KR20030093295A - Polyester-based resin sheet-like material and resin-covered metal plate using the resin sheet-like material - Google Patents

Abstract

Providing a resin-coated metal sheet excellent in workability and flaw resistance and excellent in chemical resistance such as hot water resistance (boiling water resistance) and alkali resistance without using a halogen-containing resin, and very suitable for producing this resin coated metal sheet. It is an object to provide a polyester resin sheet-like material.

A predetermined polyester resin sheet-like substance (B) is coated on the surface of the base metal plate (A).

Description

POLYESTER-BASED RESIN SHEET-LIKE MATERIAL AND RESIN-COVERED METAL PLATE USING THE RESIN SHEET-LIKE MATERIAL}

Conventionally, as a resin-coated metal plate having designability used for household electrical appliances, industrial equipment, building interior materials, and the like, a printing layer is provided on a predetermined resin layer, and a transparent resin film is further laminated thereon. Has been used. As a transparent resin film in this structure, it is common to use the ethylene-vinyl alcohol copolymer film of 10-50 micrometers in thickness, the acrylic ester type copolymer film, the biaxially stretched polyethylene terephthalate-type resin (PET) film, etc., Among these, the biaxially stretched PET film which is excellent in the balance of various physical properties and excellent also in the transparency of the base printing layer is used preferably.

Moreover, as said resin layer, what added the pigment and coloring generally is used, and what used the soft vinyl chloride type resin layer as this material was common. Since the flexibility can be arbitrarily changed by adding a plasticizer to the vinyl chloride-based resin, this flexible vinyl chloride-based resin is used, even when the transparent biaxially stretched PET film is laminated and formed into a laminated film. In addition to being good, the flexible vinyl chloride resin is excellent in acid resistance, alkali resistance and other chemical resistance, and also excellent in heat resistance, hot water resistance (boiling water resistance), etc., so as to be used as a so-called precoated steel sheet. It is because sufficient workability can be provided and it can use suitably also for uses, such as a bath unit.

However, in recent years, problems of heavy metal compounds due to stabilizers of vinyl chloride resins, problems of VOC (volatile organic compounds) and endocrine disruption (environmental hormone action) caused by some plasticizers and stabilizers, hydrogen chloride gas at the time of combustion Due to the problem of generating other chlorine-containing gas, the vinyl chloride resin has been restricted in its use.

On the other hand, by replacing the soft vinyl chloride-based resin as the resin layer, a polyolefin-based resin such as polypropylene is mainly used, and a thermoplastic elastomer such as styrene-based or copolymerized olefin-based as a soft-nitriding component is compounded therein. The thing made into the physical property approximated to soft vinyl chloride type resin is used.

However, when a resin containing a soft component such as a styrene resin or a copolymerized olefin resin is used mainly as the polyolefin resin as described above, a sufficient workability is imparted to the precoated steel sheet, the soft vinyl chloride resin coating The scratch resistance is inferior to that of the metal plate. Moreover, when the flaw resistance is made equal to the soft vinyl chloride-based resin coated metal sheet, there is a problem that satisfactory workability cannot be obtained, and it is not widely used. In addition, since polyolefin is inherently inferior in adhesiveness, it requires a process such as surface treatment such as corona treatment or primer coating to give a print design, There is also a problem such as inferior sealing property of the joint.

On the other hand, using the polyester resin as said resin layer has been examined for the purpose of solving these various faults. The metal plate coated with polyester resin can make both flaw resistance and workability higher than the soft vinyl chloride resin coated metal plate, and can solve the above-mentioned various drawbacks in the polyolefin resin coated metal plate. .

However, since the glass transition temperature (Tg) is lower than 100 degreeC as resin which forms said resin layer when using amorphous polyester resin which can be shape | molded by a calender molding method also in polyester resin, The boiling water resistance test generally included as an evaluation item of the resin-coated metal sheet for building interiors cannot be satisfied.

On the other hand, the film using polyester resin which has crystallinity, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), as colored resin layer formation resin satisfies the boiling water immersion test. Although it does not, it does not pass the alkali-immersion test prescribed | regulated by JIS. For this reason, when an alkaline aqueous solution resulting from a detergent or the like comes into contact with a portion of the surface of the transparent biaxially stretched PET film at the time of processing, at the time of use, or during use, the appearance may deteriorate remarkably and frequently such as a bath unit. There was a problem in use for the use washed with detergent.

The present invention relates to a polyester resin sheet-like material and a resin coated metal plate using the same.

1 is a cross-sectional view showing an example of a resin-coated metal plate according to the present invention, FIG. 2 is a cross-sectional view showing another example of the resin-coated metal plate according to the present invention, FIG. 3 is a cross-sectional view showing another example of the resin-coated metal plate according to the present invention. 4 is a cross-sectional view showing another example of the resin-coated metal sheet according to the present invention.

Thus, the present invention provides a resin-coated metal sheet which is excellent in workability and scratch resistance and excellent in chemical resistance such as hot water resistance (boiling water resistance) and alkali resistance without using a halogen-containing resin, and the resin coating It is an object to provide a polyester-based resin sheet-like material which is very suitable for producing a metal plate.

This invention is a mixture which consists of the following (b1) component and (b2) component, and the ratio of each component is (b1) / (b2) = 50-95 / 50-5 (the sum of quantum is 100) by weight ratio, The above problems are solved by using a polyester-based resin sheet-like material which is excellent in alkali resistance and boiling resistance.

(b1) Component: The polyester-based resin whose crystal melting heat measured by the differential scanning calorimeter is 10 [J / g] or less.

(b2) Component: The polyester-based resin which has the crystal melting peak observed with the differential scanning calorimeter, and whose heat amount is 30 [J / g] or more.

The polyester resin sheet-like material described above is excellent in scratch resistance and workability because the entire sheet-like material is made of polyester resin. And alkali resistance is ensured by (b1) component, and boiling resistance is ensured by (b2) component.

Furthermore, in the said polyester resin sheet-like substance, (b2) component is made into polybutylene terephthalate resin, and the mixing ratio ((b1) / (b2)) of (b1) component and (b2) component It can be made into the range of 60-80 / 4O-20 in weight ratio.

Since (b2) polybutylene terephthalate-based resin is used as a component, compared with the case where polyethylene terephthalate-based resin is used, workability when forming a sheet or sheet-like material by extrusion molding from polyester-based resin is improved. do.

Furthermore, in said polyester resin sheet-like substance, (b2) component is made into polypropylene terephthalate resin, and the mixing ratio ((b1) / (b2)) of (b1) component and (b2) component Can be made into the range of 60-80 / 40-20 by weight ratio.

Since the polypropylene terephthalate-based resin is used as the component (b2), the workability is as good as that of the polybutylene terephthalate, and the physical properties are better than the polybutylene terephthalate between the polyethylene terephthalate and the polybutylene terephthalate. .

Furthermore, in said polyester-based resin sheet-like substance, (b2) component is made into polybutylene terephthalate resin, and the mixing ratio ((b1) / (b2) of (b1) component and (b2) component ) Can be made into a range of 50-65 / 50-35 by weight ratio.

Since (b2) polybutylene terephthalate-based resin is used as a component, compared with the case where polyethylene terephthalate-based resin is used, processability when forming a sheet or sheet-like material by extrusion molding from polyester-based resin is improved. do.

Furthermore, in said polyester resin sheet-like substance, (b2) component is made into polypropylene terephthalate resin, and the mixing ratio ((b1) / (b2)) of (b1) component and (b2) component Can be made into the range of 50-65 / 50-35 by weight ratio.

Since the polypropylene terephthalate-type resin is used as the component (b2), the workability is as good as that of the polybutylene terephthalate, and the physical properties are better than that of the polybutylene terephthalate between the polyethylene terephthalate and the polybutylene terephthalate. .

Moreover, any one of said polyester-based resin sheet-like substance (B) is coat | covered on the surface of base metal plate (A), and a resin coating metal plate can be obtained.

Since the polyester-based resin sheet-like material (B) is coated on the surface of the base metal plate (A), it is excellent in workability and scratch resistance, without using halogen-containing resins such as soft vinyl chloride resins, and at the same time, hot water resistance and water resistance. A resin coated metal sheet excellent in alkalinity can be obtained.

Furthermore, the laminated sheet which laminated | stacked the transparent resin film (C) on the colored polyester-type resin sheet-like substance (B ') which mix | blended the coloring agent as a structural component in any one of said polyester-based resin sheet-like substance (B). A phase substance can be coat | covered on the surface of the base metal plate (A), and a resin coating metal plate can be obtained.

Furthermore, the colored polyester resin sheet-like substance (B '), the printed layer (D), and the transparent resin film which mix | blended the coloring agent as a structural component in any one of said polyester resin sheet-like substance (B) (( The laminated sheet-like material in which C)) is sequentially laminated can be coated on the surface of the base metal plate (A) to obtain a resin-coated metal plate.

Moreover, it is apply | coated between the printing layer (D) and colored polyester-type resin sheet-like substance (B '), or between said base metal plate (A) and colored polyester-based resin sheet-like substance (B'). A die-like adhesive layer E can be provided and laminated integrally.

In addition, a biaxially stretched polyethylene terephthalate resin sheet-like substance can be used as the transparent resin film (C).

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The polyester resin sheet-like substance (B) which concerns on this invention makes the mixture which mixed the polyester resin which consists of two types of predetermined | prescribed components in a predetermined ratio into a sheet form. Moreover, the resin coating metal plate which concerns on this invention coat | covers the said polyester-type resin sheet-like substance (B) on the surface of the base metal plate (A).

In addition, in this invention, a "sheet-like substance" means a sheet or a film. The distinction between the sheet and the film is a case where the thickness is less than 0.25 mm (250 µm) as the film, and the case where the thickness is 0.25 mm or more, similarly to the ordinary distinction.

The said polyester-type resin sheet-like substance (B) makes the mixture which mixed the following (b1) component and (b2) component into a sheet form.

The component (b1) is a polyester resin that functions to improve alkali resistance of the polyester resin sheet-like material (B), and the amount of crystal melting heat observed by a differential scanning calorimeter is 10 [J / g]. It is necessary to be the following. When the amount of crystal melting heat exceeds 10 [J / g], the alkali resistance of the polyester resin sheet-like substance (B) cannot be improved, which is not preferable.

As the diol component, the polyester resin constituting the component (b1) is ethylene glycol, propylene glycol, 1,4-cyclohexane dimethanol, and the like. Copolyesters are suitably used. The ratio of each diol component and dicarboxylic acid component is suitably selected so that the amount of crystal melting heat observed by the differential scanning calorimeter of the obtained polyester-type resin may be 10 [J / g] or less.

As an example of the polyester resin which comprises this (b1) component, the brand name PET-G by Eastman Chemical Co., Ltd. which substituted about 30-60 mol% of ethylene glycol of polyethylene terephthalate with 1, 4- cyclohexane dimethanol, As a copolymer containing terephthalic acid as a dicarboxylic acid component and ethylene glycol and 1,4-cyclohexane dimethanol as a diol component, PCTG of the same company having a high ratio of 1,4-cyclohexane dimethanol is commercially available. Can be.

The polyester resin constituting the component (b1) has low crystallinity and is excellent in alkali resistance alone, but at a temperature exceeding Tg, the elastic modulus rapidly decreases and becomes soft. Moreover, generally Tg of a polyester resin is 100 degrees C or less, and when a polyester resin with low crystallinity is coat | covered with a metal plate in this way, it will soften in boiling water and a bubble will swell on the surface.

The component (b2) is a polyester resin that functions to improve the boiling resistance of the polyester resin sheet-like substance (B), and a crystal melting peak observed by a differential scanning calorimeter is present, and the crystal It is necessary that the amount of heat of fusion is 30 [J / g] or more. When the amount of crystal melting heat is less than 30 [J / g], the modulus of elasticity at a temperature higher than or equal to the glass transition temperature (Tg) decreases and the boiling resistance decreases, which is not preferable.

As the diol component, the polyester resin constituting the component (b2) is ethylene glycol, propylene glycol, 1,4-cyclohexane dimethanol, etc., and an ethylene terephthalate system using terephthalic acid or isophthalic acid as the dicarboxylic acid component. Copolyesters are suitably used. However, the ratio of each diol component and dicarboxylic acid component is suitably selected so that the amount of crystal melting heat observed by the differential scanning calorimeter of polyester resin obtained may be 30 [J / g] or more.

Examples of the polyester resin constituting the component (b2) include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate or polytrimethylene terephthalate (PPT), or copolymers thereof Etc. can be mentioned. It is preferable that intrinsic viscosity (IV value) is 0.7 or more from a film forming property.

In addition, the polyester resin which has the heat of fusion of crystals 30 [J / g] or more has an elasticity modulus if it is below melting | fusing point even at the temperature exceeding Tg, but since it is high crystallinity, it is inferior to alkali resistance.

The mixing ratio between the component (b1) and the component (b2) constituting the polyester-based resin sheet-like substance (B) is (bl) / (b2) = 50 to 95/50 to 5 (total quantum is 100) Preferably, a material having an elastic modulus maintained even at a Tg or more while giving alkali resistance by mixing at a weight ratio of 50 to 90/50 to 10 and balancing the blending ratio between the amorphous resin and the crystalline resin It can be obtained, and appearance defects will not occur even by contact with boiling water, immersion in boiling water, or the like.

Moreover, from the point of flaw resistance, although many crystalline components are excellent, when it exceeds 50% by weight ratio, since alkali resistance falls, it is unpreferable. If the amount of the component (b2) is too small, even if the elastic modulus of Tg or more is maintained by the crystal part, the value thereof is low, so that the boiling resistance cannot be satisfied.

The blending amount more preferable than the component (b2) is different from the case where the mirror-required property is required for the resin-coated metal plate using the polyester resin sheet-like material obtained.

When specularity is not required for the resin-coated metal sheet using the obtained polyester resin sheet-like substance, the material used as the component (b2) is (b1) / (b2) = 50 to 80/50 to 20, as PET. As PBT and PPT, (b1) / (b2) = 60-80 / 40-20 are more preferable, and it is necessary to make excess of (b1) a component all.

When (b2) is less than the said range, it may not have sufficient boiling water resistance, and when (b2) is more than the said range, the resin coating metal plate using the obtained polyester-type resin sheet-like substance is formed and mentioned later. When not laminating | stacking a transparent resin film (C), a problem may arise in alkali resistance. In addition, in the said resin coating metal plate which laminated | stacked the transparent resin film (C) mentioned later, interlayer peeling of the transparent resin film (C) in a deformation | transformation part arises, and processing part durability may become inadequate.

On the other hand, when (b2) is in the said range, it has sufficient surface hardness and is excellent in boiling water resistance. Moreover, regardless of the presence or absence of lamination of the transparent resin film (C) mentioned later, when it is excellent in alkali resistance, especially when the said transparent resin film (C) is laminated | stacked, when this scratches arise in this transparent resin film (C) Even if it is excellent in alkali resistance. In addition, the said resin coating metal plate which laminated | stacked the transparent resin film (C) mentioned later does not produce the interlayer peeling of the transparent resin film (C) in a deformation | transformation part easily, and it is easy to use enough, and has a process part durability.

Moreover, when laminating | stacking the transparent resin film (C) mentioned later on the resin coating metal plate using the polyester-based resin sheet-like substance obtained, and requesting specular property, the material used as (b2) component is PET, PBT (B1) / (b2) = 50-65 / 50-35 are more preferable in any of PPT.

When (b2) is less than the said range, the transparent resin film (C) in a deformation | transformation part is laminated | stacked on the mirror surface when the transparent resin film (C) mentioned later is laminated | stacked on the resin coating metal plate using the polyester resin sheet-like substance obtained. The interlayer peel of) may occur. On the other hand, when (b2) is more than the said range, when the resin coating metal plate using the polyester-type resin sheet-like substance obtained is formed, a problem may arise in alkali resistance, and it will become difficult to show a mirror property. In addition, in the said resin coating metal plate which laminated | stacked the transparent resin film (C) mentioned later, interlayer peeling of the transparent resin film (C) in a deformation | transformation part arises, and processing part durability may become inadequate.

On the other hand, when (b2) is in the said range, it has sufficient surface hardness and is excellent in boiling water resistance. Moreover, it has alkali resistance and can use it enough, with or without lamination of the transparent resin film (C) mentioned later. In particular, in the case where the transparent resin film (C) is laminated, even when scratches occur in the transparent resin film (C), it has alkali resistance and can be used sufficiently. Moreover, the said resin coating metal plate which laminated | stacked the transparent resin film (C) mentioned later does not produce the interlayer peeling of the transparent resin film (C) in a deformation | transformation part, but becomes an excellent thing, and becomes the thing excellent in the process part durability.

Moreover, when polyethylene terephthalate is used as said (b2) component, since it is a general purpose resin, there exists an advantage in terms of cost.

As for the amount of crystal melting heat of the said (b1) component, 10 J / g or less is preferable, and the amount of crystal melting heat of (b2) component has preferable 30 J / g or more. When the amount of crystal melting heat of the component (b1) exceeds 10 J / g, the alkali resistance may not be improved. Moreover, when the amount of crystal melting heat of (b2) component is less than 30 J / g, the elasticity modulus in Tg or more may fall, and boiling resistance may fall.

A coloring agent can be mix | blended with the mixture of (b1) component and (b2) component which comprise the said polyester-type resin sheet-like substance (B). By mix | blending the said coloring agent with the said polyester-type resin sheet-like substance (B), a colored polyester-type resin sheet-like substance (B ') can be obtained. This colored polyester-based resin sheet-like substance (B ') can achieve functions such as concealing the underlying base metal plate (A), imparting designability, and improving color development of the printed layer. The coloring agent used for the purpose of resin coloring is good as a pigment conventionally known for resin coloring, and a compounding quantity can be selected with the general amount at the time of coloring resin.

In addition to the said coloring agent, various additives of the kind which do not impair the objective of this invention are added to the mixture of (b1) component and (b2) component which comprise the said polyester-type resin sheet-like substance (B). It may be added in an amount that does not damage the. Examples of various additives include antioxidants such as thermal stabilizers, phosphorus and phenol compounds, hydrolysis inhibitors, ultraviolet absorbers, light stabilizers, nucleating agents, metal deactivators, antibacterial and mildew inhibitors, antistatic agents, lubricants, flame retardants, fillers, and the like. Can be.

Moreover, in order to improve designability, you may perform printing, embossing, etc. to the said polyester-type resin sheet-like substance (B) suitably.

The said polyester resin sheet-like substance (B) of this invention is manufactured by a well-known film forming method. For example, an extrusion cast method using an T die, an inflation method, or the like may be employed. Although not particularly limited, an extrusion cast method using a T die is preferable in view of film forming properties and stable productivity of the sheet-like material. Do.

Although the shaping | molding temperature in the extrusion cast method using a T die is suitably adjusted with the flow characteristic of a composition, film forming property, etc., it is usually more than melting | fusing point 280 degreeC, Preferably the range of 240-270 degreeC is suitable.

Moreover, it is preferable to select the thickness of sheet-like substance other than the said colored polyester-type resin sheet-like substance (B ') in the range of 50-500 micrometers among the said polyester-type resin sheet-like substance (B). When thickness is less than 50 micrometers, when used for resin coating metal plates, performance as a protective layer with respect to a metal plate, and embossing aptitude are inferior. On the other hand, when thickness exceeds 500 micrometers, secondary workability, such as the punching process for resin coating metal plates, will be inferior.

Moreover, it is preferable to select the thickness of the said colored polyester-type resin sheet-like substance (B ') in the range of 30 micrometers-250 micrometers among the said polyester-type resin sheet-like substances (B). If the thickness is less than 30 µm, in order to provide sufficient background concealability, it is necessary to mix a large amount of special pigments of high cost, and it becomes difficult to form a film, and even if the film can be formed, pin holes are likely to occur in the film, and the base metal plate It is not preferable because the protective effect against (A) is lowered. If the thickness exceeds 250 μm, even if it is thicker than this, both the concealing effect of the base base metal and the protective effect of the base metal are saturated, and further, secondary workability such as punching work and bending work decreases, and the raw material cost increases. Not desirable

Next, the resin coating metal plate which concerns on this invention is demonstrated. As described above, the resin-coated metal sheet 1 according to the present invention has the polyester-based resin sheet-like substance (B) 3 on the surface of the base metal plate (A) 2 as shown in FIG. 1. It is coated.

The said base metal plate (A) (2) becomes a base material of the resin coating metal plate which concerns on this invention. There is no restriction | limiting in particular as this base metal plate (A) (2), The metal plate used for the base material of a general resin coating metal plate can be used as it is. Specifically, various steel sheets, such as a hot rolled sheet steel, a cold rolled sheet steel, a stainless steel plate, an aluminum plate, etc. are mentioned. The steel plate may be surface-treated by plating or another method. There is no restriction | limiting in particular in the kind of plating, Hot dip galvanization, an electrogalvanization, tin plating, etc. are mentioned, A surface treatment includes chromate treatment, a phosphate coating process, etc. Although the thickness of the base metal plate (A) changes with the use of a resin coating metal plate, it can select in the range of 0.1-10 mm.

As a method of adhering the polyester-based resin sheet-like substance (B) 3 to the base metal plate (A) 2, as shown in FIG. 1, a method of using the adhesive agent 4 is not shown, There exists a method of heat-sealing, the extrusion coating, etc., without using an adhesive agent, and is not specifically limited. For example, as shown in FIG. 1, adhesives, such as polyester type and an epoxy type, on the surface of the base metal plate (A) (2) which joined the polyester-type resin sheet-like substance (B) (3) ), And a polyester resin sheet-like substance (B) 3 is coated. In this method, the surface of the base metal plate (A) (2) bonded together with a polyester-based resin sheet-like material (B) (3) using a coating equipment generally used such as a reverse roll coater and a kiss roll coater. The adhesive 4 is apply | coated so that the adhesive film thickness after drying may be about 2-4 micrometers. Subsequently, the coated surface is dried and heated by an infrared heater and a hot air heating furnace, and immediately while maintaining the surface temperature of the base metal plate (A) 2 above the melting point of the polyester-based resin sheet-like substance (B) 3. The resin-coated metal sheet can be obtained by coating and cooling the polyester-based resin sheet-like substance (B) 3 using a roll laminator.

When using said colored polyester-type resin sheet-like substance (B ') as a film laminated | stacked on the resin coating metal plate which concerns on this invention, it is not the case of laminating | stacking this independently and said colored poly as shown below. You may laminate | stack the laminated sheet-like substance which laminated | stacked the transparent resin film-like substance (C) etc. on ester resin sheet-like substance (B ').

As such a resin coating metal plate, the laminated sheet-like substance which laminated | stacked the transparent resin film (C) 5 on the colored polyester-type resin sheet-like substance (B ') (3') as shown in FIG. The resin-coated metal plate 1a coated on the surface of the base metal plate (A) 2, the colored polyester resin sheet-like substance (B ') 3' as shown in FIG. 2 or FIG. 3, and the printing layer ( D) (6) and the resin coating metal plate (1b or lc) which coat | covered the laminated sheet-like substance which laminated | stacked the transparent resin film (C) (5) sequentially on the surface of the base metal plate (A) (2), etc. are mentioned. Can be.

Moreover, when laminating | stacking the said printed layer (D) 6, between this printed layer (D) 6 and colored polyester-type resin sheet-like substance (B ') 3', or said base material An application-type adhesive bond layer (E) 4 is provided between the metal plate (A) 2 and the colored polyester resin sheet-like substance (B ') 3, and laminated and integrated to form a resin-coated metal plate 1b. Or 1c).

As a structural example of the resin coating metal plate which laminated | stacked the laminated sheet-like substance which laminated | stacked the transparent resin film-like substance (C) etc. on said colored polyester-type resin sheet-like substance (B '), the following examples are mentioned. In addition, "/" means the interface of an adjacent layer.

Transparent resin film (C) / colored polyester resin sheet-like substance (B ') / base metal plate (A) (refer FIG. 2)

Transparent resin film (C) / adhesive layer (E) / colored polyester-based resin sheet material (B ') / base metal plate (A)

Transparent resin film (C) / adhesive layer (E) / colored polyester resin sheet-like substance (B ') / adhesive layer (E) / base metal plate (A)

Transparent resin film (C) / printing surface (D) / colored polyester resin sheet-like substance (B ') / adhesive layer (E) / base metal plate plate (A) (see Fig. 3)

Transparent resin film (C) / printing surface (D) / adhesive layer (E) / colored polyester-based resin sheet material (B ') / base metal plate plate (A)

Transparent resin film (C) / printing layer (D) / adhesive layer (E) / colored polyester resin sheet-like material (B ') / adhesive layer (E) / base metal plate plate (A) (see Fig. 4)

Etc. can be mentioned.

Resin which comprises the said transparent resin film (C) aims at further improvement of a flaw resistance, protection of a printing layer, provision of a deep design, improvement of various physical properties of a surface, and if these objectives can be achieved There is no restriction | limiting in particular, Specifically, an acrylic resin, an ethylene vinyl alcohol copolymer, a polyethylene terephthalate resin, a polycarbonate, a polyamide resin, etc. are mentioned. Among them, the polyethylene terephthalate resin film biaxially stretched is very suitable from the viewpoints of transparency, smoothness, surface scratch resistance and the like.

It is preferable to make thickness of the said transparent resin film (C) thinner than colored polyester-type resin sheet-like substance (B), and it is selected in the range of 15 micrometers-75 micrometers.

As mentioned above, the printing layer (D) is formed in the back surface of the said transparent resin film (C), and the designability of the laminated sheet-like substance coat | covered by the resin coating metal plate (A) can be improved further. There is no restriction | limiting in particular as a method of forming a printed layer, It can carry out by the gravure printing method, the offset printing method, the screen printing method, etc. which are known conventionally. There is no restriction | limiting in particular in print form, Any of a grain pattern, a wood grain pattern, a geometric shape, an abstract shape, etc. may be sufficient. The printing of the print shape may be any of beta printing, partial printing, partial printing after full beta printing, and the like.

Lamination | stacking of colored polyester-type resin film (B ') and transparent resin film (C) is a co-extrusion shaping | molding method which melt | dissolves two types of raw material resin, respectively, and laminates in a die for co-extrusion shaping | molding to make two layers. , (2) Two types of resin films are produced by respective extruders, and two or more resin films are pressed by two types of resin films while the two or one resin films are in a molten state, and (3) two kinds of preliminarily manufactured Resin film can be made by the dry lamination method etc. which laminate | stack through an adhesive agent. The adhesive agent (E) used by the method of said (3) will not be restrict | limited in particular, if it can adhere | attach two types of resin films.

The manufacturing method of the laminated sheet-like substance used for the resin coating metal plate containing said printing layer (D) is not specifically limited. For example, a printing layer (D) is formed on the back surface of the transparent resin film (C), and on the surface of this printing layer (D) layer, or on the surface of the colored polyester resin sheet material (B) separately prepared. And a layer made of an adhesive agent (E) of the application type, and polymerized, and passed through a pair of heated pressure rolls to be bonded and laminated. The conditions, such as a heating temperature of a press roll, a pressure, etc. can be suitably selected by the kind of laminated sheet-like substance, the kind of adhesive agent, etc.

The resin coated metal plate concerning this invention is manufactured by adhering the said laminated sheet-like substance to the surface of the said base metal plate (A). As this manufacturing method, there exists a method of using the said adhesive agent, the method of heat-sealing without using an adhesive agent, the method of extrusion coating, etc., and is not specifically limited. When using the method of using the said adhesive agent, after performing an anchor process on the surface of the said base metal plate A previously, an adhesive agent is apply | coated to the surface on which the anchor process was carried out, and the said laminated | multilayer film is adhere | attached. Epoxy adhesive, urethane adhesive, etc. are mentioned as this adhesive agent. The coating method of this adhesive agent can be performed by methods known conventionally, such as a reverse coating method and a kiss coating method. The coated adhesive dries the coated surface by an infrared heater and a hot air heating furnace. The adhesive coated surface of the base metal (A) is heated above the melting point of colored polyester-based resin {(B) component}, and the laminated film is superimposed on this adhesive coated surface to pass through a pair of pressure rolls to bond and integrate. It can be set as the resin coating metal plate by this.

The resin-coated metal sheet according to the present invention is used for building wall materials, ceiling materials, partition wall materials, unit bath wall materials and ceiling materials, building materials for other building interior materials, housing for home electrical appliances, and other industrial equipment. . In particular, it is very suitable for the use of unit bath wall materials and ceiling materials.

Hereinafter, it demonstrates further in detail by an Example and a comparative example. In addition, the (b1) component and (b2) component which were used by each Example and the comparative example are as follows.

(1) (b1) Component (non-crystalline polyester resin)

Eastman Chemical Company: PET-G: glass transition temperature (Tg); 81 ° C., crystal melting peak; None (hereinafter abbreviated as "PET-G")

Eastman Chemical Company: PCTG: glass transition temperature (Tg); 88 ° C., crystal melting peak; None (hereinafter abbreviated as "PCTG")

(2) (b2) Component (crystalline polyester resin)

Polybutylene terephthalate (hereinafter abbreviated as "PBT"): crystal melting peak temperature; 222 ° C., heat of fusion of crystals; 41J / g

Polyethylene terephthalate (hereinafter abbreviated as "PET"): crystal melting peak temperature; 247 ° C., heat of fusion of crystals; 37J / g)

Moreover, each evaluation method in each Example and a comparative example is shown below.

[Measurement of Glass Transition Temperature (Tg), Crystal Calorific Value, and Crystal Melt Peak Temperature]

Using Parkin Elma DSC-7, 10 mg of samples were determined by measuring heating and cooling rates at 10 ° C / min in accordance with JIS-K7121 and JIS-K7122.

[Surface hardness]

Using a pencil of HB, using a pencil scraping test according to JIS-S1005 9.8 (2) pencil scraping test, applying a 500 g load while drawing an angle of 45 g with respect to the resin sheet surface of the 80 mm x 60 mm resin-coated metal sheet, The surface state of the resin sheet was visually judged, and the thing which did not generate | occur | produce a scratch at all ((circle)), the thing which left traces of a line drawing ((△)), and the thing which made the scratch clearly were shown as (x).

[Navigability test]

The resin coated metal plate of 50 mm x 60 mm was immersed in boiling water for 3 hours, the surface state of the resin sheet was visually judged, and there was no change at all (○). The swelling caused by the bubbles is indicated as (×).

[Alkali Resistance Test]

In accordance with JIS-K67445 (5), when the surface and the cut surface which do not coat | cover a resin sheet of the 50 mm * 60 mm resin coating metal plate are coat | covered with vinyl chloride resin, and a transparent resin film (C) is further used, transparent resin In the film (C), the cross-cutting part which leads to the colored polyester-type resin sheet-like substance (B ') was put in with the commercially available cutter knife. Next, under an atmosphere of 20 ° C., it was immersed in a 10% aqueous sodium hydroxide solution for 5 hours, and the surface state of the resin sheet was visually judged, and there was no change at all (○), slightly floating, swelling, or peeling off the surface. The crack (etc.) which generate | occur | produced the cracks, etc. (()) and the thing which the cracks, such as lifting, swelling, and peeling on the whole surface generate | occur | produced are shown as (x).

[Processability]

An impact adhesion bending test was performed on the resin-coated metal sheet, and the surface state of the makeup sheet of the bent portion was visually judged, and there was almost no change (○), a little crack occurred (△), and a breakage occurred (× ).

In addition, the impact adhesion bending test was done as follows. 50 mm x 150 mm samples were produced in the length direction and the width direction of the resin coated metal plate, respectively, and held at 23 ° C. for at least 1 hour, and then bent at 180 ° (bending radius in 2 mm) using a bending test machine. A columnar weight of 75 mm in diameter and 5 kg in mass was dropped from a height of 50 cm.

(Examples 1-5, Comparative Examples 1-4)

Each component of (b1) and (b2) was knead | mixed so that it may become homogeneous using the twin-screw kneading extruder provided with T die with the black colorant at the compounding ratio (weight%) shown in Table 1, and it was 150 micrometers in thickness The colored polyester resin sheet (B ') was formed into a film. Next, as adhesive (E), the adhesive film thickness after drying the polyester adhesive for commercially available polyvinyl chloride coating metal plates on the metal surface of the galvanized steel plate (thickness 0.45mm) which is a base metal plate (A) is 2-. Apply so that it will be about 4㎛. Next, the coating resin is dried and heated by a hot air heating furnace and an infrared heater, and immediately while using the roll laminator while maintaining the surface temperature of the galvanized steel sheet above the melting point of the polyester resin sheet, the polyester resin is used. The resin coated metal plate was produced by covering and cooling a sheet | seat. Said evaluation was performed using the obtained resin coating metal plate. The results are shown in Table 1.

(result)

As apparent from Table 1, workability can be satisfied with any formulation, but only in the case of amorphous polyester resin (b1) having no crystal melting peak (Comparative Example 2), but the blending amount is 95% by weight. In the case of (Comparative Example 1), the influence of amorphous resin (b1) is strong and the boiling resistance cannot be satisfied. In addition, the surface hardness slightly decreases.

In addition, when the amount of heat of fusion is only crystalline polyester resin (b2) of 30 J / g or more (Comparative Example 3), or when the blending amount exceeds 50% by weight ratio (Comparative Example 4), the crystalline resin The influence of (b2) is strong and the surface hardness is high, but the alkali resistance is inferior.

On the other hand, the blending amount of the component (crystalline polyester-based resin) is 10% or more and 50% or less in terms of weight ratio to achieve both boiling resistance and alkali resistance. It turns out that you can. However, in the formula (Example 5) in which the weight ratio of the amorphous polyester resin (b1) is 90%, both the boiling resistance and the alkali resistance are compatible, but since the surface hardness slightly decreases, the crystalline polyester It is preferable to make system resin (b2) into 20% or more by weight ratio. Moreover, when polybutylene terephthalate is used for crystalline polyester resin (b2), since the crystallization rate is fast, it is more preferable to suppress to 40% by weight ratio suitably.

(Examples 6-11, Comparative Examples 6-9)

<Preparation of laminated film>

First, (b1) component and (b2) component were weighed by the ratio (weight%) shown in Table 2, and it mixed with the black coloring agent with the mixer. The resulting mixture was melted and kneaded by setting a cylinder temperature in the range of 240 ° C to 270 ° C using a twin-screw kneading extruder equipped with a T die at the tip, and a colored polyester resin film (B ') having a thickness of 150 µm. Was prepared. To one side of a biaxially stretched polyester film (manufactured by Mitsubishi Chemical Co., Ltd.) (C) having a thickness of 25 µm, partial printing of an abstract pattern was performed by the gravure coating method, and a polyester adhesive was applied to this printing surface. And it laminated | stacked by the said colored polyester-type resin film (B '), and prepared laminated | multilayer film.

<Preparation of resin coated steel sheet>.

A polyester adhesive is applied to the entire surface of the galvanized steel sheet having a width of 50 cm, a length of 100 cm, and a thickness of 0.45 mm, which is the base metal plate (A), so that the thickness of the adhesive after drying is about 2 to 4 μm, Subsequently, the coated film was dried and heated by a hot air heating furnace and an infrared heater, and the laminated film was immediately laminated using a roll laminator while maintaining the surface temperature above the melting point of the colored polyester resin (B '). And cooling, the resin coated steel sheet was produced, and the above-mentioned evaluation of each item and the process part durability test shown below were done. The evaluation result was put together in Table 2 and shown.

[Processing Part Durability Test]

According to JIS-K6744 (Erikusen test) and JIS-K540O (same tester), the resin coating side of the 50 mm x 60 mm resin coating metal plate is made into the dice | dies side of a tester, and the center of a coating metal plate matches the center of punches, dice | dies, etc. By depressing the punch 6 mm at a constant speed, the resin coating side was deformed so as to be convex.

Subsequently, after the coating metal plate was immersed in boiling water for 1 hour, it was taken out and the external appearance of the processed part was visually evaluated. "(Circle)" and the thing which markedly floated in biaxially stretched PET of surface layer were confirmed that there was no change before boiling water immersion, and "(R)" was confirmed that a little rise of the comparative thing rather than "x" and "x" was confirmed.

From Table 2, the following becomes clear.

(1) If the resin component which comprises colored polyester resin film (B ') is content of crystalline polyester resin (b2) in the range of 10 to 50% by weight ratio, a resin coating steel plate will have boiling water resistance And alkali resistance are all excellent (see Examples 6 to 11).

(2) On the other hand, when the resin component constituting the colored polyester resin film (B ') has a content of 10% by weight or less of the crystalline polyester resin (b2), the surface of the coating resin of the resin coated steel sheet Since hardness falls, it is preferable to make crystalline polyester resin into 10 weight% or more (refer comparative example 9).

(3) Only the amorphous polyester resin (b1) which does not have a crystal melting peak of the resin component which comprises a colored polyester resin film (B ') (refer comparative example 5), or content is 90 weight% When exceeding (refer comparative example 9), in either case, although workability is excellent, the influence of amorphous resin is strong, surface hardness falls, and it is inferior to boiling water resistance.

(4) Moreover, when the amount of crystal melting heat is only 3OJ / g or more of crystalline polyester resin (b2) (Comparative Example 6), or when the content exceeds 50% by weight (see Comparative Example 7), The influence is strong and the surface hardness is high, but the alkali resistance is inferior.

(5) In addition, when the crystalline polyester resin (b2) is polybutylene terephthalate (PBT) and the PBT is 10% by weight, the durability of the processed portion is not sufficient, but as a result of other tests, The results of the surface hardness, the boiling resistance test, and the alkali resistance test were good (see Example 11).

(6) Moreover, in Example 7 in which the crystalline polyester resin (b2) is polybutylene terephthalate (PBT) and the range of PBT is in the range of 20-40 weight%, it is excellent in alkali resistance. However, the durability of the processing part is slightly inferior. In addition, in Example 9 where the range of PBT is in the range of 35 to 50% by weight, the processing part durability is excellent, but the alkali resistance durability is slightly inferior. In addition, since Example 8 exists in the range of both said PBT, it is excellent in both alkali resistance and the durability of a process part.

Therefore, the compounding of (b2) component can be distinguished and used according to which of the alkali resistance and the durability of a process part matters.

In this embodiment, the following effects are obtained.

(1) There is no crystal melting peak observed by a differential scanning calorimeter, and the amorphous melting resin component (b1) having a crystal melting calorific value of 10 [J / g] or less, and the crystal melting peak, The polyester-based resin sheet-like substance was formed from the mixture which crystal calorie | heat amount of fusion of crystalline polyester resin component (b2) of 30 [J / g] or more was mixed in a specific ratio. Therefore, the resin sheet-like material is excellent in workability and scratch resistance, and also excellent in hot water resistance and alkali resistance. As a result, it can be used suitably as a coating material of a resin coating metal plate.

(2) When general-purpose polyethylene terephthalate is used as the crystalline polyester resin, a polyester resin sheet-like material, and furthermore, a resin-coated metal sheet can be produced at low cost.

(3) Since the resin-coated metal sheet uses each of the above polyester-based resin sheet-like substances as a coating material, it is excellent in workability and resistance to scratches without using halogen-containing resins such as soft vinyl chloride resins and hot water resistance. Excellent alkali resistance.

(4) Since various steel sheets or aluminum plates are used as the metal plate, the secondary workability and durability of the resin coated metal plate are excellent.

(5) When polybutylene terephthalate is used as said crystalline polyester resin, the workability at the time of shape | molding a sheet | seat or a film by extrusion molding from polyester resin improves.

Embodiment is not limited to the above, For example, you may specify as follows.

(6) The component (b1) of the amorphous polyester resin and the component (b2) of the crystalline polyester resin are not limited to using one kind of polyester resin, but are various kinds of polyester resins. You may mix resin. For example, in the case of (b2) component, you may mix polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate.

(6-1) The thickness of the polyester resin sheet-like material may be 50 to 500 µm.

(6-2) Furthermore, the polyester resin sheet-like substance may be affixed to the surface of the metal plate using an adhesive, and the thickness of the adhesive layer may be 2 to 4 µm.

(6-3) Moreover, various steel sheets or aluminum plates may be used as the metal plate.

According to this invention, the polyester-based resin sheet-like substance (B) containing (b1) component and (b2) component is excellent in workability and flaw resistance, and also excellent in hot water resistance and alkali resistance. Moreover, the resin-coated metal plate of this invention of Claim 5 is excellent in workability and flaw resistance, and also excellent in hot water resistance and alkali resistance, without using halogen containing resin.

In addition, since the resin-coated metal sheet according to the present invention does not use a soft vinyl chloride-based resin, VOC problems caused by stabilizers and plasticizers, endocrine disruption problems, and hydrogen chloride gas and other chlorine-containing gas are generated during combustion. There is no problem at all.

Moreover, since the resin coating metal plate which concerns on this invention comprises the coating resin by the laminated | multilayer film of a specific structure simultaneously in a specific composition, it is hard to produce a scratch on the surface (excellent scratch resistance), and is excellent in workability.

Moreover, since the resin coating metal plate which concerns on this invention is comprised by the laminated | multilayer film of a specific structure at the same time in a specific composition, it is excellent also in hot water resistance, chemical resistance, etc.

Moreover, since the resin coating metal plate which concerns on this invention comprises the coating resin by the laminated | multilayer film of a specific structure simultaneously in a specific composition, it is excellent in the balance of flaw resistance, processability, hot water resistance, and chemical resistance.

Moreover, in the design resin coating metal plate in which the printing layer (D) of this invention was arrange | positioned, since the printing layer (D) is arrange | positioned between the transparent resin layer (C) and the colored resin layer (B), a printing layer This protects, exerts a design with depth, and is excellent in aesthetics.

Claims (10)

A mixture consisting of the following (b1) component and (b2) component, wherein the ratio of each component is (b1) / (b2) = 50 to 95/50 to 5 (the sum of the quantum is 100) in weight ratio, alkali resistance and navigability A polyester resin sheet-like material characterized by excellent isotropy. (b1) Component: The polyester-based resin whose crystal melting heat measured by the differential scanning calorimeter is 10 [J / g] or less. (b2) Component: The polyester-based resin which has the crystal melting peak observed with the differential scanning calorimeter, and whose heat amount is 30 [J / g] or more. The said (b2) component is polybutylene terephthalate type resin, The mixing ratio ((b1) / (b2)) of said (b1) component and (b2) component is 60 weight ratio of Claim 1 It is the range of -80 / 40-20, The polyester-type resin sheet material. The said (b2) component is polypropylene terephthalate type resin, The mixing ratio ((bl) / (b2)) of said (bl) component and (b2) component is 60-A by weight ratio, It is the range of 80 / 40-20, The polyester-type resin sheet material. The component (b2) is polybutylene terephthalate-based resin, and the mixing ratio ((b1) / (b2)) between the component (b1) and the component (b2) is 50% by weight. It is the range of -65 / 50-35, The polyester-type resin sheet material. The said (b2) component is polypropylene terephthalate type resin, The mixing ratio ((b1) / (b2)) of said (b1) component and (b2) component is 50- by weight ratio, A polyester-based resin sheet-like material, characterized in that the range of 65/50 to 35. The polyester-based resin sheet-like substance (B) of any one of Claims 1-5 was coat | covered on the surface of the base metal plate (A), The resin coating metal plate characterized by the above-mentioned. The transparent resin film (C) on the colored polyester-based resin sheet-like substance (B ') which mix | blended the coloring agent as a component in the polyester-based resin sheet-like substance (B) of any one of Claims 1-5. The laminated sheet-like substance which laminated | stacked) was coat | covered on the surface of the base metal plate (A), The resin coating metal plate characterized by the above-mentioned. The colored polyester resin sheet material (B '), the printing layer (D) which mix | blended the coloring agent as a structural component with the polyester resin sheet material (B) in any one of Claims 1-5. The laminated sheet-like substance which laminated | stacked the transparent resin film ((C)) sequentially was coat | covered on the surface of the base metal plate (A), The resin coating metal plate characterized by the above-mentioned. The said base material metal plate (A) and colored polyester-type resin sheet-like substance (B '), or between said printed layer (D) and colored polyester-type resin sheet-like substance (B'). The coated resin sheet (E) is provided between the layers and the laminate is integrated to form a resin-coated metal sheet. The resin-coated metal sheet according to any one of claims 7 to 9, wherein the transparent resin film (C) is a biaxially stretched polyethylene terephthalate resin sheet-like material.