TWI230656B - Laminating film - Google Patents

Abstract

To provide a non-polyvinyl chloride laminating film with high strength and excellent formability and to which a layer of colored resin is formed, and to which a decorating design is given by embossing. A layer of colored resin is laid on one side of a polyester resin film comprised of nonoriented polyester resin or the crystalline polyester resin blended with the resin with low crystallinity or noncrystalline resin. Further, embossing is made on the layer of colored resin or the polyester film to give decorative patterns.

Description

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1230656 Α7 Β7 V. Description of the Invention (i) [Technical Field to which the Invention belongs] Sun and Moon_ In polyester resin laminated film, it has high hardness and excellent formability, Decorative design, insulation, chemical resistance, etc., which are used in building materials, furniture, electrical tools / electronic devices, acoustic devices, office appliances, etc. [Prior art], soft plasticized polyvinyl chloride and polyethylene and polypropylene-based hydrocarbon storage, thermoplastic acrylic 0 @ 树 ^ 目 'fluorine-containing * tree purpose or biaxially drawn polyester Membrane and others are used as decorative materials for exterior or interior parts of building materials, furniture, electrical tools / electronic devices, acoustic devices, office appliances and others. Β Polyvinyl chloride resin has excellent economic efficiency. Properties, formability, etc. However, because it usually includes a large amount of plasticizer, its film is soft, and after a long period of time, there will be a problem that the plasticizer penetrates to the surface, and the chlorinated hydrocarbons generated during incineration will cause the surface deterioration. Therefore, polyolefin resins containing polyethylene or polypropylene as the main component are considered as alternative resins to polyvinyl chloride. The films made of these resins alone have excellent embossability, chemical resistance, and other properties. Characteristics, and is harder than plasticized polyvinyl chloride resin. However, when a polyolefin resin is laminated and formed with a base material, the formed parts will be whitened and the decorative design will be damaged. Furthermore, there is a case where a rubber component is mixed into the polyolefin to prevent whitening. In this case, the degree of softness of the resulting film is the same as that of the plasticized polyvinyl chloride resin. Furthermore, although thermoplastic acrylic resins and fluoride resins each have unique characteristics, the softening process of these resin films is the same as that of plasticized polyvinyl chloride. _______3___ This paper size is applicable to China National Standard (CNS) M specifications (21〇 χ297 mm) (Please read the notes on the back before filling this page) Order 1230656 Α7 Β7 V. Description of the invention (^) (Please read the notes on the back before filling this page) Same. In recent years, biaxially stretched polyester film (PET) containing ethylene peptidate as a main component has received attention as a laminated material. Biaxially stretched polyester film has high hardness and its film has excellent damage resistance (fracture, cracking, etc.). However, in the forming part of the laminated layer of the PET film and the substrate, the PE film The adhesion of the material tends to deteriorate because the film is too strong. Furthermore, there is a disadvantage that a decorative design for forming an uneven pattern by embossing cannot give a biaxially stretched polyester film. [Problems to be Solved by the Invention] As described above, various resin systems containing plasticized polyvinyl chloride resins are used as exterior plates or internal parts of building materials, furniture, electric tools / electronic devices, acoustic devices, office appliances, and others Decorative materials. However, since they have different disadvantages in either case, a resin having high strength and excellent formability is desired, and decorative design can be given by embossing. The object of the present invention is to overcome the shortcomings of conventional decorative materials and provide a non-polyvinyl chloride laminate film, which has high strength and excellent formability, and includes a layer of colored resin and a decorative design formed by embossing. [Means for solving problems] Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics The present invention is a laminated film, which is characterized in that the laminated film includes a layer of colored resin formed on one side of a non-oriented film (containing a polyester resin as a main component) The upper and lower patterns are embossed on the colored resin layer or the non-oriented film. Furthermore, the present invention is characterized by polyester resin-based polyethylene terephthalate. Furthermore, the present invention is characterized by polyester resin-based polybutylene terephthalate. 0_4______ This paper size applies Chinese national standards ( CNS) A4 specification (2 丨 〇X 297 mm) 1230656 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (^) Furthermore, the present invention is characterized by polyester resin crystalline copolymerized polyester Wherein, a part of the polyacid component or the polyhydric alcohol component of the polyethylene terephthalate is replaced by other components. Furthermore, the present invention is characterized in that the polyester resin is a waste PET bottle chip. Furthermore, the present invention is characterized in that the polyester resin is polyethylene terephthalate, polybutylene terephthalate, and / or a crystalline copolymer. Polymeric polyester (in which a part of the polyacid or polyhydric alcohol component of the polyparapeptide ethylene glycol is replaced by other components), or a mixture of any two or more of the fragments of waste PET bottles. Further, the present invention is characterized in that the non-oriented film system containing a crystalline polyester resin as a main component includes a layer of resin containing 5 to 40% by weight of a resin having a low crystallinity or an amorphous resin. Furthermore, the present invention is characterized in that the crystalline polyethylene resin is a polyethylene terephthalate, polybutylene terephthalate, and / or a crystalline copolymerized polyester (including polyethylene terephthalate, polyethylene terephthalate, etc.). Part of the polybutyric acid or polyhydric alcohol component is replaced by other components), or any one or more of the components or mixtures of the waste PET bottle fragments. Furthermore, the present invention is characterized in that the resin or amorphous resin having a low crystallinity is a copolymerized polyester (in which a part of a polyacid acid component or a polyhydric alcohol of polyethylene terephthalate or polybutylene terephthalate) Ingredients are replaced by other ingredients), polycarbonate or olefin elastomer. [Example] As mentioned above, the present invention relates to a laminated film, which is characterized in that the laminated film includes a layer of colored resin formed on a non-oriented film (containing polyester resin as the main component __ 5) This paper size applies to Chinese national standards ( CNS) A4 size (210X 297mm) (Please read the precautions on the back before filling this page)

1,1T printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1230656 A7 B7 V. Description of the invention (points) and embossed pattern on the colored resin layer or on the non-oriented film. The laminated film of the present invention is characterized in that the laminated film has high strength and excellent formability by appropriately using a specific crystalline polyester resin or a specific polyester resin preferably mixed with a low crystallinity or amorphous resin. It includes a layer of colored resin and decorative decoration β formed by embossing. That is, the object of the present invention is to find a non-polyvinyl chloride resin that does not produce harmful gases such as hydrogen chloride when incinerated, so that Environmentally friendly with high hardness and excellent formability and embossability. As a result of diligent research, the best non-oriented polyester resin was found. Therefore, the polyester resin used in the present invention must be a non-oriented resin. Polyester resin, which is formed by uniaxial or biaxial stretching, is tough and has excellent mechanical strength, chemical resistance, solvent resistance, and the like. However, a desired uneven pattern cannot be formed on the polyester resin film by embossing. Furthermore, the stretched film of polyacetate resin is not ideal because its initial properties make it poor in adhesion with the base material in the forming portion. In the present invention, the non-oriented polyester resin is a polymer in which a polybasic acid represented by a para-acid and a polyhydric alcohol represented by ethylene glycol are subjected to condensation polymerization. In the present invention, polyethylene terephthalate, polybutylene terephthalate, or a copolymerized polyester resin (wherein a part of the polybasic acid component or the polyhydric alcohol component of the polyethylene terephthalate is obtained through other components Substitute) or a mixture thereof ^ As the non-terephthalic acid polybasic acid used in the copolymerized polyester resin, aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, and Dicarboxylic acids, or aliphatic dicarboxylic acids such as adipic acid, sebacic acid or dodecanedioic acid. Furthermore, as a non-ethylene glycol polyol used in copolymerized polyester resins, (please read the precautions on the back before filling this page)

1230656 A7 B7 V. Description of the invention (r) Any one represented by the general formula HO- (CH2) n-OH can be used, such as ι, 2-propanediol, 1,4-butanediol and the like. Furthermore, in recent years, PET bottles have been widely used as containers for various beverages. From the viewpoint of environmental protection and resource recovery, efforts have been made to collect used PET bottles and make them into reusable resin fragments. The collected PET bottle fragments can be used as a polyester resin in the present invention. Furthermore, in the present invention, the basic physical properties of the polyester resin or the characteristics of the polyester resin laminated with the base material are studied in detail. As a result of diligent research, it is found that the crystalline characteristics of the resin greatly control the properties of the polyester resin. The main factor of characteristics. X-ray, differential scanning calorimeter (DSC), density, etc. are widely used to evaluate the crystallinity of polyester resins. Crystallinity is affected by heat treatment conditions and resin temperature. Poly (p-peptidate) and poly (butylene terephthalate) typically have a high crystallinity of 30 to 50%. When the polyester resin is formed by the copolymerization of the above methods, the reduction in crystallinity depends on the type or blending amount of the polybasic acid or polyol, and in some cases, low crystallinity or amorphousness can be obtained Sexual resin. Therefore, it is difficult to accurately distinguish a crystalline polyester resin from a resin having low crystallinity or an amorphous polyester resin. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Therefore, in the present invention, the resin is considered as a crystalline polyester resin when it meets the following conditions: The exothermic peak generated and the endothermic peak generated by the melting of the resin are clearly shown in the DSC shown in Figures 1 and 2, which are when the resin is hot melted and then quenched and then the resin is at 10 ° C / min. When the temperature rises, and when the resin melts, the temperature of the resin decreases to 10 ° C / minute to room temperature. Moreover, the resin, in which the exothermic peak generated by the crystallization of the resin and the endothermic peak generated by the melting of the resin are not clearly shown in the same ___7____ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1230656 A7 B7 V. Description of the invention (j) Ethylene polymer, nylon or phenolic resin. In the case of a copolymerized polyester resin, a higher ratio of the polyacid component or the polyhydric alcohol component to be copolymerized will result in a resin having a low crystallinity or an amorphous resin, and the endothermic heat generated by the crystallization of the resin The peak system is not clearly shown in the measurement of the differential scanning calorimeter. In the present invention, the thickness of the non-oriented polyester resin used to cover the base material is not particularly limited, but is determined depending on the intended use. In general, 20 to 30 microns is preferred. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) In addition, the colored resin layer of the present invention includes polyester resin film, polyurethane resin, acrylic resin or epoxy resin Or a mixture of two or more of these resins is used as a base material, and a curing agent such as melamine, a phenol resin, or others. Furthermore, the colored resin layer of the present invention includes a pigment, a dye, and the like so as to dye a desired color. The thickness of the colored resin layer is not particularly limited. However, in general, 1 to 50 microns is suitable. In addition, as for the formation of the colored resin layer, any method can be applied, in which a solution containing the above resin, pigment, etc. is applied to the non-directional polymer of the present invention. One side of the ester resin film is then dried, or a method in which a mixture of the above-mentioned resin, pigment, and the like is thermally fused, and then the hot-melt mixture is laminated on one side of the non-oriented polyester resin film of the present invention. The laminated film of the present invention can be produced by forming a desired concave-convex pattern on the colored non-oriented polyester film by embossing while the colored non-oriented polyester film is heated to a temperature close to the melting point according to the method described above. In this case, a method may be used in which the surface of the colored resin layer is embossed, or a method in which a non-oriented polyester resin film is embossed, depending on the intended use. _______9 ___ ^ • Zhang scale is applicable to Chinese national standard (milk milk) 8 4 specifications (210 '乂 297 mm) " 1230656 Printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The description of the invention (β) The laminated board of the present invention is laminated on a base material of any one of metal plates such as cold rolled steel plates, aluminum plates, stainless steel plates, steel plates, etc. The laminated plate of the present invention is used to give the metal plates different plating or surface treatments and plastics Board or plywood. In some cases, a primer layer or an adhesive layer may be interposed between the base material and the laminated film of the present invention. The properties of the polyester resin of the present invention and the properties of the laminated film were evaluated in the following manner. (1) Properties of resin The properties of the polyester resin or other resins used in the present invention were measured by DSC. The inflection point shown between 0 ° c and 100 ° c is considered when the temperature rises at 10 ° C / minute and when the resin temperature drops to room temperature at 10 ° c / minute after the resin is melted. Glass transition temperature ◊ 100 ° C and 200 ° c · The exothermic peak temperature is regarded as the crystallization temperature (when the temperature rises ·· Tel, when the temperature drops:

Tc2), and the endothermic peak temperature between 200 ° C and 270eC is regarded as the melting point (Tm). (2) The hardness of the polyester resin and the resin used in the comparative example. The hardness of the laminate of the present invention is based on JIS K 5401. The pencil hardness tester defined in and evaluated using a pencil defined in JIS S 6006. The order of hardness marks from soft to hard is 9H, 8H ... H, F, HB, 2B ... 6B, where 9Η is the hardest and 6B is the softest. (3) Evaluation of embossability and heat resistance of relief pattern. The laminated film of the present invention is heated to a temperature between 20 to 30 ° C below the melting point of the polyester resin and below its melting point to evaluate the embossability of the laminated film of the present invention; thereafter, the average roughness Ral : 5 micron embossed granular embossing_10_ __ This paper size is applicable to China National Standard (CNS) A4 (2X297mm) (Please read the precautions on the back before filling this page) #

1T 1230656 A7 B7 V. Description of the invention (1) The roller presses the laminated film. Then, the polyvinyl chloride film was pressurized at 200 to 220 ° C, and the polyolefin film was pressurized at 140 to 170 ° C, and these were taken as comparative examples of the present invention, respectively. The evaluation criteria are set to three levels by visual observation, as follows: ○: Good, △: Slightly poor, X: Poor, and the heat resistance of the relief pattern is evaluated in three levels as follows: The embossed sample is maintained at 120 ° In an atmosphere of C for five days, the average roughness Ra2 was then measured, and the retained average roughness ratio was obtained. Retained average roughness ratio = Ral / Ra2X100 (%) 〇: Retained average roughness ratio is 80 to 100% △: 50 to 80% X: less than 50% (4) Films used in the present invention and comparative examples Impact of the film _ Evaluation of formability was measured using a Du Pont impact tester (size of impact portion: 1/2 inch in diameter (, test load: 1 kg, drop height: 50 cm) as defined in JIS K5400 Impact-formability of a laminated film metal plate obtained by laminating the laminated film of the present invention or the film used in the comparative example on a metal plate. The evaluation criteria are set to three levels by visual observation, as follows: Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards and Standards (please read the precautions on the back before filling this page) 〇: No cracks in the film can be found. Examples The examples explain the present invention in more detail. Examples 1 to 17 As shown in Tables 1 and 2, a layer of colored resin is formed on a non-oriented polyester 11 sheet. The dimensions are applicable to China National Standard (CNS) A4 specifications ( 210, / 297 mm 1 " " 1230656 A7 B7 printed by the Consumer Standards Cooperative of the Central Bureau of Standards 5. Description of the invention (/ c) One side of the resin film, and the embossing roller (grain embossing with unevenness Ra = 5 micron unevenness) is lower than each The melting point (Tm) of the film is 2 (at TC temperature) to impart unevenness to the colored resin layer or polyester resin film. The following resins are used for the copolymerized polyester resins A, B, and C shown in the examples. In this case Medium 'by coating the following paint on one side of the non-oriented polyester resin film and then drying the coating film to form a colored resin layer. Copolymerized polyester resin A: 90 mol% of peptide acid and 10 mol of isoacid by copolymerization Copolymerized polyester resin B: 100 mol of peptidic acid, 88 mol of ethyl alcohol, and 1 of mol. 2-propionic acid 12 mol% to obtain resin. ~ Copolymerized polyester resin C: An acid component composed of 60 mol% of terephthalic acid and 40 mol of isoacid and 100 mol of ethylene glycol %% = phthalic ester. Neem tree copolymerized polyester resin D: Acid component composed of copolymerization of 90 mol% of terephthalic acid and 10 mol% of isoacid 100 mol% with ethylene glycol. Obtained Neem color paint A: Saturated copolymerized polyester resin: (Tg: 2 (TC) 25 wt. ° / 0 pigment (rutile titanium dioxide) 25 wt.% Curing agent (Isocyanate) 4wt ° / 〇Wax 1wt% _ 12 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling in this page)

1230656 A7 B7 V. Description of the invention (丨 1) Diluted solvent 45% by weight

Color paint B Saturated copolymerized polyester resin: (Tg: 70 ° C) 20% by weight Colorant (rutile titanium dioxide) 30% by weight Curing agent (isocyanate) 3% by weight Dilution solvent 47% by weight (please first Read the notes on the reverse side and fill out this page) The paper size printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1230656 A7 B7 V. Description of the invention (Central Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau (¾) PET: Xiang Ϊ 2 羿 neck [[¾ > PBT: fMfrr-11 worm-CoPES Λ :) F = chrysanthemum $ 翌 5? ≫ CoPES B: \ usn > ^ sco lisJV ·· PET Yin N · yan 5ίπ-CoPES C: Zhunxiang 0 > Recording {: > 衮 闼: 衮 商 盏 accompany 讅, 5 c: ac-Cl ~ rs: νπ olefin ra, Col ^ S c Collected fragments Col'ES B! ^ T Collected fragments IΉΤ Plant collected fragments r: Ir: — > Properties of types of polyester resins Non-oriented polyester resin strand 1 ^ --4 — 〇 叫 -4 N: Two N CC ο 〇〇a έ 1 one 1 — 1 — a: Ξ cc CT · N 1 «— oz 1 port CO er rs: I 1 one g 1 — g 1 — cc ΓΟ o oc oo rs: — O CC oo -vj zc 1 wj o 〒 · 1 ts: i ro 1 ro ro K: m -0 two rc n: rc cn cn — ro re rs: ctj cn — · s —a N : Re CJl S cn CJ1 ο on 2: Γ · ο ο -0 C-: oo 〇cn S 222 oooo oooo blend ratio (31% by weight) ο ogoggg § g thickness (micron) > 3 = > > Two > ~ > > > Type of lacquer colored resin cn cn cn g zr \ g thickness (micron) e ® Θ Θ © e Θ ㊀ Θ ㊀ on the colored resin layer π on polyester Top: 花 Leg flower method pz JX j— C ".-clh 222-ts: 4η〇 · S'lll > = rr: For the sake of the government, I will take care of it (1) 3¾ brew (please (Read the notes on the back before filling out this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 1230656 A7 B7 V. Description of invention (h)

at) PC: ^ fi ^ ss-CGPESD: ^^ n > ^ feD Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Γ: re Two rooms s' --i —i — " Τ η η c = c-斉 斉 耘. Waiting for eight "" to do 5f — — n c_ rq ri ~ Guang · n φ > rr: Since 1 chrysanthemum Sf s? ΤΓΓ 1½ S pu chrysanthemum wm ~ 〇 〇 12 g = 〇 一- N: Ο in-^ 3 120—K: -V) ts: Λ O cn N: O—n rC O Nong ', s · ^-1 1 — Ξ 1 1 — 1 · — XI — One WU: OC 1 1 ~ 1 1 C} 1 * — CJ OC 1 1 O CC 〇 〇 1 κ: — ο 2, 0 CT: 1 1 XX ο 1 1 cac CC ο 1 — — 〇z oz oo 1 1 wl 1 1 X 1 re r ^: n: cn 1ί Ν; WC ^:: · η 2 1 Ν: ΓΟ ζη ιη ι ro rc wi tr \ i ro re — cn w-Λ p- 1 IS; ι rc ο ο ο ο ο ο ο ο ο oo 〇ooooo: oo ο ο ο g X o 5 Sp > > > > > 簦 ο wt o ✓-v ㊀ Θ ee Θ Θ Θ rr §Ξ §S l ~ r. • one} CTT br ο J— X Ο j— JX 〇— X e, one X o — OC O —-^ 4 OC e—JX intron Jg e? SHr gg emergency 3 15 Paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page) Clothing · Order 1230656 A7 B7 V. Description of the invention (r / 10) Covered with examples 1 to 1 of the present invention The steel plate of 17 polyester resin has high hardness and excellent formability, as shown in Table 3, and also has the uneven feel given by embossing, so it has an excellent decorative design. 3 Properties of non-oriented polyester resin film (1) printed by employees' cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Example of actual property evaluation Film hardness Embossability Heat resistance impact of embossing-Formability 1 HB 〇〇〇2 HB 〇〇〇3 〇〇〇〇4 HB 〇〇〇5 HB 〇〇〇〇〇〇〇〇7 HB 〇〇〇〇8 HB 〇〇〇09 HB 〇〇 ◎ 10 HB 〇〇 ◎ 11 HB 〇〇 ◎ 12 HB 〇〇 ◎ 13 HB 〇〇 ◎ 14 HB 〇〇 ◎ 15 HB 〇〇 ◎ 16 HB 〇〇 ◎ 17 HB 〇〇 ◎ (Please read the precautions on the back before filling out this page) This paper size applies to Chinese national standards (CNS ) A4 Regulation (210X297 mm) 1230656 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (丨) Comparative Examples 1 to 10 Table 4 shows the structure of the films of Comparative Examples 1 to 10, and Table 5 shows Test results of nature. Comparative Examples 1 and 2 are cases of polyvinyl chloride films in which when the amount of plasticizer is small, 'the polyvinyl chloride film has high hardness and therefore has excellent embossability' but poor impact formability. On the other hand, when the amount of the plasticizer is increased, it has good impact-formability, but is softer. Comparative Example 3 is a case of a polyolefin resin film, in which the embossability is good ', but the hardness of the polyolefin resin film is soft compared with the laminated film of the present invention. Examples of Comparative Examples 4 to 6 are biaxially stretched polyester resin films. Among them, the film system has high hardness, but the embossability is significantly poor. Comparative Examples 7 and 8 are examples of films composed of a resin having low crystallinity or an amorphous resin monomer, in which the hardness of the film is high and it has excellent embossability and impact-formability, However, the heat resistance of the relief pattern is obviously poor. Comparative Example 9 is an example of a film composed of a crystalline polyester resin and a polyester resin having a low crystallinity. Among them, the resin having a low crystallinity has a high blending ratio, so that the relief pattern of the film is significantly inferior in heat resistance. Comparative Example 10 is an example of a film composed of a crystalline polyester resin and an amorphous resin. Among them, since the blend ratio of the polyester resin having a low crystallinity is high, the heat resistance of the embossed pattern of the film is significantly inferior. 17_ (Please read the precautions on the back before filling in this page) • ^ Yiyi · Order ^ Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1230656

A B7 V. Description of Invention (it) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (| £) PVC B: Xiang ^ [N ^ A-PVC B: Xiang: ZSB-Do.p: ® {cvs (^^ h * ttle) > Tio2: (| 潍 冷 棼 (& (* iri) -PP ·· 翔 21 ^-Ep ^ lli: z, a; 31ai ^ _-BO: MsltH— 二 满 5 1C οζ σ : 〇Ί 二-N: SS ΙΈΤ CoPES (; (; oi, ES (; ΕΤ (ΒΟ) [CoPliS A (R0) ί'ΕΤ (ΠΟ) l, P (Ti02 5 parts) R rubber-Η or: N ) zn ~ x— ^ l) V (: Λ (丨) 0 丨) 20 parts, Ti〇2 15 γ7})! Type_i Properties of polyester resin _____. Non-oriented polyester resin film CM Ο CJ1 — 〇έ -〇 1 2 1 ►— og 1 — OC ι — I 1 1 Οί Μ ►— * 0C 1 1 1 1 — 3-1 H- 1 — g 1 1 g 〇 CJ1 Oi Η—k § 1 1 1 1 -Η Ο ΙΟ 1 t ^ o CJ1 ►— * 1 cn η— 1 1 Ν3 Ν2 ζη PC ZJ1 Η- *: J1 — m LT \ 1 1 0C — zn cn ΟZ Ν: Ο ο ο ►— * ο Η— Ο ο — OC cn zn o Η- * Ο Blending ratio (% by weight) h— ^ Ο Η— * Ο ggg rc CJ1 100 ►— o ο Thickness. (microns)〉 > > > > > C3 1 1 • 1 Type of colored resin layer i οι 3ι ζη in 3ι 5ί 1 1 1 'Thickness (micron) Θ ㊀ ㊀ ㊀ θ ㊀ Θ 1 1 1 On the varnish resin chip: ① On the polyester: © embossing method 1 __ ( (Please read the notes on the back before filling out this page)

、 1T 18 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economy 1230656 A7 ____ B7 V. Description of the invention (1) Table 5 Non-oriented polyester resin film (2) Characteristics Comparative Example Characteristics Evaluation Film Hardness Embossability Embossed Heat Resistance Impact-Formability 1 HB 〇 △ X 2: 6B 〇 △ 〇3 3B 〇Δ 〇4 HB X-〇5 HB X -〇6 HB X-〇7 HB 〇- 〇8 HB 〇X 〇9 HB 〇X 〇10 HB 〇X 〇 [Inventive effect] The laminated film of the present invention includes a colored resin formed on a non-oriented film (containing Polyester resin is used as a main component) and a colored resin layer having a concave-convex pattern embossed on the non-oriented film, wherein a specific crystalline resin having low crystallinity or amorphousness is blended because a specific crystalline polyester resin is used. Resin is a specific crystalline polyester resin or polyester resin, so compared with the conventional polyvinyl chloride film, the laminated film of the present invention has higher hardness and better formability; while on the unidirectional film form The colored resin layer and embossing on the colored resin layer or unidirectional film can give the same decorative design as the conventional polyvinyl chloride film. _19_ This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X29 ^^ 1 ^ -_ (Please read the note on the back first, and then fill out this page)

1230656 A7 B7 V. Description of the invention (/ public) [Simplified description of the drawing] Fig. 1 DSC measurement example of crystalline polyester resin. Fig. 2 is another DSC measurement example of the crystalline polyester resin. FIG. 3 is a measurement example of DSC of an amorphous resin. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 20 This paper is sized to the Chinese National Standard (CNS) A4 (210X 297 mm)

Claims (1)

1230656 ... V A8 B8 C8 D8 6. Scope of patent application1. A laminated film is a colored resin layer formed on one side of a non-oriented film (with polyester resin as the main component), and an uneven pattern pressure is formed on the colored layer or film layer The laminated film of flowers is characterized in that: the non-oriented film mainly composed of polyester resin is composed of a resin layer mainly composed of crystalline polyester resin, and the resin layer contains as low as 5-40% by weight Crystalline resin or non-crystalline resin; The polyester resin is a polyparapeptide, polybutyrate, and a crystalline copolymerized polyester (part of which is a polybasic acid component of polyethylene terephthalate Or the polyol component is replaced by other components), or a mixture of any two or more of the waste PET bottle recycling debris. 2 · The laminated film according to item 1 of the scope of patent application, wherein the resin or amorphous resin having low crystallinity is a copolymerized polyester (wherein polyethylene terephthalate or polybutylene terephthalate Part of the polyacid component or polyol component is replaced by other components), polycarbonate or olefin elastomer. The size of this paper applies to China National Standard (CNS) A4 (210 X 297 mm)