JP3286071B2 - Production method of hydrophobic antimony-containing tin oxide fine particles, heat ray shielding coating liquid and its production method, and heat ray shielding glass and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophobic antimony-containing
Manufacturing method of tin oxide fine particles, heat ray shielding coating liquid and its
The present invention relates to a manufacturing method and a heat-shielding glass and a manufacturing method thereof, and particularly to a heat-shielding glass suitable for vehicles and buildings requiring high transparency and film hardness.

[0002]

2. Description of the Related Art Conventionally, as means for obtaining a heat ray shielding coating solution and a heat ray shielding glass, for example, Japanese Patent Application Nos. 5-56021 and 5-104526 disclose a heat ray shielding film and a heat ray made of tin oxide fine particles. Shielding glasses have been proposed by the present inventors. According to these inventions, by using the tin oxide fine particles and the siloxane compound, it is possible to obtain a low-cost heat ray shielding glass having high visible light transmittance, excellent heat ray shielding properties, and low cost. It is disclosed that it is suitable as a glass for use.

However, a film using a siloxane compound has a high firing temperature, and generally requires a firing temperature of 550 ° C. or higher in order to obtain abrasion resistance equivalent to that of glass. There is a problem that the energy cost increases.

Accordingly, the present inventors have proposed a Japanese Patent Application No. 5-104.
In No. 526, as a method of producing a high-heat-ray shielding film by firing at low temperature using tin oxide fine particles and a silazane polymer, first, a heat-ray shielding film is formed using an antimony-containing tin oxide (hereinafter referred to as ATO) sol. Then, a method is disclosed in which a silazane polymer solution is applied and baked to form a strong heat ray shielding film.

However, in this method, in order to produce a heat ray shielding film, application and baking must be repeated twice, the production process is complicated, and the production cost is lower than that of the method performed before this. Although it is lower cost compared,
There is a risk that it will be relatively high.

Therefore, a heat ray shielding coating solution which can disperse the ATO sol and the silazane polymer in the same solvent and apply and sinter to glass at once can be considered. However, the ATO sol is an aqueous dispersion and has a low polarity. When mixed with an organic solvent, aggregation occurs and the dispersibility is impaired.On the other hand, the silazane polymer exhibits remarkable reactivity to water and decomposes or gels. There was a problem that it was impossible to use it as a heat ray shielding coating solution for producing a heat ray shielding film having excellent shielding properties, and being transparent and excellent in film strength.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in consideration of the above circumstances . Manufacturing method of antimony-containing tin oxide fine particles,
Heat ray shielding coating liquid, its manufacturing method and heat ray shielding glass
And its manufacturing method .

[0008]

This object can be achieved by using hydrophobic antimony-containing tin oxide fine particles as antimony-containing tin oxide. The hydrophobic antimony-containing tin oxide fine particles are obtained by adding a cationic surfactant or a nonionic surfactant to an aqueous sol of antimony-containing tin oxide to obtain a precipitate, and then drying the precipitate. Obtainable. At this time, the amount of the cationic surfactant or nonionic surfactant added is preferably 4 to 26% by weight based on the amount of antimony-containing tin oxide.

Further, by dispersing the hydrophobic antimony-containing tin oxide fine particles in a silazane polymer solution, a heat ray shielding coating solution can be prepared. Also,
The particle diameter of the hydrophobic antimony-containing tin oxide fine particles,
It is preferably 100 nm or less. Further, the weight ratio of the hydrophobic antimony-containing tin oxide to the silazane polymer is such that the hydrophobic antimony-containing tin oxide: silazane polymer =
Preferably, the ratio is 19: 1 to 1: 4.

Further, a heat ray shielding glass can be produced using the above-mentioned heat ray shielding coating solution. Such a heat ray shielding glass can be produced by applying the heat ray shielding coating liquid to a part or all of the glass serving as a substrate, and then firing at 300 to 550 ° C.

[0011]

By adding a cationic surfactant or a nonionic surfactant to ATO in the form of an aqueous sol, the surface of the ATO is converted from hydrophilic to lipophilic and becomes stably dispersed in an organic solvent. .

[0012]

Hereinafter, the present invention will be described in detail. First, the method for producing the hydrophobic antimony-containing tin oxide fine particles of the present invention will be described. Hydrophobic antimony obtained by this method
The contained tin oxide fine particles (hereinafter abbreviated as organo ATO)
The surface has lipophilicity, and is thereby stably dispersed in an organic solvent.

An example of a method for producing such an organo ATO will be described below. First, ATO is converted into an aqueous sol having good dispersibility. A method for producing the ATO sol is disclosed in, for example, JP-A-2-105875. According to this method, A having a particle size of 5 to 20 nm is used.
Although a sol in which the TO fine particles are substantially monodispersed can be obtained, the method for producing the ATO fine particles and the ATO sol is not limited thereto, and any method can be used.

Subsequently, a cationic surfactant or a nonionic surfactant is added to the aqueous ATO sol to obtain a precipitate. This is achieved by changing the surface of the ATO fine particles to lipophilic and removing 100% of water from the surface.
This is because it can be dispersed in an organic solvent while maintaining the dispersibility.

As the cationic surfactant and the nonionic surfactant, any one can be used as long as it adsorbs the ATO fine particles with a hydrophilic group and makes the particle surface lipophilic. In particular, as the cationic surfactant, a primary amine salt or an alkyl quaternary ammonium salt is preferable, and as the nonionic surfactant, an alkylamine ethylene oxide condensate is preferable.

The primary amine salts include octylamine, decylamine, dodecylamine, tetradecylamine, octadecylamine, cocoalkylamine, tallowalkylamine, hardened tallowalkylamine, soybean alkylamine, tetradecylamine acetate, octadecylamine Amine acetate and the like.

As the alkyl quaternary ammonium salt,
Dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, methyldodecylbenzyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium chloride, etc. Is mentioned.

Examples of the alkylamine ethylene oxide condensate include polyoxyethylene dodecylamine, polyoxyethylene octadecylamine, polyoxyethylene cocoalkylamine, and polyoxyethylene tallowalkylamine. Such a nitrogen-based surfactant is suitable because it is effectively adsorbed on the ATO surface and the composition of the precipitate is promptly added with a small amount to make it lipophilic, and when the formed precipitate is dried, It is presumed that this is because it is possible to obtain an organo ATO that is very easily dispersed in an organic solvent without forming a clump having strong aggregation.

The amount of the cationic surfactant or nonionic surfactant added can be appropriately adjusted depending on the surface area of the ATO fine particles. In particular, the amount is 4 to 26% by weight based on the aqueous ATO sol. Is 5-20% by weight
It is preferable that If the amount is less than 4% by weight, the amount of the surfactant added is small, the entire surface of the ATO fine particles cannot be made lipophilic, and thus the dispersibility in an organic solvent may be poor. On the other hand, if the content exceeds 26% by weight, not only is the amount of the surfactant added too much, which is wasted, but also causes whitening of the film when a film is formed later.

Then, the obtained precipitate is subjected to treatment such as filtration and pressing to separate water. The method of filtration and pressing at this time is arbitrary, and an appropriate means can be used depending on the amount of the obtained precipitate. Then, the precipitate is dried. The drying temperature is preferably 160 ° C. or lower. This is because if the temperature exceeds 160 ° C., the surfactant may be volatilized and decomposed.

The organo ATO thus obtained
Is a lump immediately after production, but can be pulverized by lightly pulverizing.

Such an organo ATO is prepared by converting the ATO surface from hydrophilic to lipophilic by adding a cationic surfactant or a nonionic surfactant after converting the ATO into an aqueous sol. Since it is obtained, it can be stably dispersed in an organic solvent.

Next, a heat ray shielding coating liquid using the above-mentioned organo ATO will be described. This heat ray shielding coating liquid is a coating liquid using antimony-containing tin oxide fine particles as a heat ray shielding material.
O is dispersed in a silazane polymer solution serving as a binder.

The organo ATO has a particle size of 100 nm.
Below, preferably 3 to 100 nm, more preferably 5 to 50
nm. This is because, in order to make the heat ray shielding film obtained by the heat ray shielding coating liquid transparent, it is required that there is no absorption in the visible region and that there is little scattering. Since organoATO does not absorb visible light, transparency can be obtained by reducing scattering.
In general, scattering of light by a particle is such that the particle size is about の of the wavelength.
It is known that when the value is smaller than the above, the value becomes smaller in proportion to the sixth power of the particle size. Since the wavelength of visible light is 400 to 780 nm, the particle size is approximately 200 to 780 nm.
Since the scattering is maximum at 390 nm and the scattering is small below 390 nm, the heat ray shielding film can be made transparent by setting the particle size to 100 nm or less.

It is preferable that the organo ATO has good dispersibility when dispersed in a solvent. This is because when the organoATO aggregates during dispersion and the formed particle size is 100 nm or more, a transparent film cannot be obtained for the same reason. Therefore, the organo ATO is in a sol state (hereinafter referred to as organo A).
(Abbreviated as TO sol).

Further, the silazane polymer has the following (I)
Having a number average molecular weight of 100 to 5000 represented by the structural formula
Any inorganic polymer can be used. These can be obtained, for example, by the methods disclosed in JP-A-60-145903 and JP-A-61-89230. In the above structural formula, at least one of R ₁ , R ₂ , and R ₃ is a hydrogen atom, and the other is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, Represents an alkoxy group or the like.

The weight ratio of the organo ATO to the silazane polymer is from 19: 1 to 1: 4, preferably from 9: 1 to 1: 3, more preferably from 4: 1 to 1: 2. This is because when the amount of tin oxide containing hydrophobic antimony is larger than the ratio in the range of 19: 1 to 1: 4, the strength of the heat ray shielding film becomes insufficient, and when the amount of organo ATO is small, the heat ray shielding performance decreases. It is.

The organic solvent used as the dispersion medium of the organo ATO and the silazane weight is not particularly limited as long as the silazane polymer can be dissolved therein, and aromatic hydrocarbons such as benzene, toluene and xylene, and diethyl ether And ethers such as dibutyl ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and tetrachloromethane.

Next, a method for producing the heat ray shielding coating solution of the present invention will be described. First, antimony-containing tin oxide fine particles having a particle size of 100 nm or less are prepared, and the organo ATO is prepared.
In the same manner as in the above method, an organo ATO is produced. At this time, the organo ATO is dried until the residual moisture becomes 1% or less. This is because, when the residual water content is 1% or more, when mixing the following silazane polymer solution, the organo AT
This is because O is agglomerated, whereby the transparency of the heat ray shielding film produced is reduced, and the stability of the silazane polymer is impaired.

Next, the above-mentioned organo-ATO is added to an organic solvent and shaken or stirred to form an organo-ATO sol,
Then, it can be obtained by adding an arbitrary amount of a silazane polymer to the organo ATO sol. At this time, an ultrasonic dispersing machine, a homogenizer, or the like may be used for better dispersion.

Since such a heat ray shielding coating solution is obtained by dispersing an organo ATO in a silazane polymer solution, when a heat ray shielding film is prepared using this,
Even with a single layer film, a heat ray shielding film having excellent film strength, abrasion resistance and transparency can be produced.

Next, a heat ray shielding glass using the heat ray shielding coating solution of the present invention will be described. In this case, a heat ray shielding film formed by applying the above-mentioned heat ray shielding coating liquid and drying the glass surface is formed on at least a part of the glass surface.

As the glass, soda-lime glass,
Any glass such as E glass, hard glass, and quartz glass can be used. Further, the glass may be transparent or may be opaque, but since the heat ray shielding coating solution of the present invention can produce a transparent heat ray shielding film, the glass itself is also transparent. The greater the effect, the better.

Further, in order to substantially obtain the heat ray shielding effect, it is preferable that the difference between the visible light transmittance and the solar ray transmittance of the heat ray shielding glass (hereinafter, referred to as the solar ray shielding effect) is 8% or more.

The heat ray shielding film has a thickness of 0.1 to
It is preferably 4 μm. This is because if the thickness is 0.1 μm or less, the film strength is low and a sufficient heat ray shielding effect cannot be obtained. Further, even if the thickness is 4 μm or more, a remarkable improvement in the heat ray shielding effect is not seen, which is uneconomical. Further, the intended use of the heat ray shielding glass to be obtained and the organo A contained in the heat ray shielding film
Depending on the TO amount, it may be outside the above range.

Such a heat ray shielding glass can be obtained by applying the above-mentioned heat ray shielding coating solution to the glass by an arbitrary method such as a spin method, a dipping method, a spray method, and the like, followed by firing. The firing temperature is preferably from 300 to 550 ° C. This is because the heat ray shielding film formed at a temperature of 300 ° C. or less has poor film strength, and at a temperature of 550 ° C. or more, soda-lime glass mainly used as a substrate may be deformed.

Next, a method of using the heat ray shielding glass of the present invention will be described. The heat ray shielding glass of the present invention can be used for vehicle glass. In this case, the visible light transmittance is preferably set to 70% or more from the viewpoint of safety. This visible light transmittance is based on the organo AT contained in the heat ray shielding film.
It can be adjusted by the amount of O. Here, thickness 3.
FIG. 1 shows changes in visible light transmittance and solar radiation transmittance when a heat ray shielding film is formed on 5 mm soda-lime glass. According to FIG. 1, when the amount of the organo ATO in the heat ray shielding film is 7.2 g / m ² or less, the visible light transmittance can be 70% or more. From FIG. 1, it can be seen that the amount of organoATO in the heat ray shielding film should be 0.7 g / m ² or more in order to make the solar ray shielding effect 8% or more from the viewpoint of the heat ray shielding effect. Therefore, in order to obtain a heat ray shielding glass having a visible light transmittance of 70% or more and a solar radiation shielding effect of 8% or more by using 3.5 mm thick soda lime glass as a vehicle glass, the organosol in the heat ray shielding film is required. Set the ATO amount to 0.
What is necessary is just to be 7-7.2 g / m < ² >.

Further, it can be used for building glass. Often used as an interior for buildings,
As the glass serving as the substrate, not only a transparent glass but also any type of glass such as a colored transparent glass, an opaque glass, a glass with a beautiful pattern, or the like can be used. Further, the visible light transmittance and the solar shading rate of the heat ray shielding glass to be obtained are the same as those of the above-mentioned vehicle glass, and the organo ATO is used.
By adjusting the amount, it can be made arbitrary. Further, examples of use of the heat ray shielding glass of the present invention are not limited to these examples.

Such a heat ray shielding glass is made of an organo A
Since it has a heat ray shielding film formed of a heat ray shielding coating solution obtained by dispersing TO in a silazane polymer solution, a heat ray shielding glass having a high visible light transmittance and a high ray shielding effect is obtained. In addition, antimony-containing tin oxide having a heat ray shielding effect and a silazane polymer which is a binder of the antimony-containing tin oxide can be applied at a time, thereby simplifying the manufacturing process and reducing the manufacturing cost. can do. Furthermore, regardless of the low firing temperature, a heat ray shielding film having high abrasion resistance and high film strength can be provided, and a glass suitable for a vehicle glass and a building glass can be obtained.

(Examples) Hereinafter, specific examples will be shown to clarify the effects of the present invention. 6.2 parts by weight of SbCl ₃ ,
70 parts by weight of SnCl ₄ .5H ₂ O were dissolved in 3000 parts by weight of 6N hydrochloric acid, and 25% ammonia solution was added to ₂ parts by weight.
The reaction product was filtered and washed until ammonium chloride could not be detected. The reaction product-containing solution is heated to 350 ° C. in a closed container,
After holding for 5 hours, water vapor is released during the cooling process, concentrated to a solid content of 25% by weight, and aqueous ATO having a particle size of 1 to 10 nm.
A sol was obtained.

10 parts by weight of octadecylamine as a cationic surfactant was added to 400 parts by weight of the aqueous ATO sol to obtain an aggregated precipitate. The aggregated precipitate was taken out by filtration and dried at 70 ° C. for 2 hours to obtain a surface-treated organo ATO. 100 parts by weight of this surface-treated organo ATO and 125 parts by weight of xylene are mixed and gently stirred to give 40 parts of organo ATO.
% Organo-ATO sol was obtained. This Organo A
The TO sol had good dispersibility and did not separate or precipitate even after being left for a long time. 75 parts by weight of the organo ATO sol and 100 parts by weight of a xylene solution (PHPN-1 manufactured by Tonen Co., Ltd.) containing 20% by weight of a silazane polymer were mixed with 75 parts by weight of xylene, and the solid content was 20% by weight.
Was obtained.

The above-mentioned heat ray shielding coating solution was applied to a 3.5 mm thick soda-lime glass by a spin coating method while changing the number of revolutions so that the amount of organo ATO was 2.0 to 8.0 g / m ^2, and applied. Calcination was performed for 1 hour at each temperature in the range of ５550 ° C.

Table 1 shows the visible light transmittance, the solar radiation transmittance, and the abrasion resistance of the heat ray shielding glass. Here, the visible light transmittance and the solar transmittance were measured by the method of JIS R 3106. The abrasion resistance was indicated by a change in haze caused by abrasion 1000 times under a load of 500 g with a wear wheel of CS-10F using a Taber abrasion tester.

(Example 2) Aqueous ATO sol 4 of Example 1
To 00 parts by weight, 10 parts by weight of dodecyldimethylbenzylammonium chloride as a cationic surfactant was added to obtain an aggregated precipitate. The aggregated precipitate was taken out by filtration and dried at 70 ° C. for 2 hours to obtain a surface-treated organo ATO. This surface treated organo AT
O is mixed with 100 parts by weight and 125 parts by weight of xylene,
By lightly stirring, an organo ATO sol containing 40% of organo ATO was obtained. This organo-ATO sol also had good dispersibility similarly to Example 1, and did not separate or precipitate even after being left for a long time. This organo AT
When a heat ray shielding coating solution and a heat ray shielding glass were produced from the O sol in the same manner as in Example 1, the same results as in Example 1 were obtained.

(Example 3) Aqueous ATO sol 4 of Example 1
10 parts by weight of polyoxyethylene dodecylamine as a nonionic surfactant was added to 00 parts by weight to obtain an aggregated precipitate. The coagulated precipitate was removed by filtration, and
After drying at 2 ° C. for 2 hours, a surface-treated organo ATO was obtained. 100 parts by weight of this surface-treated organo ATO and 125 parts by weight of xylene are mixed and gently stirred to form an organo AT containing 40% of organo ATO.
An O sol was obtained. This organo-ATO sol also had good dispersibility, like Example 1, and did not separate or precipitate even after being left for a long time. When a heat ray shielding coating solution and a heat ray shielding glass were produced from this organo ATO sol in the same manner as in Example 1, the same results as in Example 1 were obtained.

(Comparative Example) Organo-ATO obtained in Example 1
75 parts by weight of the sol and 175 parts by weight of a toluene solution containing 11.4% by weight of a polysiloxane prepared by hydrolyzing and polycondensing a silicon alkoxide were mixed to give a solid content of 20%.
By weight, a heat ray shielding coating solution was obtained. This heat ray shielding coating solution is 3.5 mm thick by spin coating.
500 ℃, 550 ℃, 5
It was baked at 80 ° C. for 1 hour to obtain a heat ray shielding glass. Table 1 shows the visible light transmittance, the solar radiation transmittance, and the abrasion resistance of this heat ray shielding glass.

[0047]

[Table 1]

As is clear from Table 1, the heat ray shielding glass of the present invention shows excellent abrasion resistance even when fired at a low temperature, and has a higher visible light transmittance and a higher solar transmittance. Have. In addition, the solar shading effect is 8% or more for all the samples a to j, and it can be seen that the heat ray shading effect is not inferior.

[0049]

As described above, the hydrophobic adhesive of the present invention is used.
The antimony-containing tin oxide fine particles are prepared by adding the antimony-containing tin oxide fine particles to an aqueous sol, and then adding a cationic surfactant or a nonionic surfactant.
The surface of the antimony-containing tin oxide fine particles is converted from hydrophilic to lipophilic, and stably dispersed in an organic solvent. Further, the heat ray shielding coating solution of the present invention has a hydrophobic particle size of 100 nm or less and a residual moisture of 1% or less.
Since mon-containing tin oxide fine particles are dispersed in a silazane polymer solution, when a heat ray shielding film is produced using this, even if it is a single film, the film strength, abrasion resistance, and transparency It is possible to manufacture a heat ray shielding film having excellent heat resistance.
Furthermore, since the heat ray shielding glass of the present invention has the heat ray shielding film formed by the above-mentioned heat ray shielding coating liquid, the heat ray shielding glass has high visible light transmittance and high heat ray shielding effect. In addition, antimony-containing tin oxide having a heat ray shielding effect and a silazane polymer which is a binder of the antimony-containing tin oxide can be applied at a time, thereby simplifying the manufacturing process and reducing the manufacturing cost. can do. Further, regardless of the low firing temperature, a heat ray shielding film having high abrasion resistance and high film strength can be provided, and effects such as obtaining glass suitable for vehicle glass and building glass can be obtained.

[Brief description of the drawings]

Fig. 1 Organo-ATO applied to soda-lime glass,
Organo-AT in heat-shielding glass obtained by firing
It is a graph which shows the relationship between O amount and transmittance.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tsuneo Yanagisawa 585 Tomimachi, Funabashi-shi, Chiba Sumitomo Cement Co., Ltd. Central Research Laboratory (56) References JP-A-6-19176 (JP, A) JP-A-63 -151619 (JP, A) JP-A-61-183121 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01G 1/00-23/00 C09D 1/00 CA (STN) JICST file (JOIS)

Claims (10)

(57) [Claims] An aqueous solution of antimony-containing tin oxide fine particles.
To cationic surfactants or nonionic surfactants
Is added to obtain a precipitate, and the precipitate is dried.
Production of hydrophobic antimony-containing tin oxide fine particles
Law. 2. The method according to claim 1, wherein the cationic surfactant or the
The addition amount of the nonionic surfactant is the same as that of the antimony-containing acid.
4 to 26% by weight based on tin oxide fine particles
2. The hydrophobic antimony-containing tin oxide fine particles according to claim 1.
Particle manufacturing method. 3. The method according to claim 1, wherein the cationic surfactant is a primary amine.
Salt or alkyl quaternary ammonium salt
The hydrophobic antimony according to claim 1 or 2, wherein
Method for producing tin oxide fine particles. 4. The method according to claim 1, wherein the nonionic surfactant is an alkyl alcohol.
Characterized by being composed of a minethylene oxide condensate
The hydrophobic antimony-containing sulfur oxide according to claim 1 or 2.
Production method of fine particles. 5. Tin oxide fine particles containing hydrophobic antimony
Heat characterized by being dispersed in a silazane polymer solution
Line shielding coating liquid. 6. The fine particles of tin oxide containing hydrophobic antimony
The particle diameter of the particles is 100 nm or less
The coating liquid for heat ray shielding according to claim 5. 7. The hydrophobic antimony-containing tin oxide fine particles.
Weight ratio of the polymer and the silazane polymer is hydrophobic antimony.
-Containing tin oxide fine particles: silazane polymer = 19: 1 to 1:
7. The heating wire according to claim 5, wherein the heating wire is 4.
Shield coating liquid. 8. An antimony-containing acid having a particle size of 100 nm or less.
Aqueous sol of tin oxide fine particles, cationic surfactant or
After adding a nonionic surfactant to obtain a precipitate,
Precipitate is dried and hydrophobic antimony-containing tin oxide fine particles
And then the hydrophobic antimony-containing tin oxide fine particles
The particles are dispersed in an organic solvent to form a dispersion, and then the dispersion
Hot water characterized by mixing a silazane polymer solution
Production method of shielding coating liquid. 9. The method according to claim 5, wherein
A heat ray shielding film composed of a heat ray shielding coating liquid is
And characterized that it has been formed on at least a portion of the glass comprising
Heat ray shielding glass. 10. The method according to claim 5, wherein :
Of the heat-shielding coating liquid from the glass
Or apply to all, then apply this glass to 300-5
Heat ray shielding gas characterized by firing at a temperature of 50 ° C.
Lass recipe.