JPH10158594A - Silicone-transfer film and transfer constituent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject film to be coated with a silicone-protective layer on transferred patterns by coating the film base surface with a first coating layer of a silicone releasant, second coating layer of silicone and third coating layer of an adhesive, in this order. SOLUTION: This objective film which can be easily coated with a silicone- protective layer even on a surface with irregularities of transferred patterns by coating the film base surface with (A) a first coating layer of an addition- condensed silicone releasant, which shows ability of releasing silicone, (B) a second coating layer of silicone coating prepared by mixing a silicone compound shown by the formula Si(OR<1> )4 with another silicon compound shown by the formula R<2> Si(OR<1> )3 (R<1> and R<2> are each a monovalent hydrocarbon) in a wt. ratio of (20-200): 100 so as to have a weight-average molecular weight of at least 800 in terms of polystyrene, and (C) a third coating layer of an adhesive showing tackiness to silicone, in this order.

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 applying a silicone protective coat to the surface of a target article by a transfer method, and a transfer structure thereof.

[0002]

2. Description of the Related Art Conventionally, when a silicone protective coating is applied to the surface of a target article, a solvent-based silicone coating material is generally applied. However, in many cases, the silicone coating directly adheres. Difficult and requires a primer coating to maintain adhesion between the article and the silicone coating. Since the primer differs depending on the material of the article, it is necessary to select a primer corresponding to the type of the material. Further, since the current silicone coating materials are solvent-based, it has been difficult to apply them to articles made of materials that are eroded by solvents.

On the other hand, the present inventors have disclosed in Japanese Patent Application Nos.
No. 1050, polyethylene terephthalate (P
A transparent plastic film represented by ET) is used as a base film, the surface of which is coated with a silicone coating material and a pressure-sensitive adhesive is applied to the back surface to adhere to the surface of the article to be coated with a silicone protective coat. We have proposed a silicone-treated adhesive film that can be worn. This is in consideration of the problem of the above coating, and is itself to be a silicone protective coating layer by sticking to the surface of the article,
However, since the base film eventually remains on the surface of the article, the overall durability after application largely depends on the durability of the base film. Therefore, when used outdoors, the silicone coating material absorbs ultraviolet light. It was necessary to introduce an agent to prevent the deterioration of the base film due to ultraviolet rays. Further, the followability of the silicone-treated pressure-sensitive adhesive film to an article having a relatively complicated surface shape such as having irregularities largely depends on the elongation and the film thickness of the base film, and it is generally difficult to adhere. .

[0004]

DISCLOSURE OF THE INVENTION The present inventors have studied in order to improve the problem in view of the fact that the base film, which is a disadvantage of the silicone-treated pressure-sensitive adhesive film, remains on the surface of the target article as described above. As a result of intensive development, the present inventors have found a method of transferring only a silicone coating from a base film to a product intended to leave the base film on the surface of the product. That is, the present invention provides a silicone transfer film which can be applied to a surface of an article intended for a silicone protective coat having excellent durability by a transfer method, and a transfer component thereof.

[0005]

According to a first aspect of the present invention, there is provided a silicone transfer film comprising a first coat layer having a release property to silicone, a second silicone coat layer, and a silicone on the surface of a film substrate. On the other hand, a third coating layer made of an adhesive exhibiting adhesiveness is sequentially laminated.

The silicone transfer film according to claim 2 is the silicone transfer film according to claim 1,
The first coat layer is formed by coating an addition condensation type silicone release agent.

A third aspect of the present invention is the silicone transfer film according to the first or second aspect, wherein the second coat layer is formed by coating the following silicone coating material. It is a feature. (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 by weight.
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.

[0008] The silicone transfer film according to claim 4 is the silicone transfer film according to claim 3,
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 5 is the silicone transfer film according to claim 3 or 4, wherein the silicone coating material comprises:
(A) Part or all of the silicon compound represented by the component is colloidal silica.

The silicone transfer film according to claim 6 is the silicone transfer film according to claim 1 or 2, wherein the second coat layer is formed by coating the following silicone coating material. It is a feature. (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:
A silica-dispersed oligomer solution of an organosilane partially hydrolyzed under conditions using 0.5 moles; (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 an essential component, a polyorganosiloxane containing at least a silanol group in its molecule, and (F) a curing catalyst.

A silicone transfer film according to claim 7 is the silicone transfer film according to claim 1 or 2, wherein the second coat layer is formed by coating the following silicone coating material in the form of an emulsion. It is characterized by having. (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.

[0012] Silicone transfer film according to claim 8, in the silicone transfer film according to any one claims 3 to 7, the silicone coating material, the following average compositional formula ^{_{H (R 7 2 SiO) m}} OH (Wherein, R ⁷ represents a monovalent hydrocarbon group, and m is 3 ≦ m ≦
It is a number that satisfies 100. ) Is contained.

[0013] The silicone transfer film according to claim 9 is the silicone transfer film according to claim 8,
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 a tenth aspect of the present invention, there is provided the silicone transfer film according to any one of the third to ninth aspects, wherein the silicone coating material has the following general formula: CH ₂ = CR ⁸ (COOR ⁹ ) In the formula, R ⁸ represents a hydrogen atom or a methyl group.), And R ⁹ is a substituted or unsubstituted carbon atom having 1 to 9 carbon atoms.
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. It is characterized by containing a copolymer.

The silicone transfer film according to claim 11 is the silicone transfer film according to claim 10, wherein the content of the acrylic resin copolymer in the silicone coating material is such that the silicone in the silicone coating material is a condensed silicon compound. 0.1 to 100% by weight with respect to the sum of the weight converted and the weight of silica.

A silicone transfer film according to a twelfth aspect is the silicone transfer film according to any one of the third to eleventh aspects, wherein the silicone coating material contains a pigment.

According to a thirteenth aspect of the present invention, in the silicone transfer film according to the first to twelfth aspects, the third coat layer is formed by coating a silicone adhesive. It is assumed that.

According to a fourteenth aspect of the present invention, there is provided the transfer member according to the first aspect.
The transfer layer of the silicone transfer film according to any one of claims 13 to 13 is transferred onto the surface of a transfer-receiving body.

According to a fifteenth aspect of the present invention, there is provided a transfer structure according to the first aspect.
4. The transfer structure according to item 4, 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.

[0020] The transfer structure according to claim 16 is the first embodiment.
4. In the transfer structure according to 4, the transferred body is a plastic molded body, and 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. It is characterized by the following.

[0021]

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:
On the surface of a film substrate as a support, a first coat layer exhibiting releasability to silicone, a second coat layer of silicone, and a third coat layer of an adhesive exhibiting tackiness to silicone are sequentially laminated. It was done.

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 three-coat layer and has a strength to maintain a laminate composed of these three 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 in 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 second coat layer. The silicone transfer film of the present invention is peeled between the first coat layer and the second coat layer, and the transfer layer composed of the second and third coat layers is transferred to the surface of the transfer-receiving member on which the protective coat layer is to be provided. The transfer layer is separated from the film substrate. Therefore, it is necessary that the first coat layer has a higher adhesion to the film substrate than the second coat layer.

Examples of the material used for the first coat layer include a silicone release agent, an organic 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 at
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, since the first coat layer needs to maintain the performance of peeling the second coat layer after forming the second coat layer, for example, when an organic solvent-based silicone coating material is used as a material for forming the second coat layer In addition, the first coating layer is required to have the property of being hardly eroded by the organic solvent. On the other hand, the addition-condensation type silicone release agent has excellent coating curability as compared with the condensation type. This is because they are not easily attacked by organic solvents.

Next, the second coat layer will be described. When the silicone transfer film of the present invention is transferred to the surface of the transfer object, the second coat layer is peeled off from the first coat layer and transferred as a protective coat layer to the surface of the transfer object. Is a silicone layer that constitutes the outermost layer. The second coat layer is formed by applying a silicone coating material to the first coat layer.
It can be formed by coating on a coat layer. Examples of the silicone coating material include the following (1) to (3).

(1) Silicone Coating Material This silicone coating material is, as described in claim 3, (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 second 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 or 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 of the components (A), (B) and (C).

The 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, and conducting 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. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used in combination with these hydrophilic organic solvents.

In the 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 tellurium 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, it is preferable that the pH value of the silicone coating material is adjusted to a range of 3.8 to 6. By setting the pH value in this range, the silicone coating material can be stably used 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 paint 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.

(2) Silicone Coating Material This silicone coating material has the following general formula: (D) a general formula: R ³ _k SiX _4-k (II) 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 in which silane is dispersed in an organic solvent or water, water is used in an amount of 0.001 to 1 mole equivalent of X1.
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. 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. It is obtained by partially hydrolyzing the hydrolyzable organosilane with the water thus obtained.

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, heptyl and octyl groups; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; phenyl groups and tolyl groups 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 hydrocarbons 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 having a hydrolyzable group include mono-, di-, tri- and tetra-functional alkoxysilanes wherein 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 preferable 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-trifluoropropyltrimethoxylan. Examples of the diorganodialkoxysilane with 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%, a sufficient coating film hardness cannot be obtained, and the 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, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine as long as it is more acidic than this range. 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, the component (E) has an average composition formula represented by: R ⁴ _a S
i (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 each represent 0. 2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, a + b
It is a number that satisfies the relationship of <4. ) Is a polyorganosiloxane containing a silanol group in the molecule.

In the formula, R ⁴ is the same as R ³ in the above formula (II), and is preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, or 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 may be obtained, but such a polyorganosiloxane may be used.

The curing catalyst as the component (F) promotes the condensation reaction between the components (D) and (E) as described above, and cures the coating. 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, but there is no particular limitation as long as they are effective for the condensation reaction of the components (D) and (E).

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

Further, the addition amount of the curing catalyst as the component (F) is preferably 0.0001 to 10% by weight based on the total amount of the components (D) and (E) being 100, more preferably 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
In the presence of the curing catalyst of the component (F), a condensation reaction is caused by heating at room temperature or at a low temperature 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 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.

(3) Silicone Coating Material The silicone coating material is as follows: (G) General 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, which is an emulsion.

First, the component (G) will be described. this
As the component (G), for example, this partial hydrolyzate has a general formula: R⁶ _nSi (OR^Five)_4-n(N = 0 to 3) At least one hydrolyzable organoalkoxysilane represented by (V)
Add water, catalyst and, if necessary, suitable organic solvent
And partially hydrolyzing the hydrolyzable organoalkoxysilane.
Obtained by decomposition. Where R^FiveAnd R⁶Is monovalent
Represents a hydrocarbon group, which may be the same or different
It may be. This R^FiveIs silicone coating material
R indicated by¹And R⁶Is silicone coating material
R indicated by ^TwoCan be similar to

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, more preferably 0.4 to 1.0 mol, per 1 mol equivalent of the group. 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 reduced, 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 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,
In the case of 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) in water as an emulsion. 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 copolymers, polyhydric alcohol fatty acid partial esters, polyoxyethylenated polyhydric alcohol aliphatic esters, 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 silicone coating material in the form of an emulsion 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.

[0060] 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 (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.
It is preferably 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, 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 second coat layer against deformation such as bending and bending of the base film, It has the property of making the two-coat layer thicker.

As described above, this acrylic resin copolymer is a copolymer of the above-mentioned 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 selected from the group consisting of an epoxy group, a glycidyl group and a hydrocarbon group containing them, for example, a 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 at least three kinds in total. And one or more of the first, second and third acrylates or methacrylates.
It may be a copolymer containing one or more kinds, or one or more kinds selected from acrylic esters or methacrylic esters other than those described above.

The first acrylic acid ester or methacrylic acid ester may be a silicone coating material or
It 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 acrylic acid ester or methacrylic acid ester is a component necessary for improving the adhesion between the second 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. When 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, the average molecular weight in terms of polystyrene of the acrylic resin copolymer is desirably 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 0.1 to 100% by weight, based on the sum of the weight of silica 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 is inhibited.

Further, the silicone coating material can 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 performed by a method of directly dispersing pigment powder using a normal dynomeal or paint shaker.However, a method of directly dispersing pigment powder using a dynomeal or paint shaker in an emulsion silicone coating material 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 third coat layer will be described. The third coat layer is an essential coat layer for peeling off the second coat layer from the first coat layer to transfer and adhere to the surface of the transfer-receiving body. The adhesive used for the third coat layer is
The type is not limited as long as it adheres to the silicone second 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 second 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 regard, 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 readily available as a commercial product.

The silicone transfer film of the present invention can be obtained by sequentially laminating the first to third coat layers by successively repeating liquid coating and drying on a film base serving as a support base. In forming these first to third 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 second 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 generating cracks. 0.
1 to 15 μm is desirable. In addition, as the second 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 transfer layer of the above-described silicone transfer film, that is, the second and third 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 third coat layer of the silicone transfer film is pressed against 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 third coat layer. Thereafter, when the film substrate is peeled off, the interlayer between the first coat layer and the second coat layer is removed. Then, the transfer layer having the second coat layer as the outermost layer is transferred to the surface of the transfer object. As described above, in the transfer structure, only the transfer layer is formed on the surface as a protective film without leaving the film base as the support base, and at this time, the outermost layer is formed on the outermost layer. Since the two coat layer is formed as a silicone protective coat layer,
Excellent durability is provided.

The material to be transferred is not particularly limited, and can be transferred to articles made of various materials. For example, various materials such as thermosetting resins, thermoplastic resins, and fiber-reinforced plastics can be used. 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.

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, a silicone transfer film is set in the mold in advance and simultaneously integrally molded, thereby relatively It is possible to transfer to a complicated surface. Specifically, after the film base side of the silicone transfer film is desired to be 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 molded body formed into a predetermined shape and the transfer film 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. Further, there is no fear that the transfer object is affected by a solvent or the like.

[0076]

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 created with standard polystyrene using HLC8020 manufactured by Tosoh Corporation as a measurement model, and the calibration curve was measured as a converted value.

(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: OSCAL1432, manufactured by Catalyst Chemical Industry Co., Ltd., solid content: 30)
%), 100 parts of methyltrimethoxysilane as the component (B), and 30 parts of dimethyldimethoxysilane as the component (C), and then 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA). After dilution, 39 parts of water was added and the mixture was stirred. The resulting mixture is
Molecular weight Mw = 1200 by heating in a thermostat
To obtain a silicone coating material. The silicone coating material obtained here is called (1-1).

(Preparation Example 1-2) 90 parts of IPA organosilica sol (trade name: OSCAL1432, manufactured by Catalyst Chemical Industry Co., Ltd., solid content: 30%) as an acidic colloidal silica as the component (A); ) As a component, 100 parts of methyltrimethoxysilane were mixed, then diluted with 100 parts of IPA, and 37.7 parts of water was added and stirred. The obtained mixture was heated in a thermostat at 60 ° C. to adjust the molecular weight to Mw = 1500, thereby obtaining a silicone coating material. The silicone coating material obtained here is called (1-2).

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

(Preparation Example D-1) IPA-dispersed colloidal silica sol (trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) was placed in a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer. 10-20n
m, solid content 30%, water content 0.5%), 100 parts of methyltrimethoxysilane, and 10.8 parts of water. To perform a partial hydrolysis reaction, followed by cooling to obtain a component (D). It has a solids content of 36 when left at room temperature for 48 hours.
%Met. 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 = (Mol% of the hydrolyzable organosilane 1) 100% (Preparation Example D-2) Xylene / n- in a flask equipped with a stirrer, heating jacket, condenser and thermometer
Butanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: XBA-ST, particle diameter 10 to 20 n)
m, solid content 30%, water content 0.2%), 100 parts and methyltrimethoxysilane 68 parts while stirring and adding 6 parts.
Perform a partial hydrolysis reaction at a temperature of 5 ° C. for about 5 hours,
Upon cooling, component (D) was obtained. 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-2). The preparation conditions for (D-2) are as follows. -Number of moles of water based on 1 equivalent of hydrolyzable group methyltrimethoxysilane---7 x 10 ^-3 mole-Water content of silica in solids of component (D)----47.3% 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 into 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, the average molecular weight (M
w) A solution of about 2000% of a silanol group-containing polyorganosiloxane 40% in isopropyl alcohol was obtained. The component (E) obtained here is referred to as (E-1).

(Preparation Example E-2) 1000 parts of water and 50 parts of acetone were weighed and placed in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer.
44.8 parts (0.3 mol) of methyltrichlorosilane and 38.7 parts of dimethyldichlorosilane were added to the mixed solution.
(0.3 mol) and 84.6 phenyltrichlorosilane
A part (0.4 mol) dissolved in 200 parts of toluene was hydrolyzed with stirring and stirring. 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 solution containing hydrochloric acid was separated and removed, and the remaining toluene solution of polyorganosiloxane was subjected to stopping under reduced pressure. Molecular weight (M
w) A solution of about 3000% silanol-containing polyorganosiloxane in 60% toluene was obtained. The component (E) obtained here is referred to as (E-2).

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

(Preparation Example 2-2) The component (D) (D-
2) 60 parts, (E) component (E-2) 40 parts,
A silicone coating material was obtained by mixing 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as the component (F). The coating material obtained here is called (2-2).

(3) Preparation Example of Silicone Coating Material (Preparation Example 3-1) 70 parts of methyltrimethoxysilane and 30 parts of dimethyldimethoxysilane were mixed, and then IPA7
Diluted with 5 parts, further added 25 parts of 0.01N hydrochloric acid,
Stir. The obtained liquid was heated in a thermostat at 60 ° C. to obtain a component (G) whose molecular weight was adjusted to Mw = 1000. 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
1).

(Preparation Example 3-2) 100 parts of methyltrimethoxysilane was diluted with 70 parts of methanol, and aqueous colloidal silica dispersed in water [trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 %] And mix with stirring. The obtained liquid was heated in a 60 ° C. constant temperature bath to obtain a component (G) whose molecular weight was adjusted to Mw = 1200. The methanol in the obtained liquid was distilled off using a rotary evaporator. To 25 parts of the obtained residue, 5 parts of polyoxyethylene nonylphenyl ether (HLB 12.6) as an emulsifier as a component (H) was added, and the mixture was stirred well to make it uniform. After adding 70 parts of water with stirring, a homogenizer (300 kg / cm ² ) treatment was performed to obtain a silicone coating material. The silicone coating material obtained here is called (3-2).

(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. Of these, 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)
Under a nitrogen stream, 0.025 part of azobisisobutyronitrile was dissolved in 3 parts of toluene in a reaction solution obtained 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) and a water-dispersible pigment slurry (EP-65 Whit, manufactured by Dainichi Seika KK) as pigments to be added to the silicone coating material.
e, titanium oxide solid content: 62%). Here, the former is referred to as (6-1), and the latter is referred to as (6-2). When the above-mentioned titanium oxide powder was contained in the silicone coating material, a predetermined amount was added and dispersed in a paint shaker for 1 hour. When the water-dispersible pigment slurry was contained in the silicone coating material, a predetermined amount was added and stirred.

(Examples 1 to 15) A polyethylene terephthalate (PET) film (manufactured by Diafoil Hoechst, product number T100, thickness 50) was used as a film substrate.
μm) was prepared. On one side of this PET film, an addition condensation type silicone release agent (manufactured by Toshiba Silicone Co., Ltd., product number TPR6702, active ingredient 30%, toluene solvent) is applied as a release agent coat of the first coat layer on the film surface by a bar coater coating machine. It was applied so as to have a thickness of 0.5 μm, and then cured at 120 ° C. for 20 seconds to form a first coat layer.

As the silicone coat of the second coat layer,
For each of Examples 1 to 15, using a silicone coating material prepared by mixing the components in the amounts (parts) shown in (Table 1) and stirring and mixing, the silicone coating material was applied to a bar coater coating machine. Was applied to the surface of the first coat layer so that the thickness of the cured coating film became a predetermined film thickness shown in (Table 1), and then cured at 120 ° C. for 10 minutes to form a second coat layer.

Further, as the pressure-sensitive adhesive coat of the third coat layer, in Examples 1 to 13, a peroxide-curable silicone pressure-sensitive adhesive (manufactured by Toshiba Silicone Co., Ltd., product number YR334)
0, active ingredient 40%, toluene / xylene solvent) 100
Benzoyl peroxide (0.8 part) was applied to the surface of the second coat layer using a bar coater so that the cured coating thickness became 50 μm, and then pre-dried at 90 ° C. for 2 minutes, and The composition was cured at a temperature of 2 ° C. for 2 minutes to form a third coat layer. In Examples 14 and 15, a commercially available acrylic pressure-sensitive adhesive was applied to the surface of the second coat layer with a bar coater so that the cured coating thickness became 50 μm, and then 90 ° C. And then cured at 165 ° C. for 2 minutes to obtain a third coat layer. The performance of each of the silicone transfer film samples thus produced was evaluated by the following tests. The results are shown in Table 1.

(Test Method for Transfer Peelability of Coating Film) A cellophane pressure-sensitive adhesive tape (manufactured by Nitto Denko Corporation) having a width of 10 mm was adhered on the coating film of the third coat layer of each prepared sample, and the cellophane pressure-sensitive adhesive tape was peeled off. The peelability between the first coat layer and the second coat layer was measured.

(Peel Peeling Strength Measuring Method) Each sample of the produced silicone transfer film was cut into a width of 50 mm, and the pressure-sensitive adhesive surface of the third coat layer was pressed against an aluminum plate (pressure 1).
00 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 was manufactured by Shimadzu AG
S-50A was used.

(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, the transfer layer was transferred, and a Sunshine Super Long Life Weather Meter manufactured by Suga Test Instruments Co., Ltd. , Model number: 12 using WEL-SUN-HC type
The accelerated weathering test was performed for 00 hours, 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) to calculate delta YI (JIS).
K7103).

(Comparative Examples 1 to 3) On one side of a PET film, a silicone coat corresponding to the second coat layer in the example was directly applied, omitting the release coat as the first coat layer. That is, the respective silicone coating materials prepared by blending the components in the blending amounts (parts) shown in Table 1 and stirring and mixing were coated on one side of the PET film with a bar coater coating machine.
Apply so that the cured coating thickness is 10 μm, then
After curing at 0 ° C. for 10 minutes, a silicone coat layer was obtained.

As the pressure-sensitive adhesive coat corresponding to the third coat layer in the examples, a peroxide-curable silicone pressure-sensitive adhesive (manufactured by Toshiba Silicone Co., Ltd., product number YR3340, active ingredient 40%,
To 100 parts of toluene / xylene solvent, 0.8 parts of benzoyl peroxide was applied to the surface of the silicone coat layer using a bar coater so that the cured coating thickness became 50 μm, and then preliminarily dried at 90 ° C. for 2 minutes. The composition was cured at 165 ° C. for 2 minutes to form an adhesive layer, and a silicone transfer film sample was prepared. About the obtained sample,
In the same manner as in the example, a transfer peeling test and a peeling strength measurement method of the coating film were performed. The results are shown in Table 1. In addition, the weather resistance test of the coating film was not performed because good transfer of the transfer layer could not be performed and a coating film worthy of the test could not be formed.

Comparative Example 4 A commercially available acrylic silicone coating material was applied on one side of a PET film using a bar coater so that the cured coating thickness became 1.0 μm.
It was then cured at 120 ° C. for 10 minutes. On the acrylic silicone coating film, the same silicone coating material as used in Example 5 was cured with a bar coater coating machine to a coating film thickness of 10
It was applied to a thickness of μm and then cured at 120 ° C. for 10 minutes. Next, a peroxide-curable silicone adhesive (manufactured by Toshiba Silicone Co., Ltd., product number YR3340, active ingredient 40%,
A solution obtained by adding 0.8 part of benzoyl peroxide to 100 parts of toluene / xylene solvent was applied using a bar coater so that the cured coating thickness would be 50 μm.
After pre-drying at 165 ° C for 2 minutes,
An adhesive PET film surface-treated with a silicone coating was obtained. In this case, only the weather resistance test of the coating film was performed as follows according to the test method in the example. That is,
The pressure-sensitive adhesive PET film having been subjected to the silicone coating surface treatment was pressed against Pyrex glass and 1200 using Sunshine Super Long Life Weather Meter manufactured by Suga Test Instruments Co., Ltd., model number: WEL-SUN-HC type.
A time-dependent accelerated weathering test is performed, and the yellowing degree (YI value) before and after the accelerated weathering test is measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number # 8).
0, and delta YI was calculated (JIS K
7103).

[0101]

[Table 1]

As shown in Table 1, in Examples 1 to 15, since the first coating layer having releasability was provided on the silicone, the peel strength of the transfer layer was relatively low, and therefore the releasability was good. Thus, it can be said that good transfer can be performed. On the other hand, in Comparative Examples 1 to 3 in which the first coat layer showing the releasability of silicone was omitted, the releasability was poor due to the large peel strength of the transfer layer, and good transfer could not be performed. Here, in Examples 1 to 13 in which a silicone pressure-sensitive adhesive was used as the pressure-sensitive adhesive used in the third coat layer, the transferred coating film had excellent weather resistance, but in Example 14 in which an acrylic pressure-sensitive adhesive was used. , 15 are slightly inferior in weather resistance. Incidentally, in Comparative Example 4, since the PET film remained in the coating film, the weather resistance was poor.

[0103]

According to the silicone transfer film of the present invention, it is possible to easily apply a silicone protective coat having excellent durability to the surface of various objects to be transferred by a transfer method. Therefore, compared to the conventional coating method, the work is less troublesome, and there is no fear that the transfer object is affected by a solvent or the like. In addition, since the silicone protective coat can be applied by the transfer method, it is possible to relatively easily apply the silicone protective coat to a transfer-receiving body having an uneven surface.

In this silicone transfer film, when an addition condensation type silicone release agent is used to form the first coat layer, the addition condensation type silicone release agent has excellent curability and excellent curability. Since it has solvent resistance, the second coat layer can be easily formed.

Further, in this silicone transfer film,
By using each of the silicone coating materials according to claims 3 to 5, 6, and 7 to form the second coat layer, the second coat layer becomes a silicone layer having excellent durability. Things. 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 8 and 9. By including the acrylic resin copolymers shown in 10 and 11, 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.

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, and therefore has excellent surface durability and
Good handling for forming the protective coat results in excellent productivity.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Junko Ikenaga 1048 Kadoma, Kadoma, Osaka Prefecture Inside Matsushita Electric Works, Ltd.

Claims (16)

[Claims] 1. A first coat layer having a release property with respect to silicone, a second coat layer having a silicone property, and a third coat layer having an adhesive property having a tackiness with respect to silicone are sequentially formed on the surface of a film substrate. A silicone transfer film characterized by being laminated. 2. The silicone transfer film according to claim 1, wherein said first coat layer is formed by coating an addition condensation type silicone release agent. 3. The silicone transfer film according to claim 1, wherein the second coat layer is formed by coating a silicone coating material described below. (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 by weight.
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 above-mentioned (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 3, wherein the silicone transfer film is contained in a ratio of not more than part by weight. 5. The silicone transfer film according to claim 3, wherein in the silicone coating material, part or all of the silicon compound represented by the component (A) is colloidal silica. 6. The silicone transfer film according to claim 1, wherein the second 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:
A silica-dispersed oligomer solution of an organosilane partially hydrolyzed under conditions using 0.5 moles; (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 comprising, as essential components, a polyorganosiloxane having at least a silanol group in its molecule, and (F) a curing catalyst. 7. The silicone transfer film according to claim 1, wherein the second 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. 8. 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 silicone transfer film according to any one of claims 3 to 7, further comprising a linear polysiloxane diol represented by the formula: 9. 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.
9. The composition according to claim 8, wherein the content is 0.1 to 100% by weight.
The silicone transfer film of the above. 10. 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 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. The silicone transfer film according to any one of claims 3 to 9, wherein the silicone transfer film contains a copolymer. 11. The content of the acrylic resin copolymer in the silicone coating material is 0.1% based on the sum of the weight of silica in the silicone coating material as a condensed silicon compound and the weight of silica.
The silicone transfer film according to claim 10, wherein the amount is from 100 to 100% by weight. 12. The silicone coating material according to claim 3, wherein the silicone coating material contains a pigment.
The silicone transfer film according to any one of claims 1 to 7. 13. The silicone transfer film according to claim 1, wherein the third coat layer is formed by coating a silicone adhesive. 14. A transfer structure, wherein the transfer layer of the silicone transfer film according to claim 1 is transferred to the surface of a transfer target. 15. The transfer structure according to claim 14, 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. 16. The object to be transferred is a plastic molded body, wherein the silicone transfer film is integrally formed on the surface of the plastic molded body at the time of molding, and the transfer layer is transferred. 15. The transfer construct of claim 14, wherein