Laminate Film, Method for Manufacturing Same, and Melamine Decorative Panel

Abstract

Provided is a laminate film having excellent bonding properties, resistance to water whitening, and chemical resistance, and containing a fluororesin layer comprising a fluororesin composition, and an acrylic resin layer comprising a resin composition that contains a reactive group-containing acrylic resin, acrylic rubber particles, and a thermoplastic resin.

Claims

1. A laminate film comprising: a fluororesin layer (I) which is formed from a fluororesin composition (A); and an acrylic resin layer (II) which is formed from a resin composition (B) containing a reactive group-containing acrylic resin (B-1), wherein the resin composition (B) contains 10 to 100% by mass of (B-1), 0 to 90% by mass of acrylic rubber particles (B-2) other than (B-1), and 0 to 90% by mass of a thermoplastic resin (B-3) having a mass average molecular weight of less than 400,000 other than (B-1) and (B-2) with respect to the total 100% by mass of (B-1), (B-2), and (B-3), and further contains 0 to 50 parts by mass of an additive (C) other than (B-1), (B-2), and (B-3) with respect to the total 100 parts by mass of (B-1), (B-2), and (B-3), the reactive group-containing acrylic resin (B-1) contains a monomer unit having a reactive substituent with respect to an amino group or methylol group, and a content of the monomer unit having the reactive substituent is 4% by mass or more with respect to 100% by mass of the resin composition (B).

2. The laminate film according to claim 1, wherein the reactive substituent is a hydroxyl group.

3. The laminate film according to claim 1, wherein the reactive substituent is a secondary hydroxyl group.

4. A laminate film comprising: a fluororesin layer (I) which is formed from a fluororesin composition (A); and an acrylic resin layer (II) which is formed from a resin composition (B) containing a reactive group-containing acrylic resin (B-1), wherein the resin composition (B) contains 10 to 100% by mass of (B-1), 0 to 90% by mass of acrylic rubber particles (B-2) other than (B-1), and 0 to 90% by mass of a thermoplastic resin (B-3) having a mass average molecular weight of less than 400,000 other than (B-1) and (B-2) with respect to the total 100% by mass of (B-1), (B-2), and (B-3), and further contains 0 to 50 parts by mass of an additive (C) other than (B-1), (B-2), and (B-3) with respect to the total 100 parts by mass of (B-1), (B-2), and (B-3), the reactive group-containing acrylic resin (B-1) contains a monomer unit having a hydroxyl group, and a hydroxyl value of the resin composition (B) is 15 to 300 mgKOH/g.

5. The laminate film according to claim 1, wherein a glass transition temperature of the reactive group-containing acrylic resin (B-1) is 0 to 90° C.

6. The laminate film according to claim 1, wherein a content of an aromatic vinyl monomer unit in the reactive group-containing acrylic resin (B-1) is 0 to 3% by mass with respect to 100% by mass of the reactive group-containing acrylic resin (B-1).

7. The laminate film according to claim 1, wherein the resin composition (B) contains 10 to 90% by mass of (B-1), 10 to 90% by mass of (B-2), and 0 to 80% by mass of (B-3) with respect to the total 100% by mass of (B-1), (B-2), and (B-3).

8. The laminate film according to claim 1, wherein a gel fraction of the resin composition (B) is 0 to 80%.

9. The laminate film according to claim 1, wherein the additive (C) contains a hindered amine-based stabilizer having a molecular weight of 1,000 or more.

10. The laminate film according to claim 1, wherein the fluororesin composition (A) contains polyvinylidene fluoride.

11. The laminate film according to claim 1, wherein a thickness of the laminate film is 100 μm or less.

12. The laminate film according to claim 1, wherein a thickness of the fluororesin layer (I) is 30 μm or less.

13. The laminate film according to claim 1, wherein a fracture elongation of the laminate film is 5% or more.

14. A method for manufacturing the laminate film according to claim 1 comprising manufacturing the laminate film by a co-extrusion method.

15. A method for manufacturing the laminate film according to claim 1, comprising manufacturing the laminate film by a coating method.

16. A protection film comprising the laminate film according to claim 1.

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

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

Description

EXAMPLES

[0129] 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.

[0130] MMA: methyl methacrylate

[0131] MA: methyl acrylate

[0132] BA: butyl acrylate

[0133] St: styrene

[0134] HPMA: 2-hydroxypropyl methacrylate

[0135] HEMA: 2-hydroxyethyl methacrylate

[0136] HPA: 2-hydroxypropyl acrylate

[0137] 2EHA: 2-ethylhexyl acrylate

[0138] AMA: allyl methacrylate

[0139] BDMA: 1,3-butylene glycol dimethacrylate

[0140] CHP: cumene hydroperoxide

[0141] t-BH: t-butyl hydroperoxide

[0142] t-HH: t-hexyl hydroperoxide

[0143] LPO: n-lauryl peroxide

[0144] n-OM: n-octylmercaptan

[0145] RS-610NA: sodium mono-n-dodecyloxytetraoxyethylenephosphate (trade name: “PHOSPHANOL RS-610NA”, manufactured by Toho Chemical Industry Co., Ltd.)

[0146] SSL: sodium alkyl diphenyl ether disulfonate (trade name: “PELEX SSL”, manufactured by Kao Corporation)

[0147] LA-31: “ADK STAB LA-31RG” (trade name) manufactured by ADEKA CORPORATION

[0148] LA-57: “ADK STAB LA-57” (trade name) manufactured by ADEKA CORPORATION

[0149] Chimassorb 2020: “Chimassorb 2020” (trade name) manufactured by BASF

[0150] TV234: “Tinuvin 234” (trade name) manufactured by BASF

[0151] TV1600: “Tinuvin 1600” (trade name) manufactured by BASF

[0152] Irg1076: “Irganox 1076” (trade name) manufactured by BASF

[0153] T850: “KF Polymer T#850” (trade name) manufactured by KUREHA CORPORATION

[0154] VH: “ACRYPET VH” (trade name) manufactured by Mitsubishi Rayon Co., Ltd.

[0155] MD: “ACRYPET MD” (trade name) manufactured by Mitsubishi Rayon Co., Ltd.

[0156] Measurement of various physical properties in Examples was carried out by the following methods.

[0157] (1) Mass Average Molecular Weight (Mw) and Molecular Weight Distribution

[0158] The mass average molecular weight (Mw) and the number average molecular weight of a polymer were obtained by the following method. The measurement was performed on a sample, which has been obtained by dissolving the polymer in tetrahydrofuran, at a temperature of 40° C. by using gel permeation chromatography (machine name: “HLC-8200”, manufactured by Tosoh Corporation), a column (trade name: “TSK-GEL SUPER MULTIPORE HZ-H”, manufactured by Tosoh Corporation, inner diameter 4.6 mm x length 15 cm x 2), and an eluent (tetrahydrofuran). The mass average molecular weight (Mw) and the number average molecular weight were obtained from a calibration curve by standard polystyrene. Further, the molecular weight distribution was calculated by the following equation.

[0159] Molecular weight distribution=(mass average molecular weight)/(number average molecular weight)

[0160] (2) Glass Transition Temperature (Tg)

[0161] 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.

[0162] (3) Average Particle Diameter

[0163] Regarding the average particle diameter of the acrylic rubber particles (B-2), 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.

[0164] (4) Total Light Transmittance, Haze Value, Yellowness Index, Color Difference, and Whiteness

[0165] 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 K7103, the color difference was evaluated according to JIS Z8730, and the whiteness was evaluated according to JIS Z8715.

[0166] (5) Melamine Base Material Curing Temperature

[0167] 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.

[0168] (6) Water Whitening Resistance Evaluation

[0169] 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.

[0170] (7) Adhesiveness Evaluation

[0171] 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 case where there are 1 or more and 9 or less peeled-off sections was evaluated as “Δ”, and a case where there are 10 or more peeled-off sections was evaluated as “x”.

[0172] (8) Thicknesses of Fluororesin Layer (I) and Acrylic Resin Layer (II)

[0173] The laminate film was cut into a suitable size and then the thicknesses of the fluororesin layer (I) and the acrylic resin layer (II) were measured by using a reflectance spectral film thickness meter FE 3000 (trade name, manufactured by Otsuka Electronics Co., Ltd.).

[0174] (9) Hydroxyl Value

[0175] First, an acid value of a sample was obtained by the following method. The sample was dissolved in acetone and titrated with 0.1 mol/L of an ethanolic potassium hydroxide solution using phenolphthalein as an indicator. Further, a blank test was performed by the same operation, except that the sample was not used, and then the acid value was obtained from the following equation.

Acid value=(A−B)×f×56.1×0.1/S

[0176] f: titer of 0.1 mol/L ethanolic potassium hydroxide

[0177] S: sample amount (g)

[0178] A: ethanolic potassium hydroxide amount (ml) used in titration

[0179] B: ethanolic potassium hydroxide amount (ml) used in blank test

[0180] Next, the sample was dissolved in acetic anhydride and pyridine to perform acetylation, and then was titrated with 0.5 mol/L of an ethanolic potassium hydroxide solution using phenolphthalein as an indicator. Further, a blank test was performed by the same operation, except that the sample was not used, and then the hydroxyl value was obtained from the following equation.

Hydroxyl value=(B−A)×f×56.1×0.5/S+acid value

[0181] f: titer of 0.5 mol/L ethanolic potassium hydroxide

[0182] S: sample amount (g)

[0183] A: ethanolic potassium hydroxide amount (ml) used in titration

[0184] B: ethanolic potassium hydroxide amount (ml) used in blank test

[0185] (10) Curling Evaluation

[0186] The obtained laminate film was cut in a rectangular shape of 20 cm, placed on a flat glass plate while the fluororesin 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 case where the end portion floated from the glass surface was designated as “Δ”, and a case where the end portion was curled to be in contact with the upper surface of the laminate film was designated as “x”.

[0187] (11) Acetone Test

[0188] 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 “1”, a case where trace was slightly observed was designated as “2”, a case where trace was clearly observed and whitening was observed was designated as “3”, a case where trace was clearly observed and unevenness slightly occurs on the surface was designated as “4”, and a case where unevenness clearly occurs on the surface was designated as “5”.

[0189] (12) Coating Test

[0190] 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 (trade name: 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 “1”, a case where trace was slightly observed was designated as “2”, and a case where trace was clearly observed was designated as “3”.

[0191] (13) Fracture Elongation

[0192] The obtained laminate 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 laminate film was measured.

[0193] (14) Pencil Hardness

[0194] The obtained laminate film was laminated on an acrylic resin plate L001 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) such that the acrylic resin layer (II) was in contact with the acrylic resin plate, and then adhesion was carried out by heat press. The obtained laminate plate was evaluated according to HS K-5600-5-4 by using an electric system pencil scratch hardness tester 553-M1 (trade name, manufactured by YASUDA SEIKI SEISAKUSHO, LTD.) and Uni (trade name, manufactured by Mitsubishi Pencil Co., Ltd.).

[0195] (15) Weather Resistance Evaluation

[0196] A test for 3,000 hours was carried out independently on the melamine decorative panel and the laminate film 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 and the fluororesin layer (I) side was used as a test surface. The film adhesiveness and the color difference change of the melamine decorative panel and the yellowness index change of the laminate film alone before and after the test were evaluated in the same manner as described above.

[0197] (16) Laminate Film Appearance

[0198] The obtained laminate 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 foreign materials, 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 case where the number of fish eyes was 100 or more and less than 500 was designated as “Δ”, and a case where the number of fish eyes was 1,000 or more was designated as

[0199] (17) Gel Fraction

[0200] 50 ml of acetone was added to 0.5 g of the obtained resin composition (B) 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 mass thereof was measured, and the gel fraction was calculated by the following equation.

Gel fraction (%)=mass(g) of gel portion/0.5×100

Production Examples 1 to 4: Production of Fluororesin Compositions (A1) to (A4)

[0201] In Production Example 1, 0.1 part of Irg1076 as the additive (C) was added to 100 parts of a polymer mixture obtained by mixing 90 parts of T850 as the fluororesin (A-1) and 10 parts of VH as the thermoplastic polymer (A-2) and then was mixed using 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° C. to 240° C. and a die temperature of 240° C. to obtain a pellet, thereby obtaining a fluororesin composition (A1) for the fluororesin layer (I).

[0202] Further, in Production Examples 2 to 4, acrylic resin compositions (A2) to (A4) for the fluororesin layer (I) were obtained in the same manner as in Production Example 1, except that the blending amounts of T850 and VH were changed to values presented in Table 1.

TABLE-US-00001 TABLE 1 Fluororesin Blending [parts] composition T850 VH Irg1076 Production Example 1 A1 90 10 0.1 Production Example 2 A2 75 25 0.1 Production Example 3 A3 68 32 0.1 Production Example 4 A4 50 50 0.1

Production Examples 5 to 10: Production of Reactive Group-Containing Acrylic Resins (B-1A) to (B-1F)

[0203] In Production Example 5, a mixture of the following components was incorporated into a reaction container equipped with a stirrer, a reflux condenser, a nitrogen gas introduction port, and the like.

TABLE-US-00002 MMA 70 parts BA 15 parts HPMA 15 parts n-OM 0.17 part LPO 0.4 part Copolymer of methyl methacrylate/methacrylic 0.02 part acid salt/sulfoethyl methacrylate salt Sodium sulfate 0.3 part deionized water 145 parts

[0204] After nitrogen gas was sufficiently purged in the container, the mixture was heated up to 75° C. with stirring to allow polymerization reaction to proceed. After 2 hours, the temperature was increased to 95° C. and was further maintained for 60 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a reactive group-containing acrylic resin (B-1A).

[0205] In Production Examples 6 to 10, reactive group-containing acrylic resins (B-1B) to (B-1F) were obtained in the same manner as in Production Example 5, except that components to be used were changed as presented in Table 2. Incidentally, although not described in Table 2, the blending amount of the LPO, the copolymer of methyl methacrylate/methacrylic acid salt/sulfoethyl methacrylate salt, the sodium sulfate, and the deionized water was the same as in Production Example 5.

TABLE-US-00003 TABLE 2 Reactive group- Blending [parts] Tg containing acrylic resin MMA MA BA HPMA HEMA HPA n-OM Mw [° C.] Production Example 5 B-1A 70 0 15 15 0 0 0.17 138,000 56 Production Example 6 B-1B 70 0 15 15 0 0 0.30 81,000 56 Production Example 7 B-1C 69 1 0 30 0 0 0.25 103,000 76 Production Example 8 B-1D 60 10 0 0 30 0 0.15 159,000 77 Production Example 9 B-1E 75 10 0 0 0 15 0.30 88,100 72 Production Example 10 B-1F 55 0 30 15 0 0 0.17 152,000 28

Production Example 11: Production of Acrylic Rubber Particles (B-2A)

[0206] 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 components (ii) described below (parts of raw materials for the elastic copolymer (b-1)) were incorporated thereinto with stirring and then held for 15 minutes. Then, the remaining components (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, components (iii) described below (parts of raw materials for the elastic copolymer (b-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 (b-1).

[0207] 0.2 part by mass of sodium formaldehyde sulfoxylate was added to this latex of the elastic copolymer (b-1). Thereafter, the mixture was held for 15 minutes, components (iv) described below (raw materials for the rigid polymer (b-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 (B-2A). The average particle diameter of the acrylic rubber particles (B-2A) was 0.28 μm.

[0208] This latex of the acrylic rubber particles (B-2A) 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 (B-2A).

[0209] (i)

TABLE-US-00004 Sodium formaldehyde sulfoxylate 0.4 part Ferrous sulfate 0.00004 part Disodium ethylenediamine tetraacetate 0.00012 part

[0210] (ii)

TABLE-US-00005 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

[0211] (iii)

TABLE-US-00006 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

[0212] (iv)

TABLE-US-00007 MMA 35.6 parts MA 1.9 parts n-OM 0.11 part t-BH 0.06 part

Production Example 12: Production of Acrylic Rubber Particles (B-2B)

[0213] Under a nitrogen atmosphere, 153 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 components (ii) described below (raw materials for the elastic copolymer (b-1)) were added with stirring. Thereafter, the mixture was held for 1 hour to perform polymerization, thereby obtaining a polymer latex. Subsequently, 0.1 part of sodium formaldehyde sulfoxylate was added to the polymer latex. Thereafter, the mixture was held for 15 minutes, components (iii) described below (raw materials for the rigid polymer (b-2)) were added with stirring at 80° C. under a nitrogen atmosphere. Thereafter, the mixture was held for 1 hour to perform polymerization, thereby obtaining a latex of acrylic rubber particles (B-2B). The average particle diameter of the acrylic rubber particles (B-2B) was 0.12 μm.

[0214] This latex of the acrylic rubber particles (B-2B) 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 (B-2B).

[0215] (i)

TABLE-US-00008 Sodium formaldehyde sulfoxylate 0.4 part Ferrous sulfate 0.00004 part Disodium ethylenediamine tetraacetate 0.00012 part

[0216] (ii)

TABLE-US-00009 BA 50.9 parts St 11.6 parts AMA 0.56 part t-BH 0.19 part RS-610NA 1.0 part

[0217] (iii)

TABLE-US-00010 MMA 35.6 parts MA 1.9 parts t-BH 0.056 part n-OM 0.16 part RS-610NA 0.25 part

Production Example 13: Production of Acrylic Rubber Particles (B-2C)

[0218] Components (i) described below were preliminarily dispersed at 10,000 rpm for 5 minutes with a homomixer, and then emulsified and dispersed at a pressure of 20 MPa by a Gaulin homogenizer, thereby preparing a pre-emulsion of 2EHA.

[0219] Into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction port, a monomer addition port, and a thermometer, the pre-emulsion of 2EHA was put, 0.5 part of t-BH was put thereinto, and then the temperature in the flask was increased to 50° C. while performing nitrogen purging and mixing and stirring.

[0220] Into the flask, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediamine tetraacetate, 0.26 part of Rongalite, and 5 parts of distilled water was put. The mixed solution was left to stand for 5 hours to complete polymerization, thereby obtaining a latex.

[0221] Next, separately from the above-described flask, a second 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction port, a monomer addition port, and a thermometer, the latex was put to have 20 parts in terms of solid content, 0.7 part of SSL was put as the solid content, and 155 parts of distilled water was further put. Subsequently, components (ii) described below were put thereinto.

[0222] The inside of the flask was stirred for 10 minutes and the components (ii) were impregnated in particles of the latex. After the inside of the flask was further stirred for 10 minutes, the inside of the flask was purged with nitrogen, the temperature in the flask was increased to 50° C., a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediamine tetraacetate, 0.26 part of Rongalite, and 5 parts of distilled water was put into the flask, and then radical polymerization was initiated. The temperature in the flask was held at 70° C. for 2 hours and then polymerization was completed, thereby obtaining an acrylic composite rubber latex of a rubber having a 2EHA unit as a main component and a rubber having a BA unit as a main component.

[0223] Then, components (iii) described below were added dropwise to the acrylic composite rubber latex over 30 minutes while the temperature in the flask was held at 70° C.

[0224] After completion of dropwise addition, the temperature in the flask was held at 70° C. for 4 hours to obtain a latex of acrylic rubber particles (B-2C).

[0225] The obtained latex of acrylic rubber particles (B-2C) were coagulated by 500 parts by mass of 7.5% by mass calcium acetate aqueous solution and then subjected to heat treatment at 90° C. to be solidified. Thereafter, the solidified product was washed with hot water and then further dried to obtain a powder of acrylic rubber particles (B-2C).

[0226] (i)

TABLE-US-00011 2EHA 99.5 parts AMA 0.5 part SSL 2 parts (in terms of solid content) Distilled water 195 parts

[0227] (ii)

TABLE-US-00012 BA 68 parts AMA 1 part t-BH 0.24 part

[0228] (iii)

TABLE-US-00013 MMA 11 parts t-BH 0.1 part

Production Example 14: Production of Acrylic Rubber Particles (B-2D)

[0229] Into a container equipped with a stirrer, 8.5 parts of deionized water was incorporated. After that, components (ii) described below (parts of raw materials for the elastic copolymer (b-1)) were added with stirring and the resultant mixture was stirred for 20 minutes to prepare an emulsion.

[0230] 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.

[0231] Subsequently, components (iii) described below (parts of raw materials for the elastic copolymer (b-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 (b-1). Incidentally, Tg of the elastic copolymer (b-1) alone was −48° C.

[0232] Subsequently, components (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 (b-3) on the elastic copolymer (b-1). Incidentally, Tg of the intermediate polymer (b-3) alone was 20° C.

[0233] Subsequently, components (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 (b-2) on the intermediate polymer (b-3). According to the above processes, a latex containing 100 parts of acrylic rubber particles (B-1D) was obtained. Incidentally, Tg of the rigid polymer (b-2) alone was 84° C. Further, the average particle diameter of the acrylic rubber particles (B-1D) measured after the polymerization was 0.12 μm.

[0234] This latex of the acrylic rubber particles (B-1D) 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 (B-1D).

[0235] (i)

TABLE-US-00014 Sodium formaldehyde sulfoxylate 0.2 part Ferrous sulfate 0.0001 part Disodium ethylenediamine tetraacetate 0.0003 parts

[0236] (ii)

TABLE-US-00015 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

[0237] (iii)

TABLE-US-00016 MMA 1.5 parts BA 22.5 parts AMA 0.25 part BDMA 1.0 part CHP 0.016 part

[0238] (iv)

TABLE-US-00017 MMA 6.0 parts BA 4.0 parts AMA 0.075 part CHP 0.013 part

[0239] (v)

TABLE-US-00018 MMA 55.2 parts BA 4.8 parts n-OM 0.22 part t-BH 0.075 part

Production Example 15: Production of Thermoplastic Polymer (C1)

[0240] 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 thermoplastic polymer (C1) was 1,000,000.

Production Examples 16 to 28: Production of Resin Compositions (B1) to (B13)

[0241] In Production Example 16, 100 parts of the reactive group-containing acrylic resin (B-1A) of Production Example 5 as the reactive group-containing acrylic resin (B-1), 2.1 parts of LA-31, 2 parts of the thermoplastic polymer (C1) of Production Example 15, 0.45 part of Chimassorb 2020, 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° C. to 240° C. and a die temperature of 240° C. to obtain a pellet, thereby obtaining the resin composition (B1) for the acrylic resin layer (II).

[0242] In Production Examples 17 to 28, resin compositions (B2) to (B13) for the acrylic resin layer (II) were obtained in the same manner as in Production Example 16, except that materials as presented in Table 3 were used as the reactive group-containing acrylic resin (B-1), the acrylic rubber particles (B-2), and the additive (C). Incidentally, “Content of monomer unit having reactive substituent” in Table 3 is a value calculated from the incorporated amount of the raw material.

TABLE-US-00019 TABLE 3 Resin B-1 [parts] B-2 [parts] composition B-1A B-1B B-1C B-1D B-1E B-1F B-2A B-2B B-2C B-2D Production B1 100 0 0 0 0 0 0 0 0 0 Example 16 Production B2 80 0 0 0 0 0 20 0 0 0 Example 17 Production B3 80 0 0 0 0 0 20 0 0 0 Example 18 Production B4 80 0 0 0 0 0 20 0 0 0 Example 19 Production B5 80 0 0 0 0 0 0 20 0 0 Example 20 Production B6 90 0 0 0 0 0 0 0 10 0 Example 21 Production B7 0 80 0 0 0 0 0 20 0 0 Example 22 Production B8 0 60 0 0 0 0 0 40 0 0 Example 23 Production B9 0 0 20 0 0 0 0 0 0 80 Example 24 Production B10 0 0 10 0 0 0 0 0 0 90 Example 25 Production B11 0 0 0 20 0 0 0 0 0 80 Example 26 Production B12 0 0 0 0 70 0 0 30 0 0 Example 27 Production B13 0 0 0 0 0 70 0 30 0 0 Example 28 Content of monomer unit having C [parts] reactive Hydroxyl Gel Chimassorb substituent value fraction LA-31 C1 2020 LA-57 Irg1076 [%] [mgKOH/g] [%] Production 2.1 2 0.45 0 0.1 14.3 52 0 Example 16 Production 2.1 2 0.45 0 0.1 11.5 42 18 Example 17 Production 2.1 2 0 0.3 0.1 11.5 42 17 Example 18 Production 2.1 2 0 0 0.1 11.5 41 18 Example 19 Production 2.1 2 0 0.3 0.1 11.5 42 15 Example 20 Production 2.1 2 0.45 0 0.1 12.9 46 9 Example 21 Production 2.1 2 0.45 0 0.1 11.5 41 16 Example 22 Production 2.1 2 0.45 0 0.1 8.6 35 32 Example 23 Production 2.1 2 0.45 0 0.1 5.7 22 48 Example 24 Production 2.1 2 0.45 0 0.1 2.9 10 53 Example 25 Production 2.1 2 0.45 0 0.1 5.7 21 47 Example 26 Production 2.1 2 0.45 0 0.1 10.0 35 23 Example 27 Production 2.1 2 0.45 0 0.1 10.0 38 24 Example 28

Examples 1 to 27: Production of Laminate Film and Melamine Decorative Panel

[0243] In Example 1, T850 and the resin composition (B2) for the acrylic resin layer (II) obtained in Production Example 17 were dried at 80° C. for a whole day. The T850 was plasticized by a 30-mmφ extruder in which the cylinder temperature was set to 230° C. Further, the resin composition (B2) 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, the T850 and the resin composition (B2) were formed into a laminate film having a thickness of 50 μm by a feed block die for two kinds and two layers set to 250° C. while the fluororesin layer (I) side was in contact with a mirror-finished cooling roller. The thicknesses of the fluororesin layer (I) and the acrylic resin layer (II) were 5 μm and 45 μm, respectively.

[0244] Further, the melamine base material was laminated at the acrylic resin layer (II) surface side of the laminate film and subjected to pressing under the conditions including a temperature of 140° C., a pressure of 4 MPa, and a time of 20 minutes, thereby producing a melamine decorative panel. The evaluation results of the obtained melamine decorative panel are presented in Table 4. The curing temperature of the used melamine base material was 94° C.

[0245] Further, in Examples 2 to 27, a laminate film and a melamine decorative panel were produced by the same operation as in Example 1, except that materials as presented in Table 4 and Table 5 were used as the fluororesin composition (A) for the fluororesin layer (I) and the resin composition (B) for the acrylic resin layer (II) and the thicknesses of the fluororesin layer (I) and the acrylic resin layer (II) were set as presented in Table 4 and Table 5. The evaluation results of the obtained melamine decorative panel are presented in Table 4 and Table 5.

Comparative Examples 1 to 3

[0246] A laminate film and a melamine decorative panel were produced by the same operation as in Example 1, except that materials as presented in Table 5 were used as the fluororesin composition (A) for the fluororesin layer (I) and the resin composition (B) for the acrylic resin layer (II) and the thicknesses of the fluororesin layer (I) and the acrylic resin layer (II) were set as presented in Table 5. The evaluation results of the obtained melamine decorative panel are presented in Table 5. Comparative Example 2 is a single-layered film formed only from the acrylic resin layer (II). Comparative Example 3 is the case of not using the laminate film.

TABLE-US-00020 TABLE 4 Fluororesin Acrylic layer resin Layer Content of (I) (II) monomer unit Fracture Thickness Thickness having reactive Total light Haze Yellowness elongation Initial state A [μm] B [μm] substituent [%] transmittance [%] value index [%] Adhesiveness Whiteness Example 1 T850 5 B2 45 11.5 93.1 6.4 2.8 60 ◯ 10 Example 2 T850 5 B3 45 11.5 93.2 7.8 2.6 63 ◯ 10 Example 3 T850 5 B4 45 11.5 93.1 7.3 2.7 61 ◯ 10 Example 4 T850 5 B5 45 11.5 93.3 7.9 2.6 56 ◯ 10 Example 5 T850 3 B7 27 11.5 93.3 5.8 2.1 10 ◯ 10 Example 6 T850 5 B7 45 11.5 93.1 6.9 2.4 21 ◯ 10 Example 7 T850 5 B7 25 11.5 93.3 6.4 2.3 18 ◯ 10 Example 8 T850 8 B7 42 11.5 93.3 7.6 2.8 23 ◯ 10 Example 9 T850 5 B8 45 8.6 92.8 7.0 2.1 120 ◯ 10 Example 10 T850 5 B9 45 5.7 92.9 9.7 3.2 93 ◯ 10 Example 11 T850 5 B11 45 5.7 92.3 34.2 5.5 82 ◯ 10 Example 12 T850 5 B12 45 10.0 93.1 8.4 2.6 79 ◯ 10 Example 13 A1 5 B2 45 11.5 93.0 2.9 2.1 73 ◯ 10 Example 14 A2 5 B4 45 11.5 93.0 2.7 1.6 65 ◯ 10 Example 15 A3 5 B1 45 14.3 92.5 0.8 0.9 12 Δ 10 Weather resistance Chemical Film Laminate After resistance yellowness plate Laminate boiling test Film Pencil Coating Acetone index color plate Adhesiveness Whiteness Curling appearance hardness test test displacement difference adhesiveness Example 1 ◯ 19 X ◯ B 1 1 0.5 3.7 ◯ Example 2 ◯ 20 X ◯ B 1 1 — — — Example 3 ◯ 20 X ◯ B 1 1 — — — Example 4 ◯ 21 X ◯ B 1 1 — — — Example 5 ◯ 23 X ◯ HB 1 1 — — — Example 6 Δ 20 X ◯ B 1 1 0.7 4.2 ◯ Example 7 ◯ 22 X ◯ HB 1 1 — — — Example 8 Δ 19 X ◯ B 1 1 — — — Example 9 ◯ 17 X ◯ 2B 1 1 0.7 3.7 ◯ Example 10 Δ 28 X Δ 2B 1 1 — — — Example 11 Δ 36 X X 2B 1 1 — — — Example 12 Δ 17 X ◯ B 1 1 — — — Example 13 ◯ 19 Δ ◯ F 1 2 0.7 3.8 ◯ Example 14 ◯ 24 ◯ ◯ F 1 3 0.8 3.6 ◯ Example 15 Δ 32 ◯ ◯ F 1 4 — — —

TABLE-US-00021 TABLE 5 Fluororesin Acrylic layer resin Layer Content of (I) (II) monomer unit Fracture Thickness Thickness having reactive Total light Haze Yellowness elongation Initial state A [μm] B [μm] substituent [%] transmittance [%] value index [%] Adhesiveness Whiteness Example 16 A3 5 B2 45 11.5 92.7 1.7 1.4 72 ◯ 10 Example 17 A3 5 B3 45 11.5 92.9 1.1 1.0 70 ◯ 10 Example 18 A3 5 B5 45 11.5 93.0 1.3 1.1 36 ◯ 10 Example 19 A3 5 B6 45 12.9 92.4 3.3 2.5 32 ◯ 10 Example 20 A3 5 B7 45 11.5 92.8 0.8 0.8 9 ◯ 10 Example 21 A3 5 B13 45 10.0 92.7 1.0 1.4 197 ◯ 10 Example 22 A3 3 B8 27 8.6 93.0 1.1 0.8 155 ◯ 10 Example 23 A3 5 B8 25 8.6 93.0 0.7 0.7 147 ◯ 10 Example 24 A3 5 B8 45 8.6 92.7 1.4 0.9 159 ◯ 10 Example 25 A3 8 B8 42 8.6 93.0 1.2 0.9 154 ◯ 10 Example 26 A3 13  B8 62 8.6 92.9 1.4 1.3 179 ◯ 10 Example 27 A4 5 B4 45 11.5 92.8 1.2 1.1 28 ◯ 10 Comparative T850 5 B10 45 2.9 92.8 13.0 3.5 73 ◯ 10 Example 1 Comparative — — B1 50 14.3 92.4 0.8 0.7 7 ◯ 10 Example 2 Comparative — — — — — — — — — — — Example 3 Weather resistance Chemical Film Laminate After resistance yellowness plate Laminate boiling test Film Pencil Coating Acetone index color plate Adhesiveness Whiteness Curling appearance hardness test test displacement difference adhesiveness Example 16 Δ 25 ◯ ◯ F 1 4 0.7 3.5 ◯ Example 17 ◯ 24 ◯ ◯ F 1 4 2.1 3.6 ◯ Example 18 ◯ 26 ◯ ◯ HB 1 4 — — — Example 19 ◯ 32 ◯ ◯ F 1 4 — — — Example 20 ◯ 32 ◯ ◯ HB 1 4 — — — Example 21 ◯ 26 ◯ ◯ B 1 4 — — — Example 22 ◯ 22 ◯ ◯ B 1 4 — — — Example 23 ◯ 21 ◯ ◯ B 1 4 — — — Example 24 ◯ 18 ◯ ◯ 2B 1 4 — — — Example 25 ◯ 18 ◯ ◯ 2B 1 4 — — — Example 26 ◯ 15 ◯ ◯ 2B 1 4 — — — Example 27 ◯ 27 ◯ ◯ F 2 4 — — — Comparative X 23 X Δ 2B 1 1 — — — Example 1 Comparative ◯ 27 ◯ ◯ H 3 5 — — — Example 2 Comparative — — — — — — — — 37.7  — Example 3

[0247] From the above-described Examples and Production Examples, the following matters were clearly found. The laminate films obtained in Examples 1 to 27 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. Further, these melamine decorative panels were excellent in chemical resistance, and a change in appearance of these melamine decorative panels was suppressed even at the time of the coating test. These laminate films and melamine decorative panels have favorable adhesiveness, favorable chemical resistance, and a high industrial utility value. In particular, in Examples 1 to 12 in which the content of the fluororesin as the fluororesin layer (I) is 95% or more, a change in appearance is suppressed even at the time of the acetone test and the industrial utility value is higher. In addition, in Examples 13 to 27 in which the content of fluororesin in the fluororesin layer (I) is less than 95%, curling of the laminate film is suppressed, handleability is favorable, scratch resistance is also excellent since pencil hardness is also high, and the industrial utility value is higher.

[0248] On the other hand, in the laminate film obtained in Comparative Example 1, since the content of the monomer unit having a reactive substituent of the resin composition (B10) is less than 4% by mass and the hydroxyl value of the resin composition (B10) is less than 15 mgKOH/g, adhesiveness with the melamine base material was low and 10 or more sections were peeled off in the adhesiveness evaluation. The laminate film was easily peeled off when being used in the melamine decorative panel and it was not possible to obtain a melamine decorative panel with favorable quality. Further, the single-layered acrylic resin film obtained in Comparative Example 2 did not have the fluororesin layer (I) and thus was inferior in chemical resistance.

[0249] This application is based upon and claims the benefit of priority to Japanese Patent Application No. 2014-223955, filed Nov. 4, 2014, and the entire contents of their disclosure are incorporated herein by reference.

[0250] 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.