JP2002321019A - Method for pressing water-repellent paint coated stock - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an advantageous pressing method wherein a water-repellent constituent does not leach away in the press forming of a water-repellent paint coated stock so that deterioration of the water-repellent paint does not occur. SOLUTION: An oil compound of a mixture of 100 pt.wt of press oil of which the principal component is hydrocarbon of which carbon number is 10 to 40 and 0.1 to 10 pt.wt of specific organopolysiloxane is used as a lubricant, in the press forming of the coated stock whose surface is provided with a repellent film comprised of a compound containing 100 pt.wt of specific organopolysiloxane and 3 to 70 pt.wt of specific organopolysiloxane having the silanol group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for pressing a water-repellent coating material, and more particularly to a method for pressing a coating material on which a water-repellent coating film is formed without reducing the water-repellent performance. .

[0002]

2. Description of the Related Art Conventionally, in a heat exchanger such as an air conditioner, aluminum fins made of various aluminum materials have been used in order to meet demands for weight reduction, improvement of thermal efficiency, and further downsizing. And
Designs have been introduced to minimize the spacing between such fins. For example, in a heat exchanger such as an evaporator of an air conditioner, the surface temperature of an aluminum fin becomes equal to or lower than the dew point of the atmosphere, and water droplets adhere to the surface of the fin by condensation, and in an outdoor unit during a heating operation, Since the air temperature is low, water droplets on the fin surface become frost and freeze due to frost and the like, thereby increasing ventilation resistance and reducing the amount of air flow, thereby causing a problem that heat exchange efficiency is significantly reduced. .

[0003] Therefore, as a solution, at present,
The surface of the aluminum fins is coated with a hydrophilic coating so that water droplets adhering to the fin surface run off and the remaining of water droplets during defrosting is minimized, but the heating operation time is extended. In addition, the hydrophilic coating film formed on the fin surface deteriorates with time, and the performance of removing water droplets decreases with the deterioration. Had.

On the other hand, in place of such a hydrophilic coating, Japanese Patent Application Laid-Open No. 5-117637 discloses a method of applying a water-repellent coating composition comprising an organic resin solution and fine particles to thereby improve the fin surface. Although it is being considered to increase the frosting time by making it super water repellent,
Since the water repellency was not yet sufficient and the durability was problematic, it could not be put to practical use.

As the super water-repellent paint which provides such super-water-repellent properties, paints containing fluorine particles are often used for spray coating. However, those paints have a coating thickness of 60 μm or more. Most of them are thicker [Saito et al., "Surface Technology", Vol. 47, No. 7 (199
6), p. 558 to 561]. Therefore, it is recognized that the heat transfer efficiency is low, which makes the material unsuitable as a material for fins, and that many materials have a problem in durability.

[0006] Further, in Japanese Patent Application Laid-Open No. 11-166798, a water-sliding material is coated so that water droplets can easily flow and frost formation or frost formation can be defrosted in a short time. However, since such a coating film is obtained by grafting a fluorine-based polymer and a silicone-based resin, in order to achieve desired water-sliding performance, the coating film thickness must be 10 μm. The thermal conductivity of the coating film is extremely low compared to aluminum materials, etc.
This has led to problems such as a decrease in heat exchange efficiency, impairment of the intended performance of the heat exchanger, and poor formability such as press resistance.

Japanese Patent Application Laid-Open No. 2000-119642 proposes a composition for forming a water-repellent coating film comprising a silicone resin composed of RSiO _3/2 units and a polyalkyl hydrogen siloxane having a specific structure. By such a composition, the surface of the coating film is made smooth, so that the water droplets attached to the surface can slide down instead of rolling down, so that extremely excellent water repellency can be advantageously achieved. However, in the water-repellent coating film composed of such a composition, the properties such as flexibility, flexibility, stretchability, etc. are not enough, and the coating film is not formed when forming the aluminum coating material. It could not follow the deformation of the aluminum material and could cause cracks, wrinkles, and peeling.

Therefore, the present inventors have conducted various studies in view of such problems, and as a result, have found that 100 parts by weight of a specific organopolysiloxane and 3 to 70 parts by weight of a specific organopolysiloxane having a silanol group. By coating a composition containing and on various materials including aluminum material, excellent water repellency is achieved, and unprecedented excellent properties such as flexibility, flexibility, and stretchability. Has been formed, and it has been found that the above-mentioned problems can be completely eliminated, and
A separate application has been filed for such a composition.

However, as a result of further studies by the present inventors, bending, ironing, and drawing of a water-repellent coating material formed of a composition giving a coating film having such excellent properties have been described. When various press forming operations such as a punching process and a punching process were performed, it became clear that there was a problem that a decrease in performance such as water repellency was easily caused after such a forming process.
That is, when various press forming operations are performed, cooling, removal of aluminum powder, and formability (workability) are conventionally performed.
Press oil (lubricant)
Is used, the press oil, the water-repellent coating material, in particular, by contacting the water-repellent coating film formed on the surface, the coating film formed on the surface of the water-repellent coating material There is a possibility that the components may be eluted to easily cause deterioration of properties such as water repellency.

[0010]

Here, the present invention has been made in view of such circumstances, and an object of the present invention is to perform press molding of a water-repellent coating material.
An object of the present invention is to provide an advantageous pressing method in which a water-repellent component is not eluted and its performance is not reduced.

[0011]

According to the present invention, 100 parts by weight of an organopolysiloxane represented by the following general formula (1) and a compound represented by the following chemical formula (1) are provided in order to solve the above problems.
A coating material comprising a water-repellent coating formed on the surface by a coating operation using a composition containing 3 to 70 parts by weight of an organopolysiloxane having a silanol group represented by the general formula (2): In a press molding method, an organopolysiloxane represented by the following general formula (3) is added to 100 parts by weight of a press oil containing a hydrocarbon having 10 to 40 carbon atoms as a main component, The gist of the present invention is a method for pressing a water-repellent coating material, characterized in that the above-mentioned press molding is performed by using an oil composition blended in a ratio of 0.1 to 10 parts by weight as a lubricant. is there.

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That is, in the method for pressing a water-repellent coating material according to the present invention, the water-repellent coating material comprises a specific organopolysiloxane represented by the general formula (1) and a general formula (2) And a specific organopolysiloxane having a silanol group represented by, and a coating film composed of a composition containing the composition at a predetermined ratio is formed. This achieves properties such as flexibility, flexibility, and stretchability, and even when subjected to molding such as press working, such a coating does not cause problems such as cracking or peeling, and exhibits excellent moldability. It can be done.

In addition, in such a method for pressing a water-repellent coating material, a specific organic compound represented by the general formula (3) is applied to a press oil containing a hydrocarbon having 10 to 40 carbon atoms as a main component. Since an oil composition obtained by adding a polysiloxane at a predetermined ratio is used as a lubricant for press molding, even if such a lubricant adheres to the surface of a water-repellent coating material, it is repellent. Elution of the aqueous component into the lubricant is advantageously suppressed, and even if the water-repellent component is eluted, the specific organopolysiloxane represented by the general formula (3) contained in the lubricant is newly used. In addition, a water-repellent film is formed, and even after press molding, excellent water-repellent performance is exhibited and extremely excellent durability can be realized.

According to a preferred embodiment of the method for pressing a water-repellent coating material according to the present invention, the oil composition further comprises an organopolysiloxane represented by the following general formula (4). Contains. by this,
The adhesiveness of the water-repellent film formed by the components in the lubricant is further improved.

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According to another preferred embodiment of the method for pressing a water-repellent coating material according to the present invention, the oil composition further contains a silane having an epoxy group, an acyloxy group, an amino group or a mercapto group. It is preferable that the silane having such a functional group be used, so that the formation of a film on the surface of the coating material can be more advantageously performed.

Further, according to another desirable embodiment of the method for pressing a water-repellent coating material according to the present invention, the oil composition may further contain a curing catalyst or an organic peroxide. Preferably, this makes it possible to form a film on the surface of the coating material more advantageously.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a water-repellent coating material to which a pressing method according to the present invention is applied, an organopolysiloxane represented by the general formula (1) shown above and The material and shape of the organopolysiloxane having a silanol group represented by the general formula (2) are not limited as long as a coating film composed of a composition containing the silanol group-containing organopolysiloxane in a predetermined blending ratio is formed. It goes without saying that it is not limited. For example, when press-forming a fin material of a heat exchanger, generally, a water-repellent coating material having a thin plate shape of an aluminum material often used for such a fin material is advantageously employed. In addition, any material other than aluminum, such as a metal material such as copper, may be used.

Specifically, the organopolysiloxane represented by the general formula (1), which is one of the components essential for the composition for forming such a water-repellent coating film, is a hydrolytic condensation product. It has a resin or resin-like structure.

In the general formula (1), R ¹
And R ³ each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, and an n group.
-Propyl group, isopropyl group, n-butyl group, isobutyl group and the like can be mentioned, and among them, a methyl group is particularly preferably used. Further, R ² and R ⁴ in the general formula (1) each independently represent one or more substituents selected from a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms. Here, the type of the alkoxy group and the ratio of the hydroxyl group to the alkoxy group in one molecule of the organopolysiloxane represented by the general formula (1) are not particularly limited. In the case of the group, the reactivity increases as the number of carbon atoms decreases, and in the latter case, the reactivity improves as the ratio of the hydroxyl group to the alkoxy group increases, but the storage stability of the composition increases. From the point where the property is reduced, depending on the usage mode of the composition and the like,
It will be selected or adjusted appropriately.

In the above-mentioned organopolysiloxane represented by the general formula (1) employed in the present invention, for example, a monofunctional unit [R ^a ₃ SiO
_1/2 ] (where ^Ra is an organic group), but tetrafunctional units [SiO _4/2 ] and the like may be produced as by-products and remain, but they may exert the characteristic effects of the present invention. Needless to say, as long as the unit is not given, there is no problem even if those units remain.

Furthermore, in such general formula _{^{(1), [R 1 2}} R 2 m SiO (2-m) / 2] units and [R ³ R ⁴ _n Si
A and b each represent the number of repetitions of O _{(3-n) / 2} ] units, and 0.70 ≦ b / (a + b) ≦ 0.95, more preferably 0.80 ≦ b / (a + b) It is desirable that the numerical value satisfy the inequality ≦ 0.95. When the value of [b / (a + b)] is too small, the strength of the coating film formed on the surface of the base material such as an aluminum sheet material decreases, while when it is too large, This is because a coating film that does not have the desired properties can be obtained, so that excellent water-repellent coating material cannot be imparted with excellent moldability.

In addition, such a and b are [a +
b], in other words, the value indicating the size (degree of polymerization) of the organopolysiloxane represented by the general formula (1) is
It is desirable that the inequality satisfy 150 ≦ a + b, and more preferably, 300 ≦ a + b. If the organopolysiloxane represented by the general formula (1) satisfies the condition of 150 ≦ a + b, it may be used alone or after being diluted with an organic solvent, depending on its liquid or solid form. With the organopolysiloxane having a silanol group represented by the general formula (2), the composition according to the present invention can be constituted. Note that this [a
If the value of [+ b] is less than 150, sufficient workability cannot be imparted to the formed water-repellent coating film. The upper limit of the value of [a + b] is not particularly limited. However, as will be described in detail later, a configuration in which the organopolysiloxane is diluted with an organic solvent in order to advantageously apply the composition to a substrate. Is required to be soluble in the organic solvent used. For example, it is desirable that the solvent be soluble in benzene or the like.
000 is desirable. However, the organopolysiloxane represented by the general formula (1) has various sizes (degrees of polymerization) by adjusting the polymerization reaction during the production.
Is obtained, and by completing the polymerization reaction, an insoluble / infusible substance having a remarkably large degree of polymerization may be produced.However, such an insoluble / infusible substance is not practical. Of course, what is undesirable is, needless to say.

Further, in the general formula (1), m and n
Are 0 ≦ m ≦ 0.33 and 0 <n ≦ 1.
Satisfies the inequality of 00, and particularly within the range, 0
It is preferable that ≦ m ≦ 0.1 and 0 <n ≦ 0.2. However, when these values are excessively large, properties such as flexibility, flexibility, and stretchability of the obtained coating film are reduced, and a decrease in water repellency due to remaining hydrophilic functional groups is caused. As a result, a desired water-repellent coating material cannot be obtained.

In producing the organopolysiloxane represented by the general formula (1) as described above,
Conventionally known production methods can be adopted.For example, organotrialkoxysilanes and diorganodialkoxysilanes can be prepared using an acidic catalyst such as hydrochloric acid, or a basic catalyst such as potassium silanolate and water, and alcohol and To produce the desired organopolysiloxane by using a method of polymerizing in an aromatic solvent or a method of polymerizing organotrihalosilane and diorganodialkoxysilane in water, an alcohol and an aromatic solvent. However, the present invention is not limited to these methods.

On the other hand, an organopolysiloxane having a silanol group represented by the aforementioned general formula (2), which is another component essential for the composition for forming a coating film, is
It is oil or oily.

Here, R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the general formula (2) each independently represent an alkyl group having 1 to 5 carbon atoms. So,
And, as such an alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and the like can be exemplified, and among them, a methyl group is particularly preferable. On the other hand, R ⁷ and R
¹² represents a hydroxyl group or an alkyl group having 1 to 5 carbon atoms. However, at least one of R ⁷ and R ¹² is particularly required to be a hydroxyl group. When R ⁷ or R ¹² is an alkyl group, examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group,
An isopropyl group, an n-butyl group, an isobutyl group and the like are used, and among them, a methyl group is particularly preferable.

In the general formula (2), x and y are respectively 0 ≦ x, 0 <y, 5 ≦ x + y ≦ 10
It is preferable to satisfy the inequality of 00, and in such a numerical range, particularly, 10 ≦ x + y ≦ 300.
Moreover, such x and y are 0.8 ≦ y / (x + y) ≦
1.0, and among them, in particular, 0.9
It is desirable that the number satisfies ≦ y / (x + y) ≦ 1.0. Here, if the value of [x + y] is too small, good water repellency cannot be imparted to the method of pressing a water-repellent coating material, but the value of [x + y] is too large. This causes a problem that sufficient strength cannot be imparted to the formed coating film. Also, [y
/ (X + y)] is too small, the residual hydroxyl groups increase, and the water repellency of the coating film formed of the composition is reduced.

In preparing a composition for forming a coating film, the organopolysiloxane represented by the general formula (1) as described above and the organopolysiloxane having a silanol group represented by the general formula (2) are used. In the present invention, such a compounding ratio is based on 100 parts by weight of the organopolysiloxane represented by the general formula (1) and the general formula ( It is necessary to adopt a compounding ratio that allows 3 to 70 parts by weight of the organopolysiloxane having a silanol group represented by 2) to be added.
It is possible to form a coating film that can realize characteristics such as extremely excellent flexibility, flexibility, and stretchability,
Thus, a water-repellent coating material having extremely excellent moldability or moldability can be obtained. In particular, the general formula (2)
More preferably, the content of the organopolysiloxane having a silanol group represented by the general formula (1)
3 to 50 parts by weight is recommended based on 100 parts by weight of the organopolysiloxane represented by When the content of the organopolysiloxane having a silanol group represented by the general formula (2) is too small, the water repellency becomes insufficient. Conversely, when the content is too large, the coating film becomes poor. The mechanical properties of the material decrease.

In the composition for forming a coating film employed in the present invention, a composition used as a liquid composition by adding a diluting solvent, if necessary, is advantageously employed. Will be done. By using such a liquid composition, application to the surface of a substrate to which water repellency is to be imparted can be extremely advantageously performed.

Examples of such a diluting solvent (organic solvent) include aromatic hydrocarbon compounds such as benzene, toluene and xylene, ether compounds such as diethyl ether, diisopropyl ether and tetrahydrofuran, methanol, ethanol, propanol, butanol, and the like. Alcohol compounds such as hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone compounds such as cyclohexanone, ester compounds such as ethyl acetate and butyl acetate, chloroform, trichloroethylene, halogenated hydrocarbon compounds such as carbon tetrachloride, n-hexane, n −
Saturated hydrocarbon compounds such as octane, isooctane, and cyclohexane; silane compounds such as trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, and tetraethoxysilane; hexamethyldisiloxane; tetracyclo-1,2-dimethylsiloxane; And at least one or more of these are appropriately selected and used, but of course,
It should be understood that this is by no means limiting.

The proportion of the diluting solvent used is not particularly limited, but the organopolysiloxane represented by the general formula (1) used in the present invention and the organopolysiloxane represented by the general formula (2) are used. The total amount is preferably in the range of 0 to 10,000 parts by weight, and more preferably 10 to 2,000 parts by weight, based on 100 parts by weight of the total amount of the organopolysiloxane having a silanol group. Preferably, by adopting such a ratio, a liquid composition having such a viscosity that application to a substrate is further facilitated is obtained.

The composition comprising the above components is applied to the surface of the substrate by various known methods such as roll coating, dip coating, impregnation, flow coating, brush coating, and spraying. By coating and hardening, a water-repellent coating film having excellent properties such as flexibility, flexibility, and stretchability is formed on the surface.

In the present invention, when press-molding a coating material on which such a water-repellent coating film is formed, a press oil mainly containing a hydrocarbon having 10 to 40 carbon atoms is used. The great feature resides in that an oil composition obtained by mixing a specific organopolysiloxane at a predetermined ratio is used as a lubricant.

That is, as such a press oil (base oil), a oil mainly containing a hydrocarbon having about 10 to 40 carbon atoms, which has been generally used in the conventional press molding operation, is used. . In addition, as such a hydrocarbon having 10 to 40 carbon atoms, dodecane,
Examples thereof include pentadecane and heptadecane, but are not limited thereto. In a press oil (base oil), if these hydrocarbons having 10 to 40 carbon atoms are contained as a main component, an ester-based oily agent for imparting lubricity, an antioxidant, a metal Even if an inert agent or the like is contained, there is no problem at all.

On the other hand, as the organopolysiloxane compounded in such a press oil, those represented by the general formula (3) of the above formula (7) are employed, and R ^{13 in} such a general formula (3) is used. , R ¹⁵ , R ¹⁷ and R ¹⁸ each independently represent a monovalent organic group, and R ¹⁴ , R ¹⁶ and R ¹⁹
Each independently represents a reactive group or a monovalent organic group.

The monovalent organic group includes an alkyl group, an alkenyl group and a fluoroalkyl group. More specifically, as the alkyl group, a methyl group,
Examples of the ethyl group, propyl group and butyl group include alkenyl groups such as vinyl group and allyl group, and examples of fluoroalkyl groups include trifluoropropyl group and nonafluorohexyl group. In particular, R ¹³ ,
Among R ¹⁵ , R ¹⁷ and R ¹⁸ , among them, a methyl group is preferable. However, such a monovalent organic group includes an aryl group and a monovalent organic group as long as the characteristic properties of the present invention are not impaired.
An aralkyl group or the like may be contained.

On the other hand, the reactive group includes a hydrogen atom,
Examples thereof include a hydroxyl group, an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an alkenyloxy group, and an epoxy group, but are not limited thereto. In the case where R ¹⁴ , R ¹⁶ and R ¹⁹ are reactive groups, they vary depending on the type of press oil (base oil) to be blended.
A hydroxyl group and an alkoxy group are preferred.

Further, w and z in the general formula (3) satisfy 0 ≦ w and 0 <z, respectively, and the sum of w and z satisfies the inequality of 5 ≦ w + z ≦ 1000. Among such numerical ranges, in particular, 10 ≦ w + z ≦
Preferably it is 300. Moreover, such w and y
Is preferably a number that satisfies the inequality 0.5 <z / (w + z) ≦ 1.0. Here, when the value of [w + z] is too small or too large, a film having good water repellency cannot be formed on the water repellent coating material, and the water repellency deteriorates after molding. There is a tendency.

In the organopolysiloxane represented by the general formula (3) employed in the present invention described above, for example, a trifunctional unit [R ^b SiO
_3/2 ] (R ^b is an organic group) and the like may be produced as by-products and remain. However, as long as the characteristic effects of the present invention are not affected, these remaining units may be used. It is needless to say that there is no problem even if it has the above.

In preparing an oil composition as a lubricant, an organopolysiloxane represented by the general formula (3) is added at a predetermined ratio to the above-described press oil (base oil). In the present invention, such an addition ratio is defined as 100 parts of press oil (base oil).
The amount is preferably 0.1 to 10 parts by weight, and particularly preferably 0.1 to 5 parts by weight, based on parts by weight. If the addition amount is excessive, the lubricating performance required for the lubricant is reduced, or excessive organopolysiloxane adheres to the surface of the coating material after immersion of the lubricant, impairing the surface appearance, Problems such as stickiness may occur.

The above oil composition may further include, as necessary, a compound represented by the above general formula (3) for the purpose of improving adhesion to the coating film surface and improving reactivity with the coating film surface. It is also possible to add different specific organopolysiloxanes, silane compounds, curing catalysts, organic peroxides and the like.

Specifically, Olga different from the general formula (3)
As the nopolysiloxane, the general formula (4)
Examples of the organopolysiloxane represented by
I can do it. Note that, in the general formula (4), R²⁰Is 1
Represents a divalent organic group, ^{twenty one}Represents a reactive group.

Here, examples of the monovalent organic group include an alkyl group, an alkenyl group, and a fluoroalkyl group. More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, Examples thereof include a trifluoropropyl group and a nonafluorohexyl group, and among them, a methyl group is particularly preferable. On the other hand, examples of the reactive group include a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an alkenyloxy group, an alkyleneoxy group, and an epoxy group, but are not limited thereto. Absent. And
Although it depends on the type of press oil (base oil) to be blended, a hydroxyl group and an alkoxy group are particularly preferable.

In the general formula (4), p and q are positive numbers and satisfy the inequality p + q <2. Among them, the numbers satisfying the inequality p + q <1.5 are particularly preferable. It is desirable that Further, c represents the number of repetitions (degree of polymerization) in the general formula (4).
Is a number that satisfies the condition of 3 ≦ c, and the upper limit thereof is not particularly limited, but is preferably soluble in press oil as described above.

The addition ratio of the organopolysiloxane represented by the general formula (4) is desirably 10 parts by weight or less based on 100 parts by weight of the press oil (base oil). When the addition ratio is excessive, the coating surface after removing the oil composition as a lubricant,
This is because there is a possibility that the organopolysiloxane represented by the general formula (4) remains or the original lubricity of the lubricant is impaired.

Examples of the silane compound as the reactivity improver include silanes having an acyloxy group, an epoxy group, an amino group, a mercapto group, but are not limited to these. The proportion of the silane compound is not particularly limited, but it goes without saying that it is necessary to add the silane compound in a proportion that does not reduce the original lubricating performance of the lubricant.

Here, the silane having an epoxy group, which is an example of such a reactivity improver, is not particularly limited as long as it has the above-mentioned effects. A silane having an epoxy group can be appropriately employed.Examples include glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, and glycidoxypropylmethyldiethoxysilane. Sidoxyhexyltrimethoxysilane,
Glycidoxyhexyltriethoxysilane, epoxypropyltrimethoxysilane, epoxypropyltriethoxysilane, epoxyhexyltrimethoxysilane, epoxyhexyltriethoxysilane and the like can be mentioned, but are not limited thereto.

As the silane having an acyloxy group, which is another example of the reactivity improver, similar to the silane having an epoxy group, any silane having an effect of improving the reactivity with the coating film surface can be used. Conventionally known silanes having an acyloxy group can be appropriately employed. For example, specific examples of the silane having such an acyloxy group include acryloxypropyltrimethoxysilane, acryloxypropylmethyldimethoxysilane,
Acryloxypropyltriethoxysilane, acryloxypropylmethyldiethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyhexyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltriethoxysilane, Methacryloxypropylmethyldiethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyhexyltriethoxysilane and the like can be mentioned,
It goes without saying that the present invention is not limited to these.

Further, as the silane having an amino group,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltris (trimethylsiloxy ) Silane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminomethylmethyldimethoxysilane, 3- [N-allyl-N- (2 -Aminoethyl)] aminopropyltrimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] amine,
N, N-bis [(methyldimethoxysilyl) propyl]
Examples include amines, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis [(methyldimethoxysilyl) propyl] ethylenediamine, but are not limited thereto. .

Examples of the silane having a mercapto group include 3-mercaptopropyltrimethoxysilane and 3-silane.
Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltris (trimethylsiloxy) silane,
Examples thereof include, but are not limited to, 3-mercaptopropyltriethoxysilane, 3-mercaptomethyltrimethoxysilane, and 3-mercaptomethylmethyldimethoxysilane.

When adding a silane having an epoxy group or an acyloxy group, an amino group or a mercapto group as a reactivity improver as described above, the effect is exhibited if any one of these compounds is used. But 2
Any combination of more than one species may be used.

On the other hand, if necessary, a curing catalyst or an organic peroxide can be added as a reactivity improver to the oil composition. The ratio of the addition of the curing catalyst or the reactivity improver composed of an organic peroxide varies depending on the type of the curing catalyst and the type of the organic peroxide used. Is preferably 30 parts by weight or less based on 100 parts by weight of the organopolysiloxane represented by the formula: It ’s
If the addition ratio is excessive, problems such as an increase in the viscosity of the oil composition and precipitation of a gel-like substance may be caused.

The curing catalyst is not particularly limited as long as it improves the reactivity with the surface of the coating material, and various conventionally known curing catalysts may be appropriately employed. I can do it. For example, representatively, an organic metal compound and an amino group-containing compound are typically mentioned, and some of the more detailed specific examples will be listed below, but it is not limited to only those examples. It goes without saying. The former organometallic compounds include organic tin compounds, organic titanium compounds, organic lead compounds, organic zinc compounds, organic iron compounds, organic zirconium compounds, organic cobalt compounds, and the like. Compounds (for example, chelate titanium, chelate zirconium, chelate cobalt, etc.) will also be included.

-Organometallic compounds-Organotin compounds Tin diacetate, tin dioctylate, tin dilaurate, tin tetraacetate, dibutyl tin diacetate, dibutyl tin dioctylate, dibutyl tin dilaurate, dibutyl tin dioleate, dimethoxy dibutyl Tin, dibutyltin oxide, dibutyltin benzylmaleate, dibutyltin bis (triethoxysiloxy) dibutyltin, diphenyltin diacetate ・ Organic titanium compounds tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium , Tetra-n-butoxytitanium, tetra-i-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, di-i-propoxybis (ethylacetoacetate) titanium, dipropoxybis (acetylacetonato) titanium, di-i- Propoxybis (Acetylacetonate) titanium, dibutoxybis (acetylacetonate) titanium, tri-i-propoxyallyl acetate titanium, titanium isopropoxyoctylene glycol, bis (acetylacetonato) titanium oxide ・ organic lead compound lead diacetate, bis (2 -Ethylhexanoic acid) lead, dineodecanoate, lead tetraacetate, tetrakis (n-propionic acid)
Lead ・ Organic zinc compound Zinc diacetate, zinc bis (2-ethylhexanoate), zinc dinedecanoate, zinc diundecenoate, zinc dimethacrylate ・ Organic iron compound Iron diacetate ・ Organic zirconium compound Tetrakis (2-ethylhexanoic acid) Zirconium, zirconium tetrakis (methacrylic acid) ・ Organic cobalt compound Cobalt diacetate

-Amino Group-Containing Compound- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, tetramethylguanidine, tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidine Zirpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane, 1,8-
Diazabicyclo [5.4.0. -7-undecene, di-n-hexylamine, triethanolamine, dicyclohexylamine, di-n-octylamine, triethylamine, diethylamine, triethylbenzylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine

On the other hand, the organic peroxide is not particularly limited as long as it has an effect of improving the reactivity, and various conventionally known organic peroxides may be appropriately employed. I can do it. Specific examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and peroxides not classified into these, Specific examples of these are shown below, but are not limited thereto.

Ketone peroxide dimethyl ethyl ketone peroxide, dicyclohexanone peroxide, dimethylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide peroxyketal 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane hydroperoxide p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumin hydroperoxide, t -Hexyl hydroperoxide ・ Dialkyl peroxide Dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide Diacyl peroxide diisobutyryl peroxide, di-octanoyl peroxide, m- toluoyl benzoyl peroxide,
Dibenzoyl peroxide, di-m-toluoyl peroxide ・ Peroxy dicarbonate Diisopropyl peroxy dicarbonate, di-n-butyl peroxy dicarbonate ・ Peroxy ester Cumyl peroxy neo dodecanoate, t-butyl peroxy Neododecanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-hexylperoxybenzoate,
t-butyl peroxybenzoate, t-butyl peroxy acetate • Other peroxides t-butyl trimethylsilyl peroxide

In the case of using a reactivity improving agent composed of such a curing catalyst and an organic peroxide, it is possible to use a curing catalyst and an organic peroxide together, but the curing catalyst may be an organic peroxide. It is desirable to use each of them separately, since they may act as peroxide reaction accelerators.

The oil composition obtained by adding the above-mentioned components is used in a press molding operation in the same manner as conventionally known various press oils (lubricants). For example, for water-repellent coating materials,
After the oil composition is applied, press work such as bending, ironing, drawing, drilling, and punching is performed.Press work is performed while always supplying the oil composition to the coating material. For example, various methods known in the art, such as implementation, are appropriately selected and performed.

In short, in the method for pressing a water-repellent coating material according to the present invention, 100 parts by weight of a press oil containing a hydrocarbon having 10 to 40 carbon atoms as a main component is expressed by the following general formula (3). An oil composition comprising 0.1 to 10 parts by weight of a specific organopolysiloxane represented by the formula is used as a lubricant for press molding, and the lubricant is applied to the surface of the water-repellent coating material. Even if attached
Elution of the water-repellent component, that is, the organopolysiloxane represented by the general formulas (1) and (2), into the lubricant is advantageously suppressed, and even if the water-repellent component is eluted,
A specific water repellent film is newly formed by the specific organopolysiloxane represented by the general formula (3) contained in the lubricant, and excellent water repellency is exhibited even after press molding. Excellent durability can be realized.

Although the embodiments of the present invention have been described above in detail, it should be understood that the present invention is not construed as being limited by the specific description of such embodiments. Should.

For example, the above-mentioned composition for forming a coating film may be used, if necessary, in order to improve the adhesion between the substrate and the coating film, as an adhesion improver, a silane having an epoxy group as described above. It is also possible to add silanes having an acyloxy group. In addition, the addition ratio of the adhesion improver is 0.01 to 100 parts by weight of the organopolysiloxane represented by the general formula (1).
70 parts by weight, more preferably 0.01 to 40 parts by weight, can be advantageously employed. However, when the content ratio is excessive, not only the effect of improving the adhesiveness corresponding to the content ratio is not obtained, but also problems such as a decrease in the adhesiveness and a decrease in the strength of the coating film are caused. Because.

In order to further promote the curing of the composition for forming a coating film as described above or to shorten the curing time, if necessary, the above-mentioned curing catalyst or organic peroxide may be further used as a curing accelerator. It can also be added to the coating film forming composition. The ratio of the addition of the curing accelerator varies depending on the type of the curing catalyst and the type of the organic peroxide to be used, but is generally 100 parts by weight of the organopolysiloxane represented by the general formula (1). On the other hand, 0.
It is desirable that the amount be from 0.01 to 30 parts by weight, more preferably from 0.01 to 20 parts by weight. However, if the addition ratio of such a curing accelerator is excessive, gelation or thickening of the composition is caused, and it becomes difficult to apply the composition to a base material. The hydrophilic component contained in the peroxide and the curing catalyst and the hydrophilic component generated by the decomposition and reaction of the organic peroxide cause problems such as a decrease in the water repellency of the coating film. is there. In the case of using such a curing accelerator, it is possible to use a curing catalyst and an organic peroxide in combination, but the curing catalyst may be a reaction accelerator for the organic peroxide. Therefore, it is desirable to use each separately.

Further, a pigment, a dye, an ultraviolet coloring dye, a leveling agent,
Various known additives such as fungicides, preservatives, antiaging agents, anticorrosives, rust inhibitors, antistatic agents, flame retardants, antifouling agents, etc. are used to improve the excellent properties of the coating film formed. It can be appropriately selected and added as long as it is not inhibited.

In the present invention, the water-repellent coating material may be provided with a base coat for the purpose of further improving the adhesion of the coating film. For example, when the base material is a metal material such as aluminum, to impart rust resistance and the like, and to further improve the adhesion with the coating film,
Those having a chemical conversion coating or a primer (undercoat) coating are advantageously employed. Then, by applying such a base coat, a multilayer film is formed on the surface of the functional device, and thus, even if an extremely large external force is applied, the coating film is cracked or cracked.
Problems such as wrinkles and peeling are not caused, and excellent durability can be realized.

Here, the chemical conversion treatment employed above is not particularly limited, and a chromium-based treatment such as a phosphoric acid chromate treatment or a chromate chromate treatment, a titanium-based treatment such as a titanium phosphate treatment, or a phosphorus-based treatment. Zirconium-based treatments such as zirconium oxyphosphate treatment, molybdenum-based treatments such as molybdenum phosphate treatment, and zinc-based treatments such as zinc phosphate treatment.
Various known chemical conversion treatments can be exemplified.

The primer paint used for the primer coating is not particularly limited as long as it has good adhesion to the substrate and the coating film and good workability.
Examples include silane coupling agents, silicone resin-based, acrylic resin-based, polyamide resin-based, epoxy resin-based, alkyd resin-based, urethane resin-based, amino resin-based, and polyvinyl alcohol-based paints. In addition, the coating method of the primer paint, roll coating,
Conventionally known various methods such as bar coating can be appropriately adopted. Further, even under the conditions of curing or baking of the primer coating film, generally, depending on the type of the coating material and the coating method, it is preferably room temperature to 350 ° C, more preferably 50 ° C to 3 ° C.
The temperature is appropriately set within the range of 00 ° C. Here, the thickness of the primer coating is 10 μm so that cohesive failure is not caused in the primer coating and the adhesion is not reduced.
Hereinafter, more preferably, 0.5 μm to 5 μm will be advantageously employed.

By the way, the water-repellent coating material is obtained by coating and curing the above-mentioned composition for forming a coating film on the surface of a substrate,
Although it is produced by forming a coating film, such a coating method is not limited at all, and is performed by appropriately adopting various conventionally known techniques, thereby , Where necessary on the substrate,
A smooth coating film that can achieve the desired characteristics is formed.

The curing conditions for forming such a coating film depend on the components and the like contained in the coating film forming composition, but when the above-mentioned curing accelerator is not added, Is generally curable in 2 days at room temperature, within 2 hours at 50 ° C., within 1 minute at 250 ° C., and within several seconds at 350 ° C.

On the other hand, when a curing accelerator such as a curing catalyst or an organic peroxide is added to the coating film forming composition, the curing time is shortened as compared with the case where no curing accelerator is used. Excellent curability, such as the ability to perform, can be realized. In addition, as such a curing temperature, it is desirable to adopt room temperature to 350 ° C., and among them, practically, it is particularly desirable to be in a temperature range of 50 ° C. to 300 ° C. If the temperature at the time of curing is too low, the reaction does not proceed sufficiently. Conversely, if the temperature is too high, siloxane may be decomposed.

The film thickness of the coating film formed by curing is not particularly limited, but may have desired properties such as excellent flexibility and flexibility.
In order for the stretchability to be maximized, for example, 0.2
μm to 30 μm, more preferably 0.5 μm to 10 μm
But it is desirable. If the film thickness is too small, the water repellency of the coating film cannot be sufficiently exhibited,
When the film thickness is excessively large, brittle fracture occurs in the coating film during the molding process, and cracking and peeling of the coating film are easily caused.

[0072]

EXAMPLES Hereinafter, some examples of the present invention will be described to clarify the present invention more specifically. However, the present invention imposes some restrictions by the description of such examples. It goes without saying that you don't receive anything. In addition, in addition to the following examples, the present invention may further include various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention. , Improvements and the like can be added.

First, 100 parts by weight of the organopolysiloxane represented by the following formula 9 is added to the organopolysiloxane having a silanol group represented by the following formula 10:
0 parts by weight and the mixture is mixed with 10 parts of xylene.
The mixture was diluted with 0 parts by weight to prepare a film-forming composition (paint).

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Next, the coating film forming composition prepared as described above was applied to a 0.100 mm thick aluminum plate (JIS-A1100) using a bar coater No. 6
And baked in a drying oven at 250 ° C. for 60 seconds to prepare a water-repellent coating material.

Then, before performing the press molding described below,
In other words, before contact with the lubricant (oil composition),
The contact angle and the falling angle shown below were measured.

-Measurement of Contact Angle (θ)-A water droplet of 2 μL was dropped on the surface of the water-repellent coating material obtained as described above, and the water-repellent coating material was pressed as shown in FIG. The angle between the tangent at the contact point between the method and the water droplet and the surface of the coating material: the contact angle (θ) was measured, and the results are shown in Table 5 below as the initial contact angle.

-Measurement of falling angle (α)-Further, 5 μL of water droplets were respectively dropped on the surface of the water-repellent coating material, and the water droplets placed on the water-repellent coating material as shown in FIG. The angle between the coating material and the horizontal plane when the material starts falling when the material is inclined: the falling angle (α) was measured, and the results are shown in Table 5 below as the initial falling angle.

On the other hand, in order to prepare an oil composition to be used for press molding, first, an oil composition having 10 to 10 carbon atoms is used.
AF-2A (manufactured by Idemitsu Kosan) and Proformer K18B (manufactured by Showa Shell) shown in Table 1 below were prepared as press oils (veil oils) containing 40 hydrocarbons as main components.

[0079]

[Table 1]

Then, an organopolysiloxane represented by the general formula (3) having a structure shown in Table 2 below (hereinafter abbreviated as A component) with respect to the press oil (veil oil), And the general formula (4)
The organopolysiloxane represented by the formula (1) has a structure represented by the following formula (hereinafter abbreviated as B component), and has an epoxy group or an acyloxy group, an amino group, and a mercapto group shown in Table 3 below. A silane (hereinafter, abbreviated as C component) and a curing catalyst or an organic peroxide (hereinafter, abbreviated as D component) shown in Table 3 below are prepared, and are blended as shown in Table 4 below. The oil compositions according to Examples 1 to 15 and Comparative Examples 1 to 7 were prepared by adding the components in a ratio and mixing and stirring. In addition,
In Chemical Formulas 9 and 10, Table 2 below, and Chemical Formula 11, [a +
b] and c are standards using gel permeation chromatography (GPC) [apparatus: HLC-8020 (manufactured by Tosoh Corporation), column: TSKgelGMHXL-L and G1000HXL (manufactured by Tosoh Corporation), solvent: toluene] Calculated from the measured value of the weight average molecular weight (Mw) in terms of polystyrene, [b / (a + b)],
m, n, [x + y], [y / (x + y)], [w +
z], [z / (w + z)], p and q were determined from the measured values of ²⁹ Si NMR spectrum [apparatus: ACP-300 (manufactured by Bruker, Germany)].

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

Embedded image

[0084]

[Table 4]

The following evaluation tests were carried out using the oil compositions according to Examples 1 to 15 and Comparative Examples 1 to 7 prepared as described above as lubricants.

-Evaluation of Moldability (Workability)-Examples 1 to 15 and Comparative Examples 1 to 5 obtained as described above
After immersing the water-repellent coating material in the lubricant (oil composition) according to No. 7 and taking out the coating material, the paint general test method (JIS-K-
5400-1900), a 200 g weight is dropped from a height of 10 cm on a punch having a diameter of 1/2 inch as shown in FIG. The state of the film was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 5 below. Evaluation criteria: 1: No peeling of coating film, no oil residue. 2: No peeling of coating film, oil residue. 3:
Coating peeling.

—Evaluation of Oil Resistance— Examples 1 to 15 and Comparative Examples 1 and 2 obtained as described above
After the water-repellent coating material was immersed in the lubricant according to No. 7, taken out, and heated and dried at 140 ° C. for 10 minutes, the contact angle (θ) and the falling angle (α) were determined in the same manner as described above. The measurement was performed, and the results are shown in Table 5 below.

[0088]

[Table 5]

As apparent from Table 5, Comparative Example 1
In addition, the lubricant according to Comparative Example 5 did not contain the organopolysiloxane represented by the general formula (3), so that the components of the coating film were eluted and the falling angle after immersion in the lubricant increased. It can be seen that the water repellency (sliding water) was reduced. Further, in the lubricant according to Comparative Example 2, the amount of the organopolysiloxane represented by the general formula (3) was small, and the effect of the addition did not appear. Further, in the lubricant according to Comparative Example 3, although the addition amount of the organopolysiloxane represented by the general formula (3) was excessive, the increase in the falling angle was hardly observed, but the surface of the coating film was not increased. Stickiness occurred and the appearance was poor. Further, in the lubricants according to Comparative Examples 4 and 6, since the value of [w + z] representing the degree of polymerization in the general formula (3) was out of the range of the present invention, the effect of the addition did not appear. In addition, in the lubricant according to Comparative Example 7, since the amount of the organopolysiloxane represented by the general formula (4) was too large, the moldability was reduced and the fall angle was increased.

On the other hand, the coating materials immersed in the lubricant according to Examples 1 to 15 have excellent water repellency and excellent moldability even after immersion. I understand.

[0091]

As is apparent from the above description, in the method for pressing a water-repellent coating material according to the present invention, a specific organopolysiloxane and a specific organopolysiloxane having a silanol group are mixed at a predetermined ratio. In addition to employing a water-repellent coating material on which a coating film made of the composition contained in the above is formed, the number of carbon atoms is 10 to 4 in the molding operation.
Bending, ironing, drawing, drilling, punching, etc., from the use of an oil composition obtained by adding a predetermined amount of a specific organopolysiloxane to a press oil containing hydrocarbons as a main component as a lubricant. When performing various types of press working such as press working, extremely excellent formability is realized, and good water repellency can be maintained even after the forming.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a contact angle (θ) measured in an example.

FIG. 2 is an explanatory diagram of a falling angle (α) measured in an example.

FIG. 3 is an explanatory diagram of a forming process adopted in a formability evaluation of an example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/04 C09D 183/04 // C10M 105/02 C10M 105/02 155/02 155/02 C10N 40: 24 C10N 40:24 A (72) Inventor Tsukasa Kasuga 5-11-3 Shimbashi, Minato-ku, Tokyo Inside Sumitomo Light Metal Industries Co., Ltd. (72) Inventor Akihiro Seiya 5-11-3 Shimbashi, Minato-ku, Tokyo (72) Inventor Teruhito Maruyama 1-17-7 Higashi-Otake, Isehara-shi, Kanagawa F-term (reference) EB32 EB33 EB36 EB38 EB39 EB43 EB56 EC07 EC37 EC45 EC54 4H104 BA01 CJ09 CJ10 LA20 PA23 4J038 DL031

Claims (4)

[Claims] 1. 100 parts by weight of an organopolysiloxane represented by the following general formula (1) and 3 to 3 parts by weight of an organopolysiloxane having a silanol group represented by the following general formula (2): In a coating operation using a composition containing 70 parts by weight, a coating material having a water-repellent coating film formed on the surface is press-molded, and mainly comprises a hydrocarbon having 10 to 40 carbon atoms. With respect to 100 parts by weight of the press oil as a component, the following general formula (3)
0.1 to 1 of the organopolysiloxane represented by
An oil composition formulated in a ratio of 0 parts by weight,
A method for pressing a water-repellent coating material, wherein the press molding is performed using a lubricant. Embedded image Embedded image Embedded image 2. The method for pressing a water-repellent coating material according to claim 1, wherein the oil composition further contains an organopolysiloxane represented by the following general formula (4). Embedded image 3. The method for pressing a water-repellent coating material according to claim 1, wherein the oil composition further contains a silane having an epoxy group, an acyloxy group, an amino group or a mercapto group. 4. The method for pressing a water-repellent coating material according to claim 1, wherein the oil composition further contains a curing catalyst or an organic peroxide.