RESIN LAMINATE FILM, METHOD FOR MANUFACTURING SAME, AND MELAMINE DECORATIVE PANEL

Abstract

The present invention provides an acrylic resin laminate film having excellent bonding properties, as well as an excellent appearance and resistance to water whitening. The present invention is a laminate film provided with a resin layer (I) comprising an acrylic resin composition (A) or a fluororesin composition (B), and a second resin layer (II) comprising a resin composition (C) that contains an acid anhydride copolymer (C-1) and acrylic rubber particles (C-2).

Claims

1. A laminate film, comprising: a resin layer (I) which is formed from an acrylic resin composition (A) or a fluororesin composition (B); and a resin layer (II) which is formed from a resin composition (C) comprising an acid anhydride copolymer (C-1) and acrylic rubber particles (C-2).

2. The laminate film according to claim 1, wherein a content of a monomer unit having an acid anhydride structure in the copolymer (C-1) is 4% by mass or more with respect to 100% by mass of the resin composition (C).

3. The laminate film according to claim 1, wherein a glass transition temperature of the resin composition (C) is 50° C. or higher and 105° C. or lower.

4. The laminate film according to claim 1, wherein an average particle diameter of the acrylic rubber particles (C-2) is 0.15 μm or more.

5. The laminate film according to claim 1, wherein a thickness of the laminate film is 40 μm or less.

6. The laminate film according to claim 1, wherein the laminate film contains a triazine-based ultraviolet absorbing agent.

7. The laminate film according to claim 1, wherein the resin layer (I) comprises a release agent.

8. The laminate film according to claim 1, wherein a storage elastic modulus at 100° C. of the resin layer (I) is 1 MPa or more and 500 MPa or less.

9. The laminate film according to claim 1, wherein a gel fraction of the resin layer (II) is 5% or more and 30% or less.

10. The laminate film according to claim 1, wherein a gel fraction of the resin layer (II) is 45% or more and 80% or less.

11. The laminate film according to claim 1, wherein a thickness of the resin layer (II) is 1 μm or more and 4 μm or less.

12. The laminate film according to claim 1, wherein the resin layer (I) comprises a fluororesin.

13. The laminate film according to claim 1, wherein a thickness of the resin layer (I) is 1 μm or more and 4 μm or less.

14. The laminate film according to claim 1, comprising a resin layer (I) which is formed from a fluororesin composition (B), wherein a content of a fluororesin in the fluororesin composition (B) forming the resin layer (I) is 60% or more and 95% or less with respect to 100% by mass of the fluororesin composition.

15. A protection film, comprising the laminate film according to claim 1.

16. A melamine decorative panel surface protection film, comprising the laminate film according to claim 1.

17. A melamine decorative panel, comprising the laminate film according to claim 1 and a melamine base material laminated in order of the resin layer (I), the resin layer (II), and the melamine base material.

Description

EXAMPLES

[0153] Hereinafter, the invention will be described in more detail by means of Examples. However, the invention is not limited to these Examples. The term “part(s)” in Examples represents “part(s) by mass”. In addition, abbreviations in Examples are as described below.

[0154] MMA: methyl methacrylate

[0155] MA: methyl acrylate

[0156] BA: butyl acrylate

[0157] St: styrene

[0158] AMA: allyl methacrylate

[0159] BDMA: 1,3-butylene glycol dimethacrylate

[0160] CHP: cumene hydroperoxide

[0161] t-BH: t-butyl hydroperoxide

[0162] n-OM: n-octylmercaptan

[0163] RS-610NA: sodium mono-n-dodecyloxytetraoxyethylenephosphate (trade name: “PHOSPHANOL RS-610NA”, manufactured by Toho Chemical Industry Co., Ltd.)

[0164] LA-31: “ADK STAB LA-31RG” (trade name) manufactured by ADEKA CORPORATION

[0165] LA-57: “ADK STAB LA-57” (trade name) manufactured by ADEKA CORPORATION

[0166] TV1600: “Tinuvin 1600” (trade name) manufactured by BASF

[0167] Irg1076: “Irganox 1076” (trade name) manufactured by BASF

[0168] T850: “KF Polymer T#850” (trade name) manufactured by KUREHA CORPORATION

[0169] VH: “ACRYPET VH001” (trade name) manufactured by Mitsubishi Rayon Co., Ltd.

[0170] SZ15170: “Xiran SZ15170” (trade name) manufactured by Polyscope Polymers BV (maleic anhydride copolymerization amount: 15% by mass, Tg: 131° C.)

[0171] SZ08250: “Xiran SZ08250” (trade name) manufactured by Polyscope Polymers BV (maleic anhydride copolymerization amount: 8% by mass, Tg: 116° C.)

[0172] Measurement of various physical properties in Examples was carried out by the following methods.

[0173] (1) Glass Transition Temperature (Tg)

[0174] The glass transition temperature was calculated by using a value described in Polymer HandBook (J. Brandrup, Interscience, 1989) or a catalog value of a monomer manufacturer from the Fox equation.

[0175] (2) Average Particle Diameter

[0176] Regarding the average particle diameter of the acrylic rubber particles (A-1), the final particle diameter of a polymer latex of a polymer obtained in emulsion polymerization was measured by using a light scattering photometer (product name: “DLS-700”, manufactured by Otsuka Electronics Co., Ltd.) and a dynamic light scattering method.

[0177] (3) Total Light Transmittance, Haze Value, Yellowness index, Color Difference, and Whiteness

[0178] The total light transmittance was evaluated according to JIS K7361-1, the haze value was evaluated according to JIS K7136, the yellowness index was evaluated according to JIS K7373, the color difference was evaluated according to JIS K5600-4-6, and the whiteness was evaluated according to JIS Z8715.

[0179] (4) Melamine Base Material Curing Temperature

[0180] An endothermic peak temperature when the melamine base material was heated from 25° C. to 200° C. at 10° C./min under a nitrogen stream was measured by using DSC 6200 (product name, manufactured by SII Nano Technology Inc.) and then the measured endothermic peak temperature was regarded as a melamine base material curing temperature.

[0181] (5) Water Whitening Resistance Evaluation

[0182] A boiling test was carried out at 100° C. for 2 hours according to CEN (European Committee for Standardization) standards, EN438-2 to measure a change in whiteness before and after the boiling test.

[0183] (6) Adhesiveness Evaluation

[0184] Cutting of a lattice pattern with 100 sections at an interval of 1 mm was made on the melamine decorative panel in a room temperature state by a cutter knife, and then peeling-off property was checked by using a cellophane tape (manufactured by NICHIBAN CO., LTD.). This test was performed before and after the boiling test. A case where there is no peeled-off section was evaluated as “A”, a case where there are 1 or more and 9 or less peeled-off sections was evaluated as “B”, and a case where there are 10 or more peeled-off sections was evaluated as “C”.

[0185] (7) Thicknesses of Resin Layers (I) and (II)

[0186] The laminate film was cut into a suitable size and then the thickness of the resin layer (I) or (II) was measured by using a reflectance spectral film thickness meter FE 3000 (trade name, manufactured by Otsuka Electronics Co., Ltd.).

[0187] (8) Weather Resistance Evaluation

[0188] A test was carried out on the melamine decorative panel by using a superxenon weather meter SX75 (trade name, manufactured by Suga Test Instruments Co., Ltd.) at an irradiation intensity of 60 W/m.sup.2 (300 to 400 nm) with a filter #275 in such a manner that irradiation (63° C., 50% RH) for 102 minutes and irradiation+spraying (95% RH) for 18 minutes (120 minutes in total) were regarded as one cycle. The adhesiveness and the color difference change before and after the test were evaluated in the same manner as described above.

[0189] (9) Curling Evaluation

[0190] The obtained laminate film was cut in a rectangular shape of 20 cm, placed on a flat glass plate while the resin layer (I) was set as the upper surface, and held at 25° C. and a humidity of 50% for 6 hours, and the state of the film end portion was observed by visual inspection. A case where the end portion was in contact with the glass surface was designated as “A”, a case where the end portion floated from the glass surface was designated as “B”, and a case where the end portion was curled to be in contact with the upper surface of the laminate film was designated as “C”.

[0191] (10) Storage Elastic Modulus Measurement

[0192] A resin to be measured was formed into a 50-μm film, and the storage elastic modulus thereof was measured by DMS6100 manufactured by Seiko Instruments Inc. The measurement conditions were set to 100° C. and 0.1 Hz.

[0193] (11) Pencil Hardness

[0194] The pencil hardness was measured according to JIS K-5600-5-4 by using a pencil scratch tester manufactured by Taiyu Kizai Co., Ltd. and “Uni” pencil manufactured by Mitsubishi Pencil Co., Ltd.

[0195] (12) Release Property

[0196] After the melamine decorative panel was produced, a case where the melamine decorative panel and a stainless plate were naturally peeled off was designated as “A”, and a case where the melamine decorative panel and a stainless plate were not naturally peeled off was designated as “B”.

[0197] (13) Embossing Property

[0198] A melamine decorative panel was produced in the same method as described later, except that an embossed press plate (arithmetic average roughness Ra: 5 μm) was used instead of a mirror-surface stainless plate at the time of producing the melamine decorative panel and the pressing condition were set to 100° C. for 20 minutes, and then 60° glossiness was measured by a gloss meter GM-60 manufactured by Konica Minolta, Inc.

[0199] (14) Chemical Resistance (Acetone)

[0200] Acetone was dropped on the surface of the melamine decorative panel. After 1 minute, the surface was wiped with a cloth and then the appearance thereof was observed by visual inspection. A case where there is no trace was designated as “A”, a case where trace was slightly observed was designated as “B”, and a case where trace was clearly observed and whitening was observed was designated as “C”.

[0201] (15) Chemical Resistance (Coating Test)

[0202] Coating was performed on the surface of the melamine decorative panel by using a coating spray (trade name: Silicone Lacquer Spray Black, manufactured by Kanpe Hapio Co., Ltd.) and then a petri dish was placed for 5 minutes at the coating place while facing down so as to be sealed in order to adjust the drying speed. Thereafter, drying was performed at room temperature for 1 hour or longer. Thereafter, coating was removed by using a wiping spray (KSR-300, manufactured by ABC TRADING CO., LTD.) and then appearance thereof was observed by visual inspection. A case where there is no trace was designated as “A”, a case where trace was slightly observed was designated as “B”, and a case where trace was clearly observed was designated as “C”.

[0203] (16) Film Appearance

[0204] The obtained film was cut into an A4 size. By using a fish eye counter manufactured by MEC Co., Ltd., fish eyes with a surface area of 0.01 mm.sup.2 or more were selected, and those derived from thermal degradation, namely, those not derived from contamination, and in other words, those having no profile among the selected fish eyes were counted by an observation under a microscope. The detection was performed on an area of 0.04 m.sup.2, and the counts were converted to the number per 1 m.sup.2. A case where the number of fish eyes was less than 100 was designated as “A”, a case where the number of fish eyes was 100 or more and less than 500 was designated as “B”, and a case where the number of fish eyes was 1,000 or more was designated as “C”.

[0205] (17) Fracture Elongation

[0206] The obtained film was cut in 150 mm×15 mm with the film formation direction as a long side, a tension test was carried out using Autograph Tension Tester (trade name, manufactured by Shimadzu Cooperation) at an inter-chuck distance of 100 mm and a tension rate of 50 mm/min, and then the fracture elongation of the film was measured.

[0207] (18) Gel Fraction

[0208] 50 ml of acetone was added to 0.5 g of the obtained resin composition (C) and the resultant mixture was stirred at 65° C. for 4 hours. Thereafter, centrifugal separation was performed at 4° C. and 14,000 rpm for 30 minutes to remove the supernatant, then 50 ml of acetone was added again, and centrifugal separation was performed again under the same conditions. After removing the supernatant, the precipitated gel portion was subjected to vacuum drying for 8 hours, then the weight thereof was measured, and the gel fraction was calculated by the following equation.

[0209] Gel fraction (%)=weight (g) of gel portion/0.5×100

Production Example 1: Production of Acrylic Rubber Particles (A-1A)

[0210] Under a nitrogen atmosphere, 206 parts of deionized water was put into a reaction container equipped with a reflux condenser and heated to 80° C. Components (i) described below were added thereto, and 1/10 of raw materials (ii) described below (parts of raw materials for the elastic copolymer (a-1)) were incorporated thereinto with stirring and then held for 15 minutes. Then, the remaining raw materials (ii) were continuously added such that the increase rate of the monomer mixture with respect to water became 8% by mass/hr. Thereafter, the mixture was held for 1 hour to perform polymerization, thereby obtaining a polymer latex. Subsequently, 0.2 part of sodium formaldehyde sulfoxylate was added to the polymer latex. Thereafter, the mixture was held for 15 minutes, raw materials (iii) described below (parts of raw materials for the elastic copolymer (a-1)) were continuously added with stirring at 80° C. under a nitrogen atmosphere such that the increase rate of the monomer mixture with respect to water became 4% by mass/hr. Thereafter, the mixture was held for 2 hours to perform polymerization, thereby obtaining a latex of the elastic copolymer (a-1).

[0211] 0.2 part of sodium formaldehyde sulfoxylate was added to this latex of the elastic copolymer (a-1). Thereafter, the mixture was held for 15 minutes, raw materials (iv) described below (raw materials for the rigid polymer (a-2)) were continuously added with stirring at 80° C. under a nitrogen atmosphere such that the increase rate of the monomer mixture with respect to water became 10% by mass/hr. Thereafter, the mixture was held for 1 hour to perform polymerization, thereby obtaining a latex of acrylic rubber particles (A-1A). The average particle diameter of the acrylic rubber particles (A-1A) was 0.28 μm.

[0212] This latex of the acrylic rubber particles (A-1 A) was filtered by a filter having a mesh of 50 μm. Subsequently, coagulation using calcium acetate, aggregation, and a solidification reaction were performed thereon, and then the resultant product was filtered, washed with water, and then dried to obtain acrylic rubber particles (A-1A).

TABLE-US-00001 (i) Sodium formaldehyde sulfoxylate 0.4 part Ferrous sulfate 0.00004 part Disodium ethylenediamine tetraacetate 0.00012 part (ii) MMA 11.25 parts BA 12.5 parts St 1.25 parts AMA 0.094 part BDMA 0.75 part t-BH 0.044 part RS-610NA 0.75 part (iii) BA 30.9 parts St 6.6 parts AMA 0.66 part BDMA 0.09 part CHP 0.11 part RS-610NA 0.6 part (iv) MMA 35.6 parts MA 1.9 parts n-OM 0.11 part t-BH 0.06 part

Production Example 2: Production of Acrylic Rubber Particles (A-1B)

[0213] Into a container equipped with a stirrer, 8.5 parts of deionized water was incorporated. After that, raw materials (ii) described below (parts of raw materials for the elastic copolymer (a-1)) were added with stirring and the resultant mixture was stirred for 20 minutes to prepare an emulsion.

[0214] Next, 191.5 parts of deionized water and components (i) described below were put into a polymerization container equipped with a condenser, and the temperature was increased to 70° C. Subsequently, the prepared emulsion was added dropwise into the polymerization container over 8 minutes with stirring under nitrogen, and the reaction was continued for 15 minutes.

[0215] Subsequently, raw materials (iii) described below (parts of raw materials for the elastic copolymer (a-1)) were added dropwise over 90 minutes in the polymerization container, and then the reaction was continued for 60 minutes to obtain a latex of the elastic copolymer (a-1). Incidentally, Tg of the elastic copolymer (a-1) alone was −48° C.

[0216] Subsequently, raw materials (iv) described below were added dropwise over 45 minutes in the polymerization container, and then the reaction was continued for 60 minutes to form the intermediate polymer (a-3) on the elastic copolymer (a-1) Incidentally, Tg of the intermediate polymer (a-3) alone was 20° C.

[0217] Subsequently, raw materials (v) described below were added dropwise over 140 minutes in the polymerization container, and then the reaction was continued for 60 minutes to form the rigid polymer (a-2) on the intermediate polymer (a-3). According to the above processes, a latex containing 100 parts of acrylic rubber particles (A-1B) was obtained. Incidentally, Tg of the rigid polymer (a-2) alone was 84° C. Further, the average particle diameter of the acrylic rubber particles (A-1B) measured after the polymerization was 0.12 μm.

[0218] This latex of the acrylic rubber particles (A-1B) was filtered by a filter having a mesh of 50 μm. Subsequently, coagulation using calcium acetate, aggregation, and a solidification reaction were performed thereon, and then the resultant product was filtered, washed with water, and then dried to obtain acrylic rubber particles (A-1B).

TABLE-US-00002 (i) Sodium formaldehyde sulfoxylate 0.2 part Ferrous sulfate 0.0001 part Disodium ethylenediamine tetraacetate 0.0003 part (ii) MMA 0.3 part BA 4.5 parts AMA 0.05 part BDMA 0.2 part CHP 0.025 part RS-610NA 1.1 parts (iii) MMA 1.5 parts BA 22.5 parts AMA 0.25 part BDMA 1.0 part CHP 0.016 part (iv) MMA 6.0 parts BA 4.0 parts AMA 0.075 part CHP 0.013 part (v) MMA 55.2 parts BA 4.8 parts n-OM 0.22 part t-BH 0.075 part

Production Example 3: Production of Processing Aid

[0219] 200 parts of deionized water was incorporated into a reaction container purged with nitrogen, and 1 part of potassium oleate as an emulsifier and 0.3 part of potassium persulfate were incorporated thereinto. Next, 40 parts of MMA, 10 parts of BA, and 0.005 part of n-OM were incorporated thereinto and the resultant mixture was stirred at 65° C. for 3 hours under a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture formed from 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours, and after completion of dropwise addition, was held for 2 hours to complete the polymerization. The obtained latex was added to 0.25% by mass of sulfuric acid aqueous solution, and a polymer was coagulated with acid. Thereafter, dehydrating, washing with water, and drying were performed and then the polymer was recovered in a powder state. The mass average molecular weight of the obtained processing aid was 1,000,000.

Production Examples 4 to 16: Production of Resin Compositions (A1) to (A4), (B1) to (B3), and (C1) to (C6)

[0220] In Production Example 4, 16 parts of the acrylic rubber particles (A-1A) of Production Example 1, 84 parts of VH, 2 parts of the processing aid of the Production Example 3, 2.1 parts of LA-31 0.3 part of LA-57, and 0.1 part of Irg1076 were used and mixed with a Henschel mixer. Next, the resultant mixture was melted and kneaded by using a 35-mmφ twin screw extruder (L/D=26) under the conditions including a cylinder temperature of 200 to 240° C. and a die temperature of 240° C. to obtain a pellet, thereby obtaining the resin composition (A1).

[0221] In Production Examples 5 to 16, resin compositions (A2) to (A4), (B1) to (B3), and (C1) to (C6) were obtained in the same procedures as described above, except that materials as presented in Tables 1 to 3 were used. Incidentally, the content of the acid anhydride group presented in Table 3 is a value calculated from catalog values of SZ15170 and SZ08250.

TABLE-US-00003 TABLE 1 Blending [parts] Storage D-1 elastic Acrylic resin A-1 A-2 Processing Stearic modulus composition (A) A-1A A-1B VH aid LA-31 TV1600 LA-57 Irg1076 acid [MPa] Production A1 16 — 84 2 2.1 — 0.3 0.1 — 600 Example 4 Production A2 16 — 84 2 — 2.1 0.3 0.1 — — Example 5 Production A3 16 — 84 2 2.1 — 0.3 0.1 0.2 — Example 6 Production A4 — 100 — 2 2.1 — 0.3 0.1 —  10 Example 7

TABLE-US-00004 TABLE 2 Blending [parts] Fluororesin B-1 B-2 D-2 Storage elastic composition (B) T850 VH Irg1076 modulus [MPa] Production B1 100 — — 570 Example 8 Production B2 90 10 0.1 — Example 9 Production B3 68 32 0.1 50 Example 10

TABLE-US-00005 TABLE 3 Content of Blending [parts] acid Gel C-1 C-2 D-3 anhydride fraction Resin composition (C) SZ15170 SZ08250 A-1A A-1B LA-31 LA-57 Irg1076 Tg [° C.] group [%] [%] Production C1 20 — — 80 2.1 0.3 0.1 — 3.0 48 Example 11 Production C2 30 — — 70 2.1 0.3 0.1 103 4.5 42 Example 12 Production C3 — 30 — 70 2.1 0.3 0.1  95 2.4 42 Example 13 Production C4 70 — — 30 2.1 0.3 0.1 — 10.5 18 Example 14 Production C5 70 — 30 — 2.1 0.3 0.1 — 10.5 27 Example 15 Production C6 100  — — — 2.1 0.3 0.1 — 15.0 0 Example 16

Examples 1 to 14: Production of Laminate Film and Melamine Decorative Panel

[0222] In Example 1, the acrylic resin composition (A1) for the resin layer (I) obtained in Production Example 4 and the resin composition (C1) for the resin layer (II) obtained in Production Example 11 were dried at 80° C. for a whole day. The C1 was plasticized by a 30-mmφ extruder in which the cylinder temperature was set to 230° C. Further, the acrylic resin composition (A1) was plasticized by a 40-mmφ extruder in which the cylinder temperature was set to 240° C. and a screen mesh having 400 meshes was provided. Next, a resin laminate film having a thickness of 50 μm was formed by a feed block die for two kinds and two layers set to 240° C. The thicknesses of the resin layers (I) and (II) were 45 μm and 5 μm, respectively.

[0223] Further, the melamine base material was laminated at the resin layer (II) surface side of the laminate film, both surfaces were sandwiched by a mirror-surface stainless plate, and then pressing was performed thereon under the conditions including a temperature of 140° C., a pressure of 4 MPa, and a time of 20 minutes or 10 minutes to thereby produce a melamine decorative panel. The evaluation results of the obtained melamine decorative panel are presented in Tables 4 and 5. The curing temperature of the used melamine base material was 94° C.

TABLE-US-00006 TABLE 4 Resin layer (I) Resin layer (II) Storage Content Gel Total Whiteness elastic Thick- of acid frac- Thick- light Yellow- Before After Pencil Compo- modulus ness Compo- anhydride tion ness transmit- Haze ness boiling boiling hard- sition [MPa] [μm] sition group [%] [%] [μm] tance value index test test Curling ness Example 1 A1 600 45 C1 3.0 48 5 91% 1.4 1.4 11 18 A 2H Example 2 A1 600 45 C2 4.5 42 5 92% 2.3 2.2 11 19 A 2H Example 3 A2 — 45 C2 4.5 42 5 93% 1.8 1.8 11 14 A — Example 4 A1 600 27 C2 4.5 42 3 92% 1.8 1.7 11 25 A 3H Example 5 A1 600 45 C3 2.4 42 5 92% 2.1 2.9 11 20 A — Example 6 A3 — 45 C2 4.5 42 5 93% 1.7 1.4 11 20 A 3H Example 7 A4  10 45 C2 4.5 42 5 91% 1.9 3.0 11 23 A 5B Example 8 A1 600 45 C4 10.5 18 5 91% 3.1 3.9 11 19 A — Example 9 A1 600 45 C5 10.5 27 5 90% 6.3 6.9 11 19 A — Example 10 A1 600 47 C2 4.5 42 3 92% 2.1 1.7 11 20 A — Example 11 B1 570 6 C2 4.5 42 44 92% 10.8 3.8 11 16 C 4B Example 12 B1 570 4 C2 4.5 42 46 93% 6.9 3.5 11 16 C 2B Example 13 B2 — 4 C2 4.5 42 46 93% 4.9 2.2 11 18 B B Example 14 B3  50 4 C2 4.5 42 46 92% 2.5 6.0 11 20 A HB Comparative — — — C2 4.5 42 50 93% 1.2 1.5 11 30 A 4B Example 1 Comparative A1 600 45 C6 15.0 0 5 92% 1.4 1.4 11 18 A 2H Example 2

TABLE-US-00007 TABLE 5 Adhesiveness Adhesiveness (pressing for (pressing for After weather 20 minutes) 10 minutes) resistance test Chemical Before After Before After Color resistance boiling boiling boiling boiling difference Release Emboss Coating Film Fracture test test test test Adhesiveness change property Glossiness Acetone test appearance elongation Example 1 A A B C — — B — C C B 67% Example 2 A A A B A 4.5 B 6.4 C C B 32% Example 3 A A — — — — B — C C B — Example 4 A A — — — — B — C C B — Example 5 A A A A — — B — C C B — Example 6 A A — — — — A — C C B — Example 7 A A — — — — B 2.5 C C B — Example 8 A B — — — — B — C C A 19% Example 9 A A — — — — B — C C A 31% Example 10 A A — — A 3.9 B — C C B — Example 11 A A — — — — A — A A B — Example 12 A A — — — — A — A A B 60% Example 13 A A — — — — A — B A B — Example 14 A A — — A 4.1 A — C B B — Comparative A A A C A 8.4 C — C C B — Example 1 Comparative B C C C C 4.8 B — C C A — Example 2

[0224] Further, in Examples 2 to 14, a laminate film and a melamine decorative panel were produced by the same operation as in Example 1, except that materials as presented in Tables 4 and 5 were used and the thicknesses of the resin layers (I) and (II) were set as presented in Tables 4 and 5. The evaluation results of the obtained melamine decorative panel are presented in Tables 4 and 5.

Comparative Examples 1 and 2

[0225] A laminate film and a melamine decorative panel were produced by the same operation as in Example 1, except that materials as presented in Tables 4 and 5 were used and the thicknesses of the resin layers (I) and (II) were set as presented in Tables 4 and 5. The evaluation results of the obtained melamine decorative panel are presented in Tables 4 and 5. Comparative Example 1 is a single-layered film formed only from the resin layer (II).

[0226] From the above Examples and Production Examples, the following matters were clearly found. The laminate films obtained in Examples 1 to 14 were excellent in adhesiveness with the melamine base material, and in the melamine decorative panels using these laminate films, there was no case where 10 or more sections were peeled off in the adhesiveness evaluation.

[0227] In Examples 2 to 14 in which the content of the acid anhydride group in the resin layer (11) was 4% by mass or more, even in the case of shortening the pressing time at the time of producing the melamine laminate plate, adhesiveness is exhibited and productivity is excellent.

[0228] Further, in Example 3 in which TV1600 that is a triazine-based compound was used as the ultraviolet absorbing agent, an increase in whiteness after the boiling test is suppressed and appearance is excellent.

[0229] Further, in Example 4 in which the thickness of the laminate film was set to be less than 40 μm, the pencil hardness of the melamine laminate plate is improved and scratch resistance is excellent.

[0230] Further, in Example 5 in which the Tg of the resin layer (II) was lower than 100° C., even in the case of shortening the pressing time at the time of producing the melamine laminate plate, adhesiveness is exhibited and productivity is excellent.

[0231] Further, in Example 6 in which the release agent was added to the resin layer (I), the release property from the press plate at the time of producing the melamine laminate plate is favorable and productivity is excellent.

[0232] Further, in Example 7 in which a composition having a storage elastic modulus of 500 MPa or less was used in the resin layer (I), the transferring of the embossed shape is favorable and appearance is excellent.

[0233] Further, in Example 9 in which rubber having an average particle diameter of 0.15 μm or more was contained in the resin layer (II), adhesiveness after the boiling test is improved and durability is excellent.

[0234] Further, in Example 10 in which the thickness of the resin layer (II) was set to 3 μm, the color difference change after the weather resistance test is small and weather resistance is excellent.

[0235] Further, in Examples 11 to 14 in which a fluororesin was used in the resin layer (1), chemical resistance is excellent.

[0236] Further, in Examples 13 and 14 in which a fluororesin and an acrylic resin were contained in the resin layer (I), curling is suppressed, handleability is excellent, pencil hardness is also improved, and scratch resistance is excellent.

[0237] On the other hand, the film obtained in Comparative Example 1 was poor in weather resistance since the resin layer (I) was not included, and was whitened after the weather resistance test. In addition, the laminate film obtained in Comparative Example 2 was insufficient in toughness since the acrylic rubber particles were not contained in the resin layer (II), was peeled off from the melamine laminate plate by the boiling test and the weather resistance test, and was poor in weather resistance and durability.

[0238] Hereinbefore, the invention of the present application has been described with reference to the embodiments and examples. However, the invention of the present application is not limited to those embodiments and examples. Various modifications that can be understood by those skilled in the art can be made on configuration and details of the invention of the present application within the scope of the invention of the present application.

INDUSTRIAL APPLICABILITY

[0239] According to the invention, it is possible to provide a laminate film which is excellent in bondability, water whitening resistance, and appearance.