WO2020031300A1

WO2020031300A1 - Snow-ice accretion preventing agent, snow-ice accretion prevention structure, and production method for snow-ice accretion prevention structure

Info

Publication number: WO2020031300A1
Application number: PCT/JP2018/029804
Authority: WO
Inventors: 駿介長井; 智彦小竹
Original assignee: 日立化成株式会社
Priority date: 2018-08-08
Filing date: 2018-08-08
Publication date: 2020-02-13
Also published as: JP7279720B2; JPWO2020031300A1

Abstract

The present invention pertains to a snow-ice accretion preventing agent that comprises a liquid composition containing at least one selected from the group consisting of: polysiloxane compounds having a hydrolyzable functional group or a condensed functional group; and hydrolysate products of said polysiloxane compounds having a hydrolyzable functional group.

Description

Snow- and ice-preventing agent, snow-and-ice prevention structure, method for manufacturing snow-and-ice prevention structure

The present invention relates to a snow and ice prevention agent, a snow and ice prevention structure, and a method for manufacturing a snow and ice prevention structure.

In snowy and cold districts, there is the problem of snow and ice that causes snow and ice to remain attached to the surface of the target structure. The attached snow and ice may cause not only deterioration of the function of the target structure, but also breakage and collapse of the target structure. In addition, an accident due to falling of attached snow and ice is also assumed.

雪 As a countermeasure against such snow and ice, a snow prevention paint is known (for example, Patent Document 1). Patent Document 1 discloses a snow-prevention paint in which a fluorine-based powder is mixed with a fluorine resin or the like.

JP-A-8-3479

An object of the present invention is to provide a novel snow and ice preventing agent capable of imparting excellent snow and ice preventing properties to a surface to be treated of an object. Another object of the present invention is to provide a snow and ice prevention structure using the snow and ice prevention agent and a method of manufacturing the snow and ice prevention structure.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a liquid composition containing a polysiloxane compound having a reactive group (hydrolyzable functional group or condensable functional group) in the molecule. The present inventors have found that a snow and ice preventing agent obtained by using the above exhibits excellent snow and ice preventing properties, and have completed the present invention.

The present invention provides a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and at least one selected from the group consisting of hydrolysis products of the polysiloxane compound having the hydrolyzable functional group. The present invention provides a snow and ice inhibitor comprising a liquid composition containing: According to such a snow and ice preventing agent, excellent snow and ice preventing properties can be imparted to the surface of the object to be treated. In addition, the snow and ice prevention part formed from the snow and ice prevention agent has excellent adhesion to the surface to be processed.

When the hydrolyzable functional group is an alkoxy group, the polysiloxane compound includes a compound represented by the following formula (B). Thereby, more excellent snow and ice prevention and adhesion can be achieved.

[In the formula (B), R ^1b represents an alkyl group, an alkoxy group or an aryl group, R ^2b and R ^3b each independently represent an alkoxy group, and R ^4b and R ^5b each independently represent an alkyl group or an aryl group. And m represents an integer of 1 to 50. ]

In the snow and ice prevention agent, the liquid composition is a group consisting of a silane monomer having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of the silane monomer having the hydrolyzable functional group. It may further contain at least one selected from more. As a result, it is possible to achieve more excellent snow and ice prevention and adhesion.

において In the snow and ice prevention agent, the liquid composition may further contain airgel particles. As a result, the ability to prevent snow and ice is further improved.

The snow / ice prevention agent may be used to form a snow / ice prevention part on the surface of the object to be processed. By forming such a snow and ice prevention part, further excellent snow and ice prevention can be achieved. In this case, the snow and ice prevention part may include aerogel.

The present invention also provides a snow and ice preventing agent having a ladder-type structure including a support portion and a bridge portion, wherein the bridge portion includes a snow and ice preventing component containing a compound represented by the following formula (2). provide. Such a snow and ice prevention agent has excellent snow and ice prevention and durability due to the ladder type structure.

[In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50. ]

化合物 As the compound having a ladder structure, a compound having a structure represented by the following formula (3) can be given. Thereby, more excellent snow and ice prevention and durability can be achieved.

[In the formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b represents 1 to 50 Indicates an integer. ]

The snow and ice prevention unit may include aerogel. The snow and ice prevention component may be aerogel. Thereby, more excellent snow and ice prevention properties can be achieved.

The present invention also includes an object and a snow and ice prevention unit on a surface to be processed of the object, wherein the snow and ice prevention unit includes a dried product (reactant) of the snow and ice prevention agent. Provide a structure. The snow and ice prevention structure has a snow and ice prevention portion containing a dried product of the snow and ice prevention agent, and thus has excellent snow and ice prevention properties, and also has excellent adhesion between the surface to be processed and the snow and ice prevention portion. .

The present invention also provides a method for manufacturing a snow and ice preventing structure, comprising a step of applying the snow and ice preventing agent to a surface to be processed of an object.

According to the present invention, it is possible to provide a novel snow and ice preventing agent capable of imparting excellent snow and ice preventing properties to a surface to be processed of an object. Further, according to the present invention, it is possible to provide a snow and ice prevention structure using the snow and ice prevention agent and a method for manufacturing the snow and ice prevention structure.

The snow and ice protection agent of the present invention can be used, for example, for structures such as bridge girders, steel towers, buildings, houses, ships, vehicles, aircraft, telecommunications facilities, road traffic signs, traffic lights, electric wires, snow gutters, and pipelines. It can be applied to prevent snow and ice from adhering to these structures.

FIG. 3 is a diagram illustrating a method for calculating a biaxial average primary particle diameter of particles. FIG. 3 is a view showing a solid-state ²⁹ Si-NMR spectrum of a snow and ice preventing component contained in a snow and ice preventing agent 12 measured by a DD / MAS method. It is a figure showing typically the snow-and-ice prevention structure concerning one embodiment of the present invention. It is a figure showing typically the snow-and-ice prevention structure concerning one embodiment of the present invention. It is a figure showing typically the snow-and-ice prevention structure concerning one embodiment of the present invention. It is a figure showing typically the test method of the icing power test.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments.

<Definition>
In the present specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit or the lower limit of a numerical range in one step may be replaced with the upper limit or the lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment. “A or B” may include one of A and B, and may include both. The materials exemplified in the present specification can be used alone or in combination of two or more, unless otherwise specified. In the present specification, the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition means.

<Snow and ice protection agent>
Examples of the snow and ice prevention agent of the present embodiment include the following first to fourth aspects. By adopting each of the aspects, it is possible to obtain the snow-and-ice prevention property and the adhesiveness according to each of the aspects.

(First embodiment)
In one embodiment, the snow and ice protection agent comprises a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in a molecule), and hydrolysis of the polysiloxane compound having the hydrolyzable functional group. A liquid composition containing at least one selected from the group consisting of products (hereinafter, sometimes referred to as “polysiloxane compound group”) is included (the snow and ice inhibitor may be the liquid composition). The snow and ice protection agent is also selected from the group consisting of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group. And a condensate of a liquid composition containing at least one of the above. According to such a snow and ice preventing agent, excellent snow and ice preventing properties can be imparted to the surface of the object to be treated. The snow and ice prevention agent may be used to form a snow and ice prevention part on the surface to be processed of the object. The snow and ice prevention part formed from the snow and ice prevention agent has excellent snow and ice prevention properties and also has excellent adhesion to the surface to be processed. The snow / ice prevention unit is, for example, at least a film-shaped snow / ice prevention unit (hereinafter, also referred to as “snow / ice prevention film”) and a particulate snow / ice prevention unit (hereinafter, also referred to as “snow / ice prevention particles”). It may be a form including one. That is, the snow and ice prevention agent according to the present embodiment may form a snow and ice prevention film and / or snow and ice prevention particles on the surface to be processed of the object.

For example, since a snow and ice protection film formed of a fluorine-based material as in Patent Document 1 has low adhesion to an object, in order to enhance the adhesion of such a snow and ice protection film, the surface to be treated is required. It is considered necessary to form an adhesion layer (for example, an oxide film and a film having a hydroxyl group) on the substrate. On the other hand, since the snow and ice prevention agent of the present embodiment has high adhesion to an object, such an adhesion layer is not necessarily required. Further, the snow and ice prevention agent of the present embodiment can maintain the snow and ice prevention function for a long period of time because of its excellent adhesion and adhesion.

Furthermore, it is considered that the snow and ice prevention part formed from the snow and ice prevention agent of the present embodiment does not easily adhere to hydrophilic stains and easily removes such stains. Therefore, it is considered that the snow and ice prevention agent can be easily applied to applications to which hydrophilic dirt is likely to adhere.

雪 The snow and ice prevention film using the conventional fluorine-based material has adhesiveness and chemical resistance, but is considered to be easily scratched due to low film hardness and softness. In addition, since the temperature for curing such a snow and ice prevention film is several hundred degrees or more, it is considered that the application site and the base material are limited. On the other hand, it is considered that the snow and ice prevention part formed from the snow and ice prevention agent of the present embodiment is excellent in adhesiveness and chemical resistance, is hardly damaged, and is hardly limited in application places and base materials.

Here, the present inventors speculate as follows why the snow and ice prevention agent of the present embodiment exhibits excellent snow and ice prevention properties. Since the snow and ice prevention agent of this embodiment contains a polysiloxane compound group, it is considered that the base material surface can be made hydrophobic. It is conceivable that a water film is formed at the interface between the snow and the base material as a condition for the start of snow sliding.However, on the surface of the hydrophobized base material, the slipperiness of water after the formation of the water film is high, so that the icing power is low. It is estimated to decrease. From the above, it is considered that excellent snow and ice prevention properties are exhibited.

アルコキシ Examples of the hydrolyzable functional group include an alkoxy group. Examples of the condensable functional group (excluding the functional group corresponding to the hydrolyzable functional group) include a hydroxyl group, a silanol group, a carboxyl group, and a phenolic hydroxyl group. The hydroxyl group may be contained in a hydroxyl group-containing group such as a hydroxyalkyl group. The polysiloxane compound having a hydrolyzable functional group or a condensable functional group is a reactive group (hydrolyzable functional group or condensable functional group) different from the hydrolyzable functional group or the condensable functional group. (A functional group that does not correspond to a functional group). Examples of the reactive group include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group. The epoxy group may be included in an epoxy group-containing group such as a glycidoxy group. These polysiloxane compounds having a functional group and a reactive group may be used alone or in combination of two or more. Among these functional groups and reactive groups, an alkoxy group, a silanol group, and a hydroxyalkyl group can improve the compatibility of the snow and ice inhibitor and suppress layer separation. Further, from the viewpoint of improving the reactivity of the polysiloxane compound, the alkoxy group and the hydroxyalkyl group may have, for example, 1 to 6 carbon atoms.

Examples of the polysiloxane compound having a hydroxyalkyl group include a compound having a structure represented by the following general formula (A).

In the formula (A), R ^1a represents a hydroxyalkyl group, R ^2a represents an alkylene group, R ^3a and R ^4a each independently represent an alkyl group or an aryl group, and n represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In the formula (A), two R ^1a may be the same or different, and similarly, two R ^2a may be the same or different. In formula (A), two or more R ^3a may be the same or different, and similarly, two or more R ^4a may be the same or different.

By using the snow and ice inhibitor containing the polysiloxane compound having the above structure, it becomes easier to obtain excellent snow and ice prevention and adhesion. From such a viewpoint, in the formula (A), as R ^1a , a hydroxyalkyl group having 1 to 6 carbon atoms and the like can be mentioned, and as the hydroxyalkyl group, a hydroxyethyl group and a hydroxypropyl group can be mentioned. . In the formula (A), R ^2a includes an alkylene group having 1 to 6 carbon atoms, and the alkylene group includes an ethylene group and a propylene group. In the formula (A), R ^3a and R ^4a each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group and the like, and the alkyl group includes a methyl group and the like. In the formula (A), n may be, for example, 2 to 30, or 5 to 20.

As the polysiloxane compound having the structure represented by the above formula (A), commercially available products can be used, and compounds such as X-22-160AS, KF-6001, KF-6002, and KF-6003 (all of which are described below) Shin-Etsu Chemical Co., Ltd.), compounds such as XF42-B0970, XF42-C5277, Fluid {OFOH} 702-4% (all manufactured by Momentive).

{Examples of the polysiloxane compound having an alkoxy group include a compound having a structure represented by the following general formula (B).

In the formula (B), R ^1b represents an alkyl group, an alkoxy group or an aryl group, R ^2b and R ^3b each independently represent an alkoxy group, and R ^4b and R ^5b each independently represent an alkyl group or an aryl group. , M represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In the formula (B), two R ^1b may be the same or different, and two R ^2b may be the same or different. ^3b may be the same or different. In the formula (B), when m is an integer of 2 or more, two or more R ^4b may be the same or different, and similarly, two or more R ^5b may be the same. May also be different.

By using a snow- and ice-protecting agent containing the polysiloxane compound having the above structure or a hydrolysis product thereof, it becomes easier to obtain excellent snow-and-ice protection and adhesion. From such a viewpoint, in the formula (B), as R ^1b , an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and the like can be mentioned, and the alkyl group or the alkoxy group is methyl. Group, methoxy group, ethoxy group and the like. In the formula (B), R ^2b and R ^3b each independently include an alkoxy group having 1 to 6 carbon atoms, and the alkoxy group includes a methoxy group and an ethoxy group. In the formula (B), R ^4b and R ^5b each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group and the like, and the alkyl group includes a methyl group and the like. In the formula (B), m may be, for example, 2 to 30, or 5 to 20.

The polysiloxane compound having the structure represented by the general formula (B) can be obtained by appropriately referring to the production methods reported in, for example, JP-A-2000-26609 and JP-A-2012-233110. Can be.

Since the alkoxy group hydrolyzes, the alkoxy group-containing polysiloxane compound may be present as a hydrolysis product in the liquid composition, and the alkoxy group-containing polysiloxane compound and its hydrolysis product May be mixed. In the polysiloxane compound having an alkoxy group, all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.

These polysiloxane compounds having a hydrolyzable functional group or a condensable functional group, and hydrolysis products of a polysiloxane compound having a hydrolyzable functional group may be used alone or as a mixture of two or more. May be used.

雪 The snow and ice inhibitor of the present embodiment may further contain silica particles from the viewpoint of further improving the snow and ice prevention and the adhesion. That is, the liquid composition comprises silica particles, a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group. And at least one selected from the group. The reason why the snow / ice preventing property is improved in such a snow / ice preventing agent is that when the snow / ice preventing agent contains silica particles, it is easy to control Q + T: D described later in the compound constituting the snow / ice preventing part. Further, it is considered that the amount of the hydroxyl group in the compound is easily reduced.

The silica particles can be used without any particular limitation, and include, for example, amorphous silica particles. Examples of the amorphous silica particles include fused silica particles, fumed silica particles, and colloidal silica particles. Among these, the colloidal silica particles have high monodispersibility and easily suppress aggregation in a snow and ice prevention agent.

形状 The shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a cocoon shape, and an association type. Among them, the use of spherical particles as the silica particles makes it easier to suppress aggregation in the snow and ice prevention agent. The average primary particle diameter of the silica particles is, for example, 1 nm or more from the viewpoint that it is easy to obtain a snow and ice prevention film and / or snow and ice prevention particles having appropriate hardness, and it is easy to improve durability against thermal shock and scratches. May be 5 nm or more, or may be 20 nm or more. The average primary particle diameter of the silica particles is, for example, 200 nm or less, 150 nm or less, or 100 nm or less from the viewpoint of easily obtaining a transparent snow and ice prevention film and / or snow and ice prevention particles. There may be. From these viewpoints, the average primary particle diameter of the silica particles may be, for example, 1 to 200 nm, 5 to 150 nm, or 20 to 100 nm. Further, the silica particles may be particles having a hollow structure, a porous structure, or the like.

平均 The average particle size of the silica particles can be measured from the raw material. For example, the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, when colloidal silica particles having a solid content of 5 to 40% by mass and usually dispersed in water are taken as an example, a chip obtained by cutting a wafer with a pattern wiring into 2 cm square is added to a dispersion of colloidal silica particles. After soaking for about 30 seconds, the chip is rinsed with pure water for about 30 seconds and dried with nitrogen blow. Thereafter, the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, silica particles are observed at a magnification of 100,000, and an image is taken. 20 silica particles are arbitrarily selected from the obtained image, and the average of the particle diameters of the particles is defined as the average particle diameter. At this time, when the selected silica particle has a shape as shown in FIG. 1, a rectangle (circumscribed rectangle L) circumscribing the silica particle P and arranged so that the long side is the longest is led. Then, the long side of the circumscribed rectangle L is set to X, the short side is set to Y, and (X + Y) / 2 is used to calculate the biaxial average primary particle diameter, which is defined as the particle diameter of the particle.

The number of silanol groups per 1 g of the silica particles is, for example, 10 × 10 ¹⁸ / g from the viewpoint of having good reactivity and easily imparting excellent snow and ice prevention properties and adhesion at a low temperature in a short time. Or more, may be 50 × 10 ¹⁸ / g or more, or may be 100 × 10 ¹⁸ / g or more. The number of silanol groups per gram of the silica particles is, for example, 1000 × 10 3 from the viewpoint that it is easy to suppress abrupt gelation during the snow and ice prevention treatment and to easily obtain a uniform snow and ice prevention film and / or snow and ice prevention particles. ^The number may be ¹⁸ / g or less, 800 × 10 ¹⁸ / g or less, or 700 × 10 ¹⁸ / g or less. From these viewpoints, the number of silanol groups per 1 g of the silica particles may be, for example, 10 × 10 ¹⁸ to 1000 × 10 ¹⁸ / g, or 50 × 10 ¹⁸ to 800 × 10 ¹⁸ / g. And may be 100 × 10 ¹⁸ to 700 × 10 ¹⁸ / g.

The content of the silica particles is, from the viewpoint of improving the reactivity of the snow and ice inhibitor, and from the viewpoint of easily imparting excellent snow and ice prevention properties and adhesion in a short time at a low temperature, the total amount of the liquid composition is 100 mass Per part, for example, it may be 0.01 part by mass or more, 0.1 part by mass or more, or 0.5 part by mass or more. The content of the silica particles is preferably 100 parts by mass in terms of the total amount of the liquid composition from the viewpoint that a snow and ice prevention film and / or snow and ice prevention particles having appropriate hardness are easily obtained and durability against thermal shock and scratches is easily improved. On the other hand, for example, it may be 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the content of the silica particles may be, for example, 0.01 to 30 parts by mass or 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the liquid composition. It may be 0.5 to 10 parts by mass.

The liquid composition may further contain a silicon compound (excluding the polysiloxane compound) other than the polysiloxane compound, for example, from the viewpoint of further improving the snow-ice protection property and the adhesion. That is, the liquid composition is a silane monomer having a hydrolyzable functional group or a condensable functional group, and at least one selected from the group consisting of a hydrolysis product of a silane monomer having a hydrolyzable functional group. (Hereinafter, sometimes referred to as “silane monomer group”). The number of silicon atoms in the molecule of the silane monomer can be 1 to 6.

シラン The silane monomer having a hydrolyzable functional group is not particularly limited, but examples include an alkyl silicon alkoxide. Among the alkyl silicon alkoxides, those having three or less hydrolyzable functional groups can further improve the water resistance. Examples of such an alkyl silicon alkoxide include monoalkyl trialkoxysilane, monoalkyl dialkoxy silane, dialkyl dialkoxy silane, monoalkyl monoalkoxy silane, dialkyl monoalkoxy silane, and trialkyl monoalkoxy silane. Examples thereof include methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxysilane.

The silane monomer having a condensable functional group is not particularly limited. Examples thereof include silanetetraol, methylsilanetriol, dimethylsilanediol, phenylsilanetriol, phenylmethylsilanediol, diphenylsilanediol, n-propylsilanetriol, Hexylsilanetriol, octylsilanetriol, decylsilanetriol, trifluoropropylsilanetriol and the like can be mentioned.

(4) The silane monomer having a hydrolyzable functional group or a condensable functional group may further have the above-described reactive group different from the hydrolyzable functional group and the condensable functional group.

The number of hydrolyzable functional groups is 3 or less, and as a silane monomer having a reactive group, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.

Further, as a silane monomer having a condensable functional group and having a reactive group, vinyl silane triol, 3-glycidoxypropyl silane triol, 3-glycidoxy propyl methyl silane diol, 3-methacryloxy propyl silane triol, 3-methacryloxypropylmethylsilanediol, 3-acryloxypropylsilanetriol, 3-mercaptopropylsilanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl ) -3-Aminopropylmethylsilanediol and the like can also be used.

Also, use is made of silane monomers having three or less hydrolyzable functional groups at the molecular terminals, such as bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, ethyltrimethoxysilane, and vinyltrimethoxysilane. Can be.

These silane monomers having a hydrolyzable functional group or a condensable functional group, and the hydrolysis products of the silane monomers having a hydrolyzable functional group may be used alone or as a mixture of two or more. You may.

Since a hydrolyzable functional group such as an alkoxy group hydrolyzes, a silane monomer having a hydrolyzable functional group may be present as a hydrolysis product in the liquid composition, The silane monomer having the above functional group and its hydrolysis product may be mixed. In the silane monomer having a hydrolyzable functional group, all of the hydrolyzable functional groups in the molecule may be hydrolyzed or partially hydrolyzed.

Content of polysiloxane compound group (content of polysiloxane compound having hydrolyzable functional group or condensable functional group, and content of hydrolysis product of polysiloxane compound having hydrolyzable functional group) Of the liquid composition may be, for example, 0.01 parts by mass or more, or 0.1 parts by mass or more based on 100 parts by mass of the total amount of the liquid composition, from the viewpoint of further improving the snow and ice prevention properties. And may be 0.5 parts by mass or more. The content of the polysiloxane compound group is preferably 100% in terms of the total amount of the liquid composition, from the viewpoint that a snow- and ice-preventing film and / or snow-and-ice prevention particles having appropriate hardness are easily obtained and the durability against thermal shock and scratches is easily improved. For example, the amount may be 50 parts by mass or less, 30 parts by mass or less, or 10 parts by mass or less with respect to parts by mass. From these viewpoints, the content of the polysiloxane compound group may be, for example, 0.01 to 50 parts by mass, or 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the liquid composition. And 0.5 to 10 parts by mass.

When the snow and ice protection agent of the present embodiment further contains a silane monomer group in the liquid composition, the content of the polysiloxane compound group and the content of the silane monomer group (hydrolyzable functional group or condensable The ratio of the content of the silane monomer having a functional group and the total content of the hydrolysis products of the silane monomer having a hydrolyzable functional group) is favorable from the viewpoint that the snow-and-ice prevention property is further improved. From the viewpoint that easy compatibility is easily obtained, for example, the ratio may be 1: 0.1 or more, or 1: 1 or more. The ratio of the content of these compounds is, for example, 1:10 or less from the viewpoint that a snow and ice prevention film and / or snow and ice prevention particles having appropriate hardness are easily obtained and durability against thermal shock and scratches is easily improved. And may be 1: 5 or less. From these viewpoints, the ratio of the content of the polysiloxane compound group to the content of the silane monomer group may be, for example, from 1: 0.1 to 1:10, or from 1: 1 to 1: 5. There may be.

The sum of the contents of the polysiloxane compound group and the silane monomer group is, from the viewpoint of further improving the snow and ice prevention properties, based on 100 parts by mass of the total amount of the liquid composition, for example, even 0.01 parts by mass or more. It may be 0.1 parts by mass or more, or 0.5 parts by mass or more. The sum of the contents is preferably 100 parts by mass of the total amount of the liquid composition from the viewpoint that a snow- and ice-preventing film and / or snow and ice-preventing particles having appropriate hardness are easily obtained and durability against thermal shock and scratches is easily improved. On the other hand, for example, it may be 60 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the total content of the polysiloxane compound group and the silane monomer group may be, for example, 0.01 to 60 parts by mass, or 0.01 to 60 parts by mass with respect to 100 parts by mass of the total amount of the liquid composition. The amount may be 30 parts by mass, 0.1 to 20 parts by mass, or 0.5 to 10 parts by mass. At this time, the ratio of the content of the polysiloxane compound group to the content of the silane monomer group can be within the above range.

雪 The snow and ice prevention agent of the present embodiment may contain airgel particles from the viewpoint of improving snow and ice prevention. That is, the liquid composition comprises airgel particles, a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group. And at least one selected from the group. Airgel is a porous body having nanometer-sized micropores. The airgel particles are considered to exhibit excellent snow and ice prevention properties because the surface has few hydroxyl groups and water hardly enters the micropores.

As the airgel particles, conventionally known airgel particles can be used without any particular limitation, and airgel particles formed using a polysiloxane compound, a silane monomer, or the like contained in the liquid composition as a raw material may be used. Note that such aerogels (particles) can be obtained by drying a wet gel that is a condensate of a sol containing a polysiloxane compound or the like.

The average primary particle size of the airgel particles is, for example, 0.1 to 10000 nm, 1 to 1000 nm, or 2 to 100 nm from the viewpoint that good snow and ice prevention properties are easily obtained. You may.

The content of the airgel particles may be, for example, 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass based on 100 parts by mass of the total amount of the liquid composition, from the viewpoint that good dispersibility is easily obtained. It may be parts by mass, or 0.8 to 3 parts by mass.

雪 The snow and ice prevention agent according to another embodiment may be a mode including a snow and ice prevention component. The snow and ice prevention component may be, for example, a condensate of the liquid composition described above. The shape of the snow and ice prevention component according to the present embodiment may be, for example, particulate. Hereinafter, specific embodiments of the snow and ice prevention agent containing the snow and ice prevention component will be described as the second to fourth embodiments.

(Second aspect)
The snow and ice prevention agent of the present embodiment may include a snow and ice prevention component containing a polysiloxane having a main chain containing a siloxane bond (Si—O—Si). The snow and ice prevention component can have the following M unit, D unit, T unit or Q unit as a structural unit.

中 In the above formula, R represents an atom bonded to a silicon atom (such as a hydrogen atom) or an atomic group (such as an alkyl group). The M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom. The D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms. The T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms. The Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms. Information on the content of these units can be obtained by Si-NMR.

The snow and ice inhibitor of the present embodiment is derived from Q and T when the silicon-containing bonding units Q, T and D are defined as follows in a solid-state ²⁹ Si-NMR spectrum measured by the DD / MAS method. And a ratio of the signal area derived from D to the signal area derived from D, Q + T: D, in a ratio of 1: 0.01 to 1: 0.70.

Q: a silicon-containing bonding unit having four oxygen atoms bonded to one silicon atom.
T: a silicon-containing bonding unit in which three oxygen atoms are bonded to one silicon atom and one hydrogen atom or a monovalent organic group is one.
D: a silicon-containing bonding unit having two oxygen atoms bonded to one silicon atom and two hydrogen atoms or monovalent organic groups.

However, the organic group is a monovalent organic group in which an atom bonded to a silicon atom is a carbon atom.

Such a snow and ice protection agent is excellent in snow and ice prevention and adhesion.

The ratio of the signal area derived from Q and T to the signal area derived from D, Q + T: D, may be, for example, from 1: 0.01 to 1: 0.50, and from 1: 0.01 to 1 : 0.30, 1: 0.02 to 1: 0.20, or 1: 0.03 to 1: 0.10. When the signal area ratio is 1: 0.01 or more, more excellent snow and ice prevention properties tend to be easily obtained, and when the signal area ratio is 1: 0.50 or less, adhesion tends to be more easily obtained.

「The“ oxygen atom ”in the following Q, T and D is an oxygen atom mainly bonding between two silicon atoms, but for example, an oxygen atom of a hydroxyl group bonded to a silicon atom may be considered. The “organic group” is a monovalent organic group in which the atom bonded to the silicon atom is a carbon atom, and examples include an unsubstituted or substituted monovalent organic group having 1 to 10 carbon atoms. Examples of the unsubstituted monovalent organic group include hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the substituted monovalent organic group include a hydrocarbon group (substituted organic group) in which a hydrogen atom of these hydrocarbon groups is substituted with a halogen atom, a predetermined functional group, a predetermined functional group-containing organic group, or the like. And hydrocarbon groups in which ring hydrogen atoms such as an alkyl group, an aryl group, and an aralkyl group are substituted with an alkyl group. Examples of the halogen atom include a chlorine atom, a fluorine atom and the like (that is, a halogen atom-substituted organic group such as a chloroalkyl group and a polyfluoroalkyl group). Examples of the functional group include a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an amino group, a cyano group, an acryloyloxy group, and a methacryloyloxy group. Examples of the functional group-containing organic group include an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted aminoalkyl group. Is mentioned.

The signal area ratio can be confirmed by a solid-state ²⁹ Si-NMR spectrum. In general, the method of measuring solid ²⁹ Si-NMR is not particularly limited, and includes, for example, the CP / MAS method and the DD / MAS method. In the present embodiment, the DD / MAS method is adopted from the viewpoint of quantitativeness. ing.

The chemical shifts of the silicon-containing bonding units Q, T and D in the solid-state ²⁹ Si-NMR spectrum are as follows: Q unit: -90 to -120 ppm, T unit: -45 to -80 ppm, D unit: 0 to -40 ppm, respectively. As observed, it is possible to separate the signals of the silicon-containing bonding units Q, T and D and calculate the signal area derived from each unit. At the time of spectrum analysis, an exponential function can be used as a Window function, and a Line Broadening coefficient can be set in a range of 0 to 50 Hz from the viewpoint of improving analysis accuracy.

For example, FIG. 2 is a diagram showing a solid-state ²⁹ Si-NMR spectrum of a snow and ice preventing component contained in the snow and ice preventing agent 12 measured using the DD / MAS method. As shown in FIG. 2, the signals of the silicon-containing bonding units Q, T and D can be separated by solid-state ²⁹ Si-NMR using the DD / MAS method.

Here, a method for calculating the signal area ratio will be described with reference to FIG. For example, in FIG. 2, a Q unit signal derived from silica is observed in the chemical shift range of -90 to -120 ppm. Further, in the chemical shift range of -45 to -80 ppm, a signal of a T unit derived from the polysiloxane compound and the trimethoxysilane reactant is observed. Further, in the chemical shift range of 0 to -40 ppm, signals of D units derived from the polysiloxane compound and the dimethyldimethoxysilane reactant are observed. The signal area (integral value) is obtained by integrating the signal in each chemical shift range. Assuming that the signal area of the sum of the Q unit and the T unit is 1, the signal area ratio Q + T: D in FIG. 2 is calculated to be 1: 0.15. The signal area is calculated by using general spectrum analysis software (for example, NMR software “TopSpin” (TopSpin is a registered trademark) manufactured by Bruker).

(Third aspect)
The snow and ice prevention agent of the present embodiment may contain a snow and ice prevention component including a compound having a structure represented by the following formula (1). The snow and ice prevention component according to the present embodiment can include a compound having a structure represented by the following formula (1a) as a structure including the structure represented by the formula (1). For example, the condensate of the liquid composition containing the polysiloxane compound having the structure represented by the formula (A) includes a compound having the structure represented by the formula (1) and the formula (1a) in the skeleton. A snow and ice protection component may be included.

In Formula (1) and Formula (1a), R ¹ and R ² each independently represent an alkyl group or an aryl group, and R ³ and R ⁴ each independently represent an alkylene group. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. In addition, examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. p represents an integer of 1 to 50. In formula (1a), two or more R ¹ may be the same or different, and similarly, two or more R ² may be the same or different. In the formula (1a), two R ³ may be the same or different, and similarly, two R ⁴ may be the same or different.

When the snow and ice prevention agent contains a snow and ice prevention component containing a compound having the structure represented by the above formula (1) or (1a), the snow and ice prevention and the adhesion are further improved. From such a viewpoint, in the formulas (1) and (1a), R ¹ and R ² each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like. And a methyl group. In the formulas (1) and (1a), R ³ and R ⁴ each independently include an alkylene group having 1 to 6 carbon atoms, and the alkylene group includes an ethylene group, a propylene group, and the like. Is mentioned. In the formula (1a), for example, p may be 2 to 30, or 5 to 20.

(Fourth aspect)
The snow and ice prevention agent of the present embodiment has a ladder-type structure including a support portion and a bridge portion, and the bridge portion includes a snow and ice prevention component including a compound represented by the following formula (2). It may be. By including the compound having such a ladder-type structure in the skeleton, the snow-and-ice prevention component can further improve the snow-and-ice prevention properties and the mechanical strength. That is, the snow and ice prevention agent of the present embodiment has excellent snow and ice prevention and durability due to the ladder type structure. For example, as a condensate of a liquid composition containing a polysiloxane compound having a structure represented by the above formula (B), a compound having a ladder type structure having a crosslinked portion represented by the formula (2) in the skeleton is used. Including snow and ice protection components can be included. In the present embodiment, the “ladder type structure” refers to a structure having two struts and bridges connecting the struts (bridges) (having a so-called “ladder” form). It is. In this embodiment, the ladder structure may be an embodiment included in a part of the compound.

In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In addition, in Formula (2), when b is an integer of 2 or more, two or more R ⁵ may be the same or different, and similarly, two or more R ⁶ may be the same. May also be different.

The structure to be the support part and the chain length thereof, and the interval between the structures to be the bridge part are not particularly limited, but from the viewpoint of further improving snow and ice prevention, mechanical strength and durability, the ladder type structure is as follows. A ladder-type structure represented by the general formula (3) is given.

In the formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b represents 1 to 50 Indicates an integer. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In the formula (3), when b is an integer of 2 or more, two or more R ⁵ may be the same or different, and similarly, two or more R ⁶ may be the same. May also be different. Further, in the formula (3), when a is an integer of 2 or more, two or more R ⁷ may be the same or different, and similarly, when c is an integer of 2 or more, two or more R ⁷ R ⁸ may be the same or different.

In addition, from the viewpoint of obtaining more excellent snow and ice prevention properties, R ⁵ , R ⁶ , R ⁷ and R ^{8 in} the formulas (2) and (3) (where R ⁷ and R ⁸ are only used in the formula (3)) ) Independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group and the like, and the alkyl group includes a methyl group and the like. Further, in the formula (3), a and c may each independently be, for example, 6 to 2000 or 10 to 1000. In the formulas (2) and (3), b may be, for example, 2 to 30, or 5 to 20.

雪 The snow / ice prevention component contained in the snow / ice prevention agent may be composed of aerogel from the viewpoint of improving the snow / ice prevention properties. Since airgel has a high porosity, the snow- and ice-preventing component composed of aerogel (and the snow and ice-preventing film and the snow-and-ice preventing particles formed thereby) have a small refractive index and high transparency. Conceivable.

<Snow and ice prevention structure>
Next, a snow and ice prevention structure obtained by using the above snow and ice prevention agent will be described. In the snow and ice prevention structure of the present embodiment, a snow and ice prevention part is formed on the surface to be processed, and the snow and ice prevention part includes a dried product of the snow and ice prevention agent. If the snow and ice prevention agent contains a condensate of the above liquid composition, the condensation reaction is considered to proceed further when the snow and ice prevention part is formed, and the snow and ice prevention agent is not liquid. In the case of the composition itself, it is considered that a condensation reaction occurs when the snow and ice prevention part is formed. Therefore, it can be said that the snow and ice prevention unit includes a reactant of the snow and ice prevention agent.

雪 The snow and ice prevention unit may be in a form including at least one of a snow and ice prevention film and a snow and ice prevention particle. The snow and ice prevention structure according to the present embodiment has a snow and ice prevention portion containing a dried product of the snow and ice prevention agent of the present embodiment, and thus has excellent snow and ice prevention properties, and has a surface to be processed and a snow and ice prevention portion. Excellent adhesion with Further, such a snow and ice prevention structure has excellent durability. The snow and ice prevention structure of the present embodiment may be, for example, a snow and ice prevention film and / or snow and ice prevention particles formed on the surface to be processed by the above-described snow and ice prevention agent. Here, the preferred form of the snow and ice prevention part (snow and ice prevention particles and the like) formed on the surface to be processed may be, for example, the same as the snow and ice prevention component described above.

(4) The snow / ice prevention portions (snow / ice prevention films, snow / ice prevention particles, etc.) formed on the surface to be processed may include aerogel from the viewpoint of further improving the snow / ice prevention properties. That is, for example, the snow and ice prevention film and the snow and ice prevention particles formed on the surface to be processed may be a film containing aerogel and a particle containing aerogel, respectively.

FIG. 3 is a diagram schematically illustrating a snow and ice prevention structure according to an embodiment of the present invention. The snow and ice prevention structure 100 shown in FIG. 3 has a structure in which a snow and ice prevention part 10 made of a snow and ice prevention film 1 is formed on a processing surface 2 a of a snow and ice prevention target 2. Here, the snow and ice prevention unit 10 includes a dried product of the snow and ice prevention agent of the present embodiment. The snow / ice prevention structure 100 includes a snow / ice prevention unit 10 made of the snow / ice prevention film 1 on the surface 2a to be processed, thereby imparting snow / ice prevention properties, which are chemical characteristics of the snow / ice prevention film. It is thought that it becomes. Here, it can be said that the snow and ice prevention unit in this embodiment is not a monolithic film but a film formed by depositing minute snow and ice prevention particles (snow and ice prevention components).

FIG. 4 is a diagram schematically illustrating a snow and ice prevention structure according to an embodiment of the present invention. The snow and ice prevention structure 200 shown in FIG. 4 has a structure in which a snow and ice prevention part 10 made of snow and ice prevention particles 3 is formed on a processing surface 2 a of a snow and ice prevention target 2. Here, the snow and ice prevention unit 10 includes a dried product of the snow and ice prevention agent of the present embodiment. Since the snow-and-ice prevention structure 200 includes the snow-and-ice prevention unit 10 made of the snow-and-ice prevention particles 3 on the surface 2a to be processed, the Lotus effect due to the fine unevenness which is a physical characteristic of the snow-and-ice prevention particles is reduced. It is considered to be obtained and provided with high snow and ice prevention properties. Here, it can be said that the snow and ice prevention part in the present embodiment is formed by snow and ice prevention particles (snow and ice prevention components) that have grown to a somewhat large size adhere to the surface to be processed.

FIG. 5 is a diagram schematically illustrating a snow and ice prevention structure according to an embodiment of the present invention. The snow / ice prevention structure 300 shown in FIG. 5 has a structure in which a snow / ice prevention part 10 including a snow / ice prevention film 1 and snow / ice prevention particles 3 is formed on a surface 2a to be processed of a snow / ice prevention object 2. Have. Here, the snow and ice prevention unit 10 includes a dried product of the snow and ice prevention agent of the present embodiment. The snow / ice prevention structure 300 includes the snow / ice prevention part 10 including the snow / ice prevention film 1 and the snow / ice prevention particles 3 on the surface 2a to be processed, thereby forming the snow and ice prevention particles having the chemical characteristics. It is considered that a more excellent snow and ice prevention property is provided because the snow and ice prevention property is imparted and the lotus effect is obtained by the fine irregularities which are the physical characteristics of the snow and ice prevention particles.

とおり As described above, it is possible to obtain snow / ice prevention portions having various aspects depending on the size of the particles formed from the snow / ice prevention agent. That is, when the snow and ice prevention particles are minute, the film-like appearance is deposited with a predetermined thickness, and when the snow and ice prevention particles are somewhat large, the particle appearance is individually arranged in a plane. In such a case, a snow- and ice-preventing portion is formed in a combined appearance.

In addition, in view of the fact that the snow / ice prevention part of the snow / ice prevention structure is not a so-called monolithic airgel film, the heat conductivity of the snow / ice prevention structure of the present embodiment has the same thermal conductivity as that of the object. Show. For example, the thermal conductivity of the snow and ice prevention structure of this embodiment using an object having a thermal conductivity of about 1.0 W / (m · K) is 1.0 W / (m · K), which is equivalent to that of the object. It is about.

において In the snow / ice prevention structure of the present embodiment, the thickness of the snow / ice prevention film may be, for example, 1 to 500 nm or 20 to 200 nm. By setting the thickness to 1 nm or more, more excellent snow and ice prevention properties can be achieved, and by setting the thickness to 500 nm or less, more excellent adhesion can be achieved.

において In the snow / ice prevention structure of the present embodiment, the size of the snow / ice prevention particles may be, for example, 0.1 to 10000 nm or 1 to 1000 nm. When the size of the snow and ice prevention particles is 0.1 nm or more, more excellent snow and ice prevention properties can be achieved, and when it is 10000 nm or less, more excellent adhesion can be achieved. .

In the snow and ice prevention structure of the present embodiment, the number of snow and ice prevention particles adhering to the surface to be treated is, for example, one or more per 1 mm square from the viewpoint of achieving even better snow and ice prevention properties. Is also good. The number of snow and ice prevention particles adhering to the surface to be processed can be calculated using, for example, a scanning electron microscope (SEM). For example, in the case of snow and ice prevention particles having an average particle diameter of 100 nm, a square area A (1.0 × 10 ⁻⁴ ) having a length 100 times the average particle diameter (1.0 × 10 ⁻² mm) as one side. mm ² ). The number B (pieces) of the particles in the square is measured, and B / A is calculated. This is repeated 10 times, and the average value of the obtained B / A is defined as the amount of particles attached.

From the above, in the snow and ice prevention structure of the present embodiment, the thickness of the snow and ice prevention portion may be, for example, 1 to 10000 nm or 20 to 1000 nm.

<Production method of snow and ice prevention agent>
Next, a method for producing a snow and ice inhibitor will be described. The method for producing the snow and ice inhibitor is not particularly limited, but for example, it can be produced by the following method.

雪 The snow and ice protection agent of the present embodiment can be manufactured by, for example, a manufacturing method mainly including a compounding step and, if necessary, a condensation reaction step.

Hereinafter, each step of the method for producing a snow and ice inhibitor according to the present embodiment will be described.

(Blending process)
The compounding step is a step of mixing the above-mentioned polysiloxane compound and, if necessary, silica particles, a silane monomer, a solvent and the like. By this step, a hydrolysis reaction of a silicon compound such as a polysiloxane compound can be performed. The silica particles may be mixed in a state of a dispersion liquid dispersed in a solvent. In this step, an acid catalyst may be further added to the solvent in order to promote the hydrolysis reaction. Further, a surfactant can be added to the solvent. When a silicon compound having a condensable functional group is used, the hydrolysis reaction is not always essential.

As the solvent, for example, water or a mixture of water and alcohols can be used. Examples of alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, t-butanol and the like. From the viewpoint of reducing the interfacial tension with the surface to be treated, the alcohols may have a low surface tension and a low boiling point, for example. Examples of the alcohol having a low surface tension and a low boiling point include methanol, ethanol and 2-propanol. These may be used alone or as a mixture of two or more.

Examples of the acid catalyst include inorganic acids such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, and hypochlorous acid; Acidic phosphates such as aluminum, acidic magnesium phosphate and acidic zinc phosphate; organic carboxylic acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid and azelaic acid And the like. Among them, organic carboxylic acids can be mentioned as an acid catalyst capable of promoting a hydrolysis reaction in consideration of environmental pollution. The organic carboxylic acids include acetic acid, but may be formic acid, propionic acid, oxalic acid, malonic acid, or the like. These may be used alone or as a mixture of two or more.

By using the acid catalyst, the hydrolysis reaction of the polysiloxane compound and the silane monomer is promoted, and a hydrolysis solution can be obtained in a shorter time.

The amount of the acid catalyst may be, for example, 0.001 to 600.0 parts by mass based on 100 parts by mass of the total of the polysiloxane compound group and the silane monomer group.

非 As the surfactant, a nonionic surfactant, an ionic surfactant or the like can be used. These may be used alone or as a mixture of two or more.

As the nonionic surfactant, for example, a compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, a compound containing a hydrophilic part such as polyoxypropylene and the like can be used. Examples of the compound containing a hydrophilic portion such as polyoxyethylene and a hydrophobic portion mainly composed of an alkyl group include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and the like. Examples of the compound containing a hydrophilic portion, such as polyoxypropylene, include polyoxypropylene alkyl ether, a block copolymer of polyoxyethylene and polyoxypropylene, and the like.

Examples of the ionic surfactant include a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride, and examples of the anionic surfactant include sodium dodecylsulfonate. In addition, examples of the amphoteric surfactant include an amino acid-based surfactant, a betaine-based surfactant, and an amine oxide-based surfactant. Examples of the amino acid-based surfactant include acylglutamic acid. Examples of the betaine-based surfactant include betaine lauryldimethylaminoacetate and betaine stearyldimethylaminoacetate. Examples of the amine oxide-based surfactant include lauryl dimethylamine oxide.

These surfactants are considered to have an effect of improving the dispersibility of the polysiloxane compound and, in some cases, silica particles and silane monomers in the solvent in the compounding step. In addition, these surfactants act to reduce the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer in the condensation reaction step described below, thereby improving dispersibility. It is considered to have

The amount of the surfactant added depends on the type of the surfactant, or the type and amount of the polysiloxane compound and the silane monomer.For example, with respect to the total amount of 100 parts by mass of the polysiloxane compound group and the silane monomer group, The amount may be 1 to 100 parts by mass, or 5 to 60 parts by mass.

The hydrolysis in the compounding step depends on the types and amounts of the polysiloxane compound, silane monomer, silica particles, acid catalyst, surfactant and the like in the mixed solution, but, for example, under a temperature environment of 20 to 60 ° C. It may be performed for 10 minutes to 24 hours, or may be performed for 5 minutes to 8 hours in a temperature environment of 50 to 60 ° C. As a result, the hydrolyzable functional groups in the polysiloxane compound and the silane monomer are sufficiently hydrolyzed, and the hydrolysis product of the polysiloxane compound and the hydrolysis product of the silane monomer can be obtained more reliably.

A polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and at least one selected from the group consisting of hydrolysis products of the polysiloxane compound having the hydrolyzable functional group, A snow- and ice-preventing agent comprising a liquid composition containing

(Condensation reaction step)
If necessary, a condensation reaction of the polysiloxane compound having a condensable functional group and a silane monomer, a hydrolysis reaction product obtained in the compounding step, and the like can be performed by a condensation reaction step. In this step, a base catalyst can be used to promote the condensation reaction. In this step, a thermohydrolyzable compound that generates a base catalyst by thermohydrolysis can also be added.

Examples of the base catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride, and ammonium bromide; sodium metaphosphate Sodium phosphates such as sodium, sodium pyrophosphate and sodium polyphosphate; calcium carbonate, potassium carbonate, sodium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, ammonium carbonate, copper (II) carbonate, iron (II) carbonate, carbonate Carbonates such as silver (I); hydrogencarbonates such as calcium hydrogencarbonate, potassium hydrogencarbonate, sodium hydrogencarbonate, ammonium hydrogencarbonate; allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, diethylamine Ruamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, t-butylamine, aliphatic amines such as sec-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxyamine, dimethylethanolamine, methyldiethanolamine, diethanolamine and triethanolamine; morpholine Heterocyclic compounds such as N-methylmorpholine, 2-methylmorpholine, piperazine and its derivatives, piperidine and its derivatives, imidazole and its derivatives, etc. And the like. Among them, carbonate or hydrogen carbonate is preferable from the viewpoint of safety in handling and odor, and sodium carbonate or sodium hydrogen carbonate is more preferable from the viewpoint of economy. The above base catalysts may be used alone or in combination of two or more.

By using a base catalyst, the polysiloxane compound group in the hydrolysis solution, the silane monomer group and the silica particles, can promote the dehydration condensation reaction, the dealcoholization condensation reaction, or the reaction of both, in a shorter time. A snow and ice protection agent can be obtained.

The addition amount of the base catalyst may be, for example, 0.1 to 500 parts by mass or 1.0 to 200 parts by mass with respect to 100 parts by mass of the total of the polysiloxane compound group and the silane monomer group. . By setting the addition amount of the base catalyst to 0.1 parts by mass or more, the condensation reaction can be performed in a shorter time, and by setting the addition amount to 500 parts by mass or less, layer separation is easily suppressed.

(4) It is considered that the thermally hydrolyzable compound generates a basic catalyst by thermal hydrolysis, makes the reaction solution basic, and promotes the condensation reaction. Therefore, the thermally hydrolyzable compound is not particularly limited as long as it can make the reaction solution basic after the thermal hydrolysis, and urea; formamide, N-methylformamide, N, N-dimethylformamide, acetamide, Acid amides such as N-methylacetamide and N, N-dimethylacetamide; and cyclic nitrogen compounds such as hexamethylenetetramine. Among these, urea is particularly easy to obtain the above-mentioned promoting effect.

The amount of the thermally hydrolyzable compound to be added is not particularly limited as long as the condensation reaction can be sufficiently promoted. For example, when urea is used as the thermally hydrolyzable compound, its addition amount may be 1 to 200 parts by mass, or 2 to 150 parts by mass, based on 100 parts by mass of the total of the polysiloxane compound group and the silane monomer group. It may be parts by mass. By setting the addition amount to 1 part by mass or more, it becomes easier to obtain good reactivity, and by setting the addition amount to 200 parts by mass or less, layer separation is easily suppressed.

反応 The reaction in the condensation reaction step may be performed in a closed container so that the solvent and the base catalyst do not volatilize. The reaction temperature may be, for example, from 20 to 90 ° C, or from 40 to 80 ° C. By setting the reaction temperature to 20 ° C. or higher, the condensation reaction can be performed in a shorter time. Further, by setting the reaction temperature to 90 ° C. or lower, the volatilization of the solvent (particularly, alcohols) is easily suppressed, so that the condensation reaction can be performed while suppressing the layer separation.

The condensation reaction time depends on the type of the polysiloxane compound group, the silane monomer group, etc. and the reaction temperature, but may be, for example, 2 to 480 hours or 6 to 120 hours. By setting the reaction time to 2 hours or more, more excellent snow and ice prevention and adhesion can be achieved, and by setting the reaction time to 480 hours or less, layer separation is easily suppressed.

場合 In addition, when silica particles are contained in the hydrolysis solution, the condensation reaction time can be further reduced. The reason is that the silanol group, the reactive group, or both of the polysiloxane compound group and the silane monomer group in the hydrolysis solution have a hydrogen bond, a chemical bond, or a combination of these bonds with the silanol group of the silica particles. It is inferred that this is to form In this case, the condensation reaction time may be, for example, 10 minutes to 24 hours, or 30 minutes to 12 hours. By setting the reaction time to 10 minutes or more, more excellent snow and ice prevention properties and adhesion can be achieved. By setting the reaction time to 24 hours or less, layer separation is easily suppressed.

By the condensation reaction step, a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and at least one selected from the group consisting of hydrolysis products of the polysiloxane compound having the hydrolyzable functional group. It is possible to obtain a snow and ice inhibitor containing a condensate of a liquid composition containing one kind. Further, by this step, a snow and ice preventing agent containing the above-described snow and ice preventing component can be obtained.

The size of the snow and ice prevention particles can be adjusted by, for example, changing the condensation reaction time, the size of the silica particles, the size of the airgel particles, and the like. Thus, a desired snow and ice prevention structure can be obtained.

<Method of manufacturing snow and ice prevention structure>
Next, a method for manufacturing the snow and ice prevention structure will be described. The method for manufacturing the snow-and-ice prevention structure is not particularly limited, but can be manufactured, for example, by the following method.

The snow and ice prevention structure of the present embodiment can be manufactured by, for example, a manufacturing method including a step of applying the snow and ice prevention agent to a surface to be processed (hereinafter, also referred to as an “application step”). The method for manufacturing a snow-and-ice prevention structure according to the present embodiment may include, for example, a coating step and a drying step (aging step), and include a coating step, a cleaning step, and a drying step (preliminary drying step and aging step). Step).

Hereinafter, each step of the method for manufacturing a snow and ice prevention structure according to the embodiment will be described.

(Coating process)
The application step is, for example, a step of applying the snow and ice prevention agent to the surface to be treated. In some cases, the surface to be treated may be dried after application to evaporate the solvent. For example, a snow and ice prevention part (snow and ice prevention film and / or snow and ice prevention particles) can be formed on the surface to be processed by this step. The snow and ice protection agent may be applied to the entire surface to be processed or may be selectively applied to a part of the surface to be processed.

The coating method is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a spray coating method, a flow coating method, a bar coating method, and a gravure coating method. In particular, the spray coating method is preferable from the viewpoint that a snow- and ice-preventing film having a uniform thickness is easily formed even on a surface to be processed having irregularities, that the productivity is high, and that the use efficiency of the snow-and-ice preventing agent is high. These methods may be used alone or in combination of two or more.

雪 The snow and ice preventing agent may be applied to the surface to be treated by applying or impregnating the film or cloth with the snow and ice preventing agent in advance to the surface to be treated. The application method can be freely selected depending on the amount of the snow and ice prevention agent used, the area of the surface to be treated, the characteristics, and the like.

(4) The temperature of the snow and ice inhibitor used in the coating step may be, for example, 20 to 80 ° C. or 40 to 60 ° C. By setting the above temperature to 20 ° C. or higher, there is a tendency that the snow accretion prevention property and the adhesiveness are further improved, and by setting the above temperature to 80 ° C. or lower, the transparency of the snow accretion prevention part is obtained. It tends to be easy. The treatment time with the snow and ice inhibitor can be, for example, 0.5 to 4 hours.

材料 The material constituting the surface to be treated is not particularly limited, but examples thereof include metal, ceramics, glass, plastic, and materials combining these (composite materials, laminated materials, etc.). The snow and ice prevention agent of the present embodiment can be applied to paper, fiber, cloth, nonwoven fabric, rubber, leather, and the like. When the surface to be treated is dried to evaporate the solvent after the application of the snow and ice inhibitor, the material constituting the surface to be treated may be, for example, a water-soluble organic compound or a water-soluble inorganic compound. Among these, the material constituting the surface to be processed is preferably a transparent material such as glass or plastic.

Examples of the metal include stainless steel, aluminum, copper, galvanized steel sheet and iron. Examples of the ceramic include alumina, barium titanate, boron nitride, and silicon nitride. Examples of the glass include ordinary soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and aluminosilicate glass. Examples of the plastics include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET).

Examples of the water-soluble organic compound include glucose, sucrose, starch, polyacrylamide, polyvinyl alcohol, and methylcellulose. Examples of the water-soluble inorganic compound include water glass, sodium chloride, sodium phosphate, sodium carbonate, sodium vanadate, sodium borate, potassium chloride, potassium carbonate, and a sulfate compound.

塗布 After applying the snow and ice prevention agent, the obtained structure is dried and the solvent is volatilized, whereby the adhesion of the snow and ice prevention part can be further improved. The drying temperature at this time is not particularly limited and varies depending on the heat-resistant temperature of the surface to be treated. For example, the drying temperature may be 20 to 250 ° C., 60 to 250 ° C., There may be. By setting the temperature to 60 ° C. or higher, better adhesion can be achieved, and by setting the temperature to 250 ° C. or lower, deterioration due to heat can be suppressed.

(Washing process)
The cleaning step is, for example, a step of cleaning the structure obtained in the coating step. By performing this step, impurities such as unreacted substances and by-products in the snow and ice prevention unit can be reduced, and a snow and ice prevention unit with higher purity can be obtained.

The washing step can be repeatedly performed using, for example, water and / or an organic solvent. At this time, the cleaning efficiency can be improved by heating.

Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, heptane, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, Various organic solvents such as methylene chloride, N, N-dimethylformamide, dimethylsulfoxide, acetic acid, and formic acid can be used. The above organic solvents may be used alone or in combination of two or more.

Generally, organic solvents have extremely low mutual solubility with water. Therefore, when washing with an organic solvent after washing with water, a hydrophilic organic solvent having high mutual solubility in water is preferable. Among the above organic solvents, examples of the hydrophilic organic solvent include methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane and the like. In addition, methanol, ethanol, methyl ethyl ketone, etc. are preferable in terms of economic efficiency.

水 The amount of water and / or organic solvent used in the washing step may be, for example, 3 to 10 times the total mass of the snow and ice prevention unit. The washing can be repeated until the water content of the surface to be treated becomes 10% by mass or less.

The washing temperature can be set to a temperature equal to or lower than the boiling point of the solvent used for washing. For example, when methanol is used, it may be about 20 to 60 ° C. The cleaning efficiency can be improved by heating. The washing time can be, for example, 3 to 30 minutes.

(Drying process: preliminary drying process)
The pre-drying step is, for example, a step of pre-drying the structure cleaned in the cleaning step.

The method of drying is not particularly limited, and for example, a known drying method under atmospheric pressure can be used. The drying temperature varies depending on the heat resistant temperature of the surface to be treated and the type of the cleaning solvent. The drying temperature may be, for example, from 20 to 250 ° C. or from 60 to 180 ° C., from the viewpoint that the evaporation rate of the solvent is sufficiently fast and deterioration of the snow and ice prevention unit is easily prevented. The drying time varies depending on the mass of the snow and ice prevention unit and the drying temperature, but may be, for example, 1 to 24 hours.

(Drying process: aging process)
The aging step is, for example, a step of aging (heating aging, etc.) the snow-and-ice prevention unit dried in the preliminary drying step. Thereby, a final snow and ice prevention structure can be obtained. By performing the aging step, the snow-and-ice prevention property and the adhesion of the snow-and-ice prevention structure are further improved. When the washing step and the preliminary drying step are omitted, for example, the snow and ice prevention unit formed in the coating step may be aged.

This step may be performed, for example, as additional drying after the preliminary drying step. It is considered that the aging reduces the number of hydrophilic groups in the snow and ice prevention part, and further improves the snow and ice prevention. Further, when the snow and ice prevention unit has contracted in volume in the preliminary drying step and the transparency has been reduced, the transparency may be improved by restoring the volume by springback.

The aging temperature varies depending on the heat-resistant temperature of the surface to be treated, and may be, for example, 100 to 250 ° C or 120 to 180 ° C. By setting the aging temperature to 100 ° C. or higher, more excellent snow and ice prevention properties and adhesion can be achieved. By setting the aging temperature to 250 ° C. or lower, deterioration due to heat can be suppressed.

The aging time varies depending on the mass of the snow and ice prevention part and the aging temperature, but may be, for example, 1 to 10 hours or 2 to 6 hours. By setting the aging time to 1 hour or more, it is easy to achieve more excellent snow and ice prevention properties and adhesion, and by setting the aging time to 10 hours or less, the productivity is not easily reduced.

Although the example of the method for manufacturing the snow and ice preventing agent and the method for manufacturing the snow and ice preventing structure according to the embodiment has been described above, the method for manufacturing the snow and ice preventing agent and the method for manufacturing the snow and ice preventing structure is not limited thereto.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.

(Preparation of polysiloxane compound A)
In a 1-liter three-necked flask equipped with a stirrer, thermometer and Dimroth condenser, 100.0 parts by mass of hydroxy-terminated dimethylpolysiloxane “XC96-723” (product name, manufactured by Momentive), methyltrimethoxysilane Was mixed with 0.51.3 parts by mass of t-butylamine and reacted at 30 ° C. for 5 hours. Thereafter, the reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a bifunctional alkoxy-modified polysiloxane compound at both ends (polysiloxane compound A).

(Preparation of snow and ice prevention agent)
To 15 mL of 100 mM isopropyl acetate alcohol solution, 0.45 mL of methyltrimethoxysilane KBM-13 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0% of dimethyldimethoxysilane KBM-22 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) .15 mL and 0.15 mL of polysiloxane compound A were added and stirred for 60 minutes. 420 mL of pure water was added dropwise thereto, followed by stirring for 60 minutes to obtain a snow and ice inhibitor.

(Preparation of snow and ice prevention structure)
A slide glass S7213 (manufactured by Matsunami Glass Industry Co., Ltd., product name) was dipped in the snow and ice prevention agent obtained above, and dried at room temperature for 30 minutes to obtain a snow and ice prevention structure.

(Icing test)
FIG. 6 is a diagram schematically illustrating a test method of the icing power test. The icing power test was performed as follows.
(1) The temperature of the thermostat in which the load measuring device was set was set to -9 ° C.
(2) The sample and the stainless steel ring were set in a thermostat and allowed to stand for 2 hours.
(3) Water was injected into the stainless steel ring, and left still for 30 minutes. Thereby, as shown in FIG. 6, ice 22 was formed in the stainless steel ring 21 placed on the sample 23.
(4) A load S was applied from outside the stainless ring, and the maximum load point was measured.
(5) The maximum load was converted per unit area to obtain the icing power (N / cm ² ). The stainless steel ring had an inner diameter of 2.5 cm and an icing area of 4.9 cm ² .

When the snow-and-ice prevention structure obtained above was used as a sample, the icing power was about 19 N / cm ² . On the other hand, when the slide glass S7213 was used as the sample, the icing power was about 36 N / cm ² . The icing power was greatly reduced by using snow and ice inhibitors.

氷 Icing performance tests were also conducted on aluminum fins for air conditioning in the same manner as above. When the treatment with the snow and ice protection agent was not performed, a certain degree of icing was observed, but when the treatment was performed, icing was not observed.

From the above, it can be seen that the snow and ice preventing agent of the present invention can impart excellent snow and ice preventing properties to the surface to be treated.

L: circumscribed rectangle, P: silica particles, 1: snow and ice prevention film, 2 ... snow and ice prevention target object, 2a: surface to be treated, 3 ... snow and ice prevention particles, 10: snow and ice prevention part, 21 ... stainless steel ring , 22 ... ice, 23 ... sample, 100, 200, 300 ... snow and ice prevention structure.

Claims

A liquid containing at least one selected from the group consisting of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. A snow and ice inhibitor comprising the composition.
The snow and ice inhibitor according to claim 1, wherein the polysiloxane compound includes a compound represented by the following formula (B).

[In the formula (B), R 1b represents an alkyl group, an alkoxy group or an aryl group, R 2b and R 3b each independently represent an alkoxy group, and R 4b and R 5b each independently represent an alkyl group or an aryl group. And m represents an integer of 1 to 50. ]
The liquid composition is a silane monomer having a hydrolyzable functional group or a condensable functional group, and at least one selected from the group consisting of a hydrolysis product of the silane monomer having the hydrolyzable functional group. The snow and ice protection agent according to claim 1 or 2, further comprising:
雪 The snow and ice inhibitor according to any one of claims 1 to 3, wherein the liquid composition further contains airgel particles.
(5) The snow and ice prevention agent according to any one of (1) to (4), which is used for forming a snow and ice prevention part on a surface to be processed of an object.
6. The snow and ice preventing agent according to claim 5, wherein the snow and ice preventing portion includes aerogel.
A snow and ice inhibitor having a ladder-type structure including a support portion and a bridge portion, wherein the bridge portion includes a snow and ice prevention component containing a compound represented by the following formula (2).

[In the formula (2), R 5 and R 6 each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50. ]
The snow and ice prevention agent according to claim 7, comprising the snow and ice prevention component containing a compound having a structure represented by the following formula (3).

[In the formula (3), R 5 , R 6 , R 7 and R 8 each independently represent an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b represents 1 to 50 Indicates an integer. ]
雪 The snow and ice preventing agent according to claim 7 or 8, wherein the snow and ice preventing component is aerogel.
An object, and a snow and ice prevention unit on a surface to be processed of the object,
A snow and ice prevention structure, wherein the snow and ice prevention unit includes a dried product of the snow and ice prevention agent according to any one of claims 1 to 9.
A method for manufacturing a snow and ice prevention structure, comprising a step of applying the snow and ice protection agent according to any one of claims 1 to 9 to a surface to be processed of an object.