JPH0729396B2 - Colored film with excellent appearance and weather resistance - Google Patents

Description

The present invention relates to a novel and useful colored film having good surface gloss and excellent weather resistance. More specifically, the present invention relates to a pigmented film on a specific substrate. The present invention relates to a colored film obtained by forming a clear layer and then a colored layer, particularly for protecting the surface of an article used outdoors and for cosmetics, and for displaying characters and patterns.

[Conventional technology]

Conventionally, in order to improve the appearance and weather resistance of metal exterior building materials and synthetic resin moldings, or to display letters or patterns, a colored film is attached to the surface of various substrates as listed above. Is being carried out.

However, such a colored film is often inferior in surface glossiness because it is a binder containing a vinyl chloride resin as a main component and containing metal powder, a pigment, and the like. In addition, the weather resistance was unsatisfactory due to the fact that the weather resistance was poor and that the metal powder, the pigment and the like were directly deteriorated by the air and moisture which were in contact therewith.

In order to improve such a defect, a method of laminating a clear film made of a thermoplastic acrylic resin or a thermoplastic polyester resin on the surface of the colored layer has also been proposed.

Although the surface gloss is improved by such a method, when the clear film is a thermoplastic film and has almost no cross-linked structure, it can be used outdoors for a long period of time. Has a drawback in that it causes a remarkable discoloration and a decrease in gloss, resulting in a decrease in aesthetics.

In order to improve these drawbacks, it has been attempted to use a crosslinkable resin for the clear layer, and by such a method, a colored film having excellent weather resistance can be obtained.

At that time, as a method for obtaining a clear film of a crosslinkable resin (curable resin), there is a method of coating the crosslinkable resin composition on a substrate having good releasability and surface smoothness, and drying and curing. is there.

Then, as a method for forming a colored layer on the clear film formed on the above-mentioned substrate, a method of thermocompression bonding the colored film and the clear layer prepared in advance, and a known and commonly used adhesive layer for the clear layer is used. Forming, and then bonding a previously prepared colored film, a method of forming an adhesive layer on the previously prepared colored film, and then bonding this with a clear layer,
Alternatively, a solution of a crosslinkable resin (curable resin) composition or a thermoplastic resin composition is mixed on the clear layer with a metal powder and / or a coloring pigment, that is, a "coloring layer forming material" is applied and dried and cured. A typical method is a method for carrying out the method, but the method described above is advantageous as a method for performing it on an industrial scale.

That is, when the above-mentioned method is followed, the shape is likely to change due to the thermocompression bonding step and the adhesive strength is not sufficient, and when the above-mentioned method is followed, the steps are both complicated and not preferable.

In exchange for that, the above-mentioned method is a process in which the metallic feeling determined by the degree of orientation in the layer of the metal powder or the like becomes excellent, particularly when an attempt is made to obtain a metallic coloring film containing the metal powder. It is advantageous.

However, even in the method described above, when the coloring layer forming material is applied onto the clear layer, the coloring layer is softened and swelled by the solvent in the forming material, and as a result, the clear layer is in a wavy state (so-called lifting phenomenon). ) Is caused, or the interlayer adhesion between the clear layer and the colored layer (interlayer adhesion)
However, the conventional problem that it is insufficient and practically difficult is largely posed.

[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 the use of a specific curable (crosslinkable) material for forming the clear layer provides the appearance and weather resistance. The inventors have found that a colored film having excellent properties can be obtained, and have completed the present invention.

[Means for solving problems]

That is, the present invention has a weight average molecular weight (▲ ▼) of 200,000 to 50 on a substrate having good releasability and surface smoothness.
A copolymer (A) of a polymerizable monomer having an unsaturated double bond having a glass transition point (Tg) of 10 to 70 ° C. and a hydroxyl value (OHV) of 5 to 15 at 0,000. , Mw 10,000 to 15
(A) / (B) = (000), Tg = 10 to 70 ° C., and OHV = 20 to 100 with a copolymer (B) of a polymerizable monomer having an unsaturated double bond. A cross-linking resin composition comprising a mixture of 10/90 to 90/10 by weight and a curing agent (C) is applied, dried and cured to form a clear layer (I), and then the clear layer (I) is formed. Further obtained by forming a colored layer (II) on the layer (I), which has excellent appearance and weather resistance, particularly for sticking to the surface of an article for outdoor use for protection and cosmetics, Aims to provide a colored film for displaying characters and patterns.

Here, as the polymerizable monomer having an unsaturated double bond constituting each of the above-mentioned copolymers (A) or (B), methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (Meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate. (Meth) acrylic acid aesthetic Dialkyl esters of unsaturated dihydrochloric acid such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate, dibutylitaconate; (meth) acrylic acid, monobutylmalate, monobutylfumarate, croton Monomers containing carboxyl groups such as acids, maleic acid, fumaric acid and itaconic acid; monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride; (meth) acrylamide, N, N
-Carboxamide group-containing monomers such as dimethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide; p-styrenesulfonamide, N-methyl -Sulfonamide group-containing monomers such as p-styrenesulfonamide and N, N-dimethyl-p-styrenesulfonamide; Cyano group-containing monomers such as (meth) acrylonitrile; Α, β- such as hydroxyalkyl esters
Monomers having a phosphoric acid ester group, which is a condensation product of hydroxyalkyl esters of ethylenically unsaturated carboxylic acids and phosphoric acid or phosphoric acid esters; p-styrenesulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid Sulfonic acid group-containing monomers such as; vinyl acetate,
Vinyl benzoate, "Veova" (product of Shell, Switzerland)
Such as vinyl ester; "biscoat 8F, 8FM, 3F or 3FM" [fluorine-containing (meth) acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, diperfluorocyclohexyl fumarate or N -Fluoroalkyl group- or perfluoroalkyl group-containing monomers such as i-propyl-fluorooctanesulfonamidoethyl (meth) acrylate; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, hexafluoropropylene,
Halogenated olefins such as chlorotrifluoroethylene; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, p-tert-butylstyrene; dimethylaminoethyl (meth) acrylate,
Dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate; N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide , N-dimethylaminopropyl (meth) acrylamide, N-dialkylaminoalkyl (meth) acrylamides such as N-diethylaminopropyl (meth) acrylamide; further tert-butylaminoethyl (meth) acrylate, tert-butylaminopropyl ( Typical examples are (meth) acrylate, aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, and piperidinylethyl (meth) acrylate. However, in obtaining the colored film of the present invention, from the viewpoint of performance as the film, various polymerizable monomers having an unsaturated double bond as described above are appropriately combined. Should be used as a result, and the effect of the combination is expected by doing so.

Then, by using such various unsaturated double bond-containing polymerizable monomers, mainly by a known and commonly used polymerization method,
The copolymer (A) and the copolymer (B), which are bisected by ▼ and OHV, are respectively obtained. Of these, the copolymer (A) should be obtained by the suspension polymerization method. , This is recommended.

As the polymerization initiator used when the copolymer (A) is obtained by the suspension polymerization method, a known and conventional radical polymerization initiator can be used as it is. A typical example thereof is azobis. Isobutyronitrile,
Azo compounds such as azobisisovaleronitrile, or organic peroxides such as lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, tert-butyl peroxybenzoate, etc. Of course, not only one kind but also a combination of two or more kinds may be used, and when such a polymerization initiator is not used, a polymerization method by a physical means such as heat or ionizing radiation can be used. Of course.

Also, as the molecular weight regulator, known and commonly used ones can be applied, and among them, representative ones are alkyl halides, alkyl mercaptans or α-methylstyrene dimers.

The suspension polymerization reaction in obtaining the copolymer (A) includes a known dispersant (including a dispersion stabilizer and a co-stabilizer,
Hereinafter, these are collectively referred to as a stabilizer. ), A surfactant can be applied, and various known and conventional reaction devices suitable for suspension polymerization can be applied as the reaction device. However, should the suspension polymerization not dissolve the various monomers as described above at all? Alternatively, the monomer is dispersed in a medium in which it is hardly dissolved, mainly in water, and is dispersed by a polymerization method in which the monomer is hardly soluble in the medium and the polymerization reaction proceeds in small droplets of the suspended monomer. Polymerization proceeds in the form of droplets, and the final polymer is often obtained as beautiful transparent particles or pearls, so this polymerization method is sometimes called granular polymerization or pearl polymerization. Stirring in water to disperse it, and generally, various known and commonly used stabilizers are added to carry out the polymerization reaction. Those used as such stabilizers are water-soluble polymers and hardly soluble inorganic fine powder. It is roughly divided into compounds and Is gelatin, tragacanth gum, starch, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol or polyacrylic acid salt, while the latter is barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, calcium phosphate, bentonite, diatomaceous earth or clay. (Clay) is a typical example.

Further, if necessary, known conventional additives such as lubricants, plasticizers, antioxidants or surfactants can be used in obtaining the colored film of the present invention.

The thus-produced polymer suspension is treated by usual operations such as "draining" and drying steps, and the copolymer beads thus obtained are dissolved in a desired solvent to give a solution of the copolymer (A). can get.

On the other hand, it is recommended that the copolymer (B) used in the present invention should be obtained by a solution polymerization method.

This solution polymerization is usually a hydrocarbon solvent such as toluene, xylene, ethylbenzene or ethylcyclohexane;
-Polymerization in an alcohol solvent such as butanol; an ester solvent such as butyl acetate; or a ketone solvent such as methyl isobutyl ketone at a temperature from room temperature to 200 ° C for 2 to 30 hours. It is suitable to react.

As the polymerization initiator, benzoyl peroxide, di-te
Peroxides such as rt-butyl peroxide, or azo compounds such as azobisisobutyronitrile are used,
Further, the polymerization can be carried out by a known and commonly used redox system.

If necessary, the molecular weight can be adjusted by using a chain transfer agent such as lauryl mercaptan or octyl thioglycolate.

Copolymer (A) and copolymer (B) thus obtained
Are regulated and limited as follows.

That is, first, as the copolymer (A),
Must be in the range of 200,000 to 500,000,
If it exceeds 500,000 and is too large, the solubility in a solvent will decrease, and it will be difficult to prepare a crosslinkable resin composition, and conversely, if it is less than 200,000, water resistance or Both are not preferable because the film strength and the like decrease.

Further, the OHV of the copolymer (A) is required to be within the range of 5 to 15, and when it is less than 5, the compatibility with the copolymer (B) and the weather resistance are obtained. And the like, and conversely exceeds 15, the clear layer (I)
Since the interlayer adhesiveness between the colored layer (II) and the colored layer (II) is reduced, neither is preferable.

Next, as for the copolymer (B), its ▲ ▼ is 10,000-
It is necessary to be in the range of 150,000, and if it exceeds 150,000 and is too large, the compatibility with the copolymer (A) decreases, and conversely if it is less than 10,000,
Both are not preferable because weather resistance, film strength, etc. are lowered and lifting is likely to occur.

Further, the OHV of the copolymer (B) is required to be in the range of 20 to 100, and when it exceeds 100, the interlayer adhesiveness between the clear layer (I) and the coloring layer (II). And if it is less than 20, on the other hand, the weather resistance will be deteriorated, and therefore both are not preferable.

Furthermore, the glass transition points of both copolymers (A) and (B) must both be in the range of 10 to 70 ° C.
If it is less than 70 ° C, the strength of the film will be lowered. On the contrary, if it exceeds 70 ° C, the film will be fragile.

The copolymers (A) and (B) regulated in such a range have a weight part ratio of (A) / (B) = 10/90 to 90/10, preferably 30/70 to 70 / Suitably mixed in a ratio of 30 parts by weight.

Speaking of the copolymer (A), when the amount of the copolymer (A) is out of the above range, the interlayer adhesion between the clear layer (I) and the colored layer (II) becomes poor, On the contrary, if it is greatly deviated, the weather resistance is deteriorated, and therefore, both are not preferable.

Then, a crosslinkable resin composition is obtained by combining the mixture of these copolymers (A) and (B) with a curing agent (C) reactive with a hydroxyl group.

Examples of the curing agent (C) include aminoaldehyde resins and isocyanate compounds, which are reactive with hydroxyl groups. First, typical aminoaldehyde resins are melamine, urea, acetoguanamine, and benzoguanamine. , A condensation product obtained by reacting an amino group-containing compound such as steroguanamine or spiroguanamine with an aldehyde compound such as formaldehyde, paraformaldehyde, acetylaldehyde or glyoxal by a conventional method, or a condensation product of each of these. There is a so-called modified product obtained by etherification of the above with a monohydric alcohol, and in addition to such a typical product, any of those that are used for paints can be applied.

Typical examples of the above-mentioned isocyanate compound include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; isophorone diisocyanate, methylcyclohexane-2,4.
-(Or 2,6-) diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) or 1,3
An alicyclic diisocyanate such as di (isocyanatomethyl) cyclohexane; or an adduct of each of these diisocyanates with a polyhydric alcohol, a low molecular weight polyester, water or the like (isocyanate prepolymer), and each diisocyanate as listed above. Examples thereof include polymers of two types or isocyanate burettes, and (co) polymers (including oligomers) of the above-mentioned diisocyanates.

Further, those obtained by blocking each of the polyisocyanates listed above with a known blocking agent such as methyl ketoxime or caprolactam may also be used as an isocyanate compound depending on the material to be the substrate and the curing conditions. You can

The amount of aminoaldehyde resin or isocyanate compound used as the curing agent (C) is in the range of 5 to 50 parts by weight based on 100 parts by weight of the total amount of the copolymers (A) and (B). The inside is appropriate.

If the amount of the curing agent (C) component used is less than 5 parts by weight, the coating film tends to be insufficiently crosslinked, and the weather resistance, hardness, solvent resistance, etc. are deteriorated. On the other hand, when it exceeds 50 parts by weight, the interlayer adhesion between the clear layer (I) and the colored layer (II) is deteriorated, and further, the obtained film is liable to be brittle. Is also not preferable.

Furthermore, when obtaining the colored film of the present invention, a curing catalyst can be used, if necessary.

At that time, when an aminoaldehyde resin is used as the above-mentioned curing agent (C), p-
Toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid, phosphoric acid ester or hydrochloric acid, or those whose acid groups are blocked with amines, or dicarboxylic acids such as phthalic acid or halogenphthalic acid _It is suitable to use a product obtained by semi-esterifying with a monohydric alcohol of _{1 to} C ₄ (semi-esterified product) and the like. On the other hand, when an isocyanate compound is used as the above-mentioned curing agent (C), the curing It is suitable to use dibutyltin diacetate, dibutyltin dilaurate, triethylamine or diethanolamine as the catalyst.

The crosslinked resin composition thus obtained may further contain, if necessary, various known conventional additive components such as an ultraviolet absorber, an antioxidant, a flow regulator or a surface tension improver. Of course.

Further, as the above-mentioned substrate having good mold releasability and surface smoothness, a steel plate having a smooth surface is plated with nickel, chromium, copper, or the like, or a wax or silicone is further coated thereon. , Or various known conventional release agents such as amides such as bisamide stearate, or various conventional release agents such as those listed above for polymer compound materials such as polyester having a smooth surface. The one coated with the agent is typical.

Needless to say, these substrates should be appropriately selected according to the properties of the above-mentioned various crosslinkable resin compositions and the dry curing conditions.

The coating and formation of the clear layer (I) on these substrates 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. From the viewpoints of productivity and layer uniformity, it is preferable to use a dry laminating method using a roller or a knife.

In coating the clear layer (I), the type of solvent of the crosslinkable resin composition and the curing conditions are not particularly limited, and may be appropriately selected depending on the characteristics of the resin used and the curing method. It is desirable to select it.

The thickness of the clear layer (I) thus formed is appropriately in the range of 30 to 150 μm. If it is too thin, the appearance and weather resistance are insufficient, and conversely if it is too thick, the sheet of the present invention. Is difficult to prepare, and is disadvantageous from the economical point of view as well.

On the other hand, the colored layer (II) formed on the clear layer (I) contains a metal powder and / or a coloring pigment in a crosslinkable resin composition (curable resin composition) or a thermoplastic resin composition. It is a thing.

Further, such a crosslinkable curable resin composition is a combination of a solution or dispersion of a resin containing a functional group in the molecule with a curing agent having reactivity with the functional group, or the functional group It is mainly a solution or dispersion of a so-called room temperature curable or thermosetting resin having a self-crosslinking property or capable of being crosslinked by moisture in the air.

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 containing a functional group include an acrylic resin, a fluorine resin, or a polyester resin containing a functional group as described below.

Among them, when the functional group present in the resin is a hydroxyl group, a suitable curing agent includes an aminoaldehyde resin, an isocyanate compound or a metal alkoxide compound, and as a curing agent for a resin whose functional group is an amino group. Are polyvalent epoxy compounds or polycarboxylic acid compounds. Curing agents for resins having an epoxy group as a functional group include polyvalent amine compounds, polyvalent carboxylic acid compounds, polyvalent phosphoric acid compounds, and polyvalent thiol compounds. Alternatively, a polyvalent isocyanate compound or the like can be used, and a suitable curing agent for a resin having a carboxyl group as a functional group includes a polyvalent epoxy compound or a polyvalent amine compound.

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, and the self-crosslinking (self-curing) resins, and the resins that can be crosslinked and cured by the moisture in the air are all known and commonly used resins. It is one kind or a mixture of two or more kinds appropriately selected from those used as agents.

As the other thermoplastic resin composition, a mixture of one or more kinds of various known and commonly used resins such as acrylic resin, polyester resin, polyamide resin or urethane resin is dissolved or dispersed in a commonly known solvent. There are some.

The thermoplastic resin composition thus obtained, as in the case of the cross-linking resin composition as described above, further, if necessary, an ultraviolet absorber, an antioxidant, a flow regulator or a surface tension improver, etc. It is needless to say that various known and commonly used additive components such as the above can be added and blended.

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

On the other hand, typical examples of the color pigments include titanium oxide, iron oxide, inorganic pigments such as scaly mica treated with titanium oxide, and organic pigments such as cyanine or quinacridone pigments.

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, but the crosslinkable (curable) resin composition or thermoplastic resin 1 to 100 parts by weight of the resin composition
The range of up to 100 parts by weight is suitable.

Further, the coating formation (that is, coating) of the thus obtained colored layer (II) on the clear layer (I) is carried out by known methods such as brush coating, dip coating, roll coating, knife coating, flow coating or spray coating. The coating method can be carried out by the above method, but from the viewpoint of productivity and uniformity of layers, it is preferable to use the dry laminating method using a roller or a knife.

When coating such a colored layer, a cross-linking type (curing type)
A resin composition or a thermoplastic resin composition containing a metal powder and / or a coloring pigment, that is, the kind of solvent of the composition for forming a colored layer and the drying conditions are not particularly limited and may be used. It is desirable to select it appropriately according to the characteristics of the resin.

The thickness of the colored layer (II) thus formed is 30 to 20.
The range of 0 μm is suitable.

The colored film of the present invention thus obtained has a colored layer (I
A known and conventional adhesive is applied to a surface other than the surface of the clear layer (I) in I), that is, the other surface of the colored layer (II) not in contact with the clear layer (I). Or, in the form of applying a known and commonly used adhesive to the surface of an article to which the colored film is to be applied, and sticking it to such an article, or by heat-pressing the colored layer film and the article as described above. can do.

Among them, in particular, a surface different from the surface of the above-mentioned colored layer (II) on which the clear layer (I) is formed-that is,
According to the present invention, an adhesive is applied to the other free surface of the colored layer (II) which is not in contact with the clear layer (I), and the adhesive-coated surface is protected by a known release paper. It is convenient to put the colored film of the present invention into practical use, and when actually applying the colored film of the present invention in such a form, specifically, the film is attached or adhered to various parts as shown below. It is convenient to peel off the release paper and put it into practical use before use.

To show representative ones as an article to which the colored film of the present invention can be applied, various constructions such as those found in houses and roofs, various constructions such as those found in buildings and their accessories or bridges and bridge girders, Examples include structures and their accessories, or molded articles of various plastics such as polyester, polyethylene, polypropylene, polyamide, polystyrene or ABS, and the materials of the articles are ferrous or non-ferrous metals and slate. , Various inorganic materials other than the above metals such as cement concrete, asbestos concrete or marble, or various plastics listed above, and further FRP or F
Examples include fiber processing materials such as RTP.

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, and for the interior and exterior of various vehicles. Used in the form of signs, signs or cosmetics for exterior (surface) of molded articles of the same class, or for exteriors of various vending machines, various automated teller machines, public telephones, telephone poles, and various bulletin boards. To be

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 forming layers of the clear layer (I) and the colored layer (II) respectively constituting the colored film, a colored layer A surface different from the surface on which the clear layer (I) is formed in (II), that is, the layer (I)
On the other free surface of the layer (II), which is not in contact with at all, a soft elastic film or sheet, a soft resin foam sheet, or a film or sheet reinforced by a non-woven fabric or glass fiber can be layered or laminated. You can also

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 specifically described with reference to Reference Examples, Examples, Comparative Examples, Application Examples and Comparative Application Examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Preparation Example of Copolymer (A)] A 1% aqueous solution of polyvinyl alcohol having a saponification degree of 80% and a polymerization degree of 24,000 was placed in a flask equipped with a thermometer, a turbine-type stirring blade and a reflux condenser. Charge 20 parts and 2,000 parts of water, and add 704 of methyl methacrylate (MMA).
Part, 276 parts of n-butyl acrylate (n-BA), 2-
Charged with 2 parts of hydroxyethyl methacrylate (HEMA) and 15 parts of azobisisobutyronitrile (AIBN)
Polymerization was carried out at 80 ° C. with stirring at 150 rpm.

After the polymerization, the mixture was cooled to room temperature, separated from the polymer, then drained, and then fluidized and dried.

The solid polymer thus obtained was dissolved in xylene to obtain a solution of the copolymer (A-1) having a nonvolatile content (NV) of 20%.

This product has Tg of 40 ℃, OHV of 9, and ▲ ▼ is 28.
It was 0,000.

Reference Example 2 [Preparation Example of Copolymer (B)] A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 700 parts of xylene and 300 parts of -n-butyl acetate and heated to 90 ° C. In addition, MMA 577 parts, n-BA 35
0 part, 70 parts of HEMA, 3 parts of methacrylic acid (MAA) and AI
A mixture consisting of 5 parts of BN was added dropwise over 4 hours, and the reaction was carried out at the same temperature for 6 hours to obtain a solution of the target copolymer (B). Hereinafter, this is a copolymer (B-1)
The Tg of the product was 25 ° C, the OHV was 31, and the ▲ ▼ was 110,000.

Reference Example 3 [Preparation Example of Copolymer (A)] Tg was 60 ° C. in the same manner as in Reference Example 1 except that the composition of the unsaturated double bond-containing unsaturated monomer was changed as described below. OHV
Is 12 and ▲ ▼ is 300,000 (A-
A solution of 2) was obtained.

MMA 762 parts Acrylic-i-butyl (i-BA) 210 parts HEMA 28 parts Total 1,000 parts Reference Example 4 [Preparation example of copolymer (B)] Composition of unsaturated double bond-containing polymerizable monomer Same as Reference Example 2 except that the Tg was 36 ° C and OHV
Is 60 and ▲ ▼ is 100,000 (B-
A solution of 1) was obtained.

MMA 530 parts i-BA 377 parts HEMA 140 parts MAA 3 parts Total 1,000 parts Reference Example 5 [Preparation example of composition for forming colored layer] MMA, n-BA and HEMA are 60%, 20% and 20%, respectively.
% Of the resin solution consisting of 40 parts of acrylic copolymer resin containing 100,000 of ▲ ▼, 40 parts of xylene and 20 parts of -n-butyl acetate, "Fastgen Blue NK" Cyanine blue pigment manufactured by Dainippon Ink and Chemicals, Inc.] was mixed, and the mixture was dispersed in a sand mill for 1 hour to obtain a blue paste.

Thereafter, using this blue paste, a room temperature curable and thermosetting coating liquid, that is, a target composition was obtained by the following formulation.

Blue paste 90 parts "Sap 700N" [Aluminum manufactured by Showa Powder Co., Ltd.
Paste] Part 4 "Barnock DN-950" [Dainippon Ink and Chemicals, Inc.]
18 parts xylene 5 parts Reference Example 6 (same as above) 20 parts of acrylic copolymer resin granules containing 350,000 MMA and n-BA at a ratio of 70% and 30%, respectively. A resin solution was prepared by dissolving 60 parts of xylene and 20 parts of toluene.

Then, using this resin solution, a thermoplastic coating liquid, that is, a composition for forming a colored layer was obtained by the following formulation.

Resin solution 100 parts "Sap 700N" 4 parts Reference Example 7 [Preparation Example of Control Copolymer] Same as Reference Example 1 except that the composition of the unsaturated double bond-containing polymerizable monomer was changed as follows. And Tg is 104 ℃, OHV
Is 12 and ▲ ▼ is 310,000 (A'-
A solution of 1) was obtained.

MMA 980 parts HEMA 20 parts Total 1,000 parts Reference Example 8 (same as above) Tg was 40 ° C. in the same manner as in Reference Example 1 except that the composition of the unsaturated double bond-containing polymerizable monomer was changed as follows. OHV
Is 0 and ▲ ▼ is 300,000 (A'-
A solution of 2) was obtained.

MMA 720 parts n-BA 280 parts Total 1,000 parts Reference Example 9 [Preparation example of control copolymer] Reference Example 2 except that the composition of the unsaturated double bond-containing polymerizable monomer was changed as follows. Similarly, Tg is 25 ℃, OHV
Is 12 and ▲ ▼ is 105,000 (B'-
A solution of 1) was obtained.

MMA 613 parts n-BA 356 parts HEMA 28 parts MAA 3 parts Total 1,000 parts Reference Example 10 (Same as above) Reference Example 2 except that the amount of AIBN used was changed to 50 parts and the temperature condition was changed to 120 ° C. Similarly, at Tg of 25 ° C, OH
Copolymer (V'-with V = 31 and ▲ ▼ 8,000)
A solution of 3) was obtained.

Reference Example 11 (same as above) Except that the composition of the unsaturated double bond-containing polymerizable monomer was changed as follows, Tg was 25 ° C. and OHV was the same as in Reference Example 2.
Is 120 and ▲ ▼ is 100,000 (B'-
A solution of 4) was obtained.

MMA 192 parts n-BA 248 parts HEMA 557 parts MAA 3 parts Total 1,000 parts Examples 1 to 8 Copolymers (A) and (B) obtained in Reference Examples 1 to 4
To prepare a coating liquid composition for forming a clear layer (I) at a compounding composition ratio as shown in Table 1, and then to prepare each coating liquid composition by "therapy" [Toyo Metallizing Industry]. Releaseable polyester resin film]
It is coated by a roll coater so that the dry film thickness is 60 μm. Then, when an isocyanate compound is used as the curing agent (C) component, it is dried and cured at 120 ° C. for 30 minutes, while the curing agent (C) is used. When an aminoaldehyde resin was used as a component, it was dried and cured at 140 ° C. for 30 minutes to obtain a clear layer (I) separately.

Then, each of the compositions for forming a colored layer obtained in Reference Examples 5 and 6 was subjected to a treatment on the clear layer (I) by a roll coater according to the treatment shown in the table so that the dry film thickness was 40 μm. Separately coating, after that, when an isocyanate compound is used as the curing agent (C) component,
The desired colored film of the present invention was obtained by drying at 120 ° C. for 30 minutes and, on the other hand, when an aminoaldehyde resin was used as the curing agent (C) component, at 140 ° C. for 30 minutes.

The same table summarizes the results of testing the lifting state and the transparency of the clear layer (I) for each of the colored films.

Comparative Examples 1 to 7 Each of the copolymers (A-1) or (B-1) obtained in Reference Examples 1 or 2 is used alone, or Reference Examples 7 to 11 are used.
Each control copolymer (A ') or (B') obtained in 1.
A colored film for control was obtained in the same manner as in Examples 1 to 8 except that was also used.

The blending conditions of each example are as shown in Table 1, and the test of the lifting state and the transparency of the clear layer (I ') for each colored film is as shown in the same table.

Application Examples 1 to 8 and Comparative Application Examples 1 to 3 Each of the colored films obtained in Examples 1 to 8 and Comparative Examples 1 to 3 was separately attached to a zinc phosphate-treated steel sheet having a thickness of 0.8 mm. Got a processed product.

The colored films for comparison obtained in Comparative Examples 4 to 7 were all excluded from the fact that the shape and appearance of the film were not practical.

Next, Table 2 collectively shows the results of the comparative examination of the performances of the pasted products.

[Effect of the invention] As is clear from the results in Tables 1 and 2, the colored film of the present invention can be prepared very easily,
Moreover, it is known that it has excellent performances such as weather resistance.

Claims (6)

[Claims] 1. A substrate having good releasability and surface smoothness, which has a weight average molecular weight of 200,000 to 500,000, a glass transition point of 10 to 70 ° C., and a hydroxyl value of 5 to 15 ,
Copolymer of polymerizable monomer having unsaturated double bond (A)
And a weight average molecular weight of 10,000 to 150,000, a glass transition point of 10 to 70 ℃, and a hydroxyl value within a range of 20 to 100, a copolymer of a polymerizable monomer having an unsaturated double bond ( A mixture of (A) / (B) = 10/90 to 90/10 by weight and a curing agent (C) are applied, and a cross-linking resin composition is applied and dried and cured. A colored film having excellent appearance and weather resistance, which is obtained by forming a clear layer (I) and then forming a colored layer (II) on the clear layer (I). 2. The colored film according to claim 1, wherein the curing agent (C) is an aminoaldehyde resin. 3. The colored film according to claim 1, wherein the curing agent (C) is an isocyanate compound. 4. The colored layer (II) according to claim 1, wherein the room temperature-curable resin composition contains a metal powder and / or a color pigment. Colored film. 5. The colored layer (II) according to claim 1, wherein the thermosetting resin composition contains a metal powder and / or a coloring pigment. Colored film. 6. The colored layer (II) according to claim 1, wherein the thermoplastic resin composition contains a metal powder and / or a coloring pigment. Colored film.