TW459006B - Resin film excellent in emboss processability, emboss processing method for the said resin film and the decorative metal sheet coated with the said resin film - Google Patents

Abstract

Disclosed is to provide a resin film that can be used in the construction materials such as unit bath, the resin film having excellent emboss processability superior to that of conventional flexible polyvinyl chloride film, and a decorative metal sheet coated with said resin film which having high grade feeling in appearance. By using resin film of TMA relation value below 10 as raw material being coated onto a decorative metal sheet, then subjected to rolling treating by using a carving roll, on the basis of using Tss (softening starting temperature measured by TMA), Tse (softening ending temperature measured by TMA) and Tmp measured by DSC, the surface temperature Tr of chilled roll that contacted with the resin film is set in the range of Tss-10≤Tr≤Tse(DEG C) and Tr<Tmp(DEG C), subjected to emboss processing, an embossing surface of high grade feeling which is superior to that of conventional polyvinyl chloride resin can be obtained. The TMA relation value (DEG C) is equal to Tse-Tss, wherein the Tss(DEG C) is the softening starting temperature measured by using TMA, and the Tse(DEG C) is the softening ending temperature measured by using TMA.

Description

V. Description of the invention (1) Technical field to which the invention belongs The present invention relates to a resin film having excellent embossability for integrally formed bathrooms, water tanks, various industrial supplies, tanks, etc., which are used for building materials or industrial materials that require water resistance. Or sheet (hereinafter referred to as "resin film"). The present invention relates to a decorative metal plate coated with the resin film. Conventional technology Decorative metal plates are widely used in one-piece bathrooms, water tanks, various industrial supplies, tanks and other building materials or industrial materials that require water resistance. At this time, the main purpose of coating the resin film on the surface is to provide the anti-corrosion effect to the metal plate of the raw material. However, it also has the purpose of giving the decorative metal plate a high-level sense. Since the embossing pattern has been added for a long time, Extensive implementation. The thin-film material with an embossing pattern used for this purpose has long been required to be easily embossed and low in price. For example, soft polyethylene gas resin has been used. Problems to be Solved by the Invention However, in order to make it easy to form a soft polyethylene gas resin, phthalic acids such as DBP (dibutyl phthalate) and DOP (dioctyl phthalate) are added as a plasticizer and added. In the case of softening, it is difficult to use it in high-temperature places such as bathtubs, and the disposal of products containing such products has various problems. In addition, when the resin film that has been embossed and then laminated is used on a metal plate, the beauty of the product varies depending on the metal plate used, the combination between the metal plate and the resin, etc. less. In other words, because

459006 V. Description of the invention (2) The use of products for this purpose, etc., because of the aesthetic sense, especially the existence of high problems, it is appropriate to carry out the embossing process under the most suitable conditions. The combination of conditions is a question to rule out the disadvantages of plasticizers, and the aesthetics of the resin at the embossing processing place is difficult to obtain. Polyethylene 1 polypropylene resin These resins are embossed and post-processed. In order to solve this problem, if a rubber component is added, a dibutyl soft acid resin, which is the same as a vinyl resin, has excellent characteristics of deterioration. However, on the other hand, the general treatment items have not been put into practical use. Under considerable review, the situation in the field is mostly. The present invention is to solve the soft polyethylene gas resin 4

The type of resin and the embossing processing conditions The aesthetic sensibility of the grade is susceptible to the problem. The treatment is based on the relationship with the resin used. Therefore, the type of resin and the most suitable embossing problem are. Rigid polyvinyl chloride resin films have low processability and are usually difficult to handle. There are also problems with embossing. In the case of using olefin-based resins instead of polyvinyl chloride resins, although the workability is good, there is a problem that the lamination process part is whitened on the metal plate to damage the aesthetics. Although there are proposals to add a rubber component, however, There is a problem that the polyethylene resin is newly transformed and the polymer resin is present. In addition, polyparaphenylene has water resistance and less strength after being placed in water. It is highly desirable to be used as a covering material in this field. It is suitable for embossing due to its low embossing processability. In terms of conditions, for a long time, we have not deliberately accumulated experienced knowledge in order to respond to the above-mentioned problems in order to provide a resin thin film with excellent embossing processability equal to or more than conventional.

Page 6 5. Description of the invention (3) The purpose of the film and the decorative metal plate covered with the resin film is high-quality and rich in sensibility. Means for Solving the Problem The resin film described in the first patent application scope of the present invention is characterized in that the TMA relationship value given by the following formula is 10 or less. ΤΜΑ relation value (° C) = Tse —Tss

Tss (° C) is the softening start temperature measured using TMA, and Tse (° C) is the softening end temperature measured using TMA. Such a film preferably contains polybutylene terephthalate in the resin. In addition, the embossing processing method described in item 2 of the scope of patent application of the present invention uses the above-mentioned resin film as a raw material, and after the resin film is coated on a decorative metal plate, the embossing is performed by a rolling process using an engraving roller. In the case of flower processing, the softening start temperature Tss, softening end temperature Tse, and Tmp measured by DSC were used as the reference, and the roller surface temperature Tr of the portion in contact with the resin film was set to Tss-10 STr. S Tse (° C) and Tr &lt; Tmp (° C) are necessary for embossing, so that the best embossability can be obtained under this condition. Here, Tmp (t) is the endothermic peak temperature of the temperature rise process measured by DSC. The decorative metal plate according to item 3 of the scope of patent application of the present invention is characterized by being coated with a film covered by item 1 of the scope of patent application or a resin film treated under embossing conditions under the scope of the second scope of patent application.

V. Description of the invention (4) The embodiment of the invention The sample inventors and other inventors carefully examined the relationship between the characteristics of the resin film and the embossing processability. It was found that the thermal mechanical analysis (Therma 1 Mechanical Analysis, TMA) The softening start temperature Tss (° c) and the softening end temperature Tse (.0 calculated TMA relationship value (Tse-Tss) value is within the range of 10 or less, as for this resin film, for example, Polybutylene terephthalate resin or polyethylene terephthalate resin film containing polybutylene terephthalate resin, etc. The resin film is used as a raw material, and the resin film is coated on a decorative metal plate. After the above, when the embossing process is performed by the rolling process of the engraving roller, the softening start temperature T ss, the softening end temperature Tse, and the Tmp measured by DSC, which are measured using TMA, will be compared with the resin. The surface temperature Tr of the roller contact part is set to Tss-10 STr ^ Tse (° C), and TrCTmp (° C) is embossed. The embossability of these resin films will be greatly improved. While It is found that a product made of a decorative metal plate having an embossed film on the surface can impart a more classy feeling than a conventional article. As a result, a resin film having such characteristics is laminated, even in In the case of processing such as bending, there is no problem in that the processing part is whitened and the design is impaired. 'The embossing processability equivalent to that of the polyethylene gas resin can be improved.' Furthermore, the water resistance and in-situ conditions can be maintained while maintaining the original state. It has excellent properties such as so-called polybutylene terephthalate resin, which has less deterioration in strength after being placed in water.

A59 006 Five 'invention description (5) The content of the present invention will be described below. In the present invention, a resin film is adhered to a metal plate in advance, and then the metal plate and the resin film are passed through a engraving roller at a certain speed and embossed. (Used metal plate) As for the metal plate used in the present invention when the resin film is laminated and treated before the embossing process, it is a steel plate, an aluminum plate, a copper plate, etc., and it can be widely used as a metal plate. As for the steel sheet, a cold rolled steel sheet of ordinary steel having a thickness of 0.10 to 1.20 mm is suitable. Among them, the ordinary steel cold-rolled steel sheet with a thickness of 0.10-0. 50mm is more suitable. Although cold-rolled products are preferably made of low-carbon steel or ultra-low-carbon aluminum deoxidized steel, non-aging / (stabilizing) steel with Nb, Ti, etc. can also be used, containing 3 to 1 8 Cr steel by weight%, stainless steel plates with various compositions, etc. The surface of these cold-rolled steel sheets is preferably a surface-treated one in terms of durability. As for the surface treatment method, there are electroplating treatment and coating treatment, among which electroplating treatments include galvanization, galvanization-aluminum alloy, galvanization-cobalt-molybdenum, tin plating, nickel plating, nickel plating, phosphorus plating, nickel plating, cobalt plating, Nickel plating, tin plating, etc., and coating treatment are performed by baking and coating in accordance with various coating properties. (Resin film used, etc.) The thickness of the resin film and the like is not particularly limited, but a polybutylene terephthalate (PBT) resin, such as 0.02 to 0.30 mm, preferably 0.080 to 0.150 mm, may be used. PBT Blend resins in various proportions with other resins, such as blends of polyethylene terephthalate (PET) resins, polycarbonate (PC) resins, ionomers, etc., or this Blends of three or more resins, or copolymers of PBT and other resins or compounds, / :, 7

Page 9 V. Description of the invention (6) For example, a composite resin film obtained from a resin film of a copolymer of isophthalic acid and adipic acid, etc., and the above-mentioned various resin films are laminated at different thickness ratios. Wait.

J A colored resin may be added to these resin films and the like. The reason for using two or more kinds of blended resins is, for example, that although superior in impact strength, resins with poor adhesion to metals are intended to improve only their adhesion, and there are blends and metals. In the case of a resin with good adhesion, the use of a composite resin is due to the use of a resin with excellent adhesion characteristics on the bonding surface with the metal. The resin used in these resin films needs to have a TMA relationship value of 10 or less given by the following formula. ΤΜΑ relation value (° C) = Tse —Tss

Tss (° C) is the softening start temperature measured using TMA, and Tse (° C) is the softening end temperature measured using TMA. When a resin film having such a TMA relationship value is used as a raw material resin film, after the resin film is coated on a decorative metal plate, the embossing process is performed by using a rolling treatment of an engraving roller, and the measurement is performed by using TM A The softening start temperature Tss, the softening end temperature Tse, and the Tmp measured by DSC are used as the reference. The roller surface temperature Tr of the portion in contact with the resin film is set to Tss-lOSTrSTse (° C), and Tr &lt; Tmp (° C ) And the need for embossing processing. These resin films are coated on a metal plate just before the embossing process. As a method for coating a resin film on a metal plate, epoxy is used.

Page 10 V. Description of the invention (7), cyanoacrylate-based adhesives, etc., but the method of pressing on a metal plate that has been heated above the melting point of the resin may be followed. In the case where the resin film is adhered to the metal plate by the heating and pressing method, it is preferable to treat the surface of the metal plate in advance to obtain a strong adhesive strength. As for the surface treatment method of the metal plate, a method known to those skilled in the art, such as electrolytic chromic acid treatment, followed by primer coating treatment, can be used. The reason for limiting the TMA value of the resin to less than 10 is due to the embossing process using the concave and convex engraving rollers (sand marks) of Ra = Π # m. 0 # m The average surface roughness Ra after processing is 4.0 / zm, so the average surface roughness benchmark for comparison with conventional products to make the embossing processability good is set to 4. 0 # m Caused by. If a resin film or the like having such a TMA relationship value is used, the reason for improving the embossing processability is within a certain temperature range between the softening start temperature T ss and the softening end temperature T se, within this temperature range, The resin can effectively absorb the compression energy or friction energy accompanying the embossing process, so it can be considered as whether the resin can maintain a high degree of deformation after cooling. In the case where the resin film having such a TMA relationship value is used as a raw material resin thin film and the embossing process is performed by using the rolling treatment of the engraving roller, the softening start temperature Tss and the softening end temperature Tse measured by TMA are used. And using Tmp measured by DSC as a reference, the roller surface temperature Tr of the part in contact with the resin film is set to Tss-1 0 STr STse (° C), and Tr &lt; Tmp (° C) is embossed. The reason is that the embossing process has been performed in this temperature range, and the high-grade feeling of the product is extremely superior. As for embossing processing temperature and laminated resin film and decorative metal plate

V. Description of the invention (8)

There are still many unknown points in the perceptual relationship between them, but by the time when most of the crystalline field part, which is also called the softening start temperature of the resin, still exists, it can be regarded as the need to impart deformation to the occurrence of high-level sense. Is there an association. In addition, the reason why the roller surface temperature Tr is set to be lower than the T mp (° C) measured by DSC and to be within a very limited range lower than the T se measured by TIM A is because It prevents the resin from adhering to the roller during the embossing process to deteriorate workability. In general, the relationship between the value of TMA and the average surface roughness Ra after the embossing of the resin film tends to be inversely proportional. The average surface roughness R a is largely related to the value (creativeness) of the design of the product, and a range of 4 # m or more can be considered as an appropriate value. The more suitable range of the average surface roughness Ra is 5 to 8. In addition, when a resin using such a TMA relationship value is embossed simultaneously with a decorative metal plate that has been laminated with the resin film, a decorative metal plate that has been laminated with a resin film has been used. For example, the high-quality feeling of a bathtub, the first condition is based on the softening start temperature Tss, softening end temperature Tse, and Tmp measured by DSC as the reference, and the surface temperature of the portion where the roller contacts the resin film Tr is set to Tss-lOSTrSTse (° C) and necessary for embossing. In addition, the second condition is based on Ttnp measured by DSC, the roller surface temperature Tr is set to Tr &lt; Tmp (° C), and embossing is performed. In the case of embossing processing under the combination of this condition, the resin having the aforementioned certain TIM A relationship value has been used for subsequent, lamination processing of gold.

Page 12 V. Description of the invention (9) The products of the plate type can be found to have a very good texture, that is, a product with a high-grade feeling. The measurement of various units required for the calculation of the TMA relationship value and the DSC relationship value is performed under the following conditions. Using TMA and TAS-300 manufactured by Rigaku Electric Co., Ltd., a load of 100 g was applied to a needle with a front end R = 0.2 or less (front end angle 60 °), and measured at 1 〇 based on JIS-K-7 1 9 6 ° C / mi η The depth of penetration of the needle into the film when the temperature rises. An example of the measurement curve of the TMA relationship value is shown in Fig. 1. The penetration of the needle here is the value obtained by dividing the penetration depth by the thickness of the film. The softening end temperature Tse, as shown in Fig. 1, is a temperature obtained from the curve of a sharp change in penetration and the intersection of the tangent line of the baseline after softening. The same softening start temperature Tss is the temperature obtained from the intersection of the tangent of the curve used by Tse and the tangent of the baseline nearby. The Tmp measured by DSC was measured under the following conditions. A differential calorimeter DSC-7 manufactured by Perkin-Elmer was used, and about 5 mg of the accurately weighed sample was heated at 20 ° C / m i η under a nitrogen atmosphere, and the endothermic peak was the melting point Tmp of DSC. (Embossing processing method) For embossing processing methods such as resin film, there are a method of directly passing a multi-layer film between cooling rollers, and heating a brown film (brw port fi 1 m) through a cooling roller. Various methods, such as a method of embossing with a vacuum force by rotating a screen roller, a method of passing a multi-layer film through a hot needle process between perforators, a method of using a engraving roller and compressing it, etc. , But the case of the present invention is the resin to be supplied by the τ_ mold

4 § 9 000 Five 'Invention Description (ίο) The film is then embossed on a separately supplied metal plate.

In the case of embossing by this method, the surface of the roller of the portion that will come into contact with the resin film is based on the softening start temperature Tss, softening end temperature Tse, and Tmp measured by DSC as measured by τ Μ A. The temperature Tr is set to Tss-lOSTrSTse (DC), and TrCTmp (.0) is embossed. As for the embossed shape, you can use random, square, diamond, deep drawing according to the needs of the product Patterns, sand marks (hereinafter referred to as SG marks), etc. (determination of good embossability) The determination of whether the embossability of the resin film or the like of the present invention is good or not depends on the pressure of the resin film. The surface roughness Ra (// m) after the flower processing is judged. Generally good embossing property refers to the embossing pattern when rolling and embossing processing such as engraving roller at the temperature before and after the melting point of the resin. It can be easily formed on the surface of the resin film, and the embossing pattern can be maintained for a long time even after the temperature is increased. Therefore, the measurement of the surface roughness is to pass the resin film at a certain speed to The resin uses the softening start temperature Tss and the softening end temperature Tse of the heating process measured by TMA as the reference, and has been set to Tss-1 0 STr S Tse (° C), and the average surface roughness of Tr &lt; Tmp (° C) RaMl // in engraved roller with concave and convex sand marks. At this time, the surface temperature of the roller can be set and adjusted by a method in which a certain amount of heat medium flows in the piping provided in the roller.

Resin film laminated metal plate was cooled at room temperature afterwards, using a SURFCOM surface roughness meter manufactured by Tokyo Precision Co., Ltd. based on JIS B0601 &lt;

Page 14 Examples The following Example 1 was prepared. The steel plate upper plate was heated to the terephthalocyanine laminated steel plate 2. Secondly, a steel sheet Ra having sand and embossing is 6. V. Description of the invention (11) The surface rough chain degree Ra (/ z in) is measured, and the average surface rough shuttle degree is 4.0 or more as the embossing property. good. In addition, this measurement is based on the resin film that has been embossed. Five resin test strips are arbitrarily taken. The surface roughness of each test strip is measured at four different positions, and the average value is calculated as the surface roughness Ra (/ / m) 〇 The present invention will be described more specifically with reference to examples. A 0.50mm aluminum deoxidized cold-rolled steel sheet having a carbon content of 0.030% was galvanized to a thickness of 0.02 mm. Then, the melting point of this coated steel resin was τπρ ± 10 ° C, and a PBT (polybutylene acid) resin film having a thickness of 0.100 mm was hot-pressed on the surface, and made. The inherent viscosity of the resin film is 1.4, and the T A relationship value is 7. • The surface temperature of the embossing roller is adjusted to 2 15 ° C, and the engraving roller with the trace pattern is used to synchronize the steel plate with the resin Pressing, flower processing, and then rapidly cooling to room temperature. The average surface roughness obtained by evaluating the embossability of the resin film as described above is 7 // m. Examples 2-4 Except that the type of resin was changed, a laminated steel plate was produced in the same manner as in Example 1, and T ss measured by T M A, softening end temperature Tse, and Tmp measured by DSC were used for the resin used. The value is based on the setting of the roller temperature.

V. Description of the invention (12) Embossing processing and evaluation of embossability β Example 2 is a case where the intrinsic viscosity is the same as Example 1 but 1.4, but a PBT resin with a TIMA relationship value of 2.9 is used. Example 3 is a case where a PBS resin having an intrinsic viscosity of 1.0 and a TMA relationship value of 3.3 is used, and Example 4 is a method of using a layered poly (p-phenylene terephthalate) with a thickness ratio of 1: 4 ( PET) and 10 m ο 1% of copolymer resin thin film of methylene dibenzoic acid and polybutylene terephthalate (PBT) resin film make the PBT layer contact the engraving roller. Comparative Examples 1 and 2 The types of resins were changed, and laminated steel plates similar to those in Example 1 were produced. T ss measured by T M A, softening end temperature Tse, and Tmp measured by DSC were used. The value is a quasi-set roller temperature, and an embossing process is performed to evaluate the embossability. Comparative Example 1 is a case where a PET resin having a TMA relationship value of 28.8 is used, and Comparative Example 2 is a case where a polycarbonate resin having a TMA relationship value of 18.9 is used. The conditions and measured values of these examples and comparative examples are summarized and shown in Table 1.

V. Description of the invention (13) PBT: 舛 liang ^-^-δ ^ τ- ^ δτρΕΗ ^^^^^ ψ ^ Γ '^^-ρί :: ^^^^ Bu pro: ΒΒΤ / 3 舛 hf 琛10 mol. / 0 and tabine PET &gt; 趄 t (T4 / l Comparative Example 2 Comparative Example 1 Example 4 Example 3 Example 2 Example 1 F Η PC resin PET resin two-layer film PBT resin (inherent viscosity = 1.0) PBT resin (intrinsic viscosity = 1.4) PBT resin (intrinsic viscosity = 1.4): Types of resin used and their appearance 178 5, 104.1 216.7 220.5 220.9 221.4 3 TMA measurement value 1 197.4: 126.9 225.4 223.8 223.8 228.6 〇 ° ^ W 邝 00 NJ to bo 00 U &gt; Ui k) TIMA relationship value 1 248.0 220.7 220.1 218.8 1 218.9 Tmp ro Ό 〇 〇 using DSC t 〇 Ν &gt; t-t U \ N) ί / 1 NJ Κ) 1- »Ln Roller target temperature ΓΟ NJ HL OS bo 00 ί / 1 '〇σ \ Average surface rough chain degree Ra (Um) | Zhun Shang grade ψ quenched 1¾ grade 3 ° V two grade Μ 1¾ presence or absence of sense &gt; 1 6 渖 53 客 声 踪 'All Η 菰 菰 菰 菰 菰 .SUnJl 鼾 陴 萆 踣 Secret Plant ~ &gt; Lying Axe Page 17

459006 V. Description of the invention (14)

For the samples thus obtained, the following tests were performed to check the presence or absence of sense of quality. First, prepare three pieces of laminated steel sheet cut into 30x20cm sizes and place them on a table in a room that is not exposed to sunlight, and illuminate the sample with 5 20W white fluorescent lamps. Five persons with different ages and genders were marked with the following scoring points at different observation positions and angles, and the average value of the scoring points was obtained for comprehensive evaluation. When compared with the conventional PVC laminated steel sheet, the rating point is 5 points when it has a sense of quality equal to or higher than that of the PVD laminated steel sheet, which is slightly inferior to the PVD laminated steel sheet but can be obtained slightly. The case of high-grade feeling was evaluated as 4 points, and the case of coarse feeling compared with the poly-vinyl chloride laminated steel plate was evaluated as 3 points. When performing this scoring, there is roughly a relationship with the surface roughness. A resin film with a TIMA relationship value of 10 or less is used. The roller temperature T r is set to the softening start temperature Ts measured by TM A. s and softening end temperature Tse, an example processed in the temperature range of Tss-lOSTrSTse (° C) and using Tmp measured by DSC and set within the temperature range of Tr &lt; Tmp (° C) The sample of 4 has a sufficient sense of quality no matter what. On the other hand, in the case of the sample of the comparative example which does not meet these requirements, no sense of high quality was obtained.

Page 18 V. Description of invention (15) board. Furthermore, the decorative metal plate of the present invention is a material suitable for use in integrally formed bathrooms, water tanks, various industrial supplies, tanks, and other building materials or industrial materials that require water resistance. Brief Description of the Drawings Figure 1 is an example of the measurement curve of the TM A relationship value.

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Claims (1)

6. Scope of patent application .............................. 1! A resin film with excellent embossing processability, which is characterized by the following TMA relationship value (° C) = Tse — Tss (In the formula, Tss (° C) is the softening start temperature measured by TMA, Tse (° C) is the softening end temperature measured using TMA) and the TMA relationship value is less than 10. 2. —A kind of embossing processing method, which is the softening measured by TMA when the resin film is applied on the decorative metal plate after applying the patent application No. 1 to the decorative metal plate, and the embossing processing is performed by the embossing roller. The start temperature Tss, the softening end temperature Tse, and the Tmp measured by DSC are used as the reference. The roller surface temperature Tr of the portion in contact with the resin film is set to Tss-10 S TrSTse (° C), and Tr &lt; Tmp (° C ) And embossed. 3. —A decorative metal plate, which is coated with a film covered by the scope of patent application No. 1 or an embossed film covered by scope of patent application No. 2. Page 20