may be replaced with halogen, and at least one _-CH2- is independently -O. -, -CH = CH-, or cycloalkylene having 5 to 20 carbon atoms may be replaced, and at least one hydrogen may be independently replaced with halogen in the alkyl having 1 to 40 carbon atoms. At least one -CH _2- may be independently replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms.
n is an integer from 1 to 30.
Examples of the compound represented by the formula (d) include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexaphenyldisiloxane, octaphenyltrisiloxane, decaphenyltetrasiloxane, and Gelest's DMA-T07R. Can be mentioned.

Equilibrium polymerization can be adopted in the above steps (i) and (ii).
The equilibrium polymerization can be carried out, for example, with reference to the method described in JP-A-2017-014320. It is preferable to use the following solvent and acid catalyst for the reaction. Further, it is preferable to carry out the reaction in an inert atmosphere such as nitrogen (N ₂ ). Further, it is preferable to carry out the reaction while stirring. The reaction temperature is, for example, 25 to 120 ° C.

<Solvent>
The solvent used in the reaction is not particularly limited as long as it can dissolve the raw material compounds (a), (b) and / or (c). Preferred solvents are hydrocarbon solvents such as butane, hexane, heptane, octane, cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylen, anisole; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane. , Ether solvent such as tetrahydrofuran (THF), dioxane, halogenated hydrocarbon solvent such as methylene chloride, carbon tetrachloride; ester solvent such as ethyl acetate; glycol ester solvent such as propylene glycol monomethyl ether acetate (PGMEA). Nitrogen-containing solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), pyridine; alcohol solvents such as methanol, ethanol, isopropanol, butanol; acetone, It is a ketone solvent such as methyl ethyl ketone. Preferred are toluene, mesityrene, anisole, tetrahydrofuran, cyclopentylmethyl ether, propylene glycol monomethyl ether acetate and 2- (2-ethoxyethoxy) ethyl acetate, and more preferably toluene and propylene glycol monomethyl ether acetate (PGMEA). One type of solvent may be used, or two or more types may be used. Further, the solvent may be dehydrated before use. The amount of the solvent used is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, and usually 1000% by mass or less, preferably 500% by mass or less, based on the raw material compound. ..

<Catalyst>
It is preferable to use an acid catalyst for the equilibrium polymerization.
Examples of the acid catalyst include phosphoric acid, toluene sulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, sulfuric acid, nitric acid, acetic acid and benzoic acid, and DIAION ™ RCP-160M (strongly acidic ion exchange). Resin, manufactured by Mitsubishi Chemical Co., Ltd.) can be mentioned.
The amount of the catalyst added is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and usually 10% by mass or less, based on the polysiloxane copolymer. It is preferably 5% by mass or less, more preferably 3% by mass or less. When two or more kinds of catalysts are used, it is preferable that the total content is within the above range.

<Infrared reflective filler>
The infrared reflective filler is a filler having a volume resistivity of 50 Ω · cm or less. This is because a filler having a high conductivity also has a high infrared reflectance (see Non-Patent Document 1).
When used as an infrared reflective filler for parts requiring transparency such as windows and light emitting parts, tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, phosphorus-doped tin oxide, indium tin oxide, and A transparent conductive filler composed of at least one of zinc oxide, aluminum-doped zinc oxide, and gallium-doped zinc oxide can be mentioned. Specifically, in the case of a transparent conductive filler, infrared rays are reflected by plasma reflection of electrons as carriers, so that it is desirable that the conductivity is high, that is, the number of carriers is large, and zinc oxide is conductive only by oxygen deficiency. , Fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, or gallium-doped zinc oxide is preferable to zinc oxide in that the reflectance of infrared rays per unit volume is higher.
On the other hand, when a non-transparent material such as a mechanical part or an energy transport system may be used, a transparent conductive filler may be used, but it is preferable to use a metal powder in terms of high reflectance per unit mass and price. Specifically, when the infrared reflective filler is silver, aluminum, tin, titanium, nickel, chromium, and an alloy containing these, the infrared reflecting ability can be increased.
It is desirable that the polysiloxane copolymer has a shape and a length that absorbs less infrared rays, can efficiently bond between these infrared reflective fillers, and can protect the fillers from the atmosphere and rain on the coating film surface. The type, shape, size, addition amount, etc. of the infrared reflective filler can be appropriately selected according to the purpose. When the obtained infrared reflective material or infrared low emissivity material is transparent, a filler close to a spherical shape is preferable because the filling amount of the infrared reflective filler can be increased, and when it is opaque, a flake-shaped metal powder is preferable. It is preferable because the surface can be covered with a small amount of coating material.

The average particle size of the infrared reflective filler is preferably 0.001 to 500 μm. More preferably, it is 0.01 to 100 μm. When it is 0.01 μm or more, the transparency is good, and when it is 100 μm or less, the dispersibility is good and the filling rate can be increased.
In the present specification, the average particle size is based on the particle size distribution measurement by the laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle size by the wet method using the analysis by Franhofer diffraction theory and Mie's scattering theory, the diameter on the large side and the small side are equal (volume basis). Was taken as the median diameter.

<Near infrared absorber>
In addition to the polysiloxane copolymer and the infrared reflective filler, the composition for infrared reflecting material or the composition for infrared low emissivity material contains tungsten oxide, lanthanum boride, molybdenum oxide, and these as near-infrared absorbing materials. It may further contain an inorganic filler consisting of at least one of the composite oxides, or an organic dye. With this configuration, the amount of near-infrared rays that raise the temperature of human skin and make it feel hot can be reduced among the light incident on the window, so it is possible to add the effect of lowering the human sensible temperature. can.

<Additives>
As an additive, a dispersant / defoaming agent / coloring pigment / silane coupling agent may be further added to the composition for an infrared reflector or the composition for an infrared low emissivity material.
By adding 1 to 35 parts by weight of the dispersant to 100 parts by weight of the filler, aggregation of the filler can be prevented and storage stability can be improved.
The defoaming agents are silicone-based defoaming agents, modified silicone-based defoaming agents, silica-based defoaming agents, waxes, polysiloxanes, polyether-modified polydimethylsiloxanes, defoaming polymers, paraffin oils, and defoaming fatty groups. Defoamers and the like can be mentioned. By adding 0.1 to 5 parts by weight with respect to 100 parts by weight of the paint, defoaming property is exhibited and the workability of the application process of the water-based paint is improved.
The silane coupling agent not only enhances the affinity between the infrared reflective filler and the polysiloxane copolymer, but can also be expected to have the effect of improving the adhesion between the material to be coated and the coating film. By adding 0.1 to 5 parts by weight with respect to 100 parts by weight of the coating material, the affinity between the inorganic part and the polysiloxane copolymer can be improved, and the adhesion and durability of the coating film are improved.

<Unbound polymer compound>
The composition for an infrared reflector or the composition for an infrared low emissivity material may contain a polymer compound that adjusts the properties of the coating film as a component. As such a polymer compound, a compound that does not reduce the film-forming property and the mechanical strength is preferable. The polymer compound may be a polymer compound that does not react with an infrared reflective filler, a surface treatment agent, and a siloxane complex or a cross-linking agent. For example, silsesquioxane has an oxylanyl group and a silane coupling agent has an amino group. In this case, a polyolefin resin, a polyvinyl resin, a silicone resin, a wax and the like can be mentioned. The content is an amount that can fill the porosity by first preparing a composition for an infrared reflecting material or a composition for an infrared low emissivity material that does not contain a non-bonded polymerizable compound, and measuring the porosity. It is desirable to add a high molecular compound.

<Solvent>
The composition for an infrared reflector or the composition for an infrared low emissivity material may contain a solvent. When the component to be polymerized is contained in the composition, the polymerization may be carried out in a solvent or in the absence of a solvent. The composition containing the solvent may be applied onto a substrate by, for example, a spin coating method, and then the solvent may be removed before photopolymerization. Further, after photo-curing, it may be heated to an appropriate temperature and post-treated by thermosetting.
Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone. , Cyclohexanone, PGMEA and the like. The above solvent may be used alone or in combination of two or more.
It is not so meaningful to limit the ratio of the solvent used at the time of polymerization, and it may be determined for each individual case in consideration of polymerization efficiency, solvent cost, energy cost and the like.

<Others>
Stabilizers may be added to the composition for infrared reflectors or the composition for infrared low emissivity materials for ease of handling. As such stabilizers, known stabilizers can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
Further, an additive (oxide or the like) may be added to adjust the viscosity or color of the composition for an infrared reflector or the composition for an infrared low emissivity material. For example, titanium oxide for whitening, carbon black for blackening, and fine powder of silica for adjusting the viscosity can be mentioned. In addition, additives may be added to further increase the mechanical strength. For example, inorganic fibers and cloths such as glass fibers, carbon fibers and carbon nanotubes, or as polymer additives, fibers or long molecules such as polyvinyl formal, polyvinyl butyral, polyester, polyamide and polyimide can be mentioned.

<Manufacturing method>
Hereinafter, a method for producing a composition for an infrared reflector or a composition for an infrared low-emissivity material, and a method for producing an infrared reflector or an infrared low-emissivity material from the composition will be specifically described.

To prepare a composition for an infrared reflector or a composition for an infrared low emissivity material, an infrared reflective filler is added to a solution of a polysiloxane copolymer, and the mixture is stirred and defoamed using a stirrer such as a rotating / revolving mixer. , Mix until the agglomeration of the filler is eliminated. For example, after stirring at a rotation speed of 2000 rpm for 10 minutes, defoaming is performed at a rotation speed of 2200 rpm for 10 minutes. In addition to the rotation / revolution mixer, it can be dispersed by using a stirring motor, a raider, a three-roll, a ball mill, a rotation / revolution mill, a planetary mill, a bead mill, a jet mill, or the like.
At the time of mixing, an additive such as a dispersant may be added if necessary, or a solvent may be added to adjust the viscosity of the coating material according to the coating method.

As the coating method, it is preferable to use a wet coating method for uniformly coating the composition for an infrared reflector or the composition for an infrared low emissivity material. Of the wet coating methods, the spin coating method, which enables simple and homogeneous film formation when producing a small amount, is preferable. When productivity is important, gravure coat method, die coat method, bar coat method, reverse coat method, roll coat method, slit coat method, dipping method, spray coat method, kiss coat method, reverse kiss coat method, air knife coat A method, a curtain coating method, an inkjet method, a flexo printing method, a screen printing method, a rod coating method and the like are preferable. The wet coating method can be appropriately selected from these methods according to the required film thickness, viscosity, curing conditions and the like.

As a pre-curing condition for curing the composition for infrared reflective material or the composition for low infrared radiation material by thermal polymerization, the curing temperature is room temperature to 350 ° C., preferably room temperature to 250 ° C., more preferably 120 ° C. to 220 ° C. The temperature is in the range of ° C., and the curing time is in the range of 5 seconds to 10 hours, preferably 1 minute to 8 hours, and more preferably 5 minutes to 5 hours. After the polymerization, it is preferable to slowly cool the mixture in order to suppress stress-strain and the like. Further, the strain may be relaxed by performing a reheat treatment.

Infrared reflectors or low emissivity infrared materials are used in the form of sheets, films, thin films, fibers, molded bodies and the like. Preferred shapes are sheets, films and thin films. The film thickness of the sheet in the present specification is 1 mm or more, the film thickness is 3 μm or more, preferably 5 to 999 μm, more preferably 20 to 300 μm, and the film thickness of the thin film is less than 3 μm. The film thickness may be appropriately changed according to the intended use. The composition for an infrared reflector or the composition for an infrared low emissivity material can be used as it is as an adhesive or a filler.

[Electronics]
The electronic device according to the third embodiment of the present invention includes an infrared reflector or an infrared low emissivity material according to the second embodiment, and an electronic device having a heat generating portion or a cooling portion. The infrared reflector is arranged in the electronic device so as to face the heat generating portion. When arranged in this way, it is possible to obtain the effect of making it difficult for heat to be transferred from the heat generating portion to the member in which the infrared reflector is installed. On the other hand, the infrared low emissivity material is arranged in the outermost layer of the module including the heat generating portion. By arranging in this way, the effect of confining the heat of the heat generating portion inside can be obtained. The shape of the infrared reflective material or the infrared low-emissivity material may be any of a heat-dissipating electronic substrate, a heat-dissipating plate, a heat-dissipating sheet, a heat-dissipating film, a heat-dissipating adhesive, a heat-dissipating molded product, and the like.
For example, electronic devices include high-brightness displays and light sources. Since these light sources have a high energy density and a large amount of heat generation, a person located in front of them feels heat due to radiant heat (= radiant heat), but the coating film of the present invention blocks the radiant heat and suppresses the feeling of heat. Can be done. In addition, if it is used for the outermost layer of a surveillance camera in which the cover freezes white due to radiative cooling without a heater, it is possible to minimize the power consumption of the heater for preventing freezing.

The present invention has been described above as the present invention being formed by an infrared reflective filler and a polysiloxane copolymer to obtain an infrared reflective material or an infrared low emissivity material having high heat insulating properties, heat retention and high heat resistance. Not limited to this.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the contents described in the following examples.

The materials constituting the infrared reflective material or the infrared low emissivity material used in the examples of the present invention are as follows.

<Polysiloxane copolymer>
[Synthesis Example 1]
Preparation of Silicon Compound 1 A cooling tube, a magnetic stirrer, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. In the formula (A), the compound in which R ⁰ is phenyl and R ¹ is methyl 10.0 g, octamethylcyclotetrasiloxane (D4) 2.3 g, methanesulfonic acid 0.47 g, dehydrated toluene 10.2 g, 4-methyl 2.6 g of tetrahydropyran was placed in a flask. After stirring at 80 ° C. for 7 hours, 30.0 g of water and 56.3 g of ethyl acetate were added, and the aqueous layer was extracted. After washing the organic layer with brine three times, 5.0 g of sodium sulfate and 4.2 g of Kyoward 500 were added, and the mixture was stirred overnight. The solid was filtered off by vacuum filtration and the filtrate was concentrated. Heptane and methanol were added to the concentrate, and the obtained precipitate was dried under reduced pressure at 80 ° C. to obtain 9.9 g of a white solid. The white solid obtained by ¹ H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and the white solid obtained by ¹ H-NMR and GPC analysis is represented by the formula (1'). It is a silicon compound represented by a polymer in which each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1') is alternately bonded, and the number n of DMS units is 2.7 on average. It turned out that there was. From GPC analysis, the number average molecular weight of silicon compound 1 was Mn = 45,300, and the weight average molecular weight was Mw = 110,000.

[Synthesis Example 2]
Preparation of Silicon Compound 2 A cooling tube, a mechanical stirrer, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. In the formula (A), R ⁰ is phenyl and R ¹ is methyl 10.0 g, octamethylcyclotetrasiloxane (D4) 4.50 g, methanesulfonic acid 0.681 g, dehydrated toluene 12.1 g, 4- 3.04 g of methyltetrahydropyran was placed in a flask. The mixture was stirred at 80 ° C. for 5 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water, anhydrous sodium sulfate and Kyoward 500 were added, and the mixture was stirred. Anhydrous sodium sulfate and Kyoward 500 were separated by filtration, and the obtained solution was concentrated under reduced pressure. The obtained crude product was reprecipitated with heptane and purified. The obtained white solid was vacuum dried at 80 ° C. to obtain 9.53 g of the white solid. ¹ The white solid obtained by H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1'). It was found that the polymer was formed by alternately binding and the number n of DMS units was 3.8 on average. From the GPC analysis, the number average molecular weight of the silicon compound 2 was Mn = 40,000, and the weight average molecular weight was Mw = 93,500.

[Synthesis Example 3]
Preparation of Silicon Compound 3 A cooling tube, a magnetic stirrer, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. In the formula (A), R ⁰ is phenyl and R ¹ is methyl 10.0 g, octamethylcyclotetrasiloxane (D4) 2.3 g, methanesulfonic acid 3.2 g, dehydrated toluene 12.6 g, 4- Methyltetrahydropyran. 2 g was placed in a flask. After stirring at 80 ° C. for 2 hours, the mixture was refluxed for 5 hours. 0.0 g of water and 46.6 g of ethyl acetate were added, and the aqueous layer was extracted. After washing the organic layer twice with brine, 5.0 g of sodium sulfate and 32.0 g of Kyoward 500 were added, and the mixture was stirred overnight. The solid was filtered off by vacuum filtration and the filtrate was concentrated. Heptane and methanol were added to the concentrate, and the obtained precipitate was dried under reduced pressure at 80 ° C. to obtain 9.5 g of a white solid. The white solid obtained by 1H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and the white solid obtained by 1H-NMR and GPC analysis is represented by the formula (1'). It is a silicon compound, which is a polymer in which each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1') is alternately bonded, and the number n of DMS units is 3.2 on average. I understood. From GPC analysis, the number average molecular weight of the silicon compound 3 was Mn = 10,300, and the weight average molecular weight was Mw = 15,100.

[Synthesis Example 4]
Preparation of Silicon Compound 4 A cooling tube, a mechanical stirrer, and a thermometer protection tube were attached to a 1000 mL flask, and the inside of the flask was replaced with nitrogen. In the formula (A), R ⁰ is phenyl and R ¹ is methyl 100 g, octamethylcyclotetrasiloxane (D4) 30.0 g, methanesulfonic acid 5.35 g, dehydrated toluene 108 g, 4-methyltetrahydropyran 27. .1 g was placed in a flask. The mixture was stirred at 80 ° C. for 5 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water, anhydrous sodium sulfate and Kyoward 500 were added, and the mixture was stirred. Anhydrous sodium sulfate and Kyoward 500 were separated by filtration, and the obtained solution was concentrated under reduced pressure. The obtained crude product was reprecipitated with heptane and purified. The obtained white solid was vacuum dried at 80 ° C. to obtain 107 g of the white solid. ¹ The white solid obtained by H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1'). It was found that the polymer was formed by alternately binding and the number n of DMS units was 2.6 on average. From the GPC analysis, the number average molecular weight of the silicon compound 4 was Mn = 43,600, and the weight average molecular weight was Mw = 141,400.

The measurement conditions for GPC measurement are shown below.
<Measurement conditions>
Column: Shodex KF-804L 300 x 8.0 mm
Chromatography KF-805L 300 × 8.0mm 2 series Mobile phase: THF
Flow velocity: 1.0 ml / min
Temperature: 40 ° C
Detector: RI
Molecular Weight Standard Sample: PMMA with Known Molecular Weight

<Infrared reflective filler>
-Antimony-doped tin oxide powder (manufactured by Mitsubishi Material Denshikase Co., Ltd.), (trade name) transparent conductive powder T-1)
-Tin oxide powder (manufactured by Mitsubishi Material Denshikase Co., Ltd.), (trade name) Antimony-free transparent conductive powder S-2000)
-Phosphorus-doped tin oxide powder (manufactured by Mitsubishi Material Denshikase Co., Ltd.), (trade name) transparent conductive powder SP-2)
-Indium tin oxide powder (manufactured by Mitsubishi Material Denshikase Co., Ltd.), (trade name) transparent conductive powder E-ITO)
・ Aluminum powder (manufactured by Toya Dye Shop Co., Ltd.), (trade name) Silver powder (aluminum powder)
-Tin powder (manufactured by Amazing Craft Co., Ltd.), (trade name) tin powder # 325

[Example 1]
<Preparation of infrared reflector or infrared low emissivity material>
An example of preparation of an infrared reflector or an infrared low emissivity material is shown below.
5 mL of NMP was added to 5 g of <siloxane polymer composite coating solution 1>, and the mixture was stirred overnight. Then, 5 g of antimony-doped tin oxide powder (T-1 manufactured by Mitsubishi Materials Electronics Co., Ltd.) was added to this solution, and the mixing and degassing treatment for 3 minutes was repeated twice with Vacuum Foaming Rentaro.

-The mixed coating liquid was applied to a non-alkali glass plate (Gorilla glass manufactured by Corning: 100 mm × 100 mm × 0.6 mm) and an aluminum plate (commercially available aluminum plate: 40 mm × 40 mm × 0.5 mm) using an applicator. The gap was adjusted so that the film thickness after drying was about 10 μm, being careful not to allow the applicator and the glass substrate to come into contact with each other (Example 1). The coated glass substrate was pre-baked on a hot plate at 110 ° C. for 30 minutes, and then fired in a clean oven at 220 ° C. for 4 hours. The same was true for the aluminum substrate. The sample applied to the glass substrate was evaluated as a heat ray reflecting member, and the sample applied to the aluminum plate was evaluated as a low heat ray emitting member (low heat loss member).

<Evaluation method of low emissivity characteristics>
Double-sided tape (manufactured by Sumitomo 3M Co., Ltd.) is attached to the aluminum surface side of the low heat ray emitting member having a cured film (coating film) formed on the aluminum plate and the transistor (silicon NPN triple diffusion type 2SD2012 manufactured by Toshiba Transistor), which was created in Example 1. It was bonded using a heat conductive adhesive transfer tape No. 9885). A K thermocouple (ST-50 manufactured by Rika Kogyo Co., Ltd.) was attached to the surface on which the model number of the transistor was written, and the temperature was recorded on a personal computer using a data logger (GL220 manufactured by GRAPTHC). Place the low heat ray radiating member to which this transistor is attached on a heat insulating holder made of foamed styrene placed in the center of a constant temperature bath set at 40 ° C, and after confirming that the temperature of the transistor is constant at 40 ° C, direct current to the transistor. 1.40V was applied using a stabilized power supply, and the temperature change of the transistor was measured (FIG. 2). In this method, since the calorific value of the transistor is constant, the smaller the amount of heat released from the cured film (coating film) (the amount of infrared radiation), the higher the transistor temperature is maintained. That is, it means that there is little heat loss due to infrared radiation and the heat retention is high.

<Evaluation method of heat ray reflection characteristics>
The heat ray reflecting member having a cured film (coating film) formed on a glass plate, which was created in Example 1, was placed in an irradiation circle of a solar simulator (XiL-05BKP type manufactured by Celic Co., Ltd., 100 mW / cm ² ). Natural graphite (20 mm x 20 mm x 0.076 mm) with a K thermocouple (ST-50 manufactured by Rika Kogyo Co., Ltd.) attached to the surface of the solar simulator, which was left standing on a table processed with foamed styrol so that the infrared rays would not be transmitted. ) Was set as an infrared absorber (Fig. 3). When the irradiation of pseudo-sunlight starts from the solar simulator, natural graphite absorbs the light and the temperature gradually rises. The temperature change was recorded using a data logger (GL220 manufactured by GRAPTHC). It can be said that the heat ray reflection characteristics are so good that the temperature of natural graphite does not rise.

<Heat resistance evaluation>
-Thermogravimetric (TG) measurement The 5% weight loss temperature of the infrared reflective material or the infrared low-emission material is changed from 140 ° C to 900 ° C using a thermogravimetric / differential thermal measuring device (TG-8121 manufactured by Rigaku Co., Ltd.). It was calculated from the temperature when the amount of decrease was 5% by weight when the amount of decrease was 100% by weight. Before mixing the infrared reflective filler, the 5% weight loss was about 550 ° C.
Furthermore, the yellowing resistance of the cured film was confirmed as an index of heat resistance. Leave it in an electric oven set at 220 ° C for 4 hours, "not yellowed" is ◎, "slightly yellowed" is 〇, "deeply yellowed" is △, "brown""Things that have been burnt" to "Things that have been burnt and peeled off" are marked as x.

<Example 2>
A sample was prepared in the same manner as in Example 1 except that the infrared reflective filler was tin oxide powder (S-2000), and evaluated as a low heat ray emitting member.

<Example 3>
A sample was prepared in the same manner as in Example 1 except that the infrared reflective filler was made of phosphorus-doped tin oxide powder (SP-2), and evaluated as a low heat ray emitting member.

<Example 4>
A sample was prepared in the same manner as in Example 1 except that the infrared reflective filler was indium tin oxide powder (E-ITO), and evaluated as a low heat ray emitting member.

<Example 5>
A sample was prepared in the same manner as in Example 1 except that the infrared reflective filler was made of aluminum powder, and evaluated as a low heat ray emitting member.

<Example 6>
A sample was prepared in the same manner as in Example 1 except that the infrared reflective filler was made of metallic tin powder, and evaluated as a low heat ray emitting member.

[Example 7]
<Silicon compound 2> 1 g was added to 4 mL of NMP, and the mixture was stirred overnight. After that, a sample was prepared in the same manner as in Example 1 except that 36 mg of MS-51, 1.26 mg of DBTDL, and 1 g of antimony-doped tin oxide powder (T-1 manufactured by Mitsubishi Materials Electronics Co., Ltd.) were added. It was evaluated as a radial member.

[Example 8]
<Silicon compound 1> 1 g was added to 4 mL of NMP, and the mixture was stirred overnight. After that, a sample was prepared in the same manner as in Example 1 except that 32 mg of MS-51, 1.12 mg of DBTDL, and 1 g of antimony-doped tin oxide powder (T-1 manufactured by Mitsubishi Materials Electronics Co., Ltd.) were added. It was evaluated as a radial member.

[Example 9]
1 g of <silicon compound 3> was added to 4 mL of NMP, and the mixture was stirred overnight. After that, a sample was prepared in the same manner as in Example 1 except that 140 mg of MS-51, 4.91 mg of DBTDL, and 1 g of antimony-doped tin oxide powder (T-1 manufactured by Mitsubishi Materials Electronics Co., Ltd.) were added. It was evaluated as a radial member.

[Example 10]
1 g of <silicon compound 4> was added to 1 mL of NMP, and the mixture was stirred overnight. After that, a sample was prepared in the same manner as in Example 1 except that 33 mg of MS-51, 1.15 mg of DBTDL, and 1 g of antimony-doped tin oxide powder (T-1 manufactured by Mitsubishi Materials Electronics Co., Ltd.) were added. It was evaluated as a radial member.

<Comparative Example 1>
A heat-resistant paint (heat-resistant paint coat black (product number 1064) manufactured by Kure Engineering Co., Ltd.) was applied to an aluminum substrate and evaluated as a low heat ray emitting member in the same manner as in Example 1.

<Comparative Example 2>
A commercially available heat ray absorbing film (Tamiya Spray No. 27 Matte White) was applied to the aluminum substrate, and the evaluation was performed as a low heat ray emitting member in the same manner as in Example 1.

Sumika Bayer Urethane Co., Ltd. (trade name) Bihydrol UH2342 (1-methyl-2-pyrrolidone 5% by weight) in which Marusu Glazing Joint Stock Company (trade name) Synthetic Cordierite SS-1000 is dispersed as an aqueous urethane dispersion ) Was applied and evaluated as a low heat ray emitting member in the same manner as in Example 1.

<Comparative Example 3>
A commercially available heat ray absorbing film (manufactured by Asahipen Corporation, heat shield sheet SG-21 clear for glass) was attached to a glass substrate and evaluated in the same manner as in Example 1.

The evaluation of low heat radiation characteristics is shown in Table 1.
<Table 1>

From Table 1, the composite material using the polysiloxane copolymer used in the present invention of Examples 1 to 10 and the conductive oxide filler and the metal filler as the infrared reflective filler emits infrared rays more than the commercially available heat-resistant paint. It can be seen that the amount is small and the heat insulating effect is high. In particular, the effect is high when a metal filler is used. It is considered that this is because the reflectance of the metal due to free electrons has a higher reflectance per unit volume than the plasma reflection of the transparent conductive oxide. Since the heat-resistant paint used in Comparative Example 1 was black, a commercially available white paint was measured in the same manner just in case (Comparative Example 2), but the temperature changed only about 0.3 ° C, so the color was visually visible. It seems that there is almost no effect. Further, when a heat-dissipating filler (cordierite) having a high far-infrared radiation function was dispersed as the heat-dissipating paint, the temperature was further lowered as compared with the commercially available heat-resistant paint. Therefore, the paint of the present invention can be said to be a heat-insulating paint, which is the opposite of the heat-dissipating paint.
Further, in the polysiloxane composite material of the present invention, yellowing, which is a guideline for deterioration of the coating material, is not observed up to 240 ° C. In Comparative Example 1, since the black pigment was contained, the degree of yellowing could not be observed. Since the heat loss due to radiation is proportional to the fourth power of the temperature, the effect of the coating material of the present invention becomes greater as it is used at a higher temperature. The thermal decomposition temperature of the polysiloxane used in the present invention is around 550 ° C., and it is considered to be effective as a radiative cooling measure for equipment in the temperature range such as a solder reflow furnace.

Table 2 shows the evaluation of the heat ray reflection characteristics.
<Table 2>

From Table 2, in Example 1, the temperature of the infrared reflective material is about 2.6 ° C. lower than that in the case of using a commercially available heat ray absorbing film (Comparative Example 4) in terms of the characteristics of the heat ray reflecting glass. I understand. Further, since the infrared reflector of the present invention has high heat resistance and less yellowing, it can be seen that it can be used as a heat ray reflector that can be used for a long period of time.

The composition for infrared reflectors and the composition for infrared low emissivity of the present invention have high heat resistance and low absorption of infrared rays, so that the coating material having high heat resistance, high reflectance and low emissivity, and the coating material are cured. It is used for the coated film.

21. Aluminum substrate 22. Coating film 23. Transistor (heating element)
24. Thermocouple 25. Sample holder (Styrofoam)
31. Solar simulator 32. Coating film 33. Glass substrate 34. Infrared absorber (graphite)
35. thermocouple

Claims (13)

A polysiloxane copolymer consisting of an infrared reflective filler and a cage-type silsesquioxane repeating unit represented by the formula (A) and a chain siloxane repeating unit represented by the formula (B);
Compositions for infrared reflectors or compositions for infrared low emissivity materials.

In formula (A),
^R0 is independently an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms, at least one hydrogen is contained. It may be replaced with a halogen or an alkyl having 1 to 20 carbon atoms;
^R1 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, and an aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. An alkyl having 5 to 20 carbon atoms may be replaced with a cycloalkylene having 1 to 40 carbon atoms, and at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
x is greater than or equal to 1;
In formula (B),
^R2 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, and an aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms, or in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or carbon. May be replaced with the number 5-20 cycloalkylene;
y is 1 or more. The composition for an infrared reflector or a composition for an infrared low emissivity material according to claim 1, wherein the infrared reflective filler is a metal oxide. Claim 1 in which the infrared reflective filler comprises at least one of tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, phosphorus-doped tin oxide, indium tin oxide, and zinc oxide, aluminum-doped zinc oxide, and gallium-doped zinc oxide. Alternatively, the composition for an infrared reflective material or the composition for an infrared low-emission material according to 2. The method according to any one of claims 1 to 3, further comprising an inorganic filler composed of tungsten oxide, lanthanum borohydride, molybdenum oxide, and at least one of composite oxides containing these as a near-infrared absorbing material, or an organic dye. The composition for an infrared reflector or the composition for an infrared low emissivity material according to the above. The composition for an infrared reflector or a composition for an infrared low emissivity material according to claim 1, wherein the infrared reflective filler is a metal powder. The composition for an infrared reflector or a composition for an infrared low emissivity according to claim 1 or 5, wherein the infrared reflective filler comprises at least one of silver, aluminum, tin, titanium, nickel, chromium, and an alloy containing these. thing. The composition for an infrared reflective material or a composition for an infrared low emissivity material according to any one of claims 1 to 6, wherein the infrared reflective filler is in the form of an amorphous powder, a spherical shape, a scale, or a flake. The composition for an infrared reflector or a composition for an infrared low emissivity material according to any one of claims 1 to 7, wherein the weight average molecular weight of the polysiloxane copolymer is in the range of 2,000 to 10,000,000. thing. The composition for an infrared reflector or a composition for an infrared low emissivity material according to any one of claims 1 to 8, wherein the glass transition temperature of the polysiloxane copolymer is 0 ° C. or higher. The infrared reflector according to any one of claims 1 to 9, wherein the crosslink density n of the polysiloxane copolymer, which is obtained from the calculation formula represented by the formula (α), is 150 mol / m ³ or more. Compositions or compositions for infrared low emissivity materials.
n = E'/ 3RT ... (α)
In formula (α), n: crosslink density (mol / m ³ ), E': storage elastic modulus (Pa), R: gas constant ((Pa · m ³ ) / K · mol)), T: temperature (K). ) An infrared reflective transparent coating material comprising the composition for an infrared reflective material according to any one of claims 1 to 9. An infrared reflective window agent, a transparent cover, or an infrared cut filter obtained by applying the infrared reflective transparent coating material according to claim 11 to glass, a transparent heat-resistant resin, or a translucent ceramic and curing it. The infrared reflective transparent coating material according to claim 11 is applied to an inorganic structural material or a structural material made of engineering plastic having a heat resistant temperature of 150 ° C. or higher, and reflects infrared rays emitted from the outside of the structural material. Sheets, structural materials, mechanical parts, or electronic devices that suppress the temperature rise and reduce the emissivity of infrared rays emitted from the inside to the outside to provide heat retention.

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