JP3225859B2 - Silicone transfer film and transfer structure thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone transfer film used for immobilizing a material having a purifying, antibacterial or deodorizing function on a surface of a target object by a transfer method, and a transfer structure thereof. Things.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting a self-purifying function to the surface of an article, a material having a purifying, antibacterial or deodorizing function such as photocatalytic titanium oxide fine particles and silver-glass powder is coated in a coating resin. There is a method of dispersing and immobilizing on the article surface as a dispersing component in the coating layer. However, according to this method, most of the materials having a purifying, antibacterial or deodorizing function immobilized on the article surface are buried in the coating resin as a binder, so that only a part of the material is exposed to the surface of the coating film, and therefore the dispersion is prevented. The antibacterial effect or deodorant effect obtained with respect to the total amount of the powder obtained is small. In order to exert a sufficient antibacterial action or deodorant action, it is necessary to increase the amount of the dispersed powder with respect to the amount of the coating resin.
Inconveniences such as impairment of the original performance of the coating agent such as adhesion to the article surface are caused.

[0003] On the other hand, purification of the powder form on the surface of the coating film,
As a method of allowing a material having an antibacterial or deodorizing function to be present at a high density, a method has been proposed in which an uncured coating film coated on the surface of an article is coated with a powder dispersion and fixed to the coating film surface. Depending on the uncured state of the coating film, inconveniences such as agglomeration and non-uniformity of the powder may be caused.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, the present inventors have conducted intensive research and development to improve the drawbacks. The present invention has found a method in which a material having a high-purity, antibacterial or deodorizing function is immobilized only on the surface layer of the protective layer applied to the protective layer, and the intrinsic performance of the protective layer is not impaired. . That is, an object of the present invention is to provide a silicone transfer film capable of providing a protective layer having a good self-purifying function on the surface of a target article by a transfer method, and a transfer structure thereof.

[0005]

According to a first aspect of the present invention, there is provided a silicone transfer film, wherein a silicone substrate
First coating layer that shows releasability to the skin, purification, antibacterial
Alternatively, a porous second material made of a material having a deodorizing function
Coat layer, silicone third coat layer, silicone
Sequentially laminated with a fourth coat layer of adhesive showing tackiness
The third coat is formed in the porous pores of the second coat layer.
Part of the coating layer penetrates, purifying, antibacterial or deodorant function
Is fixed to the bottom of the third coat layer
Be those who are, the third coating layer is characterized in that it is intended to be formed by coating the following silicone coating material. (A) a silicon compound represented by the general formula: Si (OR ¹ ) ₄ , (B) a silicon compound represented by the general formula: R ² Si (OR ¹ ) ₃ , wherein R ¹ and R ² are 1 (A) is an essential component, (A) is 20 to 200 parts by weight, and (B) is 1 part.
A silicone coating material which is contained at a ratio of 00 parts by weight and whose weight average molecular weight is 800 or more in terms of polystyrene.

The silicone transfer film according to claim 2 is the silicone transfer film according to claim 1 ,
The silicone coating material, in addition to the (A) (B), ( C) the general formula: R ² ₂ Si (OR ¹⁾ a silicon compound represented by the ₂ (wherein R ^1, R ² is a monovalent Represents a hydrocarbon group.)
It is characterized in that it is contained at a ratio of not more than parts by weight.

The silicone transfer film according to claim 3 is the silicone transfer film according to claim 1 or 2 , wherein the silicone coating material is
(A) Part or all of the silicon compound represented by the component is colloidal silica.

[0008] The silicone transfer film according to the fourth aspect exhibits releasability from silicone on the surface of the film substrate.
Has a first coat layer and a purifying, antibacterial or deodorizing function
Porous second coat layer made of a material
Third coat layer, adhesive showing adhesion to silicone
And a fourth coating layer of the agent.
Part of the third coat layer penetrates into the porous pores of the coat layer
In addition, the above materials with purification, antibacterial or deodorant functions
The third coat layer is fixed to the bottom of the three coat layer, and the third coat layer is formed by coating the following silicone coating material. (D) General formula: R ³ _k SiX _4-k (wherein, R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and k is an integer of 0 to 3) , X represents a hydrolyzable group) in a colloidal silica in which a hydrolyzable organosilane represented by the following formula (1) is dispersed in an organic solvent or water;
A silica-dispersed oligomer solution of an organosilane partially hydrolyzed under a condition using 0.5 mol; (E) average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (wherein R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b represent 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b, respectively.
It is a number that satisfies the relationship of <4. A) a silicone coating material containing, as essential components, a polyorganosiloxane containing at least a silanol group in its molecule, and (F) a curing catalyst.

[0009] The silicone transfer film according to claim 5 exhibits a peeling property to silicone on the surface of the film substrate.
Has a first coat layer and a purifying, antibacterial or deodorizing function
Porous second coat layer made of a material
Third coat layer, adhesive showing adhesion to silicone
And a fourth coating layer of the agent.
Part of the third coat layer penetrates into the porous pores of the coat layer
In addition, the above materials with purification, antibacterial or deodorant functions
The third coat layer is fixed to the bottom of the three coat layer, and the third coat layer is formed by coating the following silicone coating material in an emulsion form. (G) General formula R ⁶ _c SiO _d (OR ⁵ ) _e (OH) _f (wherein R ⁵ and R ⁶ represent a monovalent hydrocarbon group, and c, d,
e and f are respectively c + 2d + e + f = 4, 0 ≦ c <
3, 0 <d <2, 0 <e <4, and 0 <f <4. And (H) an emulsifier, and water, which are mixed with an organosiloxane partially hydrolyzed product having an average molecular weight of 600 to 5000 represented by the formula (1).

The silicone transfer film according to claim 6 is the silicone transfer film according to any one of claims 1 to 5, wherein the silicone coating material is
Average structural formula ^{_{H (R 7 2 SiO) m}} OH ( wherein shown below, R ⁷ represents a monovalent hydrocarbon group, m is 3 ≦ m ≦
It is a number that satisfies 100. ) Is contained.

The silicone transfer film according to claim 7 is the silicone transfer film according to claim 6 ,
The content of the linear polysiloxane diol in the silicone coating material is 0.1 to 100 with respect to the sum of the weight of silica in the silicone coating material as a condensed silicon compound and the weight of silica.
% By weight.

According to an eighth aspect of the present invention, there is provided the silicone transfer film according to any one of the first to seventh aspects, wherein the silicone coating material has the following general formula: CH ₂ = CR ⁸ (COOR ⁹ ) (COOR ⁹ ) In the formula, R ⁸ represents a hydrogen atom or a methyl group.), And R ⁹ is a substituted or unsubstituted carbon number of 1 to 9
At least one first acrylate or methacrylate which is a monovalent hydrocarbon group of the formula: and at least one second acrylate wherein R ⁹ is an epoxy group, a glycidyl group or a hydrocarbon group containing the same Acrylic resin obtained by co-polymerizing an ester or methacrylate with at least one third acrylate or methacrylate in which R ⁹ is a hydrocarbon group containing an alkoxysilyl group or a halogenated silyl group. It is characterized by containing a copolymer.

[0013] The silicone transfer film according to claim 9 is the silicone transfer film according to claim 8 ,
The content of the acrylic resin copolymer in the silicone coating material is 0.1 to 100% by weight based on the sum of the weight of silica in the silicone coating material as a condensed silicon compound and the weight of silica. It is characterized by the following.

[0014] Silicone transfer film according to claim 10 is the silicone transfer film according to any one claims 1 to 9, is characterized in that the silicone coating material contains a pigment.

According to an eleventh aspect of the present invention , in the silicone transfer film according to any one of the first to tenth aspects, the third coat layer is formed by coating a silicone adhesive. It is characterized by the following.

A silicone transfer film according to a twelfth aspect is the silicone transfer film according to any one of the first to eleventh aspects, wherein the first coat layer is formed by coating an addition condensation type silicone release agent. It is characterized by being.

A silicone transfer film according to a thirteenth aspect is the silicone transfer film according to any one of the first to twelfth aspects, wherein the second coat layer is formed by coating metal oxide fine particles having a photocatalytic function. A porous coating layer.

[0018] The silicone transfer film according to claim 14 is the silicone transfer film according to any one of claims 1 to 12 , wherein the second coating layer is formed by coating a powder containing a component having an elution-type antibacterial property. It is characterized by being a porous coat layer formed.

According to a fifteenth aspect of the present invention , in the silicone transfer film according to any one of the first to twelfth aspects, the second coat layer is formed by coating a flavone derivative. It is a feature.

[0020] According to a sixteenth aspect of the present invention, there is provided the transfer member according to the first aspect.
A transfer layer of the silicone transfer film according to any one of claims 15 to 15 is transferred to the surface of a transfer-receiving body.

[0021] According to a seventeenth aspect of the present invention, there is provided the transfer member according to the first aspect.
6. The transfer structure according to item 6 , wherein the object to be transferred is any one of a plastic molded body, a glass molded body, an inorganic molded body, a metal molded body, and a composite molded body thereof.

[0022] The transfer construct according to claim 18 is provided by claim 1.
6. The transfer structure according to 6 , wherein the object to be transferred is a plastic molded body, and the silicone transfer film is integrally formed on the surface of the plastic molded body when the plastic molded body is molded, and the transfer layer is transferred. It is characterized by the following.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the silicone transfer film of the present invention will be described in more detail.

The silicone transfer film according to the present invention comprises:
A first coat layer having a silicone release property on the surface of the film substrate, a porous second coat layer made of a material having a purifying, antibacterial or deodorizing function;
A coat layer and a fourth coat layer of an adhesive exhibiting adhesiveness to silicone are sequentially laminated, and a part of the third coat layer penetrates into the porous pores of the second coat layer. In addition, the material having the purifying, antibacterial or deodorizing function is fixed to the bottom of the third coat layer.

First, the film substrate will be described.
The above-mentioned film base material is first to first laminated on the surface thereof
As long as the support is a four-coat layer and has the strength to maintain the laminated body composed of these four coat layers, its transparency and coloring properties are not particularly limited. What is necessary is just to select a material excellent in durability against the diluting solvent used for the drying and the drying conditions. For example, polyethylene terephthalate (PET),
Polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), acrylic (PMMA), polyvinyl chloride (PVC), nylon, polyacrylonitrile, polycarbonate (PC), polyimide, etc. Can be mentioned. Among them, PE having a film thickness of 5 to 50 μm is used from the viewpoint of versatility, handleability, and availability.
T films are preferred.

Next, the first coat layer will be described. In the silicone transfer film of the present invention, the first coat layer is a coat layer that exhibits releasability from the silicone of the third coat layer. The silicone transfer film of the present invention peels off between the first coat layer and the third coat layer (including the second coat layer) to purify the second coat layer.
The third and fourth coats, which are transfer layers that are transferred to the surface of the object to be transferred in a state in which some or all of the material having an antibacterial or deodorizing function is fixed to the bottom of the third coat layer The layer and the film substrate are separated from each other, and a material having a purification, antibacterial or deodorizing function of the second coat layer is provided on the outermost layer of the transfer layer finally transferred on the surface of the transfer-receiving body. It will be distributed at high density. Therefore, this first
It is necessary that the coat layer has an adhesive force to the film substrate larger than the adhesive force to the second and third coat layers.

Examples of the material used for the first coat layer include a silicone release agent, an organically modified silicone release agent which is a copolymer with an organic resin such as an acrylic resin or an epoxy resin, a polyolefin release agent, and an alkyd resin release agent. And a fluororesin release agent. These release agents can be easily obtained as commercial products. Among the above-mentioned release agents, it is desirable to use a silicone-based release agent because of the wide selection range of the release performance.

The case where a silicone-based release agent is used as the first coat layer will be described. The silicone-based release agent contains a silanol group-containing polysiloxane as a base polymer and a polymethyl hydrogen siloxane as a crosslinking agent. Dehydrogenation condensation occurs in the presence of an organotin acylate catalyst, a condensation type that forms and cures a siloxane bond, and a polysiloxane containing a vinyl group as a base polymer, and polymethyl hydrogen siloxane as a cross-linking agent is blended. Causes an addition reaction,
There is an addition condensation type that forms a methylene bond and cures. Among them, in the present invention, it is desirable to form the first coat layer using the latter addition condensation type silicone release agent. That is, the first coat layer needs to maintain the performance of peeling the second and third coat layers after the formation of the second and third coat layers. For example, when a coating material containing a solvent is used, the first coating layer is required to be less susceptible to the organic solvent, and the addition condensation type silicone release agent is compared with the condensation type. This is because they have excellent coating film curability and are not easily attacked by organic solvents.

Next, the second coat layer will be described. The second coat is a porous thin layer made of a material having a purifying, antibacterial or deodorizing function. As a method for forming the second coat layer, for example, a powder of a material having a purifying, antibacterial or deodorizing function is dispersed in a dispersion medium such as water or an organic solvent, and this powder dispersion solution is applied to the first coat layer. It can be formed by coating on top. At this time, when the aqueous dispersion is applied on the second coat layer, the wettability, leveling property or drying property of the coated surface may be adjusted as necessary. In this case, for example, butyl carbitol, ethyl cellosolve, butyl cellosolve A small amount of an amphiphilic organic solvent such as isopropyl alcohol, diacetone alcohol, or an aqueous leveling agent may be added.

As an example of the material having a purifying, antibacterial or deodorizing function used as the material of the second coat layer, metal oxide fine particles having a photocatalytic function can be mentioned. Examples of the metal oxide fine particles having a photocatalytic function include, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, Examples thereof include copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, rhenium oxide, and a mixture of two or more of these. The size of the metal oxide fine particles is not particularly limited. For example, when it is desired to impart transparency to the obtained silicone transfer film, the average primary particle size is desirably 50 μm or less. Various metal oxide fine particles having a photocatalytic function are generally available as a commercial product, and the commercial product can be easily obtained not only as a powder but also as an aqueous dispersion. Generally, the aqueous dispersion contains 1 to 10% by weight of metal oxide fine particles as a solid content, and is acidic or basic and stably dispersed. Further, a dispersion of metal oxide fine particles to which a small amount of an aqueous inorganic binder has been added in order to reinforce the strength of the coating film is also commercially available.

Another example of a material having a purifying, antibacterial or deodorizing function used as the material of the second coat layer is a powder containing a component having an eluting antibacterial property. The component having the antibacterial performance of the elution type,
It is included as one component in the powder, and gradually elutes out of the system to exhibit its antibacterial performance.For example, silver, copper, zinc, nickel, palladium, platinum,
Gold, cadmium, mercury, cobalt, rhodium and the like. These components can be obtained in a state of being dispersed and supported on a porous powder such as zeolite, activated alumina, and silica gel. Generally, the particle size is relatively large, from 1 to 50 μm, and can be easily dispersed in water or an organic solvent by mixing with various dispersing agents. Still another example of a material having a deodorizing function includes a flavone derivative. This flavone derivative incorporates malodorous components typified by hydrogen sulfide, trimethylamine, acetaldehyde, and the like into its large molecular structure. There is a deodorizing effect to convert to. A commercially available product of this flavone derivative can be easily obtained as an aqueous dispersion having a solid content of 1 to 10% by weight.

Next, the third coat layer will be described. When the silicone transfer film of the present invention is transferred to the surface of the transfer object, the third coat layer is peeled off from the first coat layer and transferred to the surface of the transfer object as a protective coat layer. It is. The third coat layer can be formed by coating a silicone coating material on the second coat layer.
A part of the silicone coating material penetrates into the second coat layer, and the material having a purification, antibacterial or deodorizing function constituting the second coat layer has a high density on the second coat layer side surface portion of the third coat layer. It becomes immobilized. Examples of the silicone coating material include, for example, the following (1)
To (3) are exemplified.

(1) Silicone coating material This silicone coating material is, as described in claim 1 , (A) a silicon compound represented by the general formula: Si (OR ¹ ) ₄ , (B) a general formula: R ² As an essential component, a silicon compound represented by Si (OR ¹ ) ₃ (wherein R ¹ and R ^{2 each} represent a monovalent hydrocarbon group), 20 to 200 parts by weight of (A), and (B) 10
0 parts by weight, and the weight average molecular weight is
It is prepared to be 800 or more in terms of polystyrene. Further the silicone coating material, in addition to the (A) (B), ( C) the general formula; R ² ₂ Si (OR ¹⁾ a silicon compound represented by the ₂ (wherein, R ^1, R ² is 1 (Indicating a monovalent hydrocarbon group) at a ratio of not more than 60 parts by weight with respect to the above (A) and (B), and in this case, the formed third coat layer does not contain (C) It results in a silicone layer that is relatively more flexible than the one.

The silicon compounds represented by the above components (A), (B) and (C) used in the silicone coating material are all represented by the following general formula R ² _n Si (OR ¹ ) _4-n (where n = 0-2) (I) In formula (I), but R ^1, R ² is not limited particularly as long as both a monovalent hydrocarbon group, R ²
Is practically a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group Groups; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; halogens such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group Substituted hydrocarbon group and γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ
-A substituted hydrocarbon group such as a mercaptopropyl group can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis and availability. R ¹ has 1 carbon atom
It is practical to be an alkyl group of ~ 4, for example,
Examples of the tetraalkoxysilane of n = 0 as the component (A) include tetramethoxysilane and tetraethoxysilane, and examples of the organotrialkoxysilane of n = 1 as the component (B) include methyltrimethoxysilane and Examples thereof include methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxylane, and the like. Examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. R ¹ and R ² may be the same or different for each component (A), (B) and (C).

This silicone coating material is prepared by, for example, diluting each raw material silicon compound component with an appropriate solvent, adding water and a catalyst as necessary in a required amount to the hydrolysis and polycondensation reaction. The prepolymer is prepared such that the molecular weight of the prepolymer is 800 or more in terms of polystyrene in terms of Mw (molecular weight weight average). When the molecular weight distribution of the prepolymer is smaller than this value, curing shrinkage during polycondensation tends to increase, and cracks tend to occur in the coating film after baking.

The component (A) may be partially or wholly used as colloidal silica. In this case, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used as the colloidal silica. Generally, such colloidal silica has a solid content of 20 to 5 silica.
It contains 0% by weight. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent as described later.
These are usually made from water glass, but such colloidal silica is readily available commercially.
The organic solvent-dispersed colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersed colloidal silica can be easily obtained as a commercial product, similarly to the water-dispersed colloidal silica. The type of organic solvent in which the colloidal silica is dispersed includes, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol;
Ethylene glycol derivatives such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; derivatives of diethylene glycol such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. Can be
One or more selected from the group consisting of these 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 case of a silicone coating material, water is used as a curing agent. The amount is preferably 45% or less, more preferably 25% or less, by weight in the silicone coating material. .

In the case of the silicone coating material, the concentration can be appropriately adjusted using a diluting solvent.
As the diluting solvent, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, etc., which are shown as the dispersion solvent of the above colloidal silica; ethylene glycol Glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate and the like; ethylene glycol derivatives; diethylene glycol, diethylene glycol monobutyl ether;
Examples thereof include derivatives of diethylene glycol such as ter and diacetone alcohol, and one or more selected from the group consisting of these. 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 mentioned.

Further, in this silicone coating material, it is preferable to adjust its pH value to a range of 3.8 to 6. By setting the pH value in this range, the silicone coating material can be used stably within the above-mentioned range of molecular weight. On the other hand, when the pH value is out of the above range, the stability of the silicone coating material is reduced, so that the usable period from the time of preparing the coating material is limited. Here, the method of adjusting the pH is not particularly limited. For example, when the pH becomes 3.8 or less at the time of mixing the raw materials of the silicone coating material, the pH is adjusted within a range using a basic reagent such as ammonia. The pH may be adjusted to a pH of 6. When the pH becomes 6 or more, the pH may be adjusted using an acidic reagent such as hydrochloric acid, for example. Also, pH
In some cases, when the reaction does not proceed while the molecular weight is small and it takes time to reach the above molecular weight range, the raw material mixture of the silicone coating material may be heated to accelerate the reaction, After the reaction is advanced by lowering the pH with a reagent, the pH may be returned to a predetermined pH with a basic reagent.

[0040] (2) Silicone coating material The silicone coating material, as indicated in claim 4, (D) the general ^{_{formula: R 3 k SiX 4-k}} ······ (II) ( wherein, R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, k represents an integer of 0 to 3, and X represents a hydrolyzable group. In a colloidal silica obtained by dispersing silane in an organic solvent or water, water is used in an amount of 0.001 to 0.001 molar equivalent.
A silica-dispersed oligomer solution of an organosilane partially hydrolyzed under the condition of using 0.5 mol, (E) average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2.} (III) (wherein, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b represent 0.2 ≦ a ≦ 2, 0.0001, respectively) ≦ b ≦ 3, a + b
It is a number that satisfies the relationship of <4. ), A polyorganosiloxane containing at least a silanol group in its molecule, and (F) a curing catalyst.

First, the component (D) will be described. In this silicone coating material, the silica-dispersed oligomer as the component (D) is a main component of a base polymer having a hydrolyzable group as a functional group which is subjected to a curing reaction in a coating form. In this method, one or two or more of hydrolyzable group-containing organosilanes represented by the general formula (II) are added to colloidal silica dispersed in an organic solvent or water, and water in the colloidal silica or separately added. The hydrolyzable organosilane is obtained by partially hydrolyzing the hydrolyzable organosilane with water.

The hydrolyzable organosilane is described below. In the general formula (II), R ³ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as a methyl group or an ethyl group. , Propyl group, butyl group, pentyl group,
Chain alkyl groups such as hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; phenyl group and tolyl group Aryl groups; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3,
Halogen-substituted hydrocarbon groups such as 3-trifluoropropyl group; and substituted hydrocarbon groups such as γ-methacryloxypropyl group and γ-mercaptopropyl group. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable in terms of ease of synthesis or availability. As X of the hydrolyzable group, for example, an alkoxy group, an acetoxy group, an oxime group, an enoxy group,
Examples include an amino group, an aminoxy group, and an amide group.
An alkoxy group is preferred because of its availability and ease of preparing a silica-dispersed oligomer solution.

Examples of the organosilane containing a hydrolyzable group include mono-, di-, tri- and tetra-functional alkoxysilanes in which k in the general formula (II) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferred because they are easily available and the silica-dispersed organosilane oligomer solution is easily prepared. As the alkoxysilanes, in particular, k = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having k = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane of k = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane, and k = 3 triorganoalkoxysilane. Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysila. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

In the component (D), at least 50 mol% of the hydrolyzable group-containing organosilane represented by the general formula (II) must be a trifunctional one represented by k = 1. And more preferably at least 60 mol%,
Most preferably, it is 70 mol% or more. For example, if the content is less than 50 mol%, sufficient coating film hardness cannot be obtained, and dry curability tends to be inferior.

In the silicone coating material,
The colloidal silica in the component (D) has the effect of increasing the hardness of the cured film of the silicone coating material and improving the smoothness and crack resistance. As the colloidal silica, those similar to those described in the description of the silicone coating material can be used. Here, when water-dispersed acidic colloidal silica is used as the colloidal silica, water present as a component other than the solid content can be used as a curing agent as described later.
In the component (D), the colloidal silica is preferably contained in a range of 5 to 95% by weight as a silica solid content, more preferably 10 to 90% by weight, and most preferably 20 to 85% by weight. It is. For example, if the content is less than 5% by weight, a desired coating hardness cannot be obtained, and if it exceeds 95% by weight, it is difficult to uniformly disperse silica, and the component (D) causes inconvenience such as gelation. There is.

The silica-dispersed oligomer in the component (D) can be usually obtained by partially hydrolyzing a hydrolyzable group-containing organosilane in water-dispersed colloidal silica or organic solvent-dispersed colloidal silica. The amount of water used to partially hydrolyze the hydrolyzable organosilane is 0.1 mol of water per 1 mol equivalent of the hydrolyzable group (X).
It is good to be 001-0.5 mol. For example, if the amount of water used is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. The method for the partial hydrolysis is not particularly limited, and the hydrolyzable organoalkoxysilane and the colloidal silica may be mixed and a necessary amount of water may be added and blended. At this time, the partial hydrolysis reaction proceeds at room temperature. . In order to promote the partial hydrolysis reaction, 60 to 1
It may be heated to 00 ° C, and for the purpose of further promoting the partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, Organic acids and inorganic acids such as glycolic acid, maleic acid, malonic acid, toluenesulfonic acid and oxalic acid may be used as the catalyst.

The component (D) has a pH of 2.0 to 7.0, preferably 2.
It is good to be 5-6.5, more preferably 3.0-6.0. When the pH is out of this range, the amount of water used becomes particularly (I
In the case of 0.3 mol or more with respect to 1 mol equivalent of the substituent X in the formula (I), the long-term degradation of the component (D) is remarkable. When the pH of the component (D) is out of this range, if it is more acidic than this range, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. And an acidic reagent such as acetic acid. In addition,
The adjustment method is not particularly limited.

Next, the component (E) will be described. As described above, this component (E) has an average compositional formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (wherein R ⁴ is the same or different substituted or unsubstituted carbon number) And a and b represent 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b, respectively.
It is a number that satisfies the relationship of <4. ) Is a polyorganosiloxane containing a silanol group in the molecule represented by

Examples of R ^{4 in the} formula include the same as R ³ in the above formula (II), preferably, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, and γ-glycidoxy. Substituted hydrocarbon groups such as propyl group, γ-methacryloxypropyl group, γ-aminopropyl group and 3,3,3-trifluoropropyl group, more preferably methyl group and phenyl group. Further, a and b in the formula (III) are numbers satisfying the above relationship, respectively. If a is less than 0.2 or b exceeds 3, there is a disadvantage that cracks occur in the cured film, and a More than 2 and less than 4 or b
If it is less than 0.0001, curing does not proceed well. Such a silanol group-containing polyorganosiloxane can be obtained in a large amount by a known method using one or a mixture of two or more of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and the corresponding alkoxysilane. Can be obtained by hydrolysis with water. When a silanol group-containing polyorganosiloxane is hydrolyzed by a known method using alkoxysilane, a small amount of unhydrolyzed alkoxy group may remain. In other words, silano
In some cases, a polyorganosiloxane in which a hydroxyl group and a trace amount of an alkoxy group coexist can be obtained, but such a polyorganosiloxane may be used.

The curing catalyst, which is the component (F), promotes the condensation reaction between the components (D) and (E) to cure the coating as described above. Such catalysts include metal salts of carboxylic acids such as alkyl titanates, tin octylate and dibutyltin dilaurate, dioctyltin dimalate; dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine Amine salts such as acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl Amine-based silane coupling agents such as -γ-aminopropylmethyldimethoxysilane; p-toluenesulfonic acid, phthalic acid,
Acids such as hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali catalysts such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; methyltrichlorosilane, dimethyldichlorosilane, trimethyl Examples thereof include halogenated silanes such as monochlorosilane and the like, but there is no particular limitation as long as they are effective for the condensation reaction between the component (D) and the component (E).

The mixing ratio of the component (D) and the component (E) is such that the component (E) 99
To 1 part by weight, and more preferably 5 to 95 parts of component (D).
95 to 5 parts by weight of component (E), most preferably 10 to 90 parts by weight of component (E)
0 to 10 parts by weight. If the component (D) is less than 1 part by weight, the curability at room temperature is inferior, and a sufficient film hardness cannot be obtained. On the other hand, if it exceeds 99 parts by weight, the curability is unstable and a good coating film may not be obtained.

The addition amount of the curing catalyst as the component (F) is preferably 0.0001 to 10% by weight, and more preferably 100% of the total amount of the components (D) and (E). Is 0.0005 to 8% by weight, most preferably 0.0007 to 5% by weight.
If it is less than 0.0001% by weight, it will not cure at room temperature. Also,
If it exceeds 10% by weight, heat resistance and weather resistance deteriorate.

The hydrolyzable group contained in the silica-dispersed oligomer of the component (D) and the silanol group of the component (E) are
By heating at room temperature or low temperature in the presence of the curing catalyst (F), a condensation reaction occurs to form a cured film. Therefore, the silicone coating material is hardly affected by humidity even when it is cured at room temperature. In addition, a heat treatment can promote a condensation reaction to form a cured film.

This silicone coating material can be used after being diluted with various organic solvents for ease of handling. The type of the organic solvent used at this time can be selected according to the type or the molecular weight of the monovalent hydrocarbon group of the component (D) or the component (E). -Lower alcohols such as ethanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and the like. Derivatives of diethylene glycol such as diethylene glycol, diethylene glycol monobutyl ether and the like, and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol - It can be used more than one or two selected from the group consisting.

[0055] (3) Silicone coating material silicone coating material, as indicated in claim 5, (G) the formula _{^{R 6 c SiO d (OR 5}} ) e (OH) f ······ (IV) (Wherein, R ⁵ and R ⁶ represent a monovalent hydrocarbon group, and c, d,
e and f are respectively c + 2d + e + f = 4, 0 ≦ c <
3, 0 <d <2, 0 <e <4, and 0 <f <4. And (H) an emulsifier, and water are mixed to form an emulsion.

First, the component (G) will be described. The component (G) is, for example, a partially hydrolyzed product represented by the following general formula: R ⁶ _n Si (OR ⁵ ) _4-n (n = 0 to 3) (V) It can be obtained by adding water, a catalyst and, if necessary, an appropriate organic solvent to at least one decomposable organoalkoxysilane, and partially hydrolyzing the hydrolyzable organoalkoxysilane. Here, R ⁵ and R ⁶ represent a monovalent hydrocarbon group, and may be the same or different. The R ⁵ and R ¹ shown by silicone coating material, R ⁶ may be similar to the R ² shown in silicone coating material.

The amount of water required for the component (G) is determined by the OR ^{5 of the} hydrolyzable organoalkoxysilane represented by the formula (V).
It is necessary to be in the range of 0.3 to 2.0 mol per 1 mol equivalent of the group, and more preferably 0.4 to 1.0 mol. When the amount of water is less than 0.3 mol, the disadvantage that the low molecular weight silicone compound in the molecular weight distribution of the component (G) is removed out of the system together with the organic solvent when the organic solvent is removed. On the other hand, when the amount of water exceeds 2.0, the storage stability of the component (G) is lowered, and there is a possibility of gelation. When preparing the component (G), the pH may be adjusted as necessary. The catalyst used to partially hydrolyze the hydrolyzable organoalkoxysilane is not particularly limited. Examples of the acidic catalyst include water-soluble acids such as hydrochloric acid and nitric acid, and acidic colloidal silica described below. Examples of the basic catalyst include an aqueous ammonia solution and basic colloidal silica. The lower aliphatic alcohol generated in the partial hydrolysis is an amphipathic solvent, and reduces the stability of the emulsion.

Further, c, d, e and f in the above formula (IV)
Is, as described above, c + 2d + e + f = 4,
It is a number that satisfies 0 ≦ c <3, 0 <d <2, 0 <e <4, and 0 <f <4. When c is 3 or more, there is an inconvenience that curing of the coating film does not proceed well. e and f
Must be numbers that exceed 0. f = 0
In the case of the above, the molecular terminal is only a hydrophobic group of R ⁶ group and OR ⁵ group, which is advantageous for the long-term stability of the emulsion.
Since the OR ⁵ group lacks crosslinking reactivity during curing of the coating film, a sufficient cured film cannot be obtained. Also,
When e = 0, the terminal of the molecule is an R ⁶ group and an OH group which is a hydrophilic group, so that the hydrophilicity of the whole molecule is increased and the long-term stability of the emulsion is obtained. The average molecular weight of the component (G) needs to be in the range of 600 to 5,000. When the average molecular weight is less than 600, there are disadvantages such as generation of cracks in the cured coating film, and when it exceeds 5,000, the curing does not proceed properly.

The component (H) is an emulsifier for dispersing the component (G) as an emulsion in water. As the emulsifier used in the present invention, general protective colloids and / or surfactants are used. As protective colloids, for example, polyvinyl alcohol, modified polyvinyl alcohol, ethyl cellulose, methyl cellulose, water-soluble cellulose derivatives such as hydroxy cellulose, starch, agar, gelatin, gum arabic, alginic acid, styrene maleic anhydride copolymer salts, maleated polybutadiene derivatives , Naphthalenesulfonic acid condensate, polyacrylate, acrylamide, acrylate, and the like. Surfactants include alkyl benzene sulfonates, alkyl naphthalene sulfonates, fatty acid salts, rosinates, dialkyl sulfosuccinates, hydroxyalkane sulfonates, alkane sulfonates, alkyl sulfates, alkyl phosphates Or polyoxyethylene alkyl allyl ethyl sulfate, alkylamine salt, dialkylamine salt, tetraalkylammonium salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan aliphatic ester, oxyethylene -Oxypropylene copolymer, polyhydric alcohol fatty acid partial ester, polyoxyethylenated polyhydric alcohol aliphatic ester, and the like. These substances may be used alone or in combination.

The amount of the emulsifier is 1 to 30 with respect to the component (G).
% By weight, more preferably 2 to 15% by weight. For example, if the amount of the emulsifier is less than 1% by weight, emulsification cannot be performed, while if it exceeds 30% by weight, the curability and weather resistance of the coating are impaired.

The silicone coating material is obtained by partially hydrolyzing the organosiloxane of the above component (G),
It is prepared by mixing and stirring the emulsifier of component (H) and water to form an emulsion. The amount of water used at this time is desirably 50 to 90% by weight based on the total amount of the silicone coating material. When the amount of water is out of this range, the stability of the emulsion is reduced, and disadvantages such as generation of a precipitate are caused. The stirring method at this time, the so-called emulsification method, is not particularly limited, and emulsification can be performed by a conventionally known emulsification method. For example, there is a method in which the component (G), the component (H), and water are uniformly mixed and then emulsified using an emulsifier such as a homogenizer or a homomixer.

Further, the silicone coating material may contain colloidal silica. The colloidal silica imparts excellent film forming properties to the coating film and has an effect of increasing the hardness of the coating film. In this case, the content of the colloidal silica is based on the weight obtained by converting the component (G) as R ⁶ _c SiO _{(4-c) / 2} .
The colloidal silica has a weight of 5 to 10 as a silica component.
It is desirably in the range of 0% by weight. That is, if the content of colloidal silica is less than 5% by weight in terms of silica, the desired coating film strength cannot be obtained. This is because such inconveniences may be caused.

In this case, as the colloidal silica that can be used, those dispersed in water or those dispersed in a non-aqueous organic solvent such as alcohol can be used.
When colloidal silica dispersed in water is used, there is an advantage that it can be directly introduced into an emulsion since it is an aqueous system. On the other hand, when colloidal silica dispersed in a non-aqueous organic solvent is used, the stability of the emulsion is reduced, so that it cannot be directly introduced into the emulsion.
When used as a reaction catalyst for the hydrolyzable organoalkoxysilane represented by the formula (V), it can be obtained as a mixed composition of the component (G) and colloidal silica dispersed in a non-aqueous organic solvent. If this organic solvent is removed, emulsification as a mixed composition of component (G) and colloidal silica becomes possible. In addition, the colloidal silica dispersed in water, which exists as a component other than the solid content, can be used as a curing agent for the hydrolyzable organoalkoxysilane represented by the formula (V).

If necessary, a curing catalyst may be added to the emulsion-like silicone coating material in order to accelerate the curing of the coating film. These include metal salts of carboxylic acids such as alkyl titanates, tin octylate, tin laurate, iron octylate, lead octylate, dibutyltin dilaurate, dioctyltin dimaleate; tetraisopropyl titanate, tetrabutyl Titanium compounds such as titanate and titanium tetraacetylacetonate; amine compounds such as n-hexylamine, guanidine, dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate, and hydrochlorides thereof; . When these curing catalysts are used, it is desirable to prepare an emulsion using an emulsifier and water in advance by a conventional method. When diluting, water is desirable, but if necessary, a small amount of a relatively high boiling organic solvent such as butyl carbitol, ethyl cellosolve, butyl cellosolve, etc. may be added to adjust the leveling property or drying property of the coated surface. Good.

[0065] above, the (1) has been described to (3), respectively silicone coating material - at about, these include the average compositional formula H further illustrated in the following ^{_{(R 7 2 SiO) m OH}} ····· -A linear polysiloxane diol represented by the formula (VI) may be contained.

M in the formula (VI) satisfies m ≧ 3, preferably 10 to 100. R ⁷ in the formula is the same as R ³ shown for the silicone coating material. Since this linear polysiloxane diol has no reactive group other than the terminal OH group, it is a molecule having relatively poor reactivity. Therefore, the linear polysiloxane diol blended in each of the silicone coating materials lacks complete compatibility in the coating material and is dispersed as ultrafine particles, so that the linear polysiloxane diol can be easily coordinated and singly formed on the surface of the coating film. Although a molecular layer is formed, the terminal OH group finally undergoes a condensation reaction with the bulk resin and is fixed on the surface of the coating film. As a result, there is an effect of being localized on the R ⁷ base surface and improving the releasability from the first coat layer. Those having a relatively small m in the formula have excellent compatibility, so that they not only form a layer on the surface of the coating film but also are incorporated into the bulk to give flexibility to the coating film, which also leads to a crack preventing effect. The content of the linear polysiloxane diol is based on the sum of the weight of silica and the weight of silica in each of the silicone coating material and the condensed silicon compound.
Preferably it is 0.1 to 100% by weight. When the content of the linear polysiloxane diol is less than 0.1% by weight, the releasability is weakly expressed, and when the content exceeds 100% by weight, it becomes a factor of inhibiting the curing of the coating film.

Further, a silicone coating material
Has the following general formula: CH ₂ CR ⁸ (COOR ⁹ ) (VII) (wherein, R ⁸ represents a hydrogen atom or a methyl group), and R ⁹ is Substituted or unsubstituted carbon number 1-9
At least one first acrylate or methacrylate which is a monovalent hydrocarbon group of the formula: and at least one second acrylate wherein R ⁹ is an epoxy group, a glycidyl group or a hydrocarbon group containing the same Acrylic resin obtained by copolymerizing an ester or methacrylate with at least one third acrylate or methacrylate in which R ⁹ is a hydrocarbon group containing an alkoxysilyl group or a halogenated silyl group. A copolymer may be contained.

This acrylic resin copolymer has the effect of improving the toughness of the coating film of the silicone coating material, preventing cracks in the third coat layer against deformation such as bending and bending of the base film, It has the property of making the three-coat layer thicker.

As described above, this acrylic resin copolymer is a copolymer of the first, second and third acrylates or methacrylates. The first acrylate or methacrylate is (VI
I) In the formula, R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, i Alkyl groups such as -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; 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. Also, the second acrylate or methacrylate is
(VII) R ⁹ in the formula is at least one of epoxy groups, glycidyl groups or hydrocarbon groups containing them, for example, γ-glycidoxypropyl group. The third acrylate or methacrylate is (VI
I) wherein R ⁹ in the formula is a hydrocarbon group containing an alkoxysilyl group or a halogenated silyl group, for example, trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichloro It is at least one of silylpropyl group, dichloromethylsilylpropyl group and chlorodimethylsilylpropyl. The acrylic copolymer is a copolymer of an acrylic ester or a methacrylic ester containing at least one kind in the first, second and third acrylic esters or methacrylic esters, respectively, and a total of at least three or more in total. And one or more of the first, second and third acrylates or methacrylates.
It may be a copolymer containing at least one or more acrylates or methacrylates other than those described above.

The first acrylic acid ester or methacrylic acid ester may be a silicone coating material or
Is a component necessary for improving the toughness of the coating film. For this purpose, the substituted or unsubstituted hydrocarbon group of R ⁹ preferably has a certain volume or more, and preferably has 2 or more carbon atoms. The second acrylate or methacrylate is a component necessary for improving the adhesion between the third coat layer formed by coating the silicone coating material and the third coat layer made of an adhesive. It is. When the third acrylate or methacrylate is contained in the silicone coating material, the silicone coating material is added between the acrylic resin copolymer and each of the components (A), (B) and (C) when the coating film is cured. When it is contained in the coating, the acrylic resin copolymer is chemically bonded to the component (D) and the component (E) when the coating is cured, whereby the acrylic resin copolymer is fixed in the coating. Be transformed into The third acrylate or methacrylate also has the effect of improving the compatibility of each component in each of the silicone coating materials.

The molecular weight of the acrylic resin copolymer greatly affects the compatibility with the components (D) and (E) when it is contained in a silicone coating material. If the average molecular weight in terms of polystyrene of the acrylic resin copolymer exceeds 50,000, phase separation may occur and the coating film may be whitened. Therefore, it is desirable that the average molecular weight in terms of polystyrene of the acrylic resin copolymer is 50,000 or less. The lower limit of the average molecular weight in terms of polystyrene of the acrylic resin copolymer is preferably 1,000. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease and cracks tend to occur, which is not preferable. The third acrylic acid ester or methacrylic acid ester having an alkoxysilyl group or a halogenated silyl group is desirably in a range of 2 to 50% by weight in terms of a monomer molar ratio in the copolymer.
If it is less than 2%, the compatibility between the acrylic resin copolymer and the components (D) and (E) is poor, and the coating film may be whitened. On the other hand, if it exceeds 50% by weight, the bond density between the acrylic resin copolymer and the components (D) and (E) becomes too high, and improvement in toughness, which is the original purpose of adding the acrylic resin copolymer, is observed. I can't. As a method for synthesizing this acrylic resin copolymer, a known radical polymerization method by solution polymerization, emulsion polymerization, or suspension polymerization in an organic solvent, or an anion polymerization method or a cationic polymerization method can be used.

The content of the acrylic copolymer is preferably from 0.1 to 100% by weight based on the sum of the weight of silica converted as a condensed silicon compound and the weight of silica in the silicone coating material. When the content is less than 0.1% by weight, the toughness is weakly expressed, and
If the content exceeds 00% by weight, curing of the coating film will be inhibited.

The silicone coating material can further contain a pigment. Examples of pigments to be added at this time include organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide,
Inorganic pigments such as barium sulfate, red iron oxide, and composite metal oxides are preferable, and one or two or more selected from these groups may be used in combination. Pigment dispersion in a silicone coating material may be carried out by a method of directly dispersing pigment powder using a normal dyno meal or paint shaker.However, in an emulsion silicone coating material, a method of directly dispersing pigment powder using a dyno meal or a paint shaker may be used. The emulsion is destroyed,
Since there is a possibility that inconveniences such as phase separation, gelation, and precipitation may occur, a method of adding a pigment base obtained by dispersing a pigment in water at a high concentration via a dispersant to an emulsion and appropriately stirring the emulsion is desirable. Commercially available pigment bases are readily available.
In addition to the pigments, dyes, metal powders, glass powders, inorganic antibacterial agents, ultraviolet absorbers, antistatic agents, and the like can be added to the silicone coating material.

Next, the fourth coat layer will be described. The fourth coat layer is an essential coat layer for peeling off the third coat layer from the first coat layer to transfer and adhere to the surface of the transfer-receiving body. The adhesive used for the fourth coat layer is
The type is not limited as long as it is in close contact with the silicone third coat layer. For example, polyisoprene-based pressure-sensitive adhesive, styrene-
Butadiene random copolymer adhesive, styrene-isoprene block copolymer adhesive, butyl rubber adhesive,
Various adhesives such as a polyisobutylene adhesive, an acrylic adhesive, and a silicone adhesive can be used. These adhesives can be easily obtained as a commercial product. The adhesive strength may be selected according to the material of the transfer substrate.

In particular, among the above-listed pressure-sensitive adhesives, the use of a silicone pressure-sensitive adhesive has the strongest adhesion to the third coat layer formed by using the above-mentioned silicone coating materials than the other pressure-sensitive adhesives. Is preferred because it has the effect of showing Further, in order to apply a silicone protective film having excellent durability, which is the object of the present invention, to the surface of the transfer-receiving body,
The third coat is also required to have weather resistance, and in this respect, the silicone pressure-sensitive adhesive is more effective than other pressure-sensitive adhesives in terms of weather resistance and is effective. This silicone pressure-sensitive adhesive is, for example, a high-polymerization degree dimethyl or diphenyl silicone rubber as a base polymer and a low polymerization degree bistrimethoxysiloxysiloxane or other silicone resin as a softening agent bonded together, and a peroxide such as benzoyl peroxide. It is formed by crosslinking. This silicone adhesive is easily available as a commercial product.

The silicone transfer film of the present invention can be obtained by successively repeating liquid coating and drying on a film base material serving as a support base to sequentially form first to fourth coat layers. In forming these first to fourth coat layers, the coating method of the coating material is not particularly limited. For example, a gravure roll coater, a gravure offset roll coater,
Micro gravure roll coater, drawing roll coater, air knife coater, reverse roll coater,
Bar coater, die coater, fountain coater,
Various coating methods such as a commercialer, spray, dipping, and flow can be selected. At this time, a leveling agent may be added as needed. Drying conditions may be appropriately determined according to the heat-resistant temperature of the film substrate, and for example, room temperature drying may be used. The thickness of the coating film is not particularly limited, but the first coating layer is preferably thinner as long as it exhibits releasability, for example, 0.01 to 10 μm.
The thickness of the third coating layer is preferably in the range of 0.1 to 20 μm when using a silicone coating material, for example, in order to follow the deformation during transfer without causing cracks. 0.
1 to 15 μm is desirable. In addition, as the third coat layer,
When using a silicone coating material containing the above-mentioned linear polysiloxane diol or acrylic resin copolymer to improve its peelability, crack prevention and flexibility, the thickness of the coating film is relatively thick For example, the thickness may be in the range of 0.1 to 50 μm, and more preferably 0.1 to 30 μm in order to follow the deformation during transfer without generating cracks. The thickness of the third coat layer is desirably 0.1 to 50 μm in order to maintain the adhesive force of the third coat layer on the substrate to be transferred for a long time.

Next, the transfer member according to the present invention will be described. The transfer structure according to the present invention is obtained by transferring the above-described transfer layer of the silicone transfer film, that is, the third and fourth coat layers, onto the surface of the transfer object. In transferring the transfer layer of the silicone transfer film to the surface of the transfer object, first, the fourth coat layer of the silicone transfer film is pressed along the surface of the transfer object as a close contact surface. Then, the silicone transfer film is adhered to the surface of the object to be transferred by the adhesive force of the adhesive constituting the fourth coat layer. Thereafter, when the film substrate is peeled off, the interlayer between the first coat layer and the third coat layer is removed. Then, the transfer layer having the third coat layer as the front side is transferred to the surface of the transfer object. Thus, in the transfer structure, only the transfer layer is formed on the surface as a protective film by removing the film base material as the support base, and at this time, the surface layer of the third coat layer Part 2
The material having the purification, antibacterial or deodorant function that constituted the coat layer is fixed at a high density and is exposed on the surface of the transfer member, and an excellent antibacterial or deodorant function is provided, The third coat layer has excellent durability without impairing its function as a silicone protective coat layer.

The material to be transferred is not particularly limited, and can be transferred to an article made of various materials. Plastic moldings; various glass moldings such as sodium soda glass, pyrex glass, quartz glass; fiber reinforced cement boards, ceramic siding boards, wood wool cement boards, pulp cement boards, slate / wood wool cement laminate boards, plaster boards, Inorganic molded products such as clay roof tiles, thick slate, ceramic tile, water glass decorative plate; rolled steel plate, aluminum and aluminum alloy plate, hot-dip galvanized steel plate, rolled stainless steel plate, tin plate, etc .; Composite molded articles can be mentioned.

Further, the shape of the object to be transferred is preferably a shape having a smooth surface to be transferred, such as a plate or a sheet, in consideration of ease of transfer, but is not particularly limited. There is no problem if the transfer layer can be transferred along the silicone transfer film even if the transfer surface has irregularities. In particular, when the object to be transferred is a plastic molded body, when the raw material resin is molded into a predetermined shape, the silicone transfer film is set in the mold in advance and simultaneously molded integrally, thereby relatively It is possible to transfer to a complicated surface. Specifically, the film base side of the silicone transfer film is desired on the cavity surface of the female mold for vacuum molding or injection molding, and then the film softened by heating is adhered to the molding surface of the female mold by decompression. Then, the molten resin is injected together with the male mold, and the resin film and the transfer film formed into a predetermined shape may be integrated.

According to the silicone transfer film of the present invention, a silicone protective coat layer can be provided on the surface of a transfer-receiving material by a transfer method, so that the work is less troublesome than a conventional coating method. Also, there is no danger of the transfer object being attacked by the solvent, etc. At the same time, the top surface of the silicone protective coat layer transferred to the transfer object surface is made of a high-density material with a purifying, antibacterial or deodorizing function. Since it is immobilized and exposed, a superior antibacterial or deodorant function can be imparted.

[0081]

The present invention will be described below in detail with reference to examples and comparative examples.

In the examples and comparative examples shown here, all “parts” represent “parts by weight” and all “%” represent “% by weight”. The molecular weight is GPC
(Gel permeation chromatography)
A calibration curve was prepared with standard polystyrene using HLC8020 manufactured by Tosoh Corporation as a measurement model, and measured as converted values.

(1) Preparation Example of Silicone Coating Material (Preparation Example 1-1) IPA organosilica sol which is an acidic colloidal silica as a component (A) (trade name: O, manufactured by Catalyst Chemical Industry Co., Ltd.)
SCAL1432, solid content 30%), 60 parts of methyltrimethoxysilane as the component (B), and 30 parts of dimethyldimethoxysilane as the component (C).
And then diluted with 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA), and 39 parts of water was further added and stirred. The obtained mixture was heated in a thermostat at 60 ° C. to adjust the molecular weight to Mw = 1200 to obtain a silicone coating material. The silicone coating material obtained here is called (1-1).

(2) Preparation Example of Silicone Coating Material First, a preparation example of the component (D) will be described.

(Preparation Example D-1) In a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, IPA-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-ST, particle size) 10-20 nm, solid content 30%, moisture 0.5%)
100 parts and methyltrimethoxysilane 68 parts,
10.8 parts of water was charged, and a partial hydrolysis reaction was carried out at a temperature of 65 ° C. for about 5 hours while stirring, followed by cooling to obtain a component (D). This had a solid content of 36% when left at room temperature for 48 hours. The component (D) obtained here is referred to as (D-1). The preparation conditions for (D-1) are as follows. -Number of moles of water based on 1 equivalent of hydrolyzable group methyltrimethoxysilane----0.4 mol-Water content of silica in solids of component (D)---47.3%-n = Next, an example of preparing the component (E) will be described.

(Preparation Example E-1) In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene were weighed and mixed. While stirring in the solution, 108 parts of a 1% aqueous hydrochloric acid solution was added dropwise over 20 minutes to hydrolyze methyltriisopropoxysilane. Forty minutes after the completion of the dropwise addition, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand to separate into two layers. The lower layer mixture of water / isopropyl alcohol containing hydrochloric acid was separated and removed. Then, the remaining hydrochloric acid in the resin solution of toluene was removed by washing with water, and the toluene was further removed under reduced pressure. After dilution, isopropyl alcohol 40 of a silanol group-containing polyorganosiloxane having an average molecular weight (Mw) of about 2000
% Solution was obtained. The component (E) obtained here is referred to as (E-1).

Next, a preparation example of a silicone coating material in which the components (D), (E) and (F) are mixed will be described.

(Preparation Example 2-1) 70 parts of (D-1) as the component (D), 30 parts of (E-1) as the component (E), and N-β-amino as the component (F) One part of ethyl-γ-aminopropylmethyldimethoxysilane was mixed to obtain a silicone coating material. The silicone coating material obtained here is called (2-1).

(3) Preparation Example of Silicone Coating Material (Preparation Example 3-1) 70 parts of methyltrimethoxysilane and 30 parts of dimethyldimethoxysilane were mixed, then diluted with 75 parts of IPA, and further 25 parts of 0.01N hydrochloric acid. Add and stir. The obtained liquid is heated in a 60 ° C. constant temperature bath to obtain a molecular weight Mw.
= 1000 was obtained. The methanol and IPA of the obtained liquid were distilled off using a rotary evaporator. To 25 parts of the obtained residue, 3 parts of polyoxyethylene nonylphenyl ether (HLB 13.7) as an emulsifier as a component (H) was added, and the mixture was stirred well to make it uniform. After adding 72 parts of water with stirring, the mixture was treated with a homogenizer (300 kg / cm 2) to obtain an emulsion-like silicone coating material. The silicone coating material obtained here is called (3-1).

(4) Preparation Example of Polysiloxane Diol A linear polysiloxane diol represented by the general formula (IV) (where R ⁷ is a methyl group) and having an average molecular weight (M
Two different types of w) were prepared. Among them, Mw is about 8
00 is referred to as (4-1), and Mw of about 3000 is referred to as (4-2).

(5) Preparation Example of Acrylic Resin Copolymer Stirrer, heating jacket, condenser, dropping funnel,
5.69 parts of n-butyl methacrylate (BMA) was added to a flask equipped with a nitrogen gas inlet / outlet and a thermometer,
Trimethoxysilylpropyl methacrylate (SMA)
1.24 parts, glycidyl methacrylate (GMA)
In a nitrogen gas stream, 0.025 part of azobisisobutyronitrile was dissolved in 3 parts of toluene in a reaction solution prepared by dissolving 71 parts of 0.784 parts of γ-mercaptopropylmethoxysilane as a chain transfer agent in 8.49 parts of toluene. The resulting mixture was dropped and reacted at 70 ° C. for 2 hours to obtain an acrylic resin copolymer having a molecular weight Mw = 1000. This is referred to as (5-1).

(6) Pigment Titanium oxide powder (R-820, manufactured by Ishihara Sangyo) was prepared as a pigment to be added to the silicone coating material. This is referred to as (6-1). When the titanium oxide powder was contained in the silicone coating material, a predetermined amount was added and dispersed in a paint shaker for 1 hour. (Examples 1 to 7) As a film substrate, polyethylene terephthalate (PE)
T) Film (manufactured by Diafoil Hoechst, part number T10)
0, thickness 50 μm). On one side of the PET film, an addition condensation type silicone release agent (manufactured by Toshiba Silicone Co., Ltd .;
6702, active ingredient 30%, toluene solvent) was applied using a bar coater coater so that the thickness of the cured coating film became 0.5 μm, and then cured at 120 ° C. for 20 seconds to form a first coat layer.

As the oxide fine particles having a photocatalytic function of the second coat layer, titanium oxide sol (manufactured by Ishihara Sangyo, part number ST)
S-01, solid content 30%, primary particle size 7 nm, nitric acid) was applied on the first coat layer using a bar coater so that the cured coating thickness would be 0.5 μm.
After drying for a minute, a second coat layer was formed.

As the silicone coat of the third coat layer,
Using the silicone coating materials prepared by blending the components in the amounts (parts) shown in (Table 1), stirring and mixing, etc., apply the silicone coating materials to the surface of the second coat layer using a bar coater coating machine to obtain a cured coating film thickness. Was applied so as to have a predetermined film thickness shown in (Table 1), and then cured at 120 ° C. for 10 minutes to form a third coat layer.

Further, as a pressure-sensitive adhesive coat of the fourth coat layer, a peroxide-curable silicone pressure-sensitive adhesive (manufactured by Toshiba Silicone Co., Ltd., product number YR3340, active ingredient 40%, toluene /
Benzoyl peroxide in 100 parts of xylene solvent).
8 parts was applied to the surface of the second coat layer using a bar coater coater so that the cured coating thickness became 50 μm, then preliminarily dried at 90 ° C. for 2 minutes, and then cured at 165 ° C. for 2 minutes to form a fourth coat. A coat layer was formed. The performance of each sample of the silicone transfer film thus produced was evaluated by the following test, and the results are shown in Table 1.

(Method of Measuring Peel Peeling Strength) Each sample of the produced silicone transfer film was measured for a width of 50%.
mm, the pressure-sensitive adhesive surface of the fourth coat layer was pressed against an aluminum plate (100 g / cm 2), and one end of the PET film was pulled in a direction of 180 ° with respect to the aluminum plate, and the peel strength was measured. The tensile strength tester used was AGS-50A manufactured by Shimadzu Corporation.

(Weather Resistance Test of Coating Film) Each sample of the prepared silicone transfer film was pressed against Pyrex glass, the film substrate was peeled off, and the transfer layer was transferred. , Model number: WEL-SUN-H
Using the C type, an accelerated weathering test for 1200 hours was performed.
The degree of yellowing (YI value) before and after the accelerated weathering test was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number # 80), and delta YI was measured.
Was calculated (JIS K7103).

(Evaluation of Photocatalytic Effect) Each sample of the produced silicone transfer film was press-bonded, the film substrate was peeled off, and the transfer layer was transferred to size 5
3 mm Pyrex glass plate of 0 mm x 50 mm x 1 mm
Acetaldehyde gas was injected from a gas injector so as to have a concentration of 50 ppm, and a black light of 10 W was irradiated for 1 hour, and gas chromatography (GC-14A, manufactured by Shimadzu Corporation) was performed. ) Was used to measure the residual ratio of acetaldehyde, and the removal ratio of acetaldehyde was calculated.

Comparative Example 1 Titanium oxide sol (manufactured by Ishihara Sangyo, part number STS-01, solid content 30) was added to 100 parts of the silicone coating material (1-1).
%, Primary particle diameter of 7 nm, nitric acid) was added, and the mixture was stirred and applied to a Pyrex glass plate with a bar coater so that the cured coating thickness became 5.0 μm, and then 120 ° C. For 20 minutes to produce a sample having a surface coated with a titanium oxide-dispersed silicone coating. With respect to this, the weather resistance test of the coating film and the evaluation of the photocatalytic effect were carried out in the following manner according to the test methods in Examples.

That is, in the weather resistance test, a sunshine super long life weather meter manufactured by Suga Test Instruments Co., Ltd., model number: WEL-
Using the SUN-HC type, an accelerated weathering test for 1200 hours was performed, and the yellowing degree (YI value) before and after the accelerated weathering test was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number # 80), and del
ta YI was calculated (JIS K7103). For the evaluation of the photocatalytic effect, the above sample was fixed to the bottom of a 300 ml glass container, the container was sealed, acetaldehyde gas was injected from a gas injector so as to have a concentration of 50 ppm, and 10 W black light was irradiated for 1 hour. Chromatography (GC-1 manufactured by Shimadzu Corporation)
The residual rate of acetaldehyde was measured using 4A), and the acetaldehyde removal rate was calculated. The results are shown in (Table 1).

[0101]

[Table 1]

As shown in Table 1, the silicone transfer films of Examples 1 to 7 can perform good transfer because the peel strength of the transfer layer is relatively small. Also had a high level of durability. Since the titanium oxide fine particles having a photocatalytic function are fixed at a high density on the outermost layer of the transferred silicone protective film, the titanium oxide fine particles are fixed by the conventional coating method. Also showed a generally high purification effect. Incidentally, in Comparative Example 1, the purification effect can be improved by increasing the addition amount of the titanium oxide sol.
Since the ratio of the silicone coating material in the coating film decreases, the durability of the coating film decreases.

(Examples 8 to 14) PET film (manufactured by Diafoil Hoechst, product number T1)
00, 50 μm thickness), an addition condensation type silicone release agent (manufactured by Toshiba Silicone Co., Ltd., product number TPR6702, active ingredient 30%, toluene solvent) as a release agent coat of the first coat layer, cured with a bar coater coating machine. 0.5 thickness
It was applied to a thickness of μm, and then cured at 120 ° C. for 20 seconds to form a first coat layer.

As a powder containing a solute-type antibacterial component of the second coat layer, a silver-supporting glass powder (manufactured by Toa Gosei Co., Ltd., product number Novalon AG300, particle size 0.5 μm) was dispersed in water with a paint shaker. The solution was applied on the first coat layer using a bar coater coater so that the thickness of the cured coating film became 0.5 μm, then dried at 100 ° C. for 1 minute,
A coat layer was formed.

As the silicone coat of the third coat layer,
Using each silicone coating material prepared by blending the components in the blending amounts (parts) shown in Table 2, stirring and mixing, etc., the silicone coating material was coated on the surface of the second coat layer with a bar coater coating machine, and the cured coating film thickness was ( It was applied to a predetermined thickness shown in Table 1) and then cured at 120 ° C. for 10 minutes to form a third coat layer.

Further, as the pressure-sensitive adhesive coat of the fourth coat layer, a peroxide-curable silicone pressure-sensitive adhesive (manufactured by Toshiba Silicone Co., Ltd., product number YR3340, active ingredient 40%, toluene /
Benzoyl peroxide in 100 parts of xylene solvent).
8 parts was applied to the surface of the second coat layer using a bar coater coater so that the cured coating thickness became 50 μm, then preliminarily dried at 90 ° C. for 2 minutes, and then cured at 165 ° C. for 2 minutes to form a fourth coat. A coat layer was formed. Each sample of the silicone transfer film thus produced was subjected to the peel peel strength measurement by the above-described test method and the weather resistance test of the coating film, and the antibacterial property was evaluated by the following test.
The results are shown in Table 2.

(Evaluation of Antibacterial Property) Each sample of the produced silicone transfer film was press-bonded, the film substrate was peeled off, and the transfer layer was transferred to size 5
A solution containing a fixed number of bacteria was dropped on a 0 mm × 50 mm × 1 mm alumina plate by a drop method, and the change in the number of bacteria at the initial stage and after 6 hours was measured. The bacterium used was Escherichia coli, and the measurement was performed under an illuminance of 3500 lux. The initial bacterial count was 10 6.

Comparative Example 2 100 parts of a silicone coating material (1-1) were coated with a silver-supporting glass powder (manufactured by Toa Gosei, product number Novalon AG30).
0, particle size 0.5 μm), and dispersed in a paint shaker for 1 hour, and applied to alumina and pyrex glass with a bar coater so that the cured coating thickness becomes 5 μm, and then 120 ° C. And cure for 20 minutes,
A sample having a silver-glass powder-dispersed silicone coating formed on the surface was prepared. With respect to this, the weather resistance test and the evaluation of antibacterial property of the coating film were performed in the following manner according to the test methods in Examples.

That is, in the weather resistance test, a sunshine super long life weather meter manufactured by Suga Test Instruments Co., Ltd., model number: WEL-
Using the SUN-HC type, an accelerated weathering test for 1200 hours was performed, and the yellowing degree (YI value) before and after the accelerated weathering test was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number # 80), and del
ta YI was calculated (JIS K7103). For the evaluation of antibacterial properties, a solution containing a certain number of bacteria was dropped on the coating film of the sample by a drop method, and the change in the number of bacteria at the initial stage and after 6 hours was measured. The bacterium used was Escherichia coli, and the measurement was performed under an illuminance of 3500 lux. The initial bacterial count was 10 6. The results are shown in (Table 2).

[0110]

[Table 2]

As shown in Table 2, the silicone transfer films of Examples 8 to 14 can perform good transfer because the peel strength of the transfer layer is relatively small. Also had a high level of durability. Then, since the silver-carrying glass powder is fixed at a high density on the outermost layer of the transferred silicone protective film, the silver-carrying glass powder is fixed by the conventional coating method, compared with the coating film of Comparative Example 1 in which the silver-carrying glass powder is fixed. Overall, the antibacterial effect was high. By the way, in Comparative Example 1, the antibacterial effect can be improved by increasing the amount of the silver-supported glass powder, but in this case, the ratio of the silicone coating material in the coating film is reduced, so that the coating film is reduced. Will be reduced in durability.

(Examples 15 to 21) PET film (manufactured by Diafoil Hoechst, product number T1)
00, 50 μm thickness), an addition condensation type silicone release agent (manufactured by Toshiba Silicone Co., Ltd., product number TPR6702, active ingredient 30%, toluene solvent) as a release agent coat of the first coat layer, cured with a bar coater coating machine. 0.5 thickness
It was applied to a thickness of μm, and then cured at 120 ° C. for 20 seconds to form a first coat layer.

As the flavone derivative deodorant of the second coat, a flavone derivative-containing aqueous solution (manufactured by Release Kagaku Kogyo,
Part number Pansil FG-50, active ingredient 5%) was applied on the first coat layer using a bar coater so that the thickness of the cured coating film was 0.1 μm, and then dried at 100 ° C. for 1 minute to form a second coat. A layer was formed.

As the silicone coat of the third coat layer,
Using each silicone coating material prepared by blending the components in the amounts (parts) shown in Table 3 and stirring and mixing, the silicone coating material was applied to the surface of the second coat layer with a bar coater coating machine, and the cured coating film thickness was ( It was applied so as to have a predetermined film thickness shown in Table 1), and then cured at 120 ° C. for 10 minutes to form a third coat layer.

Further, as a pressure-sensitive adhesive coat of the fourth coat layer, a peroxide-curable silicone pressure-sensitive adhesive (manufactured by Toshiba Silicone Co., Ltd., product number YR3340, active ingredient 40%, toluene /
Benzoyl peroxide in 100 parts of xylene solvent).
8 parts was applied to the surface of the second coat layer using a bar coater coater so that the cured coating thickness became 50 μm, then preliminarily dried at 90 ° C. for 2 minutes, and then cured at 165 ° C. for 2 minutes to form a fourth coat. A coat layer was formed. For each sample of the silicone transfer film thus produced, the peel peel strength was measured by the above-described test method and the weather resistance test of the coating film was performed, and the deodorizing property was evaluated by the following test.
The results are shown in Table 2.

(Evaluation of Deodorizing Property) Each sample of the produced silicone transfer film was pressed, the film substrate was peeled off, and the transfer layer was transferred to 50 mm.
× 50mm × 1mm Pyrex glass plate 1000
The glass container was fixed to the bottom of the glass container and hermetically sealed.
20 ppm, hydrogen sulfide 15 ppm) and gas chromatography (GC, Shimadzu Corporation, GC)
-14A) and the residual ratio was measured.

(Comparative Example 3) 30 parts of an aqueous solution containing a flavone derivative (manufactured by Release Kagaku Kogyo Co., Ltd., Pansil FG-50, active ingredient 5%) was added to 100 parts of the silicone coating material (1-1), and the mixture was stirred. Using a coating machine, apply on a Pyrex glass plate so that the cured coating thickness becomes 5.0 μm.
The sample was cured at 0 ° C. for 20 minutes to form a flavone derivative-dispersed silicone coating film. With respect to this, the weather resistance test and the evaluation of antibacterial property of the coating film were performed in the following manner according to the test methods in Examples.

That is, in the weather resistance test, a sunshine super long life weather meter manufactured by Suga Test Instruments, model number: WEL-
Using the SUN-HC type, an accelerated weathering test for 1200 hours was performed, and the yellowing degree (YI value) before and after the accelerated weathering test was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number # 80), and del
ta YI was calculated (JIS K7103). For the evaluation of deodorant properties, the above sample was fixed to the bottom of a 1000 ml glass container, the container was sealed, and a malodorous component (ammonia 520 pp) having a known concentration was detected from a gas injector.
m, 15 ppm of hydrogen sulfide) and gas chromatography (GC-14, manufactured by Shimadzu Corporation) for odor components after 1 hour.
The residual ratio was measured by quantification using A). Table 3 shows the results.
It was shown to.

[0119]

[Table 3]

As shown in Table 3, the silicone transfer films of Examples 15 to 21 can perform good transfer because the peel strength of the transfer layer is relatively small, and at this time, the silicone protective film applied to the transfer object Also had a high level of durability. Further, since the flavone derivative is fixed on the outermost layer of the transferred silicone protective film at a high density, the deodorization is generally higher than that of the coating film of Comparative Example 1 in which the flavone derivative is fixed by the conventional coating method. The effect was shown. Incidentally, in Comparative Example 1, an improvement in the deodorizing effect can be expected by increasing the amount of the flavone derivative added. In this case, however, the ratio of the silicone coating material in the coating film decreases, so that the The durability will be reduced.

[0121]

As described above, the silicone transfer film of the present invention has a highly durable silicone coating film on which a material powder having a purifying, antibacterial or deodorizing function is fixed at a high density on the surface of the silicone coating film. It can be easily applied by a transfer method. Therefore, it is possible to form a coating film having excellent self-cleaning properties as compared with a conventionally performed coating method,
In addition, there is no need for time and effort required for coating the coating film, and there is no fear that the transfer object is affected by a solvent or the like. Further, since the silicone protective coat can be applied by the transfer method, it is possible to relatively easily apply the silicone protective coat even to a transfer-receiving body having an uneven surface.

The silicone transfer film has the following features:
As shown in 12, when an addition condensation type silicone release agent is used to form the first coat layer, since this addition condensation type silicone release agent has excellent curability and good solvent resistance, It becomes easy to form the second and third coat layers.

Further, in this silicone transfer film,
In order to form the second coat layer, by using metal oxide fine particles having a photocatalytic function, a powder containing a component having an elution-type antibacterial performance, and a flavone derivative, as shown in claims 13 to 15 , Excellent purification, antibacterial or deodorant functions can be imparted to the coating film.

Further, in this silicone transfer film,
Claims 1 to 3 for forming the third coat layer.
By using each of the silicone coating materials described in the fourth and fifth aspects, the third coat layer becomes an excellent durable silicone layer. These silicone coating materials can improve the releasability of the second coat layer from the first coat layer by containing the linear polysiloxane diol described in claims 6 and 7. By including the acrylic resin copolymers shown in 8 and 9 , the toughness of the second coat layer can be improved. Further, the silicone coating material can be colored to a desired color by adding a pigment.

Further, in this silicone transfer film,
When a silicone pressure-sensitive adhesive is used to form the third coat layer, the durability of the third coat layer is improved, and the durability of the transfer layer as a whole is improved.

Since the transfer member of the present invention is obtained by applying a silicone protective coat to the surface of the transfer-receiving member using the above-mentioned silicone transfer film, the surface has excellent self-cleaning properties and durability. Further, since the handling for forming the protective coat is good, the productivity is excellent.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Junko Ikenaga 1048 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd. (56) References JP-A 9-227169 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C09J 7/02

Claims (18)

(57) [Claims] 1. The method according to claim 1, wherein the film substrate has a silicone
First coat layer showing releasability, purification, antibacterial or deodorant
A porous second coat layer made of a material having a function,
Silicone third coat layer, adhesive to silicone
And a fourth coat layer of an adhesive showing
And the third coat layer is placed in the porous pores of the second coat layer.
Partly penetrates and has a purifying, antibacterial or deodorizing function
The material is fixed on the bottom of the third coat layer.
A silicone transfer film , wherein the third coat layer is formed by coating the following silicone coating material. (A) a silicon compound represented by the general formula: Si (OR ¹ ) ₄ , (B) a silicon compound represented by the general formula: R ² Si (OR ¹ ) ₃ , wherein R ¹ and R ² are 1 (A) is an essential component, (A) is 20 to 200 parts by weight, and (B) is 1 part.
A silicone coating material which is contained at a ratio of 00 parts by weight and whose weight average molecular weight is 800 or more in terms of polystyrene. Wherein the silicone coating material, in addition to the (A) (B), ( C) the general _{^{formula: R 2 2 Si (OR 1}} ) a silicon compound represented by the ₂ (wherein R ^1, R ² represents a monovalent hydrocarbon group.)
The silicone transfer film according to claim 1 , wherein the silicone transfer film is contained at a ratio of not more than part by weight. 3. A the silicone coating material, (A) a silicone transfer film according to claim 1 or claim 2 wherein some or all of the silicon compound shown in component characterized in that it is a colloidal silica. 4. The method according to claim 1, wherein the surface of the film substrate is
First coat layer showing releasability, purification, antibacterial or deodorant
A porous second coat layer made of a material having a function,
Silicone third coat layer, adhesive to silicone
And a fourth coat layer of an adhesive showing
And the third coat layer is placed in the porous pores of the second coat layer.
Partly penetrates and has a purifying, antibacterial or deodorizing function
The material is fixed on the bottom of the third coat layer.
A silicone transfer film , wherein the third coat layer is formed by coating the following silicone coating material. (D) General formula: R ³ _k SiX _4-k (wherein, R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and k is an integer of 0 to 3) , X represents a hydrolyzable group) in a colloidal silica in which a hydrolyzable organosilane represented by the following formula (1) is dispersed in an organic solvent or water;
A silica-dispersed oligomer solution of an organosilane partially hydrolyzed under a condition using 0.5 mol; (E) average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (wherein R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b represent 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b, respectively.
It is a number that satisfies the relationship of <4. A) a silicone coating material containing, as essential components, a polyorganosiloxane containing at least a silanol group in its molecule, and (F) a curing catalyst. 5. The method according to claim 1, wherein the surface of the film substrate has silicone
First coat layer showing releasability, purification, antibacterial or deodorant
A porous second coat layer made of a material having a function,
Silicone third coat layer, adhesive to silicone
And a fourth coat layer of an adhesive showing
And the third coat layer is placed in the porous pores of the second coat layer.
Partly penetrates and has a purifying, antibacterial or deodorizing function
The material is fixed on the bottom of the third coat layer.
A silicone transfer film , wherein the third coat layer is formed by coating the following silicone coating material in the form of an emulsion. (G) General formula R ⁶ _c SiO _d (OR ⁵ ) _e (OH) _f (wherein R ⁵ and R ⁶ represent a monovalent hydrocarbon group, and c, d,
e and f are respectively c + 2d + e + f = 4, 0 ≦ c <
3, 0 <d <2, 0 <e <4, and 0 <f <4. And (H) an emulsifier, and water, which are mixed with an organosiloxane partially hydrolyzed product having an average molecular weight of 600 to 5000 represented by the formula (1). Wherein the silicone coating material, the following average compositional formula _{^{H (R 7 2 SiO) m}} OH ( wherein, R ⁷ represents a monovalent hydrocarbon group, m is 3 ≦ m ≦
It is a number that satisfies 100. The linear polysiloxane diol represented by the formula) is contained.
Silicone transfer film according to any one 1 to claim 5. 7. The content of the linear polysiloxane diol in the silicone coating material is determined based on the sum of the weight of silica in the silicone coating material as a condensed silicon compound and the weight of silica.
7. The composition according to claim 6, wherein the content is 0.1 to 100% by weight.
The silicone transfer film of the above. 8. The silicone coating material is represented by the following general formula CH ₂ ＣＲCR ⁸ (COOR ⁹ ), wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ is Substituted or unsubstituted carbon number 1-9
At least one first acrylate or methacrylate which is a monovalent hydrocarbon group of the formula: and at least one second acrylic acid wherein R ⁹ is an epoxy group, a glycidyl group or a hydrocarbon group containing the same Acrylic resin obtained by co-polymerizing an ester or methacrylate with at least one third acrylate or methacrylate in which R ⁹ is a hydrocarbon group containing an alkoxysilyl group or a halogenated silyl group. silicone transfer film according to any one of claims 1 to 7, characterized by containing the copolymer. 9. The content of the acrylic resin copolymer in the silicone coating material is 0.1 to 0.1 with respect to the sum of the weight of silica in the silicone coating material as a condensed silicon compound and the weight of silica.
9. The silicone transfer film according to claim 8 , wherein the amount is 100% by weight. Claims 1 to 9 10. The silicone coating material is characterized by containing a pigment
The silicone transfer film according to any one of the above. 11. The third coating layer is silicone transfer film according to any one of claims 1 to 10, characterized in that one formed by coating a silicone adhesive. 12. The first coating layer is a silicone transfer film according to any one of claims 1 to 11, characterized in that the additional condensation type silicone release agent are those formed by coating. 13. The second coating layer, according to claim 1 to claim, characterized in that the metal oxide fine particles having a photocatalytic function is porous coating layer formed by coating 1
2. The silicone transfer film according to any one of 2 . 14. The second coating layer is 1 to claim, characterized in that the powder containing a component having an elution-type antibacterial is a porous coating layer formed by coating
The silicone transfer film according to claim 12 . 15. The second coating layer is a silicone transfer film according to any one of claims 1 to claim 12, characterized in that it intended to be formed by coating the flavone derivative. 16. A method according to claim 1 or the transfer layer of silicone transfer film in accordance with claim 15, transfer structure that characterized by being transferred to the transferred surface. 17. The transfer structure according to claim 16 , wherein the object to be transferred is any one of a plastic molded body, a glass molded body, an inorganic molded body, a metal molded body, and a composite molded body thereof. body. 18. The object to be transferred is a plastic molded body, wherein the silicone transfer film is integrally molded on the surface of the plastic molded body when the plastic molded body is molded, and the transfer layer is transferred. 17. The transfer construct of claim 16, wherein