JPH02147688A - Icing-preventive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in (retentivity of) icing prevention by using a silicon resin obtained by (co)condensing an alkoxydimethylsiloxane compound with optionally a specified compound. CONSTITUTION:A silicone resin is obtained by (co)condensing an alkoxydimethylsiloxane compound of formula I [wherein R1 is methyl or ethyl; A is 0, ethylene or 1,3-propylene; a is 5 to 150; b and e are each 1 to 3; c is (3-b); d is (3-e)] with optionally 30wt.% or below alkoxysilane compound of formula II [wherein R2 is R1; R3 is a 1 to 8C alkyl; i is 0 to 3; and j is (4-i)] and/or at most 80wt.% dihydroxydimethylsiloxane compound of formula III (wherein k is 10 to 200) at 50 to 150 deg.C for 30min to 10hr in the presence of a catalyst. This resin is optionally mixed with a moisture-curable film-forming resin, a dialkoxysilyl-terminated dimethylsiloxane compound, a silicone oil or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel anti-icing composition and method.

Conventional technology and its problems In order to thaw frozen areas such as automobile windshields, wiper mirrors, tire houses, and keyholes, alcohol, ethylene glycol, surfactants, etc. are mixed with carbon dioxide gas,
Deicing materials are available on the market that are filled with a propellant gas such as LPG gas and sprayed onto frozen areas to temporarily thaw them.
It is used. However, these deicing agents have the disadvantage that their effects do not last because they temporarily thaw the ice, and they also do not have the ability to prevent ice formation by applying them in advance.

In general, the value of the icing force that allows ice to be removed without using tools such as spatulas, hammers, and sticks is approximately 1 kg/cm2 or less, but commercially available de-icing materials have a value of 1 kg/cm2 or less when refrozen after use.
Indicates a value exceeding cm2. That is, unless the area where the deicing agent is sprayed is thoroughly washed with water to prevent any chemical components from remaining, there is also the disadvantage that when it refreezes, it will freeze even more strongly.

JP-A-62-185776 discloses a homopolymer of glycol, acrylic acid or alkali metal acrylate,
Acrylamide/acrylic acid copolymer or acrylamide/alkali metal acrylate copolymer, alkali metal alkylaryl sulfonate, corrosion inhibitor, pH
A de-icing and anti-icing composition is disclosed comprising three basic compounds for conditioning and water. This composition is effective in deicing and preventing icing in situations where shearing forces are applied, such as when an airplane takes off, but its icing ability is still high in terms of deicing and preventing icing on stationary objects. It is insufficient.

Means for solving the problem Conventionally, ice can be easily removed, that is, the icing force is about 1 k
There is a desire for an anti-icing agent that is lower than g/cm2 and can maintain its anti-icing effect for a long period of time, and the inventors have conducted repeated research toward this goal.

The inventor of the present invention focused on the fact that dimethylpolysiloxane (silicone oil) is hydrophobic and has low surface energy, and conducted an investigation, but this material has a low cohesive force and does not peel off when the ice leaves. , the low icing force did not persist. Therefore, as a result of intensive research, the present inventors made use of the advantage of the low icing power due to dimethylpolysiloxane chains, and in order to obtain an anti-icing composition that could sustain the low icing power and solve the above problems, they discovered that a specific alkoxydimethyl The inventors have discovered that a composition containing a condensate using a siloxane compound can solve the above problems, and have arrived at the present invention.

That is, the present invention relates to the general formula [wherein R1 represents a methyl group or an ethyl group, and A represents an oxygen atom, an ethylene group, or a 1,3-propylene group,
a is an integer from 5 to 150, b and e are the same or different from 1 to
C represents an integer of 3, and 3-bSd represents an integer of 3-e. ] It is obtained by condensing an alkoxydimethylsiloxane compound represented by the formula (R3)i-8l (OR2)j (
II) [In the formula, R2 represents a methyl group or an ethyl group, and R
3 represents an alkyl group having 1 to 8 carbon atoms, i represents an integer of 0 to 3, and j represents 4-i. ] An alkoxysilane compound and/or a general formula represented by [where k represents an integer of 10 to 200]. ] This relates to an anti-icing composition characterized by containing a silicone resin (hereinafter abbreviated as "condensed silicone resin") obtained by co-condensing a mixture with a dihydroxydimethylsiloxane compound represented by the following.

The present invention also relates to an anti-icing composition containing the condensed silicone resin and a moisture-curable film-forming resin.

The present invention also relates to an icing prevention method in which the above-mentioned icing prevention composition is applied as an aerosol using a propellant gas agent as a medium.

The condensed silicone resin in the present invention includes (1) a condensate of an alkoxydimethylsiloxane compound represented by the general formula (I) (hereinafter abbreviated as "compound of formula (I)"), (2) a compound of formula (I). and an alkoxysilane compound represented by the general formula (n), a condensate of a compound of the formula (I) and a dihydroxydimethylsiloxane compound represented by the general formula (m), and a condensate of the compound of the formula (I) ), an alkoxysilane of formula (n) and a condensation product of dihydroxydimethylsiloxane of formula (m). A comb-shaped condensate having a hydrophobic dimethylsiloxane chain in its side chain is particularly preferred.

The above reactions (1) and (2) are carried out by a partial hydrolysis co-condensation reaction, and the reaction (2) is typically shown as follows, and
Reactions (2) and (2) can be carried out by partial hydrolysis co-condensation reaction in the same manner as above, but they can also be carried out without hydrolysis. You can also do it.

In the above reaction (■), a compound of formula (I) and a compound of formula (II)
It is preferable that the ratio of the alkoxysilane of formula (II) to the alkoxysilane of formula (II) is 30% by weight or less based on the total weight of both. If it exceeds 30% by weight, polar groups such as alkoxy groups or hydrolyzed silanol groups tend to remain, causing an increase in icing power.

In addition, in the reaction (■) above, a compound of formula (I) and a compound of formula (
The ratio of dihydroxydimethylsiloxane of formula (m) to dihydroxydimethylsiloxane of formula (m) is preferably 80% by weight or less based on the total amount of both.
It is more preferable that the content is in the range of 7<, 20 to 70% by weight. When the amount of dihydroxydimethylsiloxane of formula (m) exceeds 80% polymerization, many unreacted silanol groups tend to remain, which causes an increase in icing power.

In addition, in the reaction (①) above, the compound of formula (I), the compound of formula (I
The ratio of the alkoxysilane of I) and the dihydroxydimethylsiloxane of formula (III) is as follows: Compound of formula (I): preferably 20% by weight or more, more preferably 30 to 70% by weight, based on the total amount of the three. %, alkoxysilane of formula (U): preferably 30% by weight or less, more preferably 20% by weight or less, dihydroquine dimethylsiloxane of formula (III): preferably 80% by weight or less, more preferably 30 to 70% by weight It is appropriate that it be within the range of 96.

If the amount of the compound of formula (I) is less than 20% by weight, the amount of hydrophobic dimethylsilane groups serving as side chains will decrease, causing an increase in icing power.

When the aldoxysilane tray of formula (II) has 30% Gm by weight, alkoxy groups or hydrolyzed silanol groups, which are polar groups, tend to remain, which causes an increase in icing power.

Furthermore, if the toxicity of the dihydroxydimethylsiloxane of formula (m) exceeds 80% by weight, many unreacted silanol groups tend to remain, which causes an increase in icing power.

In the composition of the present invention, the condensed silicone resin is obtained by condensing the compound of formula (I), or the compound of formula (I) and the alkoxysilane of formula (IT) and/or the alkoxysilane of formula (III)
is obtained by co-condensing a mixture with dihydroxydimethylsiloxane of
It is preferable to appropriately select the raw material type, blending ratio, reaction catalyst type, catalyst amount, reaction temperature, and reaction time so as to fall within the range of 000 to 150,000. Reaction catalysts include mineral acids such as hydrochloric acid and sulfuric acid; organic acids such as formic acid and acetic acid; fatty acid salts of metals such as manganese, cobalt, lead, nickel, iron, tin, and zinc, such as stearates and octylates. , and acetylacetone complexes of these metals. These reaction catalysts are usually used in an amount of 0.00 parts by weight per 100 parts by weight of the silicon compounds represented by (I) to (III).
It is used in the range of 1 to 1 double plate portion. The condensation reaction is usually carried out by heating at a temperature of 50 to 150°C for 30 minutes to 10 hours.

In the present invention, the condensed silicone resin may be composed of only the condensed silicone resin, or the condensed silicone resin and an organic solvent.
In order to improve the film strength and adhesion to the base material and to improve the durability of the anti-icing effect, it is more preferable to blend a moisture-curable film-forming resin.

In the present invention, the moisture-curable film-forming resin has the general formula [wherein R5 is a hydrocarbon group selected from an alkyl group, an aryl group, and an aralkyl group having 1 to 10 carbon atoms, and Z is a halogen, alkoxy, or acyloxy , a group selected from phenoxy and thioalkoxy groups, and t is an integer of 1 to 3. ] At least 1 silicon group, preferably 2 silicon groups bonded to a hydrolyzable group at the terminal or side chain in one molecule.
It is a resin having more than

As a method for introducing the silicon group bonded to the above-mentioned hydrolyzable group into the resin, (a) General formula H-8t-Z)1 [wherein R5, Z and t are as described above. ] A method of hydrosilylating a hydrosilane compound represented by the following with a resin having a polymerizable carbon-carbon double bond in the presence of a group II transition metal catalyst; The organic residues having a double bond, R5, z and t are as described above. ] A method of radical copolymerization of a silane compound and a polymerizable unsaturated compound can be effectively used.

Specific examples of the hydrosilane compounds used in the method (a) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyljethoxysilane, methyldimethoxysilane,
Examples include various silanes such as alkoxysilanes such as phenyldimethoxysilane, trimethoxysilane and triethoxysilane; and acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane.

Among these hydrosilane compounds, halogenated silanes can also be easily used, but resins containing silicon groups bonded to hydrolyzable groups, which are obtained using halogenated silanes, release hydrogen chloride when exposed to air. Although it cures quickly at room temperature while generating hydrogen chloride, it can only be used in limited applications due to problems with the irritating odor and corrosion caused by hydrogen chloride, so the halogen functional group is subsequently converted to other hydrolyzable functional groups. It is desirable to do so.

The resin having a polymerizable carbon-carbon double bond used in method (a) must be a resin without hydroxyl groups, such as vinyl resin, polyester resin, polybutadiene resin, or urethane resin. Resin etc. can be used.

Examples of the vinyl resin include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2 - (meth)acrylic acid esters such as ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate and benzyl (meth)acrylate; styrene, α - Vinyl aromatic compounds such as methylstyrene, vinyltoluene, p-chlorostyrene, and pt-butylstyrene; (meth)acrylic acid, crotonic acid, fumaric acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, etc. Unsaturated carboxylic acids; vinyl compounds containing glycidyl groups such as glycidyl (meth)acrylate, vinyl glycidyl ether, and allyl glycidyl ether; vinyl esters such as vinyl acetate, vinyl benzoate, and rVEOVAJ (Shell Chemical ■product); (meth) acrylamide, N,
Carboxylic acid amide monomers such as N-dimethyl(meth)acrylamide, N-alkoxymethylated (meth)acrylamide, diacetone acrylamide, and N-methylol(meth)acrylamide; Cyano group-containing such as (meth)acrylonitrile Monomers, N,N-dialkylaminoalkyl (meth)acrylate-based tertiary amino group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate) and N,N-diethylaminoethyl (meth)acrylate ; It is a resin whose main component is a copolymer formed by copolymerizing vinyl compounds such as vinyl ethers such as n-butyl vinyl ether, ethyl vinyl ether, and methyl vinyl ether.

During the production of this copolymer, allyl acrylate, allyl methacrylate, etc. are partially blended and radical polymerization is performed using an azo polymerization initiator to form polymerizable carbon-carbon double bonds in the copolymer. Allyl groups can be introduced. In addition, during copolymer production, a portion of a hydroxyl group-containing polymerizable unsaturated compound such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is copolymerized, and the entire amount of hydroxyl groups is added with isophorone diisocyanate or tolylene diisocyanate and hydroxy ( 1 with meth)acrylate
/1 mole adduct, isocyanoethyl acrylate, isocyanoethyl methacrylate, and polymerizable double bonds by reacting polymerizable unsaturated compounds having isocyanate groups such as m-isopropenyl-α,α′-dimethylbenzyl isocyanate. can be introduced.

Conversely, it can also be introduced by a method of containing isocyanate groups in the copolymer and reacting the isocyanate groups with a hydroxyl group-containing polymerizable unsaturated compound. In addition to the reaction between isocyanate groups and hydroxyl groups mentioned above, reactions of functional groups that can react with each other, such as reactions between hydroxyl groups and carboxyl groups, and hydroxyl groups and acid anhydride groups, are used to create polymerizable double bonds in copolymers. can be introduced.

The polyester resin used in method (a) is mainly composed of a polyester resin obtained by condensing organic acid components and alcohol components used in the production of ordinary polyester resins as raw materials. As the organic acid component, polybasic acids are usually used, and examples of the polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroterephthalic acid, hexahydrophthalic acid, hexabitroisophthalic acid, and hexahydrophthalic acid. Terephthalic acid, hetate acid, trimellitic acid, hexahydrotrimellitic acid, pyromellitic acid, cyclohexanetetracarboxylic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylene hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid acids, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, cepatic acid, decanedicarboxylic acid, superic acid, pimelic acid, dimer of tall oil fatty acids), tetrachloro Examples include phthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4.4''-dicarboxybiphenyl, and their acid anhydrides and dialkyl esters, especially dimethyl ester.

Further, as the alcohol component, dihydric alcohol, trihydric alcohol, etc. are usually used. Examples of dihydric alcohols include ethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol, 2
, 3-butanediol, 1,2-butanediol, 1,
5-bentanediol, 1,4-bentanediol, 2
, 4-bentanediol, 2,3-dimethyltrimethylene glycol, 3-methyl-pentane-1,5-diol, 3-methyl-4,5-bentanediol, 2. 2
．． 4-trimethyl-1,3-bentanediol, 1,6
-hexanediol, 1,5-hexanediol, 1,
4-hexanediol, 2.5-hexanediol, 1
, 4-cyclohexane dimetatool, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, polyalkylene oxide, bishydroxyethyl terephthalate, (hydrogenated) alkylene oxide adduct of bisphenol A etc. Monoepoxy compounds such as Cardura E10 (manufactured by Shell Chemical Co., Ltd.), α-olefin epoxide, and butylene oxide can also be used as a type of glycol.

Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, trimethylolethane, diglycerin, pentaerythritol, dipentaerythritol, and sorbitol.

Furthermore, compounds having both carboxylic acid and hydroxyl groups in the molecule can also be used. Examples of such compounds include dimethylolpropionic acid, pivalic acid, 12-hydroxystearic acid, and ricinoleic acid. Also ε−
Lactones such as caprolactone and γ-valerolactone are also cyclic ester compounds and therefore belong to the above-mentioned category of compounds.

Some of the above organic acid components and alcohol components are combined with various natural and synthetic higher fatty acids, higher alcohols, and acrylic acid 2.
-Hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, benzoic acid, pt-butylbenzoic acid, and other monofunctional raw materials or natural oils can also be substituted.

By using an organic acid component or an alcohol component having a polymerizable unsaturated group, a polymerizable double bond can be introduced into the resin. As another method 7, when the polyester resin formed by condensing an organic acid component and an alcohol component has hydroxyl groups, the entire amount of the hydroxyl groups is reacted with the polymerizable unsaturated compound having an isocyanate group to form a polymerizable compound. Double bonds can be introduced. Furthermore, a polymerizable double bond can be introduced by reacting the entire amount of the hydroxyl groups with a polymerizable unsaturated compound having a carboxyl group or an acid anhydride group. On the other hand, when the polyester resin has a carboxyl group, a polymerizable double bond can be introduced by reacting a polymerizable unsaturated compound having a hydroxyl group equal to or less than that of the carboxyl group.

In the above method (a), a transition metal complex is required as a catalyst in the step of reacting a hydrosilane compound with a polymerizable double bond. The transition metal complex catalyst is selected from platinum, rhodium, cobalt, palladium and nickel.
Group transition metal complex compounds are effectively used, and the hydrosilylation reaction is typically carried out at any temperature between 50 and 150°C.
This is achieved by reacting for about 10 hours.

The amount of the hydrosilane compound to be used can be set arbitrarily, but it is preferably used in an amount of 0.5 to 2 times the mole of carbon-carbon double bonds contained in the vinyl resin. Although this does not preclude the use of a larger amount of silane, it will simply be recovered as unreacted hydrosilane.

Examples of the silane compounds used in the method (b) include γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldichlorosilane, γ-acryloyloxypropyltrichlorosilane, Examples include γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and the like.

As the polymerizable unsaturated compound to be copolymerized with the silane compound in the method (b), a vinyl compound used in the synthesis of the copolymer that is the main component of the vinyl resin in the method (a) can be used.

Synthesis of these copolymers of vinyl compounds and silane compounds is carried out by ordinary solution polymerization methods to obtain silyl group-containing copolymers of vinyl compounds, silane compounds, radical initiators, and appropriate molecules. If necessary, a chain transfer agent such as n-dodecylmercaptan or t-dodecylmercaptan is added to the reaction mixture at 50 to 150°C. The solvent is
It may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and acetic esters.

The molecular weight of the moisture-curable resin composition in the present invention is not particularly limited, but from the viewpoint of coating properties and film forming properties, the weight average molecular weight is 3,000 to 200,000.
is preferable, and more preferably within the range of 5,000 to 100,000.

In the resin having a silicon group bonded to a hydrolyzable group obtained by method (a) or method (b), the hydrolyzable group can be converted into another hydrolyzable group by a known method. be.

When the composition of the present invention contains the moisture-curable film-forming resin, the purpose is to rapidly advance the condensation reaction between the reactive silyl groups of the condensed silicone resin and the moisture-curable film-forming resin to increase film strength. and the general formula [wherein R3 and R4 are the same or different and represent a methyl group or an ethyl group, and D and E are the same or different and represent an oxygen atom, an ethylene group or a 1,3-propylene group. X is 3
It represents an integer of ~30, m and r are the same or different and represent an integer of 1 to 3, n represents 3-m, and S represents 3-r.

] A dimethylsiloxane compound containing an alkoxysilyl group at both terminals represented by the following can be blended as necessary.

When a mixture of condensed silicone resin and moisture-curable film-forming resin is applied to an object, the moisture-curable film-forming resin is in the lower layer (on the object side) and the condensed silicone resin is in the upper layer (atmospheric side).
The dimethylsiloxane of formula (IV) is unevenly distributed in the siloxane, promotes the bonding of both resins, and is useful for improving the long-term sustainability of low icing power.

The composition of the present invention may further contain a compound having the general formula [where y represents an integer of 1 to 20,000], if necessary. ] can be blended. (V)
By blending the silicone oil of the formula into the composition of the present invention, the hydrophobic polydimethylsiloxane chains and alkyl chains in the condensed silicone resin are promoted to the atmosphere side, and the highly polar alkoxysilyl groups are directed to the atmosphere surface side. Make it easier to prevent orientation.

In the composition of the present invention, a condensed silicone resin, a moisture-curable film-forming resin, a dimethylsiloxane of the (TV) formula, and a (
The blending ratio of the silicone oil of formula V) is preferably within the following range with respect to the total amount of these four components.

Condensed silicone resin: 2-100% by weight, preferably 5-100% by weight
95% by weight, moisture-curable film-forming resin: 98% by weight or less, preferably 3 to 95% by weight, dimethylsiloxa of formula (rV) 2230% by weight or less, preferably 20% by weight or less, silicone of formula (V) Oil: 30 weight 11% or less, preferably 20 weight % or less.

If the content of the condensed silicone resin tray is less than 2% by weight or if the amount of moisture-curable film-forming resin exceeds 98% by weight, the icing power tends to increase. If the proportion of dimethylsiloxane of formula (IV) exceeds 30% by weight, many unreacted alkoxy groups remain, which may increase the icing power. Furthermore, if the amount of silicone oil of formula (V) exceeds 30 weight, the drying properties of the applied composition film will be poor and the surface will become easily stained.
Adhesion to the substrate tends to deteriorate.

Further, the composition of the present invention may contain an organic solvent, and can be made into an aerosol injection type anti-icing agent that can be easily sprayed by filling it into a closed container together with a propellant gas agent. can. Any organic solvent that can dissolve or disperse the composition of the present invention can be used, such as xylene, toluene, methanol, ethanol, isopropanol, n-butanol, isobutanol, ethyl acetate, butyl acetate, and methyl ethyl ketone. , methyl isobutyl ketone, hexane, heptane, isooctane,
Ethylene glycol, monoethyl ether, ethylene glycol monobutyl ether, acetic acid ethylene glycol monomethyl ether, etc. can be used as appropriate. As the propellant gas agent, those normally used as propellant gas agents for aerosols can be used, such as liquefied petroleum gas (LPG), liquefied carbon dioxide, and fluorocarbon gas. The composition of the present invention can be applied as an aerosol or by brushing or spray painting.

Actions and Effects of the Invention The composition of the present invention contains a condensed silicone resin having a large number of hydrophobic dimethylsiloxane chains, and the condensed silicone resin of the present invention has a higher concentration than silicone oil, which is a linear dimethylsiloxane chain itself. It exhibits excellent anti-icing properties, and since it contains an alkoxy group and/or a silanol group, it has excellent adhesion to substrates and has an excellent long-lasting anti-icing effect. Furthermore, by blending the condensed silicone resin with a moisture-curable film-forming resin and, if necessary, a compound represented by formula (IV), it is possible to improve the film strength and maintain the anti-icing effect for an even longer period of time. .

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that hereinafter "parts" and "%" mean "parts by weight" and "% by weight."

Production Example 1 of Condensed Silicone Resin Liquid [In the formula, X represents an integer of about 10 on average. [In the formula, X represents an integer with an average of about 100. ]CH3CH2Cl-12
81 (OCII3) 3 10 parts 0.1N aqueous hydrochloric acid solution 4 parts Xylene 50 parts Methyl isobutyl ketone 50 parts The above materials were reacted at 85°C for 3 hours with stirring in a glass reaction vessel, then at 120°C. Condensation was proceeded while removing and replacing 60 parts of the solvent for 2 hours to obtain a condensed silicone resin Al liquid having a weight average molecular weight of about 38,000.

Production Example 2 [wherein, X represents an integer with an average of about 25]. ] Tin octylate catalyst 0.5 parts Toluene 100 parts The above-mentioned materials were reacted at 105°C for 2 hours with stirring in a glass reaction vessel, and 60 parts were removed for another 2 hours to proceed with condensation without solvent displacement. A condensed silicone resin A2 liquid having a weight average molecular weight of about 47,000 was obtained.

Production Example 3 [In the formula, X represents an integer of about 50 on average. ]OCH3Si
(OCH3) 3 20 parts 0.1N aqueous hydrochloric acid 4 parts Condensation was proceeded without solvent removal and substitution for 60 parts to obtain a condensed silicone resin liquid A3 having a weight average molecular weight of 34,000.

Production Example 4 [wherein, X represents an integer with an average of about 25]. ] Tin octylate catalyst 0.5 parts Toluene 100 parts The above-mentioned materials were reacted at 105°C for 2 hours with stirring in a glass reaction vessel, and then 35 parts were removed at the same temperature for 2 hours before condensation. A condensed silicone resin A4 liquid having a weight average molecular weight of 27,000 was obtained.

Production Example 5 35 parts [wherein, X represents an integer with an average of about 30]. ]OCH35i
(OCTo) 3 15 parts [wherein, X
represents an integer with an average of about 10. ]0.1N hydrochloric acid aqueous solution
5.5 parts
50 parts Methyl isobutyl ketone 50 parts The above-mentioned material was reacted at 83°C for 3 hours with stirring in a glass reaction vessel, and then at 120°C for 2 hours 60 parts to proceed with condensation without removing the solvent and replacing the solvent with a weight average molecular weight of 20,000. condensed silicone resin A
5 liquids were obtained.

Production of moisture-curable film-forming resin liquid Production Example 6 γ-methacryloxypropyltrimethoxysilane 30 parts n-butyl acrylate 20 parts Methyl methacrylate 50 parts α,α-azobisisobutyronitrile 1 part xylene 30 parts, butyl acetate 30 parts and 15 parts of n-butyl alcohol were charged into a glass reaction vessel, heated and maintained at 90°C, and the mixture of the above monomer and catalyst was added dropwise from the dropping funnel over 4 hours. After completion of the dropwise addition, the temperature was heated and maintained at 110°C, and a mixture of 10 parts of xylene, 10 parts of butyl acetate, 5 parts of n-butyl alcohol, and 1 part of 2,2'-azobis-2,4-dimethylvaleronitrile was added to the mixture. was added dropwise from a dropping funnel over a period of 30 minutes, and after the addition was completed, the temperature was maintained at 110° C. for 1 hour to obtain a solution of an alkoxysilyl group-containing acrylic resin having a weight average molecular weight of 36,000 and a solid content of 50%.

Production Example 7 γ-methacryloxypropylmethyldimethoxysilane 50 parts t-butyl methacrylate 40 parts lauryl acrylate 10 parts α,α'-azobisisobutyronitrile 0.9 parts 38 parts of xylene and 37 parts of n-butyl alcohol were added to a glass The mixture was charged into a reaction vessel made of aluminum, heated and maintained at 90°C, and the mixture of the monomer and catalyst was added dropwise from the dropping funnel over 4 hours. After dropping, heat and maintain at 110°C, add 12 parts of xylene and 13 parts of n-butyl alcohol.
A mixture of 1 part of 2゜2'-azobis-2,4-dimethylvaleronitrile was added dropwise from the dropping funnel over 1 hour, and after the addition was completed, the mixture was kept at 110°C for 30 minutes to form an alkoxysilyl with a weight average molecular weight of 42,000. A solution of about 50% solids of group-containing acrylic resin was obtained.

Production Example 8 Allyl acrylate 25 parts Methyl methacrylate 30 parts n-butyl acrylate 45 parts α,α'-Azobisisobutyronitrile 1 part Xylene 40 parts and butyl acetate 4 parts
0 part was charged into a glass reaction vessel, heated and maintained at 90°C, and the mixture of the monomer and catalyst was added dropwise from the dropping funnel over 4 hours. After completion of the dropwise addition, a mixture of 10 parts of xylene, 10 parts of butyl acetate, and 1 part of 2,2'-azobis-2,4-dimethylvaleronitrile was added dropwise to this mixture over 30 minutes while maintaining the temperature at 90°C. After completion of dripping 9
The mixture was kept at 0° C. for 1 hour to obtain an acrylic resin having a weight average molecular weight of about 40,000.

Next, the obtained resin solution was maintained at 80°C, and 0.4 parts of platinum catalyst and 28 parts of trimethoxyhydrosilane were added to this solution.
A mixture of 1 part and 28 parts of xylene was added dropwise over 3 hours. After completing the dropping, heat and maintain at 100°C, add platinum catalyst 0.1
A solution of the alkoxysilyl group-containing acrylic resin with a solid content of about 50% was obtained by blending the two parts and reacting for 2 hours.

Production Example 9 Phthalic anhydride 32.1 parts Trimethylolpropane 14.1 parts Pentaerythritol 14.5 parts Soybean oil fatty acid
46.2 parts of the above mixture was charged into a glass reaction vessel and heated and stirred. After raising the temperature to 180℃,
The mixture was kept at ℃ for 1 hour to advance the esterification reaction. Thereafter, 5 parts of xylene was added, the temperature was raised to 230°C, and the reaction was proceeded while refluxing the xylene at 230°C. After about 4 hours, the reaction was stopped when the acid value (solid content) reached 15. After cooling, xylene was added to obtain a resin solution with a solid content concentration of 50%.

The weight average molecular weight of the obtained resin was about 23,000.

Next, the obtained resin solution was maintained at 80° C., and 27 parts of isocyanoethyl methacrylate was added thereto, and the mixture was reacted until substantially no isocyanate groups were present. Next, a mixture of 21.1 parts of trimethoxyhydrosilane, 0.15 parts of platinum catalyst, and 21 parts of xylene was added dropwise into the reactant solution maintained at 80° C. over 3 hours. After completion of the dropwise addition, the mixture was heated and maintained at 100° C., 0.05 part of a platinum catalyst was added, and the reaction was carried out for 2 hours to obtain an alkoxysilyl group-containing polyester resin solution.

Example 1 Condensed silicone resin A1 liquid obtained in Production Example 1 20 parts Acrylic resin solution obtained in Production Example 6 2 parts (TV) type dimethylsiloxane (a) (Note 1) 2 parts Silicone oil (b) (Note 2) 2.5 parts isooctane 40 parts ethanol
33.5 parts 100 parts of the above mixture was packed in a sealed container along with 200 parts of LPG gas as a propellant, and coated on an aluminum plate to a dry film thickness of approximately 5 microns. After drying at room temperature for 24 hours, the icing power was measured. The results are shown in Table 2.

(Note 1): Chemical formula [wherein, X represents an average integer of 5]. ] Dimethyl silicone.

(Note 2): Chemical formula [wherein, X represents an integer with an average of about 8]. ] Silicone oil.

Examples 2 to 9 and Comparative Example 1 The same procedure as Example 1 was conducted except that the formulations shown in Table 1 were used, and the icing shear fracture strength (kg/CI!12) was measured.

The results are shown in Table 2.

In addition, (Note 3) in Table 1, (Note 5) is as follows.

(Note 3): Chemical formula [wherein, X represents an integer with an average of about 20]. ] Dimethylsiloxane.

(Note 4): Chemical formula [wherein, X represents an integer with an average of about 200]. ] Silicone oil.

(Note 5): A silicone oil with a viscosity of about 1000 Stokes (25°C) expressed by the chemical formula, where X is an integer with an average of about 1000.

Also, (Note 6), (Note 7) and (Note 8) in Table 2
The test method was conducted according to the following method.

〔Test method〕

(Note 6) @Ice shear fracture strength test method: A stainless steel ring (inner area 5 cm2) was placed on the test plate (aluminum plate coated with anti-icing composition and dried) and frozen at -10°C. Place it in a test thermostat, 9
Precool for 0 minutes. Next, 2 mQ of distilled deionized water kept at 5°C is poured into the stainless steel ring to freeze it, thereby obtaining ice that adheres to the surface of the subject. After this thing was left in this state for 2 hours at -10°C, force was applied to the ring by a metal moving rod connected to a load cell and driven by power, and the shear fracture strength when peeling off the adhered ice was measured. It was measured (unit: kg/cm2).

(Note 7) Repeated test: The icing shear fracture strength was measured when the test in (Note 6) was repeated on the same location on the test plate, and 10.20.30
．． The 40th and 50th values are listed.

(Note 8) Outdoor Bacro test: The test board was exposed to the south at an inclination angle of 35° in Hiratsuka City, Kanagawa Prefecture, and the test (Note 6) was conducted on the test board after exposure for 2, 4, 8 and 12 weeks.

Icing shear failure strength was also measured on initial test plates that had not been tested.

As is clear from the test results in Table 2, the surface coated with the anti-icing agent of the present invention has a low ice adhesion force. Such an effect is not only seen when applied by aerosol spraying (similar results were also shown when applied with a brush or air spray with a formulation that does not contain a propellant).

Moreover, compared to the composition of Example 6, the compositions of Examples other than Example 6, which were blended with a moisture-curable film-forming resin, exhibited a longer-term icing prevention effect.

(that's all)

Claims (1)

[Claims] [1] General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R_1 represents a methyl group or an ethyl group, and A represents an oxygen atom, an ethylene group, or a 1,3- represents a propylene group, a is an integer of 5 to 150, b and e are the same or different 1
Indicates an integer of ~3, c indicates an integer of 3-b, and d indicates an integer of 3-e. ] or obtained by condensing an alkoxydimethylsiloxane compound represented by the formula (I), or a compound of the general formula (I) and the general formula (R_3)i-Si-(OR_2)j(II) [wherein R
_2 represents a methyl group or an ethyl group, R_3 has 1 carbon number
~8 alkyl group, i is an integer of 0 to 3, j is 4-
Indicates i. ] Alkoxysilane compound and/or general formula represented by ▲ Numerical formula, chemical formula, table, etc. ▼ (III) [In the formula, k represents an integer from 10 to 200. An anti-icing composition characterized by containing a silicone resin obtained by co-condensing a mixture with a dihydroxydimethylsiloxane compound represented by the following. [2] The anti-icing composition according to claim 1, which contains a moisture-curable film-forming resin. [3] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) [In the formula, R_3 and R_4 are the same or different and represent a methyl group or ethyl group, and D and E are the same or different and represent an oxygen atom, ethylene group or 1,3-propylene group. X
represents an integer of 3 to 30, m and r are the same or different and represent an integer of 1 to 3, n represents 3-m, and S represents 3-r. ] The anti-icing composition according to claim 2, which contains a dimethylsiloxane compound containing an alkoxysilyl group at both terminals. [4] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (V) [In the formula, y represents an integer from 1 to 20,000. The anti-icing composition according to any one of claims 1 to 3, which contains a silicone oil represented by the following. [5] An icing prevention method comprising applying the icing prevention composition according to any one of claims 1 to 4 as an aerosol using a propellant gas agent as a medium.