JPH11152446A - Resin composition for coating reduced in adhesiveness coated product using the same, and their uses - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition used for adhesives-reduced coatings, solving the problems of conventional technology, and exhibiting sufficient adhesiveness-reducing effects against artificial stains such as labels and graffiti, to provide a coated product using the resin composition, and to provide their uses. SOLUTION: This resin composition for adhesiveness-reduced coatings contains a silica-dispersed organosilane oligomer solution, a silanol group- containing polyorganosiloxane, a linear polysiloxanediol, and a curing agent, wherein, as the linear polysiloxanediol, a plurality of the polysiloxanediols having different polymerization degrees are used together. The coated product has the cured coating film of the composition on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coating with reduced adhesion, coated articles using the same, and uses thereof.

[0002]

2. Description of the Related Art Since the environment is more severe outdoors than indoors,
BACKGROUND ART For surface protection of articles used outdoors, coating materials having excellent properties such as weather resistance, heat resistance, and chemical resistance have been developed. Furthermore, it can be said that the outdoor environment has been getting worse more and more recently such as acid rain and an increase in ultraviolet rays due to ozone depletion.

Conventionally, organic base materials such as wood and plastic base materials; glass base materials, inorganic base materials for building materials (for example, hardened inorganic materials such as concrete, slate, cement, etc.);
As a coating material for forming a durable coating film for the purpose of protecting the surface of a substrate such as an inorganic substrate such as a metal substrate (for example, a steel plate such as stainless steel or a non-ferrous metal such as aluminum), hydrolyzable organosilane is used. BACKGROUND ART A coating composition obtained by hydrolytic polycondensation or partial hydrolytic polycondensation, or a coating composition obtained by mixing colloidal silica with the coating composition is known.

[0004] For example, JP-A-51-2736,
JP-A-51-2737, JP-A-53-13073
No. 2, JP-A-63-168470 discloses an organoalkoxysilane, a hydrolyzed polycondensate and / or a partially hydrolyzed polycondensate of the organoalkoxysilane, and colloidal silica. There has been proposed a coating material obtained by converting an alkoxy group into a silanol. The coating film obtained from this coating material has good weather resistance and is excellent for protecting a substrate, but has too high hardness (pencil hardness of 9H or more) and thus has poor toughness and is not suitable for coating films having a film thickness of 10 μm or more. During heat curing, during outdoor use, when sudden temperature changes occur,
Cracks easily occur. In the painting process,
In many cases, it is difficult to precisely control the thickness of the coating film to less than 10 μm. In particular, the coating thickness tends to be 10 μm or more at the painted surface, the peripheral portion of the painted product, and the concave portion of the painted surface, and defective products are easily generated. In addition, since these coating materials require high-temperature heating of about 100 ° C. or more or long-time heat treatment in order to obtain desired coating film characteristics, a base material having a shape that is difficult to apply heat uniformly, large dimensions It cannot be used when it is difficult to apply heat, such as when coating on a substrate having heat resistance or a substrate having poor heat resistance, or when performing painting work outdoors or the like. Further, a coating material having a composition obtained by removing colloidal silica from the above-mentioned coating material has a problem that the film-forming property at the time of painting is lacking and the strength of the coating film is low.

Further, these coating compositions have a problem that silanols obtained by hydrolysis of alkoxysilanes have high reactivity, and their condensation reaction occurs gradually even at room temperature, easily gels, and has poor stability. Was. In particular, when these coating compositions are used as vehicles and pigments are added to form paints, stability is further deteriorated, and there is a drawback that paints cannot be formed.

[0006] Further, as disclosed in Japanese Patent Application Laid-Open No. 64-168, a coating material for converting an alkoxy group into a silanol hydroxyl group by adding water and a catalyst as a curing agent to a partially hydrolyzed polycondensate of alkoxysilane immediately before coating is known. Proposed. However, even this coating material has poor toughness, and cracks easily occur at a film thickness of 10 μm or more. However, this coating material has good storability and is relatively stable even when it is made into a paint by adding a pigment. However, in order to obtain desired coating properties, a heat treatment at a high temperature of about 100 ° C. or higher or for a long time is required. It is necessary to apply it to a substrate that has a shape that is difficult to apply heat evenly, a substrate that has large dimensions, a substrate that has poor heat resistance, etc. When it is difficult to apply, it cannot be used, and there is a limitation.

[0007] For the purpose of solving these drawbacks, Japanese Patent Application Laid-Open No. Sho 63-268772 proposes a coating material comprising a prepolymer mainly composed of silicon alkoxide, a curing catalyst and water, which cures at around room temperature. But
The toughness has not been improved, and processing after precoat metal coating or processing after coating of a polycarbonate plate is impossible. Further, there is a drawback that the coatability and curability are poor and the curability of the coating material is easily affected by humidity.

Japanese Patent Application Laid-Open No. 4-175388 discloses a coating material containing a partially hydrolyzed oligomer of an organosilane, a silanol group-containing polyorganosiloxane, and a curing catalyst. Although it has the advantages of improved paintability and curability, curing at room temperature and not being affected by humidity,
The toughness was not sufficiently improved.

To summarize the above, a coating material containing an organoalkoxysilane or a hydrolyzate of an organoalkoxysilane as a main component has a high hardness, is hardly damaged, and has a high weather resistance. However, due to poor toughness, cracks tend to occur in the coating process or during use, and this is particularly noticeable when the film thickness is 10 μm or more. Further, baking at a high temperature of 100 ° C. or more is required, and painting at a factory is possible, but painting outdoors or on site is difficult. Another drawback is that the coating liquid has high reactivity and is inferior in storage stability.

Further, since the above-mentioned coating material is an inorganic coating material, the coating film tends to have poor adhesion to an organic substrate or an organic coating substrate. Resins having an organic resin such as acryl, polyester, epoxy, polyether, or vinyl in the main chain and having a hydrolyzable silane functional group have also been reported (JP-A-5-287206, JP-A-5-302007). Etc.). However, since the main chain of these resins is an organic resin, the weather resistance and hardness of a coating film formed from these resins are inferior to those of inorganic resins containing organoalkoxysilane as a main component. A reactive resin having a linear polysiloxane in the main chain and having a polymerizable acrylic functional group at a terminal or a side chain is also disclosed in Japanese Patent Publication No. 5-72928 and Japanese Patent Application Laid-Open No. H5-1789.
No. 98, but because the main chain is a linear polysiloxane, the coating film hardness cannot be obtained from this resin, and in some cases, it is a rubber elastic body and is not suitable as a coating resin. .

The above-mentioned inorganic hardened materials such as concrete, slate, cement and the like are materials having excellent heat resistance and durability. However, if the surface is not coated, moisture may infiltrate or dirt may easily adhere. However, there is a disadvantage that the acid resistance is poor. Furthermore, the unpainted appearance is often not aesthetic. To compensate for these drawbacks, coating the surface of these inorganic substrates with an organic paint has been performed. However, a coating film formed from an organic coating material is 1) easily deteriorated by ultraviolet rays or the like, and is inferior in weather resistance. 2) is easily damaged due to low film hardness. 3) is inferior in adhesion to an inorganic substrate. There are drawbacks such as a tendency.

Therefore, an attempt was made to apply an inorganic coating material such as a water glass material instead of an organic material, but a satisfactory coating material could not be obtained in terms of generation of efflorescence and porosity. Also, outdoor smoke,
Although a low-contamination type coating resin has been developed in order to reduce the adhesion of dirt due to dust and the like, the performance such as the above-mentioned weather resistance and the antifouling effect are not sufficient.

On the other hand, in recent years, as a method of burying a sewer pipe or the like underground, a method of propelling a pipe from one hole has been adopted instead of a method of digging a road. The propulsion pipe is mainly made of concrete. However, concrete propulsion pipes have a high surface slip resistance, and there are limitations with off-the-shelf pushers. Therefore, it is required to reduce the sliding resistance of the propulsion pipe surface. As a method for satisfying this requirement, a method of applying a paint having an effect of reducing slip resistance to the surface of the propulsion pipe can be considered. It did not reduce.

In order to solve the above-mentioned problems, the inventors of the present invention have proposed a coating material described in Japanese Patent Application Laid-Open No. 4-175388, wherein an acrylic resin and a linear polysiloxane diol are added. A resin composition for reduction coating has recently been developed, and a patent application has already been filed (Japanese Patent Application No. 9-279244). This adhesiveness-reducing coating resin composition can be cured by heating at a low temperature of less than 100 ° C. and cured at room temperature, and has excellent adhesion to various substrates regardless of inorganic or organic,
Since it has high weather resistance and excellent toughness (flexibility), it does not crack even at a film thickness of 10 μm or more, and can form a coated cured film having neither too high nor too low hardness,
In addition, since it can be used as a vehicle when it is made into a paint by adding a pigment, it can be arbitrarily colored by adding a pigment,
In particular, it is excellent in the effect of reducing the adhesion of dirt and the like to the surface of the substrate and the effect of reducing the sliding resistance on the surface of the substrate.

[0015]

However, the above-mentioned conventional resin composition for adhesion reduction coating does not adhere to artificial stains such as stickers and graffiti which are often found on outdoor objects such as lighting poles and telephone poles. In some cases, the effect of reducing the properties was not sufficient. Regarding the adhesive paper, the glass beads and the like are partially exposed on the painted surface, and the unevenness is imparted. However, in such a method, there is a problem that graffiti and the like cannot be prevented, and that if the adhesive enters into the unevenness, it becomes difficult to remove the attached paper.

An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a resin composition for an adhesion-reducing coating which exhibits a sufficient adhesion-reducing effect even on artificial stains such as pasted paper and graffiti. An object of the present invention is to provide used paint products and their uses.

[0017]

Means for Solving the Problems The resin composition for adhesion reduction coating according to the present invention comprises the following (A), (B),
Contains components (C) and (D). Component (A): represented by the general formula R ¹ _m SiX _4-m (I) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M represents an integer of 0 to 3 and X represents a hydrolyzable group) Hydrolyzable organosilane is partially hydrolyzed in colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof in the presence of water. A silica-dispersed oligomer solution of an organosilane. Component (B): represented by an average composition formula R ⁵ _a Si (OH) _b O _{(4-ab) / 2} (IV) (where R ⁵ is the same or different and substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, and a and b represent 0.2 ≦ a <2 and 0.0001 ≦ b ≦, respectively.
3, a + b <4), a polyorganosiloxane containing a silanol group in the molecule. Component (C): curing catalyst. Component (D): represented by (wherein the general formula _{^{HO (R 4 2 SiO) n}} H ... (III) R 4 represents a monovalent hydrocarbon group, 2
R ⁴ may be the same or different, and n is 1
(D1) at least one of n in the range of 10 ≦ n ≦ 20, and (D2) n is 20 <n.
And at least one of the components (D1) and (D2) in the range of ≦ 100.
With respect to 100 parts by weight of the total solid content of the component (B), (D1)
A linear polysiloxane diol having a ratio of 1 to 60 parts by weight of the component and 1 to 40 parts by weight of the component (D2).

In the resin composition for coating for reducing adhesion of the present invention, the total amount of the components (D1) and (D2) is as follows:
The proportion is preferably from 2 to 100 parts by weight based on 100 parts by weight of the total solid content of the components (A) and (B). It is preferable that the resin composition for adhesion reduction coating of the present invention also contains the following component (E). Component (E): a monomer represented by the general formula CH ₂ ＣＲCR ² (COOR ³ ) (II) (where R ² represents a hydrogen atom and / or a methyl group), wherein R ³ is substituted or A group consisting of a first (meth) acrylate ester which is an unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ³ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group selected from the group consisting of: and a ^third (meth) acryl wherein R ³ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acid ester and

In this specification, (meth) acrylic ester refers to either or both of acrylic ester and methacrylic ester. When the resin composition for adhesion reduction coating of the present invention also contains the component (E), the compounding amount is 1 to 100 parts by weight based on 100 parts by weight of the total solid content of the components (A) and (B). It is preferred that the ratio is in parts by weight.

The coated article of the present invention is provided with a coated and cured film of the resin composition for reducing adhesion of the present invention on the surface of a substrate. The coated article of the present invention may contain a pigment in the applied cured film, if necessary, and a part of the pigment may be exposed on the surface of the applied cured film. The pigment is, for example, at least one selected from the group consisting of inorganic pigments, fluororesin-based pigments, and acrylic resin-based pigments.

[0021] If necessary, the applied and cured film may be processed so as to have irregularities on the surface before curing by using an instrument having irregularities on the surface. The resin composition for adhesion reduction coating and the coated article of the present invention are preferably used for outdoor lighting poles or telephone poles by equipping at least a part of the cured coating film of the resin composition for adhesion reduction coating. .

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The silica-dispersed oligomer solution (A) used as the component (A) of the resin composition for coating for reducing adhesion has a hydrolyzable function as a functional group which is subjected to a curing reaction when forming a cured coating film. It is a main component of the base polymer having the group (X). This is because, for example, one or two types of the hydrolyzable organosilane represented by the general formula (I) are added to colloidal silica dispersed in an organic solvent or water (including a mixed solvent of an organic solvent and water). In addition, the hydrolyzable organosilane is obtained by partially hydrolyzing the hydrolyzable organosilane with water (water contained in colloidal silica and / or water separately added).

The group R ¹ in the hydrolyzable organosilane represented by the general formula (I) is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Although not limited, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Group, 2-phenylpropyl group,
Aralkyl groups such as 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group Halogen-substituted hydrocarbon groups such as; γ-methacryloxypropyl group,
Examples thereof include a substituted hydrocarbon group such as a γ-glycidoxypropyl group, a 3,4-epoxycyclohexylethyl group, and a γ-mercaptopropyl group. Among them, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

In the general formula (I), the hydrolyzable group X is not particularly restricted but includes, for example, alkoxy, acetoxy, oxime, enoxy, amino, aminoxy, amide and the like. It is. Among these, an alkoxy group is preferable because it is easily available and the silica dispersed oligomer solution (A) of the organosilane is easily prepared.

Specific examples of the hydrolyzable organosilane include mono-, di-, tri-, and tetra-functional alkoxysilanes wherein m in the general formula (I) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and the silica-dispersed oligomeric solution of organosilane (A) is easily prepared.

Among the alkoxysilanes, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. And dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by the general formula (I), 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more,
It is a trifunctional compound represented by m = 1. This is 50
If it is less than mol%, sufficient coating film hardness cannot be obtained,
Dry curing properties are likely to be poor. The colloidal silica in the component (A) has the effect of increasing the hardness of the applied cured film of the resin composition for reducing adhesion and improving the smoothness and crack resistance. The colloidal silica is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. When using water-dispersible colloidal silica, water present as a component other than the solid content can be used for the hydrolysis of the hydrolyzable organosilane and used as a curing agent for the adhesion-reducing coating resin composition. Can be. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In the organic solvent-dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene Ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. Alternatively, two or more kinds can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

In the component (A), the colloidal silica preferably has a silica content of 5 to 95% by weight, more preferably 10 to 90% by weight, and still more preferably 20 to 90% by weight.
It is contained within the range of 85% by weight. When the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, if it exceeds 95% by weight, it becomes difficult to uniformly disperse the silica, which may cause inconveniences such as gelling of the component (A) and inhibition of curing.

The amount of water to be present in preparing the organosilane silica-dispersed oligomer solution (A) is not particularly limited. For example, 1 mole of the hydrolyzable group (X) of the hydrolyzable organosilane It is preferably in the range of 0.001 to 0.5 mol, more preferably in the range of 0.01 to 0.4 mol per equivalent. The amount of water is 0.0
If the amount is less than 01 mol, sufficient partial hydrolyzate tends not to be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate tends to deteriorate. The method of partial hydrolysis is not particularly limited. For example, it is only necessary to mix a hydrolyzable organosilane and colloidal silica. And add water.)
At this time, the partial hydrolysis reaction proceeds at room temperature. However, in order to promote the partial hydrolysis reaction, if necessary, heating (for example, 60 to 100 ° C.) or a catalyst may be used. Examples of the catalyst include, but are not limited to, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid,
One or more of organic acids and inorganic acids such as propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid and oxalic acid can be used.

The component (A) preferably has a pH of 2.0 to obtain a stable performance over a long period of time.
It is good to be 7.0, more preferably 2.5 to 6.5, and still more preferably 3.0 to 6.0. When the pH is outside this range, the performance continuity of the component (A) tends to be remarkably reduced particularly under the condition that the amount of water used is 0.3 mol or more per 1 mol equivalent of the hydrolyzable group (X). . When the pH of the component (A) is out of the above range, if it is on the acidic side of this range,
The pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. On the basic side, the pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid or acetic acid.
However, the adjustment method is not particularly limited.

The silanol group-containing polyorganosiloxane (B) used as the component (B) of the adhesion-reducing coating resin composition is a base polymer having a hydrolyzable group as a functional group subjected to a curing reaction ( It is a cross-linking agent for forming a three-dimensional cross-link in the cured coating film by a condensation reaction with the component (A), and is a component having an effect of absorbing cracks due to curing shrinkage of the component (A) and preventing the occurrence of cracks. .

R ⁵ in the above average composition formula (IV) representing the silanol group-containing polyorganosiloxane (B) is:
Not particularly limited, the formula is the same as is exemplified as R ¹ in (I), preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, .gamma.-glycidoxypropyl group, Substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-aminopropyl group and 3,3,3-trifluoropropyl group, more preferably methyl group and phenyl group. Further, in the average composition formula (IV), a and b are numbers satisfying the above-mentioned relationship, respectively, and if a is less than 0.2 or b exceeds 3, there is an inconvenience that cracks occur in the applied cured film. . When a is 2 or more and 4 or less, or when b is less than 0.0001, curing does not proceed well.

The silanol group-containing polyorganosiloxane (B) is not particularly limited.
Methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,
Alternatively, it can be obtained by hydrolyzing one or a mixture of two or more of the corresponding alkoxysilanes with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane (B) is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained, but in the present invention, such a polyorganosiloxane may be used.

In the resin composition for adhesion reducing coating,
The mixing ratio of the component (A) and the component (B) is not particularly limited. (A) 5 to 95 parts by weight of component (B)
5 parts by weight, more preferably 10 to 90 parts by weight of component (A) and 90 to 10 parts by weight of component (B) (the total of components (A) and (B) is 100 parts by weight). (A)
If the amount of the component is less than 1 part by weight, the curability tends to be poor, and sufficient film hardness tends not to be obtained. On the other hand, when the amount of the component (A) exceeds 99 parts by weight, the curability is unstable and a good coating film may not be obtained.

The curing catalyst (C) used as the component (C) of the resin composition for reducing adhesion is (A)
A component that promotes a condensation reaction between the component and the component (B) and cures the coating. Examples of the curing catalyst (C) include, but are not particularly limited to, alkyl titanates; metal carboxylate salts such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate;
Amine salts such as 2-hexoate, dimethylamine acetate, ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate;
Amines such as tetraethylpentamine, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-
amine silane coupling agents such as β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate and lithium formate Metal salts such as sodium, sodium formate, potassium phosphate and potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate; halogenation such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane Examples include silanes. But besides these,
There is no particular limitation as long as it is effective for accelerating the condensation reaction between the component (A) and the component (B).

In the resin composition for adhesion reducing coating,
The mixing ratio of the curing catalyst (C) is not particularly limited,
For example, based on 100 parts by weight of the total of the components (A) and (B), preferably in the range of 0.0001 to 10 parts by weight, more preferably in the range of 0.0005 to 8 parts by weight, and furthermore Preferably it is in the range of 0.0007 to 5 parts by weight. If the amount of (C) is less than 0.0001 part by weight, the curability tends to be low, and sufficient film hardness tends not to be obtained. If the amount exceeds 10 parts by weight, the heat resistance of the applied cured film may be reduced, or the hardness of the applied cured film may be too high to cause cracks.

The linear polysiloxane diol (D) used as the component (D) of the adhesion-reducing coating resin composition is as follows: 1) By imparting toughness to the cured coating applied to the composition, Improve cracking properties,
2) By applying the composition to the surface of the cured coating film by imparting water repellency, the surface of the coating film can be stained with soot, dust, etc.,
It makes it difficult for artificial stains such as pasted paper and graffiti to adhere, and makes it easy to remove even if these stains adhere to the surface of the coating (adhesion of stains to the surface of the coating) And 3) a component having an effect of reducing the sliding resistance of the coating surface due to the surface water repellency.

In particular, in the present invention, as the linear polysiloxane diol (D), n in the above formula (III) is 10 ≦ n
At least one kind (D1) in the range of ≦ 20 and n is 2
At least one kind (D2) in the range of 0 <n ≦ 100 is used in combination. Among these, the linear polysiloxane diol (D1) improves the crack resistance, leveling property, water repellency, etc. of the coating film as described above, and particularly, improves the graffiti removal property by improving the water repellency. The linear polysiloxane diol (D2) is a component that has an effect of improving the releasability and the like, and in particular, has the effect of improving the removability of the pasted paper by improving the releasability. By using the linear polysiloxane diols (D1) and (D2) having such effects in combination, crack resistance, leveling property, water repellency, graffiti removal property and the like of the coating film, releasability, removal of adhesive paper, etc. Sex and the like are compatible. When (D1) is missing among (D1) and (D2), crack resistance, leveling property, water repellency,
If the graffiti removal property or the like is insufficient or not obtained, and if (D2) is missing, the release property, the adhesive sheet removal property or the like will be insufficient or not obtained.

The linear polysiloxane diol (D) is shown in Table 1.
In the general formula (III), R^FourIs a monovalent hydrocarbon group
As long as it is not particularly limited, for example, in the above formula (I)
R ¹The same as described above can be used. So
R like^FourOf a linear polysiloxane diol having
Among them, the application hardness of the resin composition for adhesion reduction coating
In order to impart excellent water repellency to
Loxanediol, methylphenylsiloxanediol
Is preferred.

The linear polysiloxane diol (D) is
Since it has no reactive group other than the terminal OH group, it is a molecule having relatively poor reactivity. Therefore, the linear polysiloxane diol (D) blended in the resin composition for adhesion reduction coating lacks complete compatibility in the composition,
Since it is dispersed as ultrafine particles, it easily coordinates to the surface of the coating film to form a monomolecular layer, but eventually, the silanol group, which is a terminal reactive group, undergoes a condensation reaction with the bulk resin to form a coating film. Immobilized on the surface. As a result, the siloxane bond is localized at a high density on the surface of the cured coating film, and excellent water repellency can be imparted to the cured coating film of the resin composition for adhesion reduction for a long time. The compound (D1) having a relatively small n in the formula (III) is excellent in compatibility, so that it not only forms a layer on the surface of the coating film but also imparts elasticity and toughness to the cured coating film by being incorporated into the bulk. It also leads to a crack prevention effect. Furthermore, due to the surface water repellency, the slip resistance on the surface of the applied cured film is significantly reduced. Therefore, it is effective in reducing the friction and wear of the coating surface,
In addition, due to the heat resistance of the film, even when frictional heat is generated, the film is maintained without being thermally melted. In addition, since the coating has an appropriate hardness, the coating is not easily scratched, so that the scratch is less likely to cause an increase in frictional force.

In the above formula (III), n is in the range of 10 ≦ n ≦ 100, (D1) is 10 ≦ n ≦ 20, preferably 10 ≦ n ≦ 15, and (D2) is 2
0 <n ≦ 100, preferably 20 <n ≦ 40. n
Is less than 10, the effect of improving water repellency tends to be small. When n exceeds 100, the relative bonding strength between the linear polysiloxane diol (D) and the bulk coating decreases, and the linear polysiloxane diol (D) is not fixed to the surface of the coated and cured coating for a long time, and the expression of water repellency is not maintained. Tend.

In the resin composition for coating for reducing adhesion,
The blending amount of the linear polysiloxane diol (D1) is 1 to 60 parts by weight (preferably 5 to 50 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total solid content of the components (A) and (B). Is 5 to 40 parts by weight). If the blending amount of (D1) is less than 1 part by weight, the above-mentioned improvement effect by (D1) tends to be low or not obtained, and if it exceeds 60 parts by weight, the hardness of the obtained cured film is low. It tends to be low or the curing speed of the coating film is slow.

In the resin composition for coating for reducing adhesion,
The blending amount of the linear polysiloxane diol (D2) is 1 to 40 parts by weight (preferably 1 to 20 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total solid content of the components (A) and (B). Is 1 to 10 parts by weight). If the amount of (D2) is less than 1 part by weight, the above-mentioned improvement effect of (D2) tends to be low or not obtained, and if it exceeds 40 parts by weight, the curing speed of the coating film is low. At the same time, the leveling property of the coating film tends to deteriorate.

In the resin composition for coating for reducing adhesion,
The blending amount of the linear polysiloxane diol (D), that is, the total blending amount of the linear polysiloxane diols (D1) and (D2) is not particularly limited. For example, the components (A) and (B) To 100 parts by weight of the total solid content, preferably 2 to 100 parts by weight, more preferably 2 to 100 parts by weight
90 parts by weight, more preferably 2 to 80 parts by weight. If the total amount is less than 2 parts by weight, the expression of water repellency tends to be weak. If the amount exceeds 100 parts by weight, curing of the coating film tends to be inhibited.

The acrylic resin (E) used as a component (E), which is optionally contained in the resin composition for reducing adhesion of the present invention, is used to reduce the toughness of the applied cured film of the resin composition for reducing adhesion. Has the effect of improving
Thereby, the occurrence of cracks is prevented and the film thickness can be increased. In addition, the acrylic resin (E) is incorporated into the condensation crosslinked product of the component (A) and the component (B), which becomes a three-dimensional skeleton of the applied cured coating of the resin composition for reducing adhesion, and the condensation crosslinked product is Acrylic modification. When the condensation crosslinked product is acrylic-modified, the adhesion of the applied cured film of the resin composition for coating with reduced adhesion to the substrate is improved.

The first (meth) acrylic acid ester, which is one of the constituent monomers of the acrylic resin (E), is represented by the formula (II) wherein R ³ is a substituted or unsubstituted one having 1 to 9 carbon atoms. A monovalent hydrocarbon group such as methyl, ethyl, n-propyl, i-propyl, n-butyl,
alkyl groups such as i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; 2-phenylethyl group; Aralkyl groups such as phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; halogenated hydrocarbons such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group A hydroxy hydrocarbon group such as a 2-hydroxyethyl group; and the like.

The second (meth) acrylic acid ester which is another constituent monomer of the acrylic resin (E) is such that R ³ in the above formula (II) represents an epoxy group, a glycidyl group and at least one of these. It is at least one selected from the group consisting of at least one group selected from the group consisting of hydrocarbon groups containing one of them (for example, γ-glycidoxypropyl group).

The third (meth) acrylic acid ester, which is another constituent monomer of the acrylic resin (E), is represented by the formula (II) wherein R ³ is an alkoxysilyl group and / or a halogenated silyl group. Hydrocarbon groups including, for example, trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group , A dichloromethylsilylpropyl group, a chlorodimethylsilylpropyl group, a chlorodimethoxysilylpropyl group, a dichloromethoxysilylpropyl group, or the like.

The acrylic resin (E) is used in the first, second,
The third (meth) acrylic acid ester is a (meth) acrylic acid ester copolymer containing at least one kind and a total of at least three kinds in the first, second, and third (meth) acrylic acids. Another one selected from esters
Or two or more, or one or more selected from (meth) acrylates other than the above.
Copolymers containing more than one species may be used.

The first (meth) acrylic acid ester is an essential component for improving the toughness of the applied cured film of the resin composition for reducing adhesion.
There is also an effect of improving the compatibility between the component (A) and the component (B). For this purpose, the substituted or unsubstituted hydrocarbon group of R ³ preferably has a certain volume or more, and preferably has 2 or more carbon atoms.

The second (meth) acrylic acid ester is an essential component for improving the adhesion between the applied cured film of the resin composition for reducing adhesion and the substrate. The third (meth) acrylic acid ester forms a chemical bond between the acrylic resin (E) and the components (A) and (B) when the coating film of the resin composition for adhesion reduction coating is cured, Thereby, the acrylic resin (E) is fixed in the applied cured film. Further, the third (meth) acrylic acid ester also has an effect of improving the compatibility between the acrylic resin (E) and the components (A) and (B).

The molecular weight of the acrylic resin (E) greatly affects the compatibility of the acrylic resin (E) with the components (A) and (B). Therefore, the acrylic resin (E) is preferably 1,000 to 50,000, more preferably 1,000.
It has a weight average molecular weight in terms of polystyrene within the range of ２０20,000. If the weight average molecular weight in terms of polystyrene of the acrylic resin (E) exceeds 50,000, phase separation may occur and the coating film may be whitened. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease, and cracks tend to occur.

The second (meth) acrylic acid ester is desirably at least 2% by mole of the monomer in the copolymer. If it is less than 2%, the adhesion of the coating film tends to be insufficient. The third (meth) acrylic acid ester is desirably in the range of 2 to 50% by mole ratio of the monomer in the copolymer. If it is less than 2%, the compatibility between the acrylic resin (E) and the components (A) and (B) is poor, and the coating film may be whitened. If it exceeds 50%, the bond density between the acrylic resin (E) and the components (A) and (B) will be too high, and the improvement in toughness, which is the original purpose of the acrylic resin, will not be seen.

As a method for synthesizing the acrylic resin (E), for example, a radical polymerization method by a known solution polymerization, emulsion polymerization or suspension polymerization in an organic solvent, or an anion polymerization method or a cationic polymerization method can be used. , Is not specific to this. In the radical polymerization method by solution polymerization, for example, the first, second, and third (meth) acrylate monomers are dissolved in an organic solvent in a reaction vessel by a known method, and the radical polymerization is started. Add the agent,
Heat and react under a stream of nitrogen. Although the organic solvent used at this time is not particularly limited, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl acetate Etc. are used. Further, the radical polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and azo peroxide. Bisisobutyronitrile, hydrogen peroxide- ^{Fe2 +} salt, persulfate-
NaHSO ₃ , cumene hydroperoxide-Fe ²⁺ salt,
Benzoyl peroxide-dimethylaniline, peroxide-triethylaluminum and the like are used. In order to control the molecular weight, a chain transfer agent can be added. Examples of the chain transfer agent include, but are not limited to, quinones such as monoethyl hydroquinone and p-benzoquinone; mercaptoacetic acid-ethyl ester, mercaptoacetic acid-
n-butyl ester, mercaptoacetic acid-
Thiols such as 2-ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane and 2-mercaptoethanol; thiophenols such as di-3-chlorobenzenethiol, p-toluenethiol and benzenethiol; and γ-mercaptopropyltrimethoxysilane Thiol derivatives; phenylpicrylhydrazine; diphenylamine; tert-butylcatechol and the like can be used.

In the resin composition for coating for reducing adhesion,
The blending amount of the acrylic resin (E) is not particularly limited. For example, the total solid content of the components (A) and (B) is 1%.
The ratio is preferably 0.1 to 100 parts by weight, more preferably 1 to 90 parts by weight, and still more preferably 5 to 80 parts by weight with respect to 00 parts by weight. If the amount is less than 0.1 part by weight, the toughness tends to be weakly expressed. If the amount exceeds 100 parts by weight, curing of the coating film tends to be inhibited.

The resin composition for coating for reducing adhesion is as follows:
Pigments may be included as needed. The pigments that can be used are not particularly limited, but include, for example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, Hansa yellow, fluororesin-based pigments, and acrylic resin-based pigments;
Inorganic pigments such as titanium oxide, zinc oxide, barium sulfate, red iron oxide, and composite metal oxides are preferred.
Species or a combination of two or more species may be used. Among these, at least one selected from the group consisting of inorganic pigments, fluororesin-based pigments, and acrylic resin-based pigments is preferred because it is less likely to deteriorate and the stains can be more easily removed. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used.

The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment.
The total solid content of the components (A), (B), and (D) (if the component (E) is further contained, the components (A), (B), (D),
It is preferably 5 to 100 parts by weight, more preferably 5 to 80 parts by weight, based on 100 parts by weight of the total solid content of the component (E). If the amount of the pigment is less than 5 parts by weight, the concealing property tends to be poor, and if it exceeds 100 parts by weight, the smoothness of the coating film may be poor.

The particle size of the pigment is not particularly limited. For example, when a part of the pigment is exposed on the surface of the applied cured film as described later, if the pigment particle size is too small, the pigment is buried in the applied cured film. Therefore, the thickness is preferably 1 μm or more. The shape is preferably spherical. In addition, if necessary, a leveling agent, a dye, a metal powder, a glass powder, an antibacterial agent, an antioxidant, an antistatic agent, an ultraviolet absorber, etc. may also be used to reduce the adhesion of the present invention within a range that does not adversely affect the effects of the present invention. May be included in the resin composition for use.

The resin composition for adhesion reducing coating is as follows:
It can be used by diluting it with various organic solvents, if necessary, for ease of handling, or it may be diluted with the same organic solvent. The types of organic solvents are (A), (B),
Component (D) (when component (E) is further included, component (A)
(B), (D), the type of the monovalent hydrocarbon group contained in the (E) component, or (A), (B), (D) component (when component (E) is further included, (A) , (B), (D),
The component (E) can be selected according to the molecular weight. Examples of such an organic solvent are not particularly limited, but include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl acetate. And ethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol and the like. And one or more selected from the group consisting of these. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method for applying the resin composition for adhesion reduction coating to a substrate is not particularly limited, and examples thereof include brushing, spraying, dipping (dipping), and the like.
Various ordinary coating methods such as a flow, a roll, a curtain, and a knife coat can be selected. A method for curing the resin composition for adhesion reduction coating applied to the substrate may be a known method, and is not particularly limited.
The temperature at the time of curing is not particularly limited, either, and can be in a wide range from room temperature to heating temperature according to the desired performance of the applied cured coating film.

The thickness of the cured coating film formed from the resin composition for reducing adhesion is not particularly limited, and may be, for example, about 0.1 to 100 μm. In order to stably adhere and hold, and to prevent cracking and peeling, 1 to 50 μm
m is preferred. The substrate on which the resin composition for coating for reducing adhesion of the present invention is applied (which is also the substrate used for the coated product of the present invention) is not particularly limited. Examples thereof include an inorganic-organic composite substrate, and a coated substrate having at least one inorganic film and / or at least one organic film on any of these surfaces.

The inorganic base material is not particularly limited, but examples thereof include a metal base material; a glass base material; an enamel; a water glass decorative plate; The metal substrate is not particularly limited. For example, non-ferrous metals [for example, aluminum (JIS-H4000 etc.), aluminum alloys (duralumin etc.), copper, zinc etc.], iron, steel [for example, rolled steel (JIS) -G3101 etc.), hot-dip galvanized steel (JIS
-G3302 etc.), (rolled) stainless steel (JIS-G
4304, G4305, etc.), tinplate (JIS-G3)
303 etc.) and other metals in general (including alloys).

The glass substrate is not particularly limited, and examples thereof include sodium glass, Pyrex glass, quartz glass, and alkali-free glass. The enamel is obtained by baking and coating a glassy enamel on a metal surface. Examples of the base metal include a mild steel plate, a steel plate, cast iron, and aluminum, but are not particularly limited. The enamel may be a normal enamel, and is not particularly limited.

The water glass decorative board refers to, for example, a decorative board obtained by applying sodium silicate to a cement base such as a slate and baking it. The inorganic hardened material is not particularly limited. For example, a fiber reinforced cement board (J
IS-A5430, etc.), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminate board (JIS-A5426)
Gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A6901 etc.)
A5402), ceramic tile (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540)
6), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), and all types of base materials obtained by curing and molding inorganic materials such as ordinary bricks (JIS-R1250 etc.).

In the conventional silicone coating, the base material needs to be filled in advance because it is easily attacked by an alkali component solute from a water glass decorative plate or an inorganic cured product and cannot have long-term durability. In the case where the resin composition for adhesion reduction coating of the present invention further contains the acrylic resin (E), it is characterized in that long-term durability can be obtained because it is not easily attacked by an alkali component.

The ceramic substrate is not particularly limited, and examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like. As an organic substrate,
Although not particularly limited, for example, plastic, wood,
Examples include wood and paper. As a plastic substrate,
Although not particularly limited, for example, a thermosetting or thermoplastic plastic such as a polycarbonate resin, an acrylic resin, an ABS resin, a vinyl chloride resin, an epoxy resin, and a phenol resin, and a reinforcement of these plastics with an organic fiber such as a nylon fiber. Fiber reinforced plastic (FRP). The adhesiveness-reducing coating resin composition of the present invention has an improved toughness of its applied cured film, so that it can be applied to a relatively soft substrate such as plastic, and has a scratch-preventing effect and a stain on its surface. The effect of prevention can be obtained.

The inorganic-organic composite base material is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. The organic film constituting the coating substrate is not particularly limited, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, etc. A cured film of a coating material containing an organic resin may be used.

The inorganic coating constituting the coating substrate is not particularly limited, and includes, for example, a cured coating of a coating material containing an inorganic resin such as a silicone resin. The cured coating of the resin composition for coating of the present invention has excellent adhesion to various substrates, but in order to further enhance the adhesion, if necessary, the adhesion of the substrate to the surface of the substrate is reduced. Before forming the applied cured film of the coating resin composition, a primer layer may be formed in advance, or the surface of the base material may be polished or degreased, or preferably used in combination. The primer layer is not particularly limited, regardless of whether it is organic or inorganic. Examples of the organic primer layer include a nylon resin, an alkyd resin, an epoxy resin, an acrylic resin, and an organic modified silicone resin (for example, an acrylic silicone resin). , A cured resin layer of an organic primer composition containing at least one organic resin selected from the group consisting of a chlorinated rubber resin, a urethane resin, a phenol resin, a polyester resin, and a melamine resin in a solid content of 10% by weight or more. Examples of the inorganic primer layer include a cured resin layer of an inorganic primer composition containing 90% by weight or more of a solid content of an inorganic resin such as a silicone resin.

The thickness of the primer layer is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm.
Is more preferable, and 0.5 to 10 μm is further preferable.
If the thickness is too thin, adhesion may not be obtained,
If it is too thick, foaming and the like may occur during drying. A substrate having at least one organic primer layer and / or inorganic primer layer on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

The primer layer may contain a coloring agent such as a pigment or a dye for toning, if necessary. Examples of usable coloring agents include those described above as those that can be added to the highly hydrophilic inorganic paint. The preferred numerical range of the amount of the coloring agent to be added to the primer layer is also the same as in the case of the above-mentioned resin composition for adhesion reducing coating. However, the total solid content of the components (A), (B) and (D) (or (A), (B), (D) and (E)
Not 100 parts by weight of the total solids of the components)
It is defined based on 100 parts by weight of the total resin solid content in the total amount of the primer composition.

The form of the substrate is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Further, the base material may be a molded body of a material having these shapes, or a structure partially provided with at least one of the material having the shape or the molded body. The base material may be made of the above-mentioned various materials alone, a composite material obtained by combining at least two of the above-described various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

The cured coating film obtained from the resin composition for reducing adhesion of the present invention has surface water repellency by containing the component (D). Since the adhesion of dirt and the like to the surface is reduced, dirt and the like are hardly adhered to the surface of the painted product, and even if the dirt and the like adhere to the surface of the painted product, it is easily removed.

Examples of deposits such as dirt, the adhesion of which is reduced by the present invention, include various pollutants, such as soot, dust, (dust) dust, exhaust gas, cigarette dust, graffiti, stickers, oil, etc. in the air. In addition, water-related deposits, such as dirt around household water, dirt mixed with rainwater, mud, snow, ice, and underwater organisms such as the sea and rivers (eg, barnacles, plankton, aosa), etc. And are not particularly limited. Among these, the present invention has a particularly large effect of reducing the adhesion to underwater organisms and the adhesion of artificial dirt such as graffiti and stickers.

The resin composition for coating with reduced adhesion of the present invention and a coated article using the same can be used, for example, in the following applications. 1) Ships, marine structures, etc. that are required to prevent underwater organisms from adhering. Specific application examples (examples of base materials) include bottoms (steel plates) of general ships, leisure boats (FRP), cooling pipes for power plants (aluminum, iron, etc.), and other marine structures.

2) For vehicles requiring water repellency. Specific application examples (base materials) include automobile bodies (organic painted plates),
Windshield (glass), side mirror (glass),
Sunroof (polycarbonate), vehicles such as trains (organic painted plate, stainless steel), masking film (plastic film), etc. 3) Prevention of icing. Specific application examples (base materials) include roofs (inorganic building materials) and airplane wings (special metals).

4) Outdoor structures where snow prevention is required. Specific application examples (base materials) include roofs (inorganic building materials), electric wires (organic rubber), signs (organic painted plates, plastic film laminated steel plates), and the like. 5) Road tunnels and expressway noise barriers that require prevention of pollution by exhaust gas, smoke, dust, and the like. Specific application examples (base materials) include tunnel interior boards (slate, concrete),
Guardrail (organic painted plate, galvanized steel plate), soundproof wall (acrylic, polycarbonate, slate, concrete), sign (organic painted plate, plastic film laminated steel plate), road lighting pole (organic painted plate, glass cover), etc.

6) Around the range where oil stain prevention is required.
Specific application examples (substrate examples) are range hood (organic painted metal plate), range periphery (stainless steel, enamel, tile), cover film (PET (polyethylene terephthalate), aluminum), storage door (plastic film laminated wood) , Plastic), microwave oven (marble, artificial marble), ventilation fan (plastic), kitchen lighting cover (acrylic, polycarbonate, organic painted metal plate, glass), refrigerator cover (pre-coated steel plate, PE)
T film).

7) General interior materials which are required to prevent tobacco stains. Specific application examples (base materials) include wallpaper (polyvinyl chloride), blinds (organic painted plate), lighting equipment (acrylic, polycarbonate, glass), general electric appliances (pre-coated steel plate, plastic), and the like. 8) Other households where pollution prevention is required. Specific application examples (base materials) are bath (FRP), bathroom wall (FR)
P steel sheet, polyvinyl chloride steel sheet), toilet bowl (enamel), toilet seat (plastic), etc.

9) General outdoor structures requiring high surface durability. Specific application examples (base materials) include outer walls (inorganic building materials such as concrete and tiles, organic painted boards), rain gutters (polyvinyl chloride, stainless steel), tombs (granite), tents (polyvinyl chloride film) , Various vending machines (organic painted boards) and other general outdoor structures. 10) Outdoor structures requiring prevention of graffiti and sticking. Specific application examples (base materials) include bridge girders (steel plate, concrete), piers (steel plate, concrete), public toilets (concrete) such as toilets in parks, and inner and outer walls (slate, concrete) such as underpasses and buildings. Etc.), public telephone boxes (glass, shatterproof film), telephone poles (metal coated plates, concrete), lighting poles (steel plates, metals such as aluminum), etc.

11) Printing machine rolls and electrophotographic rolls which are required to prevent adhesion of ink and toner. Specific application examples (base materials) include fixing rolls (aluminum, iron, silicone rubber), photosensitive drums (aluminum), guide rolls (nylon-coated metal rods, FRP rods), separation claws (PE
S, PEEK), SURF (imide film), pressure roll (silicone rubber), etc.

12) Those requiring high durability and water repellency. Specific application examples (substrate examples) include fibers (various fibers),
Glazing (polycarbonate, acrylic), solar cell cover (glass), sports equipment (FRP), etc. 13) Those requiring a wax effect. Specific application examples (base materials) include skis (FRP), molded release materials (metal), release paper (paper, plastic films), floor materials (F
RP, tile).

14) Those requiring heat resistance and low slip resistance. Specific application examples (substrate examples) are the outer surface of a propulsion pipe such as a sewer pipe buried by the propulsion method (concrete), a road surface for asphalt test (asphalt), a hot press mold (metal), and the like. 15) Outdoor articles required to prevent pollution by smoke, dust, and the like. Specific application examples (base materials) include bodies of vehicles such as automobiles and trains (organic painted plate, stainless steel), tunnel interior plates (slate, concrete), guardrails (organic painted plate, galvanized steel plate), soundproof walls (Acrylic, polycarbonate, slate, concrete), sign (organic painted plate, plastic film laminated steel plate), road lighting (organic painted plate, glass cover), concrete protective wall (concrete), railing (organic painted or galvanized steel plate, Aluminum, stainless steel), road decorative board (organic painted aluminum board, fluorine film laminated steel sheet)
etc. In addition, the resin composition for adhesion reduction coating of the present invention may be directly applied to at least a part of the above-described various materials or articles and cured, but is not limited thereto. A film obtained by applying a resin composition for coating to the surface of a film substrate and curing the film,
Alternatively, the above-described resin composition for adhesion reduction coating may be applied to a metal plate, and the cured metal plate may be stuck or wound around at least a part of the above-mentioned various materials or articles. As the material of the base material of the film,
Examples include, but are not limited to, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (PP) resin, and composite resins thereof.

Further, in order to further improve the effect of reducing adhesion to the paper, irregularities may be formed on the surface of the cured coating film of the resin composition for reducing adhesion to reduce the contact area with the paper. The method of forming the irregularities on the surface of the applied cured film is not particularly limited, for example, the pigment or glass beads may be contained in the adhesion-reducing coating resin composition, and a part of them may be coated and cured. And a method of applying the resin composition for reducing adhesion to the surface of the coating, and curing the coating before the coating is cured, using a device having a surface with unevenness.

The particle size of the glass beads used in the above method is not particularly limited, but is preferably, for example, several mm. If it is 10 mm or more, the adhesive strength between the beads and the coating resin is weak, which is not desirable. Further, in the above method,
Although there is no particular limitation on the utensil having an uneven surface used for processing the surface of the coating film, for example, a commercially available pattern (design) roller can be used.

[0085]

The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. The molecular weight was measured by GPC (gel permeation chromatography) using HLC8020 manufactured by Tosoh Corporation as a measurement model by creating a calibration curve with standard polystyrene. In addition, this invention is not limited to a following example.

Prior to the examples and comparative examples, the components used for them were prepared as follows. (Preparation Example of Component A): <Preparation Example A-1> In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, isopropanol-dispersed colloidal silica sol IPA-ST (particle diameter: 10 to 10).
20 parts, solid content 30%, water content 0.5%, manufactured by Nissan Chemical Industry Co., Ltd.) 100 parts, methyltrimethoxysilane 68 parts, water 10.8 parts are added, and the mixture is stirred at 65 ° C. for about 5 hours while stirring. After performing hydrolysis, by cooling,
(A-1) The component was obtained. This had a solid content of 36% when left at room temperature for 48 hours.

Preparation conditions of A-1 • Number of moles of water per mole of hydrolyzable group 0.4 • Silica content of component (A-1) 47.3% • Hydrolyzable organosilane with m = 1 <Preparation Example A-2> In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, a xylene / n-butanol mixed solvent-dispersed colloidal silica sol XBA-S was used.
T (particle diameter 10 to 20 nm, solid content 30%, moisture 0.2
%, Manufactured by Nissan Chemical Industries, Ltd.) and 68 parts of methyltrimethoxysilane, and the mixture was subjected to a partial hydrolysis reaction at 65 ° C. for about 5 hours with stirring, followed by cooling. (A-2) A component was obtained. This had a solid content of 36% when left at room temperature for 48 hours.

Preparation conditions for A-2: • Number of moles of water per mole of hydrolyzable group: 0.007 mole • Silica content of component (A-2): 47.3% • Hydrolyzability with m = 1 Mol% of organosilane 100 mol% (Preparation example of component B): <Preparation example B-1> In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, 220 parts of methyltriisopropoxysilane ( 1 mol) is dissolved in 150 parts of toluene.
108 parts of a 1% hydrochloric acid aqueous solution was added dropwise over 20 minutes, and methyltriisopropoxysilane was hydrolyzed at 60 ° C. with stirring. The stirring was stopped 40 minutes after the completion of the dropping. When the reaction solution was transferred to a separating funnel and allowed to stand, it was separated into two layers. The mixed solution of the lower layer of water and isopropyl alcohol containing a small amount of hydrochloric acid is separated and removed, the remaining hydrochloric acid in the remaining resin solution of toluene is removed by washing with water, and the toluene is further removed under reduced pressure. The obtained reaction product was diluted with isopropyl alcohol to obtain a 40% solution of a silanol group-containing polyorganosiloxane having a weight average molecular weight (Mw) of about 2,000 in isopropyl alcohol. This is called B-1. The silanol group-containing polyorganosiloxane in B-1 has the above average composition formula (IV)
It is confirmed that it satisfies.

<Preparation Example B-2> 1000 parts of water and 50 parts of acetone were charged into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and further 44.8 parts of methyltrichlorosilane (0. 38.7 parts), 38.7 parts (0.3 mol) of dimethyldichlorosilane and 84.6 parts (0.4 mol) of phenyltrichlorosilane.
(4 mol) dissolved in 200 parts of toluene was hydrolyzed at 60 ° C. while dropwise adding a solution with stirring. The stirring was stopped 40 minutes after the completion of the dropping. When the reaction solution was transferred to a separating funnel and allowed to stand, it was separated into two layers. The lower layer of aqueous hydrochloric acid is separated and the remaining water and hydrochloric acid remaining in the toluene solution of organopolysiloxane are removed together with excess toluene by vacuum stripping to obtain a weight average molecular weight (Mw) of about 3,000. A 60% toluene solution of the silanol group-containing polyorganosiloxane was obtained. This is called B-2. The silanol group-containing polyorganosiloxane in B-2 has the average composition formula (I)
V). (Component C): N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane. (D component): <D1-1> weight average molecular weight Mw = 800, the above formula (II)
A linear dimethylpolysiloxane diol wherein n in n) is n ≒ 11 (average value). This is called D1-1.

<D1-2> Weight average molecular weight Mw = 140
0, a linear dimethylpolysiloxanediol wherein n in the formula (III) is n ≒ 19 (average value). This is called D1-2. <D2-1> weight average molecular weight Mw = 1800, the above formula (I
II) A linear dimethylpolysiloxane diol in which n is n ≒ 24 (average value). This is called D2-1.

<D2-2> Weight average molecular weight Mw = 300
0, a linear dimethylpolysiloxanediol wherein n in the formula (III) is n ≒ 40 (average value). This is called D2-2. <D2-3> weight average molecular weight Mw = 7000, the above formula (I
II) A linear dimethylpolysiloxane diol in which n is 90 (average value). This is called D2-3.

<Comparative D-1> Weight average molecular weight Mw = 4
50. A linear dimethylpolysiloxane diol wherein n in the formula (III) is n ≒ 4 (average value). This is compared with D-1 for comparison.
Called. <Comparative D-2> A linear dimethylpolysiloxane diol having a weight average molecular weight Mw = 9000 and n in the above formula (III) where n ≒ 120 (average value). This is referred to as Comparative D-2. (Preparation example of E component): <Preparation example E> Stirrer, heating jacket, condenser,
In a flask equipped with a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer, n-butyl methacrylate (BM
A) 5.69 parts, trimethoxysilylpropyl methacrylate (SMA) 1.24 parts, glycidyl methacrylate (GMA) 0.71 part, and 0.784 parts of γ-mercaptopropyltrimethoxysilane as a chain transfer agent in toluene 8. A solution obtained by dissolving 0.025 part of azobisisobutyronitrile in 3 parts of toluene was dropped into a reaction solution dissolved in 49 parts under a nitrogen stream, and reacted at 70 ° C. for 2 hours. Thereby, the weight average molecular weight Mw = 1000
To obtain a 40% toluene solution of acrylic resin. This is E
Called.

Preparation conditions for E-Monomer molar ratio BMA / SMA / GMA = 8/1/1-Weight average molecular weight 1000-Solid content 40% <Examples 1-21 and Comparative Examples 1-11> Table The components shown in Tables 1 to 5 were mixed in the proportions shown in the same table, and all were diluted with isopropyl alcohol so as to have a solid content of 20%. A resin composition for coating for comparison was obtained.

The appearance of each of the obtained resin compositions for coating was visually observed, and the results are shown in Tables 1 to 5. <Examples 22 to 44 and Comparative Examples 12 to 28> The compositions obtained above were applied to various substrates by spray coating so that the cured film thickness was 10 to 30 µm, and the curing temperature was 120.
By curing at 30 ° C. for 30 minutes to form a coating film,
A coated product of each example and a comparative coated product of each comparative example were obtained.

In addition, if necessary, as a primer,
Acrylic urethane resin (trade name: Mighty Rack, manufactured by Nippon Paint Co., Ltd.) was used. There is no particular problem with the adhesion without using a primer, but even after the treatment with boiling water for 5 hours, if sufficient adhesion is required,
It is desirable to use primers. The primer was applied to the substrate by spray coating so as to have a film thickness of about 10 μm, treated at 100 ° C. for 30 minutes, and then the above composition was applied and cured.

The following materials were used as the base material. Aluminum plate: Aluminum test piece (Product name:
Ulster, manufactured by Japan Test Panel, dimensions 150mm x 7
0mm × 0.3mm) Stainless steel plate: SUS304 plate (Dimensions 150mm × 70mm)
× 0.5 mm). PC board: Polycarbonate board (Dimensions 150mm x 70mm
× 5mm).

Slate board: fiber reinforced cement board (size 1)
50mm x 70mm x 3mm). Acrylic resin coated plate: Thermosetting acrylic resin on aluminum plate (Product name: Super Rack, manufactured by Nippon Paint Co., Ltd.)
And baked at 170 ° C for 30 minutes. Acrylic urethane coated plate: After applying a primer (trade name: Hypon, manufactured by Nippon Paint Co., Ltd.) to an aluminum plate, an acrylic urethane resin (trade name: Mighty Rack, manufactured by Nippon Paint Co., Ltd.) was applied and baked at 120 ° C. for 30 minutes. thing.

Urethane resin coated plate: A primer (trade name: Olga Select, manufactured by Nippon Paint Co., Ltd.) is applied to an aluminum plate, and then a thermosetting urethane resin (trade name: Unipon, manufactured by Nippon Paint Co., Ltd.) is applied. Baked for 30 minutes. A coating film property test was performed on the obtained coated product by the following method. The results are shown in Tables 6 to 11. (Evaluation of coating film properties): Adhesion: Adhesion to the substrate was evaluated by a cross-cut adhesive tape (using cellophane tape) peel test.

Coating film hardness: Pencil hardness test (JIS-K54)
(According to 00). Boiling water resistance (crack resistance): 4 hours after boiling with tap water, leave the test piece for 1 hour and observe the state of the coating film. Is indicated by x. Solvent resistance: Lightly press the coating with gauze impregnated with toluene and rub 100 times in reciprocation. Is indicated by x.

Weather resistance: Sunshine super long life weather meter (WEL-SUN manufactured by Suga Test Instruments)
After irradiating with the (HC type) for 2,000 hours, the coating film was observed, and no change was evaluated as ○, and a film having cracks, peeling of the coating film, etc. was evaluated as x. Adhesive paper peel test: A paper coated with an epoxy-based adhesive was applied to the coating film, and after one day, the paper peeled off without sticking was marked as ○,
The paper having less than 50% of the paper was rated as Δ, and the paper with 50% or more of the paper remaining was rated as x.

Graffiti test: The surface of the coating film was treated with an oily magic 4
When the sample was completely rubbed with cm ² and completely wiped off with gauze, the sample was marked with “○”, the sample with less than 50% of the mark of magic was marked with “△”, and the sample with 50% or more of the mark of magic was marked as “x”. <Example 45> In Example 22, the component (A) of the resin composition for adhesion reduction coating of Example 1 was used in which the particle diameter was 0.5.
A coated product was obtained in the same manner as in Example 22, except that 5 mm of glass beads were mixed at a ratio of 20 parts by weight to 100 parts by weight of the total solid content of the components (A) and (B). <Example 46> In Example 22, the component (A) of the resin composition for coating for reducing adhesion in Example 1 was added with a particle diameter of 0.5.
Same as Example 22 except that 6 mm of a fluororesin (trade name: Polyflon, manufactured by Daikin Industries, Ltd.) was mixed at a ratio of 20 parts by weight to 100 parts by weight of the total solid content of the components (A) and (B). To obtain a painted product. <Example 47> Aluminum test piece (trade name: Ulster, manufactured by Nippon Test Panel Co., Ltd., dimensions 150 mm x 70)
A primer (trade name: Neo Silica, manufactured by Isamu Co., Ltd.) was applied to the primer to a thickness of about 10 μm by spray coating, and treated at 100 ° C. for 30 minutes. The resin composition for reduction coating is applied by spray coating so that the cured coating thickness becomes 10 to 30 μm, and after 20 minutes at room temperature, a roller having protrusions is applied to the surface of the coating film and then treated at 100 ° C. for 30 minutes. By doing so, a coated product was obtained. <Example 48> A primer (commercial product) was applied to an outdoor lighting column (Matsushita Electric Works) made of a thermosetting urethane resin (trade name: Unipon, manufactured by Nippon Paint Co., Ltd.) applied to a galvanized steel sheet to a height of 2 m above the ground. Name: Neosilica, Isamu Paint Co., Ltd.) is applied by spray coating so as to have a film thickness of about 10 μm, treated at 100 ° C. for 30 minutes, and further spray-coated with the resin composition for adhesion reducing coating of Example 1 Is applied so that the cured coating thickness is 10 to 30 μm,
A coated product was obtained by treating at 120 ° C. for 30 minutes. <Example 49> A coated product was obtained in the same manner as in Example 48 except that an acrylic urethane resin (trade name: Mighty Lack, manufactured by Nippon Paint Co., Ltd.) was used instead of the thermosetting urethane resin. Was. <Example 50> A primer (up to 2 m above the ground of an outdoor lighting pole (manufactured by Matsushita Electric Works) formed by applying a thermosetting acrylic resin (trade name: Super Rack, manufactured by Nippon Paint Co., Ltd.) to a galvanized steel sheet. (Trade name: Neosilica, manufactured by Isamu Paint Co.) was applied by spray coating so that the film thickness would be about 10 μm, and treated at room temperature for 4 hours.
Was applied by spray coating so that the cured coating thickness became 10 to 30 μm, and dried at room temperature for one week to obtain a coated product. <Example 51> A silicone-modified urethane-based primer (trade name: Tosprim C, manufactured by Toshiba Silicone Co., Ltd.) was applied to a concrete power pole by brush coating so as to have a film thickness of about 5 µm, and treated at room temperature for 2 hours. Further, the resin composition for adhesion reduction coating of Example 1 was applied by spray coating so that the cured coating thickness became 10 to 30 μm, and dried at room temperature for one week to obtain a coated product. <Comparative Example 29> An outdoor lighting column (Matsushita Electric Works), which was obtained by simply applying a thermosetting urethane resin (trade name: Unipon, manufactured by Nippon Paint Co., Ltd.) to a galvanized steel sheet, was used as a comparative painted product. <Comparative Example 30> An outdoor lighting column (Matsushita Electric Works), which was obtained by simply applying an acrylic urethane resin (trade name: Mighty Rack, manufactured by Nippon Paint Co., Ltd.) to a galvanized steel sheet, was used as a comparative painted product. <Comparative Example 31> An outdoor lighting column (made by Matsushita Electric Works), which was obtained by simply applying a thermosetting acrylic resin (trade name: Super Rack, manufactured by Nippon Paint Co., Ltd.) to a galvanized steel sheet, was used as a comparative painted product. <Comparative Example 32> A concrete telephone pole to which nothing was applied was used as a comparative article.

The coated articles obtained in Examples 45 to 51 and the comparative coated articles and comparative articles obtained in Comparative Examples 29 to 32 were subjected to a peeling test and a graffiti test by the above-mentioned methods. And the effect of reducing adhesion to graffiti was evaluated. As a result, the comparative coated articles and comparative articles obtained in Comparative Examples 29 to 32 were all X, whereas the coated articles obtained in Examples 45 to 51 were all O.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

[0108]

[Table 6]

[0109]

[Table 7]

[0110]

[Table 8]

[0111]

[Table 9]

[0112]

[Table 10]

[0113]

[Table 11]

[0114]

The resin composition for coating with reduced adhesion of the present invention has excellent hardness, weather resistance, solvent resistance, boiling water resistance, etc. on the surface of various substrates irrespective of inorganic or organic. A coating cured film can be formed. The cured coating film has excellent adhesion to various inorganic and organic substrates without using a primer. This hardened coating film does not have too high hardness and has excellent toughness (flexibility). Therefore, it is difficult for cracks to be generated up to a film thickness of about 50 μm (excellent in cracking resistance) and adaptability to unevenness of the substrate. Is wide,
Further, it can widely cope with dimensional changes due to the temperature and humidity of the substrate. Further, the hardness of the applied cured film is not too low.

The cured coating film obtained from the adhesion reducing coating resin composition of the present invention has a surface water repellency, and has an effect of reducing the adhesion of dirt and the like to the surface. In addition, dirt or the like hardly adheres to the surface, and even if the dirt or the like adheres to the surface, it can be easily removed. Such an adhesiveness-reducing effect is superior to the above-mentioned conventional adhesiveness-reducing coating resin composition, particularly against artificial stains such as pasted paper and graffiti. Further, since the surface water repellency reduces slip resistance to a contact object on the coating surface, forming the coating on the surface of the substrate can reduce friction and wear of the substrate surface. it can. The coating is less susceptible to frictional resistance and moreover has excellent heat resistance, and is less likely to be denatured by frictional heat. Further, since the applied cured film has a moderately high surface hardness, it is unlikely to cause scratches due to friction, so that the increase in frictional force due to the scratches is suppressed, and the surface is resistant to scratching when removing surface dirt and the like. Also has properties.

The resin composition for coating with reduced adhesion of the present invention can be cured under accelerated heating at a low temperature of less than 100 ° C. and at ordinary temperature, and can be used in a wide range of dry curing conditions or temperatures. Therefore,
Even when it is difficult to apply heat, such as when coating on a substrate with a shape that is difficult to apply heat uniformly, a substrate with large dimensions or a substrate with poor heat resistance, or when performing painting work outdoors etc. Its industrial value is high because it can be painted.

The resin composition for coating with reduced adhesion of the present invention can be used as a vehicle when it is made into a paint by adding a pigment, and thus can be arbitrarily colored by adding a pigment. The coated article of the present invention has a high surface hardness, high weather resistance, excellent solvent resistance, excellent boiling water resistance, etc., since the coated article of the present invention is provided with a coated and cured film of the resin composition for reducing adhesion on the surface. The above-mentioned cured coating film has excellent adhesion to various inorganic and organic substrates even without using a primer. The coated and cured film has a hardness not too high and a toughness (flexibility).
Therefore, cracks hardly occur up to a film thickness of about 50 μm (excellent in crack resistance), adaptability to unevenness of the substrate is wide, and it can widely cope with dimensional changes due to temperature and humidity of the substrate. Further, the hardness of the applied cured film is not too low.

The coated and cured film of the resin composition for reducing adhesion provided in the coated article of the present invention has a water-repellent surface, and therefore has the effect of reducing the adhesion of dirt and the like to its surface. In the coated product, dirt and the like hardly adhere to the surface, and even if the dirt and the like adhere to the surface, it can be easily removed. Such an adhesion reducing effect is as follows.
Compared with a coated product obtained by using the above-mentioned conventional resin composition for reducing adhesion, it is more excellent particularly against artificial stains such as pasted paper and graffiti. Therefore, the coated product of the present invention is also excellent in landscape. In addition, since the surface water repellency reduces the slip resistance to a contact object on the surface of the coating, the coated product of the present invention has a low surface slip resistance and is hardly worn. The coated and cured film on the surface is less susceptible to frictional resistance and also has excellent heat resistance, so that it is less likely to be modified by frictional heat. Furthermore, since the coated article of the present invention has a moderately high surface hardness, scratches due to friction are unlikely to occur, so that an increase in frictional force due to scratches is suppressed and the surface is resistant to scratching when removing surface dirt and the like. Also has detergency.

The coated article of the present invention can be produced by using the above-mentioned resin composition for adhesion reduction coating which can be cured at a low temperature of less than 100 ° C. by accelerated heating and can be cured at room temperature. It can be manufactured in the condition range or temperature range. Therefore, it is possible to use a base material having a shape that is difficult to apply heat uniformly, a base material having a large dimension or a base material having poor heat resistance, and because it can be manufactured even in a work site where heat is difficult to apply such as outdoors. , Its industrial value is high.

The coated product of the present invention can be used as a vehicle when a pigment is added to form a coating, and can be produced using the resin composition for adhesion reduction coating of the present invention, which can be arbitrarily colored by adding a pigment. High design and wide range of use.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Minoru Inoue 1048 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd.

Claims (10)

[Claims] 1. The following (A), (B), (C) and (D)
A resin composition for coating with reduced adhesion, comprising a component. Component (A): represented by the general formula R ¹ _m SiX _4-m (I) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M represents an integer of 0 to 3 and X represents a hydrolyzable group) Hydrolyzable organosilane is partially hydrolyzed in colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof in the presence of water. A silica-dispersed oligomer solution of an organosilane. Component (B): represented by an average composition formula R ⁵ _a Si (OH) _b O _{(4-ab) / 2} (IV) (where R ⁵ is the same or different and substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, and a and b represent 0.2 ≦ a <2 and 0.0001 ≦ b ≦, respectively.
3, a + b <4), a polyorganosiloxane containing a silanol group in the molecule. Component (C): curing catalyst. Component (D): represented by (wherein the general formula _{^{HO (R 4 2 SiO) n}} H ... (III) R 4 represents a monovalent hydrocarbon group, 2
R ⁴ may be the same or different, and n is 1
(D1) at least one of n in the range of 10 ≦ n ≦ 20, and (D2) n is 20 <n.
And at least one of the components (D1) and (D2) in the range of ≦ 100.
With respect to 100 parts by weight of the total solid content of the component (B), (D1)
A linear polysiloxane diol having a ratio of 1 to 60 parts by weight of the component and 1 to 40 parts by weight of the component (D2). 2. The total blending amount of the components (D1) and (D2) is 2 to 100 parts by weight based on 100 parts by weight of the total solid content of the components (A) and (B). Item 4. The resin composition for coating with reduced adhesion according to Item 1. 3. The method according to claim 1, further comprising the following component (E).
3. The resin composition for coating with reduced adhesion according to item 1. Component (E): a monomer represented by the general formula CH ₂ ＣＲCR ² (COOR ³ ) (II) (where R ² represents a hydrogen atom and / or a methyl group), wherein R ³ is substituted or A first (meth) acrylate which is an unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, wherein R ³ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group selected from the group consisting of: and a ^third (meth) acryl wherein R ³ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acid ester and 4. The compounding amount of the component (E) is as follows:
1 to 10 parts by weight based on 100 parts by weight of the total solid content of the component (B)
The resin composition for coating with reduced adhesion according to claim 3, wherein the proportion is 0 parts by weight. 5. A coated article provided with a cured coating of the resin composition for coating with reduced adhesion according to any one of claims 1 to 4 on the surface of a substrate. 6. The coated article according to claim 5, wherein a pigment is contained in the cured coating film, and a part of the pigment is exposed on the surface of the cured coating film. 7. The coated article according to claim 6, wherein said pigment is at least one selected from the group consisting of inorganic pigments, fluororesin pigments and acrylic resin pigments. 8. The coated product according to claim 5, wherein the cured coating film is processed so as to have irregularities on the surface before curing by using an instrument having irregularities on the surface. 9. An outdoor lighting column comprising at least a part of a cured coating film of the resin composition for coating for reducing adhesion according to claim 1. 10. A utility pole comprising at least a part of a cured coating film of the resin composition for reducing adhesion according to any one of claims 1 to 4.