JPH0729397B2 - Colored film with excellent appearance and weather resistance - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel and useful colored film having good surface gloss and excellent weather resistance, and more specifically, to a specific substrate. First, a substantially transparent surface layer, and then a colored layer are sequentially formed, which is a colored film for protecting and beauty of articles used particularly outdoors, and for displaying characters and patterns. Regarding

[Conventional technology]

Conventionally, a colored film is attached to the surface of various substrates as described above in order to improve the appearance and weather resistance of a metal exterior building material or a synthetic resin molded article, or to display letters or patterns. Is being done.

However, such a colored film is often inferior in surface glossiness because it contains a metal powder or pigment in a binder containing a vinyl chloride resin as a main component, and moreover, such a vinyl chloride resin is originally Combined with poor weather resistance, metal powder, pigments and the like deteriorate directly due to air, moisture, etc. that come into contact with them, resulting in insufficient weather resistance.

In order to improve such a defect, a method of laminating a clear film on the surface of the colored layer has also been proposed.

Although it can be improved to a certain extent by such a method, since the coloring binder has almost no cross-linking structure, the ability to protect the metal powder and / or the coloring pigment is small, and the long-term In the case of being used outdoors for a long time, there is a drawback that the surface layer and the coloring layer are peeled off or a significant discoloration is caused, resulting in deterioration of aesthetics.

[Problems to be solved by the invention]

However, as a result of diligent studies aimed at solving various problems in the prior art as described above, the present inventors have found that a substantially transparent thermoplastic surface layer further has a crosslinkable (curable) resin composition. The present invention has been completed by finding that a colored film excellent in the desired appearance and weather resistance can be obtained by laminating a colored layer by using.

[Means for solving problems]

That is, according to the present invention, a surface layer (I) is formed by using a thermoplastic resin composition (A) having excellent durability on a substrate having good releasability and surface smoothness, and then the surface layer (I) is formed. A crosslinked resin composition (B) containing a metal powder and / or a color pigment is used on (I) to form a colored layer (I
I) which has excellent appearance and durability obtained by forming I) and is attached to the surface of articles used outdoors, especially to protect the surface and make it cosmetic, and to form letters and patterns. The present invention intends to provide a colored film that can be used for

Here, first, the above-mentioned surface layer (I) is formed by coating a thermoplastic resin composition (A) having excellent durability on a substrate having good releasability and surface smoothness, and evaporating the solvent. The thermoplastic resin composition (A) is typically formed of a urethane resin, a fluorine resin, and / or an acrylic resin. Is used in the form of a solution or dispersion, and is further disclosed in JP-A-57-1330.
It is used in the form of a solution or dispersion of a polymer as disclosed in Japanese Patent No. 62/62.

As the UV absorber used in preparing the resin composition (A), known and commonly used UV absorbers can be applied as they are, but among them, benzotriazole-based or benzophenone-based UV absorbers are preferable, and the amount thereof is used. Is from 0.1 to 20 per 100 parts by weight of the thermoplastic resin as listed above.
The proportion of parts by weight is suitable.

In addition, in preparing the resin composition (A), typical examples of coloring pigments used as necessary include titanium oxide, iron oxide, carbon black, or scaly mica treated with titanium oxide. Inorganic pigments such as those listed above, or organic pigments such as cyanine-based or quinacridone-based pigments.

The amount of these color pigments to be used should be determined according to the required appearance and color tone of the colored film, but usually 100 of the above-mentioned thermoplastic resin is used.
2 parts by weight or less is suitable for the parts by weight, in short,
It should be within the range that does not impair the transparency of the surface layer (I).

The thermoplastic resin composition (A) thus obtained may further contain, if necessary, various known and commonly used additives such as light stabilizers, antioxidants, flow control agents, surface tension improvers or matting agents. Of course, the components can be added and blended.

Further, as the above-mentioned substrate having good releasability and surface smoothness, which is used for forming the surface layer (I) using the resin composition (A) thus obtained, a steel plate having a smooth surface can be used. , Chrome or copper, etc., that has been plated, or waxes on it,
Known release agents such as silicones or amides such as stearic acid amide are coated, or a polymer compound material having a smooth surface, such as polyvinyl alcohol film, polyethylene film, polypropylene film, A typical example is a polyamide film, a cellophane film, a polyvinyl chloride film (salt vinyl film), a saturated polyester film (mylar), or the like coated with various release agents such as those listed above.

It is needless to say that these substrates should be appropriately selected according to the properties of the various thermoplastic resin compositions (A) as described above and the drying conditions, but in practice, polymeric compound materials are preferred. Post-processing is easy and advantageous.

And coating the surface layer (I) on these substrates,
Formation can be carried out by a known and commonly used method such as brush coating, dip coating, roll coating, knife coating, flow coating or spray coating. In particular, in terms of productivity and layer uniformity, a roller or knife is used. It is preferable that the dry laminating method is used.

In coating the surface layer (I), the type of solvent and the drying conditions in the resin composition (A) described above are not particularly limited, and may depend on the characteristics of the resin used and the drying method. It is desirable to select appropriately.

The thickness of the surface layer (I) thus formed is 30.
If it is too thin, the appearance and weather resistance are insufficient, and if it is too thick, it becomes difficult to prepare the sheet of the present invention, and it is also disadvantageous from the economical point of view. Therefore, both are not preferable.

On the other hand, the colored layer (II) formed on the surface layer (I) is formed by coating a crosslinkable resin composition (B) containing a metal powder and / or a coloring pigment. is there.

Such a cross-linking, so-called curable resin composition (B) means a solution or dispersion of a resin containing a functional group (reactive group) in the molecule, such as a metal powder and / or a coloring pigment as described below. In addition to the above, it is a combination of a curing agent having reactivity with the functional group, the functional group has a self-crosslinking property, or is a form that can be crosslinked by moisture in the air, so-called room temperature curing It is mainly a solution or dispersion of a thermosetting or thermosetting resin.

If necessary, a curing aid or a curing catalyst may be added to the crosslinkable curable resin composition.

Representative examples of the above-mentioned resin having a functional group (reactive group) include an acrylic resin, a fluorine resin, a vinyl resin, a polyether resin, a polyester resin or a urethane resin containing a functional group as shown below. There is.

When the functional group (reactive group) present in the resin is a hydroxyl group, suitable curing agents include aminoaldehyde resins, isocyanate compounds or metal alkoxide compounds, and the functional group is an amino group. Examples of the curing agent for the resin include a polyvalent epoxy compound or a polyvalent carboxylic acid compound, and examples of the curing agent for the resin whose functional group is an epoxy group include a polyvalent amine compound, a polyvalent carboxylic acid compound, and a polyvalent phosphoric acid compound. Examples thereof include polyvalent thiol compounds and polyvalent isocyanate compounds, and examples of suitable curing agents for resins having a carboxyl group as a functional group include polyvalent epoxy compounds and polyvalent amine compounds.

The above-mentioned self-crosslinking (self-curing) resin contains an unsaturated bond and is one which is cross-linked and cured by polymerization with an initiator or ultraviolet rays or ionizing radiation, or N-methylol conversion. Examples of the resin containing a (meth) acryl amide group and / or an alkyl ether compound, and on the other hand, examples of the resin that is crosslinked and cured by moisture in the air include those containing an isocyanate group or an alkoxysilyl group. Can be mentioned.

The resins and curing agents having various functional groups listed above, self-crosslinking (self-curing) resins, and resins that can be crosslinked and cured by moisture in the air are all known and commonly used resins. And one or a mixture of two or more selected appropriately from those used as a curing agent.

The crosslinkable resin composition (B) thus obtained may further contain, if necessary, various known and commonly used additives such as an ultraviolet absorber, an antioxidant, a flow regulator, a light stabilizer or a surface tension improver. Of course, the components can be added and blended.

Next, typical examples of the above-mentioned metal powder include gold powder, silver powder, brass powder, aluminum powder, and copper powder.

On the other hand, typical examples of the above-mentioned coloring pigments include titanium oxide, iron oxide, carbon black, or inorganic pigments such as those obtained by subjecting scaly mica to titanium oxide treatment, or organic pigments such as cyanine-based or quinacridone-based pigments. is there.

The amount of these metal powders and / or color pigments to be used should be determined according to the required appearance and color tone of the coating film. A suitable range is 1 to 100 parts by weight with respect to parts by weight.

There are various methods for coating and forming the colored layer (II) on the surface layer (I). Among them, the surface layer (I) and the colored layer prepared in advance are available. (I
I) A method of press-bonding a film and a film under heating, a so-called adhesive layer is layered on the surface layer (I) using a known and commonly used adhesive, and then a coloring layer prepared in advance is formed thereon. (II) A method of sticking the film, forming an adhesive layer on the coloring layer (II) film prepared in advance,
Then, the surface layer (I) and the colored layer (II) are attached to each other via the adhesive layer, or the crosslinkable resin composition (B), that is, various kinds of the above-mentioned various kinds of resin compositions, is added to the surface layer (I). Metal powder and / or solution or dispersion of functional group-containing resin
Alternatively, a so-called coloring layer (I
I) A typical method is to apply a forming material, dry it, and cure it.

Here, as the method for preparing the above-mentioned colored layer (II) film, the same cross-linking resin composition on the releasable substrate as that used in the preparation of the above-mentioned surface layer (I) is used. The substance (B), that is, a solution or dispersion liquid of various functional group-containing resins as described above, is mixed with a metal powder and / or a color pigment, and if necessary, other components such as a curing agent are mixed. There is a method of applying a coloring layer (II) forming material and drying and curing.

When the colored layer (II) film is prepared in any of the above-mentioned manners and in the above-mentioned manners (1) to (3), brush coating, dip coating, roll coating, knife coating, flow coating or spraying is used. The coating can be carried out by a known and commonly used coating method such as coating, but in view of productivity and layer uniformity, it is preferable to use a dry laminating method using a roller or a knife.

In coating and forming such a colored layer (II), the type of solvent of the material for forming the colored layer (II), which is a crosslinkable resin composition (B) containing a metal powder and / or a coloring pigment, and drying conditions, etc. Is not particularly limited, and the colored layer (I
I) It is desirable to select appropriately according to the characteristics of the resin used as the forming material.

The thickness of this colored layer (II) is 30 to 200 μm.
Within the range, it is appropriate.

The thus-obtained colored film of the present invention has a colored layer (II) layered on the surface layer (I), which is a surface behind the surface layer (I), that is, a layer which is opposed to the surface layer (I). If not, apply a known and commonly used adhesive to the other surface of the colored layer (II), or apply a known and commonly used adhesive to the surface of the article to which the colored film is to be attached, and It can be used in the form of sticking, or by heat-pressing the colored layer (II) film as described above and such an article.

Among them, in particular, an adhesive is applied to the surface of the above-mentioned colored layer (II) which is dorsal to the surface layer (I), that is, the other surface of the colored layer (II) which is not opposed to this layer (I). It is convenient to put the colored film of the present invention into practical use in such a form that it is coated and then the adhesive coated surface is protected by a known and commonly used release paper. It is convenient to peel off the release paper and put it into practical use when it is applied, specifically, when the film is attached or attached to various parts as described below.

Typical examples of articles to which the colored film of the present invention can be applied include various structures such as houses and roofs, structures and their accessories, or various structures such as bridges and girders. , Building or the like, or molded articles of various plastics such as polyester, polyethylene, polypropylene, polyamide, polystyrene or ABS. Therefore, as the material of the article, various iron or non-ferrous metals, slate, Examples include various inorganic materials other than the above metals such as cement concrete, asbestos concrete or marble, various plastics listed above, and fibrous processed materials such as FRP or FRTP.

And, as the applications where these various articles are specifically used, various plastics are used for the interior and exterior of the above-mentioned various buildings, buildings, structures or structures or their accessories, for interior and exterior of various vehicles, and the like. For the exterior (surface mount) of molded articles such as stainless steel, or various vending machines,
It is used in the form of signboards, signs or beauty items for exterior of various automatic teller machines, public telephones, telephone poles or various bulletin boards.

In this way, the colored film of the present invention is put into practical use by peeling off the above-mentioned substrate having good releasability and surface smoothness which constitutes the colored film. The time of peeling the substrate from the substrate should be appropriately determined depending on the method of work, the purpose of use or the conditions of use of the article to be applied (mainly pasting or pasting).

In the preparation of the colored film of the present invention, if necessary, in addition to the essential various forming layers of the surface layer (I) and the colored layer (II) respectively constituting the colored film, A soft elastic film or a sheet is provided on the surface of the colored layer (II) which is dorsal to the surface layer (I), that is, on the other free surface of the colored layer (II) which is not opposed to this layer (I). A soft resin foamed sheet, or a film or sheet reinforced by a non-woven fabric or glass fiber may be layered or laminated.

In that case, needless to say, it is necessary to further coat the third layer thus provided with an adhesive layer for the above-mentioned various articles to be attached or to be attached to the third layer. Becomes

〔Example〕

Next, the present invention will be described in more detail with reference to Reference Examples, Examples, Application Examples, and Comparative Application Examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Example of preparation of surface layer (I)] 200 parts of "Crisbon 3454" [urethane resin manufactured by Dainippon Ink and Chemicals, Inc.] and "Tinuvin 900" (UV absorption by Ciba-Geigy, Switzerland) Agent) and 1 part of "Tinuvin 292" (light stabilizer manufactured by the same company) are mixed and diluted with a mixed solvent of toluene / n-butanol = 6/4 (weight ratio) to obtain thermoplasticity. To obtain a resin composition (A).

Then, this composition (A) was coated on "CeraPeel" [a peelable polyester film manufactured by Toyo Metallizing Co., Ltd.] with a roll coater so that the dry film thickness was 60 μm, and then 50 ° C. and 70 ° C. The target surface layer (I) was obtained by sequentially drying each for 4 minutes with four hot air dryers at 90 ° C and 120 ° C. Hereinafter, this is referred to as a surface layer (I
-1) is abbreviated.

Reference Example 2 (Same as above) 20 parts of granules of an acrylic copolymer resin having a weight average molecular weight of 350,000 and containing 80% and 20% of methyl methacrylate and n-butyl acrylate, respectively, were mixed with toluene. A resin solution was prepared by dissolving 6 parts and 20 parts of xylene.

Then, using this resin solution, a thermoplastic resin composition (A) was obtained by the following formulation.

Resin solution 200 parts "Tinuvin 900" 1 part "Tinuvin 292" 1 part "Pearl Grays HM" [manufactured by Nippon Koken Kogyo Co., Ltd.
Titanium oxide-treated pigment of scaly mica] 0.4 part After that, the same operation as in Reference Example 1 was repeated except that this composition (A) was used to obtain a target surface layer (I). Hereinafter, the film is abbreviated as surface layer (I-2), but this film has a transparent feeling and has a pearly appearance.

Reference Example 3 (same as above) 24 parts of "Kynar-500" (polyvinylidene fluoride manufactured by Penwalt, USA) and 16 parts of polymethylmethacrylate having a weight average molecular weight of 300,000 and 100 parts of dimethylformamide. And 60 parts of cyclohexanone were dissolved under heating to obtain a uniform solution.

Next, "Tinuvin 900" was added to the resin solution thus obtained.
What was mixed with 1 part of the above was applied on "Therapeutic" with a roll coater and dried at 140 ° C for 30 minutes using a hot air dryer. A surface layer (I) was obtained. Hereinafter, this is abbreviated as a surface layer (I-3).

Example 1 Methyl methacrylate, n-butyl acrylate and β-hydroxyethyl methacrylate were each 60%,
A resin solution containing 40 parts of an acrylic copolymer resin having a weight average molecular weight of 100,000 and containing 40% of xylene and 20 parts of n-butyl acetate 1 copy of "Fastastogen Blue NK" [Cyanine Blue Pigment manufactured by Dainippon Ink and Chemicals, Inc.] in 100 copies
The parts were mixed and then the mixture was pigment dispersed in a sand mill for 1 hour to give a blue paste.

Then, using this blue paste, a crosslinkable resin composition (B) as a material for forming a colored layer (II) was prepared according to the following formulation.
Got

Blue paste 90 parts "Sap 700N" [Aluminum paste manufactured by Showa Aluminum Powder Co., Ltd.] 4 parts "Vernotsk DN-950" [Dainippon Ink and Chemicals, Inc.]
Polyisocyanate made of 14 parts xylene 10 parts Next, this layer forming material was dried on a surface layer (I-1) formed on the polyester film obtained in Reference Example 1 with a roll coater to obtain a dry film thickness. To 40 μm, and using a hot air dryer for 10 minutes at 60 ° C, then 120
The film was dried and hardened at 10 ° C. for 10 minutes to obtain a target film having a blue metallic tone.

Example 2 Acrylic copolymer having a weight average molecular weight of 200,000, comprising 63% of methyl methacrylate, 30% of n-butyl acrylate, 5% of β-hydroxyethyl methacrylate and 2% of acrylic acid. With 30 parts of resin,
100 parts of a resin solution consisting of 60 parts of xylene and 10 parts of n-butanol were mixed with 15 parts of "Taipec CR-90" (rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), and then mixed. The pigment was dispersed in a sand mill for 1 hour to obtain a white paste.

Then, using this white paste, a crosslinkable resin composition (B) as a material for forming a colored layer (II) was prepared according to the following formulation.
Got

White paste 115 parts "Super Betukamin L-127-75B" [n-butylated melamine resin manufactured by Dainippon Ink and Chemicals, Inc.] 5 parts Next, this layer forming material was used as the polyester obtained in Reference Example 2. -Coating on the surface layer (I-2) formed on the film with a roll coater so that the dry film thickness is 40 μm, and using a hot air dryer for 10 minutes at 60 ° C., then 140
After drying and curing at 10 ° C. for 10 minutes, a white target film was obtained.

Example 3 A crosslinked resin composition (B), which is a material for forming a colored layer (II) obtained in the same manner as in Example 1, was applied onto a “therapeutic film” with a roll coater so that the dry film thickness was 40 μm. Using a hot air drier, the film was dried and cured at 60 ° C. for 10 minutes and then at 120 ° C. for 10 minutes to obtain a blue metallic-like colored layer (II).

Separately, on the surface layer (I-3) formed on the polyester film obtained in Reference Example 3, 8 of "EPS-903" [polyurethane adhesive manufactured by Dainippon Ink and Chemicals, Inc.] was used. Parts and 1 part of "KL-75" (an aliphatic isocyanate compound manufactured by the same company) were diluted with 10 parts of ethyl acetate to give an adhesive solution having a weight of 3 to 4 g / after drying with a knife coater. m
^It was applied so as to be ^2, and dried at 80 ° C. for 3 minutes using a hot air dryer.

Then, the colored layer (II) film prepared in advance is peeled off from the "therapeutic", and the adhesive layer is layered so as to face the surface in contact with the "therapeutic". The adhesive-coated surface of the layer (I-3) was applied and laminated using a Niprol heated to 80 ° C. to obtain a target film.

Application Examples 1 to 3 and Comparative Application Example 1 Each of the colored films obtained in each Example, and on the other hand,
A commercially available vinyl chloride resin-based colored film called a "marking film" for control is applied to a zinc phosphate-treated steel sheet having a thickness of 0.8 mm. First, each colored film is Separately, it was attached to the steel plate to obtain a processed product.

Next, the performance of each colored film-adhered product was compared and examined.

The results are summarized in Table 1.

[Effect of the Invention] As is clear from the results shown in Table 1, it is known that the colored film of the present invention has good surface gloss and excellent weather resistance.

Claims (4)

[Claims] 1. A surface layer (I) is formed by using a thermoplastic resin composition (A) having excellent durability on a substrate having good releasability and surface smoothness, and then this surface layer. Coloring with excellent appearance and weather resistance obtained by forming a colored layer (II) on (I) using a crosslinkable resin composition (B) containing a metal powder and / or a coloring pigment. Film. 2. The thermoplastic resin composition (A) described above,
At least one resin selected from the group consisting of urethane resin, fluorine resin and acrylic resin;
It is composed of 0.1 to 20 parts by weight of an ultraviolet absorber with respect to 0 parts by weight, and further contains, if necessary, 2 parts by weight or less of a coloring pigment with respect to 100 parts by weight of the above resin. The colored film according to claim 1, characterized in that 3. The cross-linking resin composition (B) containing the above-mentioned metal powder and / or color pigment is a room temperature curable one, wherein the cross-linkable resin composition (B) is a room temperature curable resin composition. Colored film. 4. The crosslinkable resin composition (B) containing the above-mentioned metal powder and / or color pigment is a thermosetting one, wherein the crosslinkable resin composition (B) is thermosetting. Colored film.