JPH091995A - Transfer foil, protective layer for transfer foil, and manufacture of composition for forming of protective layer for transfer foil - Google Patents

Abstract

PURPOSE: To improve scratch resistance and weather resistance by a method wherein in a transfer foil wherein a releasant layer is provided on one side surface of a base material, and a transfer film composed of a protective layer, a metalized layer, and an adhesive layer is formed, the protective layer is formed by using a composition obtained by mixing a specific organic silicon compound and a reactive organic compound. CONSTITUTION: A releasant layer is provided on one side surface of a base material adopted for a metallic print or the like applied to fashion use such as gold thread, silver thread, sports ware, etc., applied to printed silk gold coloring treatment. Further, a transfer film composed of a protective layer, a metalized layer, and an adhesive layer is formed. In such the transfer foil, the protective layer is formed by applying a composition obtained by mixing an organic silicon compound given by the formula (in the formula, R is a 1-8C hydrocarbon group) and/or its hydrolysate, and a reactive organic compound of under 1000 molecular weight having two or more functional groups capable of condensation reaction with the organic silicon compound and/or its hydrolysate, and/or an organic compound of over 1000 molecular weight, to the base material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transfer foil, a protective layer for a transfer foil and a method for producing a protective layer forming composition for a transfer foil, and in particular, in addition to a decorative function, scratch resistance, weather resistance, chemical resistance and corrosion resistance. The present invention relates to a transfer foil having excellent properties.

[0002]

2. Description of the Related Art Transfer foils are so-called hot stamping foils, and are used in metallic prints for gold, silver, high-end apparel, sports apparel, etc. , Nylon tricot, vinyl, leather, synthetic leather, non-woven fabric, etc., synthetic resin moldings used for various containers for cosmetics, chemicals, etc., printing on sheet materials such as paper used for labels, etc. It has attracted attention as a variety of industrial materials such as heat insulation, heat insulation, various shields, and electrical conductivity, in response to diversifying needs.

Transfer foils are roughly classified into metallic transfer foils and pigment transfer foils. The structure of the metallic transfer foil is shown in FIG. Reference numeral 1 is a base material, 2 is a release layer, 3 is a protective layer, 4 is a metal vapor deposition layer, and 5 is an adhesive layer. As a substrate, a polyester film (12) suitable for vacuum deposition and excellent in heat resistance, transparency, flexibility, mechanical strength, and dimensional stability
(About 25 μm thick) is the mainstream. Using this substrate as a carrier film, a release layer is provided to facilitate transfer when heated and pressed, and a protective layer or protective colored layer is provided to protect the vapor deposition layer and impart a color effect.

High-purity aluminum metal is generally deposited on the metal vapor-deposited layer by vacuum vapor deposition of about 400 to 800 Å. In addition, special high-frequency induction heating vapor deposition, titanium, chrome, nickel, etc., which are commonly used, are also used. There are an electron beam heating vapor deposition method and a sputtering method for vapor-depositing metals, alloys such as stainless steel and brass. Due to these, in addition to gold, silver, titanium metal color, chrome metal color, nickel metal color, red, blue, green and other desired color foils, transparent foil, pigment foil, metal powder foil, special glitter foil, etc. Foil can also be obtained. Finally, an adhesive layer suitable for each type of transferred material is applied to obtain a product. In addition, a mold release and a protective layer may be overcoated in accordance with required characteristics, and various ideas have been made depending on the purpose of use.

The protective layer is made of, for example, acrylic resin, epoxy resin, epoxy-acrylate resin, urethane resin, ethylene resin, urethane-acrylic resin, melamine resin, phenol resin, urea resin, urea resin. , Urea-melamine resin, diallyl phthalate resin, ester resin, alkyd resin, maleated rosin, vinyl butyral resin, cellulose resin, amide resin, etc. thermosetting resin, UV curable resin, electron A natural resin such as a ray-curable resin or a drying oil such as linseed oil, tung oil or dehydrated castor oil, a synthetic resin, or a mixture thereof is used.

The structure of the pigment transfer foil is shown in FIG. The major difference between the pigment transfer foil and the metallic transfer foil is that the metal vapor deposition layer is not applied. For this reason, in addition to various pigment colors such as coloring and pigments, recently metal powders and pearl pigments may be used in order to give a particularly high-grade metallic sensation, and various designs can be reproduced. It has spread. In any of the pigment transfer foil and the metallic transfer foil, a protective coloring layer having a desired color tone can be obtained by adding a coloring component such as a pigment to the protective layer.
At the time of use, these transfer foils are transferred to the surface of the material by bringing the adhesive layer into close contact with the surface of the material to be transferred and heating and pressing from the surface of the base material. At this time, it is possible to form a convex portion on the surface of the material to be transferred by processing an adhesive having a printing pattern in advance and form a transfer film there, or press the surface of the substrate with a metal relief plate or the like. It can also be engraved with.

[0007]

With these transfer foils,
The so-called return-plating process, which was performed before the processing of gold and silver threads, was used to dissolve and swell an adhesive containing vinyl acetate as the main component with an organic solvent such as xylol to bond Western gold foil. Pollution caused by solvent,
Problems such as complexity of work were solved. In addition, it is now possible to easily print metallic colored patterns on various molded products and sheet-like products, and new applications have expanded. However, the surface of the print, gold thread, and silver thread obtained by the conventional transfer foil has scratches caused by friction during use and twisting during washing in clothing applications, gold threads, and silver thread applications because the protective layer directly contacts the outside air. There was a problem of peeling. Further, when it is transferred to a container, a label or the like, it may be gradually peeled off / dissolved due to contents such as chemicals and cosmetics, which may cause an aesthetic problem. For this reason, attempts have been made to address these problems by using a protective layer-forming composition to which a specific organosilicon compound has been added in addition to the conventional resin component (Japanese Patent Publication No. 7-5000, Kaisho 63-12
5387). However, it is difficult to say that the conventional protective layer of the transfer foil still has sufficient performance in terms of water resistance, abrasion resistance, acid resistance, alkali resistance, washing resistance, etc. The development of foil was desired.

[0008]

The inventors of the present invention have conducted extensive studies in view of the above-mentioned problems, and as a result, when a composition containing a specific organosilicon compound was applied and used as a protective layer, the transfer obtained was obtained. The film surface has excellent properties such as water resistance, abrasion resistance, acid resistance, alkali resistance, and washing resistance, and has also been found to have excellent compatibility with the protective layer and the metal vapor deposition layer, and has reached the present invention. did.

That is, the present invention provides a transfer foil in which a release agent layer is provided on one surface of a base material, if necessary, and a transfer film comprising at least a protective layer, a metal vapor deposition layer and an adhesive layer is formed.
The protective layer contains a functional group capable of undergoing a condensation reaction with the organosilicon compound represented by the following general formula [A] and / or its hydrolyzate and the organosilicon compound and / or its hydrolyzate.
A transfer foil or the like characterized in that a composition obtained by blending the reactive organic compound having a molecular weight of less than 1000 and / or the organic compound having a molecular weight of more than 1000 is coated on a substrate. Hereinafter, the present invention will be described in detail.

First, the base material used in the transfer foil of the present invention is not particularly limited, and any material used for a normal transfer foil having sufficient self-holding property can be used. For example, polyethylene terephthalate film, polypropylene film, polycarbonate film, polystyrene film, polyamide film, polyamideimide film, polyethylene film, synthetic resin film such as polyvinyl chloride film, artificial resin film such as cellulose acetate film, cellophane paper, glassine paper, Western paper such as Sanpei paper, film-like material such as Japanese paper or sheet-like material can be raised.

The thickness of the base material is not particularly limited and may be 6 to
It is preferable to use a film having a thickness in the range of 100 μ, preferably in the range of 12 to 25 μ, because the transfer foil without wrinkles and cracks can be easily manufactured. The release agent layer used as necessary in the transfer foil of the present invention is not particularly limited, and includes silicone resin, paraffin wax, cellulose resin, acrylic resin, urethane resin, melamine resin, urea-melamine resin. A coating film containing a benzoguanamine-based resin as a main component or a mixture thereof is used.

The thickness of the release agent layer is not particularly limited,
It is appropriately adopted from the range of about 0.1 to 2 μ. The protective layer used in the transfer foil of the present invention is characterized by using the following. That is, a reaction of an organosilicon compound represented by the following general formula [A] and / or its hydrolyzate with a molecular weight of less than 1,000 having two or more functional groups capable of undergoing a condensation reaction with the organosilicon compound and / or its hydrolyzate. A protective layer for a transfer foil, which is obtained by applying a composition obtained by blending a hydrophilic organic compound and / or an organic compound having a molecular weight of more than 1,000.

The protective layer forming composition for a transfer foil of the present invention contains an organosilicon compound represented by the following general formula [A] and / or a hydrolyzate thereof as an essential component.

Embedded image

R in the general formula [A] is a hydrocarbon group having 1 to 8 carbon atoms. Among these, R is an alkyl group having 1 to 3 carbon atoms, that is, represented by the general formula [A]. Specifically as the organosilicon compound, tetramethoxysilane,
When one or more of tetraethoxysilane and tetrapropoxysilane are used, a protective layer having particularly high hardness can be obtained. The tetramethoxysilane may be obtained by a method such as a reaction between silicon tetrachloride and methanol, a reaction between metallic silicon and methanol, or the like, but impurities can be easily removed by refining the raw material, Also, since hydrochloric acid does not form as a by-product and the problem of equipment corrosion does not occur, it is desirable to use tetramethoxysilane obtained by reacting silicon and methanol, especially for applications requiring the removal of impurities.
By using this, for example, chlorine content is 1ppm
The following protective layer forming composition can also be easily obtained.

When an organosilicon compound other than tetramethoxysilane is obtained, the reaction using various alcohols can be carried out according to the above-mentioned method, but tetramethoxysilane is subjected to transesterification reaction using various alcohols. However, it is efficient.

Further, when tetramethoxysilane is used as the organosilicon compound, it has been suggested that the tetramethoxysilane monomer itself is highly toxic, such as corroding the cornea of the eye and damaging vapor. Further, since the activity is high, heat may be generated during work and bumping may occur. In this regard,
Partial hydrolysis condensate obtained by partially hydrolyzing and condensing tetramethoxysilane (hereinafter referred to as "tetramethoxysilane.
(Hereinafter referred to as “oligomer”), it is possible to deal with these problems, to develop a coating film protective layer-forming composition that exhibits excellent coating properties over a long period of time, has reduced toxicity, and has excellent workability. Can be offered.

The hydrolysis-condensation reaction itself for obtaining the partial hydrolysis-condensation product of the organosilicon compound can be carried out by a known method. For example, a predetermined amount of water is added to the above-mentioned tetramethoxysilane monomer to form an acid catalyst. In the presence of the solvent, the alcohol produced as a by-product is distilled off, usually at room temperature to 100 ° C.
React with. By this reaction, methoxysilane is hydrolyzed, and a liquid "tetramethoxysilane oligomer" (average degree of polymerization 2-8, mostly 3-7) having two or more hydroxyl groups is partially hydrolyzed and condensed by a condensation reaction. It is obtained as a thing. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used, and the theoretical amount of water necessary for hydrolytically condensing all the hydrolyzable groups, that is, the alkoxy groups of the organosilicon compound, that is, the number of moles of these groups. It is expressed as a percentage of the actual amount of added water with respect to 1/2 the number of moles of water. In the case of tetramethoxysilane, the degree of hydrolysis is usually about 20 to 80%, preferably 30 to 6
It is selected from about 0%. When it is 20% or less, the residual monomer ratio is high and the productivity is low. If it is 80% or more, the obtained tetramethoxysilane oligomer tends to gel.

The partially hydrolyzed condensate thus obtained usually contains about 2 to 10% of a monomer. If this monomer is contained, the protective layer-forming composition may lack storage stability. Therefore, the content of the monomer is 1% by weight.
Hereafter, the monomer may be removed so that the content is preferably 0.3% by weight or less. This monomer removal can be performed by flash distillation, vacuum distillation, inert gas injection, or the like. When an organosilicon compound other than tetramethoxysilane is used to form a partially hydrolyzed condensate, hydrolysis or the like can be carried out by an operation according to the above method. That is, in the present invention, a partially hydrolyzed condensate of an organosilicon compound can be preferably used as the hydrolyzate of the organosilicon compound.

In the present invention, as a more preferred form of the hydrolyzate of the organosilicon compound, the above organosilicon compound and / or its partially hydrolyzed condensate can be theoretically hydrolyzed and condensed by 100% ( Hereinafter, these hydrolysates obtained by blending more than "hydrolyzed 100% equivalent of water") can be used. That is, water is added in an amount equal to or more than that required for hydrolytically condensing all the hydrolyzable groups of the organosilicon compound, that is, the alkoxy groups. The same applies when a partially hydrolyzed condensate of an organosilicon compound is used, and water is added in an amount not less than that required for hydrolytically condensing the remaining alkoxy groups.

As described above, any amount may be used as long as the hydrolysis is 100% equivalent or more.
The amount is 1 to 4 times, more preferably 1 to 2 times, and particularly preferably 1 to 1.5 times the% equivalent. The amount of water is 100% hydrolyzed
If it exceeds 4 times the equivalent weight, the storage stability of the composition for forming a protective layer for a transfer foil may be lowered in some cases. If the hydrolysis is less than 100% equivalent, the physical properties such as hardness of the resulting protective layer may not be sufficient.

In the present invention, a diluent can be further added. Addition of a diluent improves the storage stability of the resulting protective layer-forming composition. As the diluent, water or an organic solvent can be used depending on the purpose. When water is used, the amount of the added water may be increased to dilute it, or the resulting protective layer-forming composition may be diluted with an arbitrary amount of water.

As the organic solvent, alcohols,
Or glycol derivatives, hydrocarbons, esters,
One or a mixture of two or more of ketones, ethers and the like is used. The alcohol is methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, octanol, n-propyl alcohol, acetylacetone alcohol, etc., and the glycol derivative is ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n. -Propyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate.

The hydrocarbons include benzene, kerosene,
Toluene, xylene, etc. can be used, and as esters,
Methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like can be used. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone, and ethers such as ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan and tetrahydrofuran can be used.

Of these solvents, alcohols, especially C
₁ -C ₄ methanol, ethanol, preferably from the isopropanol or butanol good storage stability in is liquid is easy to handle, also the properties of the resulting coating film is excellent. Furthermore, by using methanol or ethanol among these, a coating film having extremely high hardness can be easily obtained.

When an organic solvent such as alcohol is used as the diluent, the amount of the solvent to be added is 50 with respect to 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product.
Up to 5000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is 50 parts by weight or less, the storage stability of the composition for forming a protective layer is lowered, and gelation easily occurs. If it exceeds 5000 parts by weight, the thickness of the protective layer obtained becomes extremely thin.

When water is used as the diluent, the blending amount is, for example, 10 parts of the above-mentioned hydrolysis based on 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product.
20 to 300 parts by weight in total with 0% equivalent of water are suitable. When water is used as the diluent, gelation of the compound is more likely to occur than when an organic solvent such as methanol or ethanol is used, and therefore pH is 3 or less, preferably pH 1 or less.
Keeping at ~ 2 prevents gelation. Therefore, p
The type and addition amount of the catalyst used to maintain H may be appropriately selected according to the amount of dilution water.

In the present invention, a curing catalyst can be added if necessary. Examples of the catalyst include inorganic acids such as hydrochloric acid, acetic acid, nitric acid, formic acid, sulfuric acid, and phosphoric acid, organic acids such as paratoluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, and oxalic acid, potassium hydroxide, and hydroxide. Alkali catalysts such as sodium potassium hydroxide and ammonia, organic metals, metal alkoxides such as dibutyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate and other organotin compounds, aluminum tris (acetylacetonate), titanium tetrakis (acetylacetate). ), Titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetone) G) and zirconium bis (isopropoxy) bis (acetylacetonate) and other metal chelate compounds, boron butoxide, boric acid and other boron compounds, and the like, but the storage stability of the composition for forming a protective layer and the resulting coating One or two kinds of organic acids such as acetic acid, maleic acid, oxalic acid, and fumaric acid, metal chelate compounds, boron compounds, and metal alkoxides from the viewpoint of excellent properties such as hardness and flexibility of the film. It is better to use the above.

It should be noted that the type of catalyst desired is the diluent used,
Also, it can be appropriately selected depending on the type of the transferred material to be transferred and the application. For example, hydrochloric acid as a catalyst,
When a strong acid such as nitric acid is used, it has good storability in a liquid, the time required for aging described below can be shortened, and the hardness of the resulting protective layer is excellent, but especially for a substrate that is easily corroded. On the other hand, there are some things you should avoid. On the other hand, for example, maleic acid has little fear of corrosion and the like, the aging time is relatively short, the hardness of the obtained coating film,
Characteristics such as storage stability in liquid are particularly excellent, which is desirable.

When methanol or ethanol is used as a diluent, in addition to the above-mentioned acid catalyst, for example, aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetate). ), Titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate) and zirconium bis (isopropoxy).
Even when a metal acetylacetonate compound such as bis (acetylacetonate) is used, the protective layer having sufficient hardness can be obtained without impairing the storage stability in a liquid.

The amount of these catalyst components added is not particularly limited as long as it can exhibit the function as a catalyst, but usually 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product is used. On the other hand, it is selected from the range of about 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. The method of blending these components is not particularly limited, and a more uniform blend may be prepared by, for example, using a catalyst component dissolved in water in advance, or blending with stirring. When a catalyst that is easily decomposed by water or other solvent is used, it is preferable to mix this with the organosilicon compound and / or its partial hydrolysis-condensation product, and mix with water or other solvent before use. Further, the catalyst component may be added to other components when used.

In the present invention, a liquid obtained by blending these components (hereinafter referred to as "blended liquid") is aged to allow hydrolysis reaction of the organosilicon compound and / or its partial hydrolysis-condensation product. It is especially desirable to do so. By passing through such an aging step, the partial crosslinking reaction by hydrolysis and condensation of the organosilicon compound and / or its partial hydrolyzed condensate is sufficiently advanced, and the organosilicon compound and / or its hydrolyzate has a hydroxyl group or an alkoxy group. It has a large number of reactive groups capable of being hydrolyzed and polycondensed, such as a group, especially a highly reactive hydroxyl group. Further, since the hydrolyzate may form fine particles described later, it is considered that the resulting protective layer has excellent properties. The liquid mixture may be left to stand for aging, but may be stirred. The time for standing is sufficient for the above-mentioned partial crosslinking reaction to proceed to the extent that the desired membrane properties can be exhibited, and depends on the type of diluent and the type of catalyst used. For example, when methanol or ethanol is used as the diluent, hydrochloric acid is sufficient at room temperature for about 1 hour or more, and maleic acid is for several hours or more, preferably about 8 hours to 2 days.

When water is used as the diluent, the pH
By hydrolyzing with stirring at 3 or less, preferably pH 1-2, with stirring for 1 to 180 minutes, usually about 5 to 20 minutes, the affinity with water increases and a transparent and uniform liquid material is obtained. After obtaining a transparent liquid in this way, it is desirable to leave it for 1 to 2 hours. The time required for aging is also affected by the ambient temperature, and in extreme cold regions it may be better to take measures such as heating to around 20 ° C. Generally, aging proceeds rapidly at high temperatures, but gelation occurs when heated to 100 ° C. or higher, so heating to 50 to 60 ° C. is suitable at most.

By sufficiently aging, it is possible to prevent whitening and peeling of the resulting protective layer. In general, aging is sufficient if the reaction mixture is allowed to cool to room temperature after the exothermic heat of hydrolysis is completed and left to stand for a time to complete the partial crosslinking reaction. In the compounded liquid of the present invention (hereinafter referred to as "aged product") thus aged, fine particles having an inertia radius of 10 Å or less, which are composed of a hydrolyzate of an organosilicon compound and / or a partial hydrolyzed condensate thereof ( Hereinafter, "reactive ultrafine silica") can be formed and can be easily confirmed by means such as small-angle X-ray scattering.
That is, due to the presence of the fine particles, the diffraction intensity distribution of incident X-rays is diffuse scattering called central scattering in the incident line direction,
That is, it shows small-angle X-ray scattering. The scattering intensity I is
It is given by the equation of inier. ^{I = C exp (-H 2 Rg} 2/3) (I: scattering intensity,
H: Scattering vector (= πsin2θ / λ), Rg: Inertial radius of microparticles, C: Const, λ: Incident X-ray wavelength, 2θ: Spread angle) Taking the common logarithm of both sides of the above Guinier's equation,
^{logI = logC- (H 2 Rg 2} /3) next, therefore, if there is fine particles, and measuring the tides, plotting the log-log graph for scattering vector, by determining the slope, the inertia of the fine particle radius Can be asked.

By the aging step described above, the hydrolyzate of the organosilicon compound and / or its partial hydrolyzed condensate forms such reactive ultrafine silica, and has an excellent affinity with the organic components described below. The cross-linking reactivity between the components becomes excellent even during film formation. Water or other various solvents or dispersion media can be further added to the aged product. In particular, when water is used as a diluent and pH is set to 3 or less when a mixed solution is obtained, it is desirable to add these to make a weak acid having a pH of about 3 to 5 for convenience of use. A strong acid having a pH of 3 or less causes problems such as corrosion of the base material and is inconvenient to use, and when it is neutral to alkaline, it easily gels and may cause a problem in storage stability of the liquid. Is.

When water is added as a diluent and water is further added to the aged product, the total amount of water to be added is usually 200 to 100, based on 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product. 000 parts by weight, preferably 350
˜35,000 parts by weight. When the weight is 100,000 or more, the resulting protective layer becomes extremely thin. Incidentally, when an organic solvent such as alcohol is used as the diluent, the OH concentration around the fine particles is lower than that when water is used as the diluent, so that the storage stability is further excellent. The organic components mentioned can also be added.

In the present invention, an organic component is then added to the above-mentioned organosilicon compound and / or its hydrolyzate. The first component (hereinafter referred to as “first component”) of the organic components that can be added has two or more functional groups capable of undergoing a condensation reaction with the above-mentioned organosilicon compound and / or its hydrolyzate. It is a reactive organic compound having a molecular weight of less than 1000. That is, the above-mentioned organosilicon compound and /
Alternatively, the hydrolyzate thereof has a large number of reactive groups capable of being hydrolyzed and polycondensed, such as a hydroxyl group and an alkoxy group. An organic compound having two or more groups capable of undergoing hydrolytic condensation with these reactive groups and having a molecular weight of less than 1000 can be blended with the organosilicon compound and / or its hydrolyzate.

Examples of such a reactive organic compound include a carboxyl group, a hydroxyl group, an amino group,
Examples thereof include those having two or more alkoxy groups (excluding the above-mentioned organosilicon compound and / or its hydrolyzate), and specifically, for example, (i) a silane coupler (generally RSiX ₃ : X is Hydrolyzable group, R is a functional group) (ii) 1,4-butanediol, glycerin, catechol, polyhydric alcohols such as resorcin, and the like.

More specifically, for example, as the silane coupler (i),

Embedded image Such as methyl acrylate,

[0039]

Embedded image Epoxy type,

[0040]

Embedded image H ₂ NC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , H ₂
NC ₂ H ₄ NHC ₃ H ₆ Si (OCH ₃ ) ₃ Si (OC
_{H 3) 3, H 2 NCONHC} 3 H 6 Si (OC
₂ H ₅ ) ₃ , etc., amino-based,

[0041]

Embedded image Vinyls such as CH ₂ ═CHSi (OC ₂ H ₅ ) ₃ , CH ₂ ═CHSi (OCH ₃ ) ₃ , CH ₂ ═CHSi (OC ₂ H ₄ OCH ₃ ) ₃ ,

[0042]

[Image Omitted] HS-C ₃ H ₆ Si (OCH ₃ ) ₃ , HS-
_{C 3 H 6 Si (OC 2} H 5) 3 HS-C 3 H 6 Si (OC
₂ H ₄ OCH ₃ ) ₃ ,

Examples thereof include mercapto type and the like. Any of these can be preferably used, but can be appropriately selected depending on the application of the transfer foil and the like. Further, the above reactive organic compounds may be used in combination of two or more depending on the purpose. When they are used in combination, two or more kinds may be blended in advance, or each may be added to the organosilicon compound and / or its hydrolyzate.

The amount of the reactive organic compound added is usually 1 to 300 parts by weight, preferably 4 parts by weight, based on 100 parts by weight of the organic silicon compound and / or its hydrolyzate as a solid content.
It is in the range of 150 parts by weight. SiO ₂ concentration in the film is 94-5
In the range of 50% by weight, preferably 80 to 10% by weight, particularly excellent membrane characteristics and storage stability in liquid can be expressed. If the amount of the reactive organic compound is too large, the hardness of the resulting protective layer tends to be low, and the storage stability of the protective layer-forming composition tends to be low. Further, when the amount of the reactive organic compound is too small, the flexibility of the protective layer is lowered, and cracks and peeling are likely to occur.

When a silane coupler is used as the reactive organic compound, water is required to hydrolyze the silane coupler. At this time, it may be added together with the silane coupler, or may be added together when water of 100% equivalent or more for hydrolysis is added in advance to hydrolyze the organosilicon compound and / or its partial hydrolysis-condensation product. It doesn't matter. As described above, the addition of the reactive organic compound as the first component has the effects of improving flexibility of the protective layer and preventing cracks and peeling. Further, the workability of the foil is improved, and problems such as cracks and curling of the foil can be prevented even after drying after coating.

Among the organic components which can be added to the organosilicon compound and / or its hydrolyzate in the present invention, the second component (hereinafter referred to as "second component") has a molecular weight of 10
00 or more organic compounds. By adding the second component, the flexibility of the protective layer and the adhesion with the metal vapor deposition film are improved. As the organic compound having a molecular weight of 1000 or more,
It preferably has a molecular weight of 20,000 or more, for example, epoxy-melamine resin, acrylic-melamine resin, melamine resin, urea resin, urea-melamine resin, maleated rosin, phenol resin, benzoguanamine resin, urethane. Resin, urethane-acrylic resin,
Epoxy-acrylate resin, alkyd resin, polyester resin, polyvinyl butyral resin, diallyl phthalate resin, cellulose resin, amide resin and the like are used. In addition, dyes and pigments may be added for coloring, if necessary. As this dye, a direct dye, an acid dye, a basic dye, a sulfur dye, a vat dye, an azoic dye, etc. are used, and as a pigment, an inorganic pigment, a nitro pigment, an azo pigment, a vat dye pigment, a quinacdrin pigment. , Phthalocyanine pigments, nitroso pigments and the like are used.

Among these organic components, even if only one of the first component and the second component is blended with the organosilicon compound and / or its hydrolyzate, the hardness and the like of the conventional protective layer will be improved. The characteristics are improved. However, it is desirable to incorporate both of these components into the aged product from the viewpoint of further improving the characteristics of the protective layer as described above. A preferable ratio of these components is, by weight ratio, the first component: the second component = 1: 1.
It is 0.1 to 1: 5, particularly preferably about 1: 0.3 to 1: 3. Further, the compounding ratio of the organosilicon compound and / or its hydrolyzate and the organic component is 50 to 80% by weight, particularly preferably the organic component, relative to 20 to 50% by weight of the organosilicon compound and / or its hydrolyzate. The organic component is 60 to 70% by weight based on 30 to 40% by weight of the silicon compound and / or its hydrolyzate. When the organic component exceeds 80% by weight, physical properties of the protective layer such as abrasion resistance are deteriorated. On the other hand, if it is less than 50% by weight, the curl of the foil becomes strong. When blending these organic silicon compound and / or its hydrolyzate with an organic component, if necessary, a solvent,
A dispersion medium, a curing catalyst, etc. can be added.

Of these solvents and dispersion media, it is usually preferable to use a solvent because the physical properties of the resulting protective layer and the stability of the protective layer-forming composition in liquid are excellent. Further, as for the kind of the solvent, a suitable one may be selected depending on the material to be transferred, the coating conditions of the transfer foil on the base material, and the like. As the solvent, those having an affinity for both the aged product and the organic component are suitable, for example, alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers, or a mixture of two or more thereof. Can be used.

Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, and octanol, and examples of glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Examples thereof include glycol mono n-propyl ether and ethylene glycol mono n-butyl ether.

The hydrocarbons include benzene, kerosene,
Toluene, xylene, etc. can be used, and as esters,
Methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like can be used. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone, and ethers such as ethyl ether, butyl ether, 2 methyl cellosolve, ethyl cellosolve, dioxane, furan and tetrahydrofuran can be used.

Incidentally, depending on the kind of the reactive organic compound,
Although there are many functional groups, it may be desirable to further add a catalyst to improve the curing rate after film formation, but in general, when an organosilicon compound is used as the hydrolyzate, the catalyst added during hydrolysis, particularly When a catalyst is added to prepare a mixed solution, these catalysts are sufficient. The order of addition when using these solvents and catalysts is not particularly limited and may be appropriately added.

The protective layer-forming composition of the present invention thus obtained is applied to the above-mentioned substrate. The coating itself can be carried out by a conventional method, and is usually performed by gravure coating or reverse coating. The film thickness can be appropriately selected. The film thickness can be selected by a conventional method, for example, by adjusting the concentration of non-volatile components in the liquid and the mesh and depth of the gravure plate. When the reverse coating is used, it can be adjusted by the concentration of non-volatile components in the liquid and the roll gap.

Furthermore, a metal vapor deposition layer and an adhesive layer can be provided by a conventional method. The metal vapor deposition layer used for the transfer foil of the present invention is not particularly limited, and any layer used for a normal transfer foil can be used. The metal vapor deposition layer is made of a metal or a metal compound, and examples of the metal include aluminum, gold, silver, copper, nickel, chromium, titanium, stainless steel, iron, cobalt, molybdenum, rhodium, palladium, gallium, indium, zinc, tin and tantalum. , Platinum, lead and the like can be used in the form of a simple substance, an alloy or a mixture. Aluminum is usually used and gold is often used for high-grade purposes, but it is appropriately used depending on the field of use.

In addition, alloys and compounds such as nickel chromium, silver-copper alloy, brass and zinc sulfide can also be used as the metal vapor deposition layer. The metal vapor deposition layer may be formed of one kind of material, but may be formed of two or more kinds. The metal vapor deposition layer usually has a uniform thickness, but it may be provided nonuniformly. Its thickness is usually 20-2
The range is about 00 nm, and the range from 35 to 65 nm is particularly preferable. If the thickness of the metal vapor deposition layer obtained by vapor deposition is less than 20 nm, the metallic luster is poor and it is not preferable (if the intense metallic luster is not desired, it is also selected from the range of 20 nm or less). On the other hand, even if it exceeds 200 nm, the brightness does not increase, and on the contrary, cracks are likely to occur, which is not preferable.

To form the metal vapor deposition layer, for example, the metal or metal compound is used to form a vapor deposition film by a conventional vapor deposition system such as a resistance heating system, a high frequency induction heating system, and an electron beam heating system. The adhesive used in the adhesive layer in the transfer foil of the present invention is not particularly limited and may be appropriately selected from the adhesives used in ordinary transfer foils. For example, vinyl acetate type, vinyl chloride type, vinyl chloride-vinyl acetate copolymer, acrylic type, polyethylene type, styrene-butadiene type, ethylene-vinyl acetate type, polyester type, chlorinated rubber type, chlorinated polypropylene type, epoxy type, The adhesive is appropriately selected and used from emulsion adhesives and organic solvent adhesives containing xylene-based, urea-based, alkyd-based, urethane-based, silicone-based, etc. adhesives alone or a mixture thereof as a main component.

[0056]

The present invention will be described in more detail with reference to the following examples. Parts and% are by weight unless otherwise specified. Example 1 [Synthesis of tetramethoxysilane oligomer] To a 500 ml four-necked round bottom flask equipped with a stirrer, a condenser for reflux and a thermometer, 234 g of tetramethoxysilane and 74 g of methanol were added and mixed, and then a mixture of 0. 22.2 g of 05% hydrochloric acid was added, and a hydrolysis reaction was performed at an internal temperature of 65 ° C. for 2 hours.

Then, replace the condenser with a distilling pipe,
The temperature was raised until the internal temperature reached 130 ° C., and methanol was distilled off. Thus, a partially hydrolyzed condensate was obtained (partial hydrolysis rate 40%). Oligomers having a degree of polymerization of 2 to 8 were confirmed, and the weight average molecular weight was 550. The amount of monomer in the tetramethoxysilane oligomer was 5%. Subsequently, the tetramethoxysilane oligomer was placed in a flask heated to 130 ° C., the vaporized monomer was discharged out of the system together with an inert gas, and the temperature was raised to 150 ° C. and maintained for 3 hours. The amount of monomers in the tetramethoxysilane oligomer thus obtained was 0.2%.

[Preparation of protective layer forming composition] To 100 g of the tetramethoxysilane oligomer thus obtained, 200 g of ethanol was added, and then 1 g of maleic acid and 23.7 g of dechlorinated water were added. The amount of water added is 127% with respect to the amount which theoretically completely hydrolyzes and condenses the tetramethoxysilane oligomer. Aged at room temperature for 2 days,
An aged product was obtained. Then, after adding 64.7 g of a silane coupler having the following structural formula (product number S210 manufactured by Chisso), 2
Left for hours. Further, as a solvent, 1000 g of methyl isobutyl ketone and 200 g of cyclohexanone were added,
Further, as an organic compound having a molecular weight of 1000 or more, 500 g of an epoxy-melamine resin, 200 g of an acryl-melamine resin, and 90 g of a maleinized rosin were added, and the mixture was left to stir for 2 hours to obtain a liquid protective layer-forming composition.

Embedded image CH ₂ ═CHSi (OCH ₃ ) ₃

[Manufacture of Transfer Foil] The above-mentioned composition for forming a protective layer was applied by a gravure coating method to the release layer side of a 12 μm-thick biaxially stretched polyethylene terephthalate film coated with a release layer and dried. A 1.2 μ thick protective layer was formed. A thin aluminum film is formed on this protective layer by a vacuum vapor deposition method, and then an adhesive solution is applied on the aluminum vapor deposition layer by a reverse coating method and dried to form an adhesive layer having a thickness of 1 μm. Obtained.

[0060] aging product obtained in Preparation Preparation of protective layer-forming composition] The above [confirmation microparticles] (hereinafter referred to as "composition A", SiO ₂ in terms of 16 wt%, 8.1vol
%), And a liquid obtained by diluting this with ethanol about 4 times (hereinafter referred to as “composition B”, a concentration converted to SiO _{2 of} 4.3% by weight, 2
vol%) was analyzed by small-angle X-ray scattering under the following conditions. Measuring device: Kratonki compact camera manufactured by Anton Paar Co. X-ray source: 50kV, 200mA, Cu-Kα ray is monochromatic by Ni-filter. Optical system condition: Distance between sample and light receiving slit = 20cm
Inner vacuum path = 19cm Entrance slit = 80μm, Light receiving slit = 20
0 μm, beam len gth 16 mm

Sample cell: Quartz capillary (diameter about 1 mm, wall thickness 10 μm) Other conditions: room temperature. step scan operation range 2θ
= 0.086 to 8.1 deg 90 sec / point Data correction: Background correction was performed by using scattering when the quartz capillary was filled with water. X-ray absorption correction was also performed. Analysis software:.. Slits correction and inverse Fourier transform analysis software ITP-81 (O.Glatter; J.Appl.Cryst, 10 41
5-421 (1977). )It was used.

Compositions A and B are shown in FIGS. 1 and 2.
The measurement data (background correction and absorption correction) of the scattering intensity with respect to the moving distance of the scattered X-rays in the light receiving slit are shown. FIG. 3 and FIG. 4 show point beam data after slit correction of the composition A and the composition B.
From these FIGS. 3 and 4, Guinier's formula I = C e
xp (−H ² Rg ² 3) (I: scattering intensity, H: scattering vector (= 2πsin2θ / λ), Rg: radius of gyration, C: C
onst, λ: Cu-Kα ray wavelength, 2θ: divergence angle), the maximum value of the radius of gyration is calculated, and as shown in FIG. 5 and FIG. From radius R = (5/3) ^1/2 Rg, radius 9.0
Å), and for composition B, it was 6.0 Å (radius 7.7 Å assuming a spherical shape). In addition, FIGS. 7 and 8 show the results of obtaining the distribution of the radius (assumed to be spherical) by inverse Fourier transforming FIGS. 3 and 4. The maximum radii were about 6Å and 7Å, respectively. The tetramethoxysilane oligomer obtained in [Synthesis of tetramethoxysilane oligomer] was analyzed by small-angle X-ray scattering under the same conditions as in [Confirmation of fine particles]. FIG. 9 shows the measurement data of the scattering intensity. As is clear from this, the structure of fine particles etc. was not recognized.

Example 2 A transfer foil was obtained in the same manner as in Example 1 except that the azo pigment was dispersed in the organic compound having a molecular weight of 1000 or more obtained in Example 1.

Comparative Example 1 A melamine resin 50 was applied to the release layer side of a 12 μm-thick biaxially stretched polyethylene terephthalate film coated with the release layer.
0g, 700g maleated rosin, 500g polyisocyanate, 1500g methyl isobutyl ketone, 500g cyclohexanone (hereinafter referred to as "protective layer forming solution") is applied by gravure coating method and dried to protect 1.2μ thick. Layers were formed. A thin aluminum film is formed on this protective layer by a vacuum vapor deposition method, and then an adhesive solution is applied on the aluminum vapor deposition layer by a reverse coating method and dried to form an adhesive layer having a thickness of 1 μm. Obtained.

Comparative Example 2 A transfer foil was obtained in the same manner as in Comparative Example 1 except that the azo pigment was dispersed in the protective layer forming solution of Comparative Example 1. After transferring the transfer foils obtained in Examples and Comparative Examples to a PP molded article as a subject, the weather resistance, scratch resistance, and content resistance of the protective layer exposed on the surface were evaluated by the following evaluation methods. The results are shown in Tables 1, 2 and 3.

<Evaluation Method> Regarding the weather resistance, the degree of deterioration of the coating film of the above-mentioned transferred product was evaluated by a sunshine weatherometer and evaluated according to the following criteria. Degree of deterioration No change was observed in the test piece (sample): 3 Some cracks were found in the test piece (sample): 2 Full cracks were found in the test piece (sample): 1

With respect to scratch resistance, an abrasion test was conducted on the above-mentioned transfer product by a traverse method, and the degree of scratches on the coating film was evaluated according to the following criteria. No change observed on the test piece (sample): 3 Slight scratches on the test piece (sample): 2 Scratches on the entire surface of the test piece (sample): 1

Regarding the content resistance, the above-mentioned transfer product was covered with gauze moistened with the content, and further wrapped with wrap to 40 ° C.
Leave in the atmosphere for 24 hours. Then, the transfer surface was rubbed 10 times with the gauze to evaluate the appearance of the transfer surface. As for the contents, shower colon, hair nick, rinse, and hair restorer were used. The test results were evaluated according to the following criteria. No change is observed in the test piece (sample): 3 Partial desorption of the coating film of the test piece (sample) is observed: 2 Full desorption is observed in the test piece (sample): 1

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

According to the present invention, it is possible to obtain a transfer foil having a protective layer which is excellent in scratch resistance, weather resistance, chemical resistance and corrosion resistance in addition to the decorative function.

[Brief description of the drawings]

FIG. 1 Measurement data of scattering intensity of composition A

FIG. 2 Measurement data of scattering intensity of composition B

FIG. 3 Point beam data of Composition A after slit correction

FIG. 4 Point beam data of Composition B after slit correction

FIG. 5: Distribution of the radius of gyration of the microparticles in composition A

FIG. 6 Distribution of radii of gyration of fine particles in composition B

FIG. 7: Distribution of assumed spherical spheres of fine particles in composition A

FIG. 8: Assumed sphere distribution of fine particles of composition B

FIG. 9: Measurement data of scattering intensity of tetramethoxysilane oligomer obtained in Example 1 [Synthesis of tetramethoxysilane oligomer]

FIG. 10: Structure of metallic transfer foil

FIG. 11 Structure of pigment transfer foil

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minor Maeda 125 Takeda Mukoyo-cho, Fushimi-ku, Kyoto-shi, Kyoto Prefecture Oike Development Laboratory Co., Ltd. (72) Inventor Hideki Yamanouchi 4 Fushimi-cho, Chuo-ku, Osaka-shi, Osaka 1-chome Mitsubishi Chemical Co., Ltd. Osaka Branch (72) Inventor Seiichiro Tanaka 1-1 Kurosaki Shiroishi, Hachimannishi-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki Development Laboratory (72) Inventor Kenji Oba Kurosaki Shiroishi, Hachimannishi-ku, Kitakyushu No. 1 in Mitsubishi Chemical Corporation Kurosaki Development Laboratory

Claims (17)

[Claims] 1. A release agent layer is provided on one surface of the base material if necessary,
Further, in a transfer foil having a transfer film formed of at least a protective layer, a metal vapor deposition layer and an adhesive layer, the protective layer comprises an organosilicon compound represented by the following general formula [A] and / or a hydrolyzate thereof and Reactive organic compound having a molecular weight of less than 1000 and / or a molecular weight of 10 and having two or more functional groups capable of undergoing a condensation reaction with a silicon compound and / or a hydrolyzate thereof.
A transfer foil, which is obtained by coating a substrate with a composition obtained by blending more than 00 organic compounds. Embedded image 2. An organosilicon compound represented by the general formula [A] and / or a hydrolyzate thereof and a functional group capable of undergoing a condensation reaction with the organosilicon compound and / or a hydrolyzate thereof.
A protective layer for a transfer foil, which is obtained by coating a substrate with a composition obtained by blending a reactive organic compound having a molecular weight of less than 1000 and / or an organic compound having a molecular weight of more than 1000. 3. An organosilicon compound represented by the general formula [A] and / or a hydrolyzate thereof and a functional group capable of undergoing a condensation reaction with the organosilicon compound and / or a hydrolyzate thereof.
A method for producing a protective layer-forming composition for a transfer foil, which comprises blending a reactive organic compound having a molecular weight of less than 1000 and / or an organic compound having a molecular weight of more than 1000. 4. A liquid containing fine particles having a radius of inertia of 10 Å or less, which is composed of a hydrolyzate of an organosilicon compound represented by the general formula [A], and can be condensed with a functional group capable of undergoing a condensation reaction of the fine particles. Molecular weight 1000 with 2 or more functional groups
A method for producing a protective layer-forming composition for a transfer foil, comprising adding a reactive organic compound of less than 1 and / or an organic compound of more than 1000 in terms of molecular weight. 5. Fine particles having an inertia radius of 10 Å or less are added to an organosilicon compound and / or a partial hydrolyzed condensate thereof in an amount not less than theoretically 100% hydrolytically condensable and further aged. It is what was obtained, The manufacturing method of the protective layer forming composition for transfer foils of Claim 4 characterized by the above-mentioned. 6. The method for producing a protective layer-forming composition for a transfer foil according to claim 3, wherein the hydrolyzate of the organosilicon compound represented by the general formula [A] is a partially hydrolyzed condensate. . 7. A hydrolyzate of an organosilicon compound represented by the general formula [A] is added to an organosilicon compound and / or a partial hydrolytic condensate thereof in an amount equal to or more than 100% theoretically for hydrolytic condensation. The method for producing a protective layer-forming composition for a transfer foil according to claim 3, 4 or 5, which is obtained by mixing water. 8. A hydrolyzate of an organosilicon compound represented by the general formula [A] is added to an organosilicon compound and / or a partial hydrolyzed condensate thereof in an amount of 100% or more theoretically for hydrolytic condensation. The method for producing a protective layer-forming composition for a transfer foil according to claim 3, 4 or 5, which is obtained by mixing water and further aging. 9. The method for producing a protective layer-forming composition for a transfer foil according to claim 3, wherein the organosilicon compound represented by the general formula [A] is tetramethoxysilane. 10. A partially hydrolyzed condensate of an organosilicon compound represented by the general formula [A] is tetramethoxysilane.
It is an oligomer, The manufacturing method of the protective layer forming composition for transfer foils in any one of Claims 5-8 characterized by the above-mentioned. 11. The method for producing a protective layer-forming composition for a transfer foil according to claim 5, 8 or 9, wherein the aging is carried out at pH 1-3. 12. The method for producing a protective layer-forming composition for a transfer foil according to claim 5, 8, 9 or 11, wherein a solvent other than water is present during aging. 13. The method for producing a protective layer-forming composition for a transfer foil according to claim 10, wherein the content of the monomer in the tetramethoxysilane oligomer is 1% by weight or less. 14. A reactive organic compound having a molecular weight of less than 1000 and having at least two functional groups capable of undergoing a condensation reaction with an organosilicon compound and / or a hydrolyzate thereof, and using at least one component having the following structural formula. Claim 3
A method for producing a protective layer-forming composition for a transfer foil according to any one of 1 to 13. Embedded image Embedded image Embedded image H ₂ NC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , H ₂ N
_{C 2 H 4 NHC 3 H 6} Si (OCH 3) 3, H 2 NCO
_{NHC 3 H 6 Si (OC 2} H 5) 3, embedded image _{CH 2 = CHSi (OC 2 H} 5) 3, CH 2 = CHSi (OCH 3) 3, CH 2 = CHSi (OC 2 H 4 OCH 3 ) ₃ , HS-C ₃ H ₆ Si (OCH ₃ ) ₃ , HS-C
_{3 H 6 Si (OC 2 H} 5) 3 HS-C 3 H 6 Si (OC 2 H 4 OCH 3) 3 15. The method for producing a protective layer-forming composition for a transfer foil according to claim 12, wherein the solvent is a C ₁ -C ₃ monohydric alcohol. 16. The transfer foil according to claim 5, wherein aging is performed in the presence of at least one of acetic acid, maleic acid, oxalic acid, and fumaric acid as a curing catalyst. For producing a protective layer-forming composition for a car. 17. An organic compound having a molecular weight of more than 1000 is epoxy-melamine resin, acrylic-melamine resin, melamine resin, urea resin, urea-melamine resin, maleated rosin, phenol resin, benzoguanamine resin. , Urethane resin, urethane-acrylic resin, epoxy-acrylate resin, alkyd resin, polyester resin, polyvinyl butyral resin, diallyl phthalate resin, cellulose resin, amide resin Item 17. A method for producing the protective layer-forming composition for a transfer foil according to any one of Items 3 to 16.