Acrylic resin laminate film, manufacturing method therefor, and melamine decorative board

Abstract

Provided is an acrylic resin laminate film which has an excellent bonding property, resistance to water blushing, and an excellent external appearance. This acrylic resin laminate film is provided with: an acrylic resin layer (I) comprising an acrylic resin composition (A); and an acrylic resin layer (II) comprising a resin composition (B) that contains a reactive group-containing acrylic resin (B-1). (B) contains 10-100 mass % of (B-1), and 0-90 mass % of (B-2), which is an acrylic resin other than (B-1), with respect to 100 mass % of the total of (B-1), and (B-2), and further contains 0-50 parts by mass of (C), which is an additive other than (B-1), and (B-2), with respect to 100 parts by mass of the total of (B-1), and (B-2). (B-1) contains a monomer unit which has a substituent that reacts with an amino group, or a methylol group. The content of the monomer unit that has the reactive substituent is 3 mass % or more with respect to 100 mass % of (B).

Claims

1. An acrylic resin laminate film comprising: a first acrylic resin layer (I) consisting of an acrylic resin composition (A) containing acrylic rubber particles (A-1) having a multilayer structure of two or more layers in which a layer containing a hard polymer (a-2) as an outer layer is formed on a layer containing an elastic copolymer (a-1) as an inner layer; and a second acrylic resin layer (II) consisting of a resin composition (B) containing 40 to 100% by mass of a first acrylic resin (B-1) containing a monomer unit having a secondary hydroxyl group in an amount of 5% by mass or more and up to 50% by mass with respect to 100% by mass of the resin composition (B); 0 to 60% by mass of a second acrylic resin (B-2) other than the first acrylic resin (B-1) with respect to 100% by mass of the first acrylic resin (B-1) and the second acrylic resin (B-2) in total; and 0 to 50 parts by mass of an additive (C) other than the first acrylic resin (B-1) and the second acrylic resin (B-2) with respect to 100 parts by mass of the first acrylic resin (B-1) and the second acrylic resin (B-2) in total.

2. The acrylic resin laminate film according to claim 1, wherein a glass-transition temperature of the first acrylic resin (B-1) is 0 C. to 90 C.

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

4. The acrylic resin laminate film according to claim 1, wherein the resin composition (B) is composed of the first acrylic resin (B-1) and the additive (C).

5. The acrylic resin laminate film according to claim 1, wherein a thickness of the acrylic resin laminate film is 100 m or less.

6. The acrylic resin laminate film according to claim 1, wherein a thickness of the second acrylic resin layer (II) is 30 m or less.

7. The acrylic resin laminate film according to claim 1, wherein the resin composition (B) contains 0.1 to 5 parts by mass of the additive (C).

8. The acrylic resin laminate film according to claim 1, wherein the content of the monomer unit having the secondary hydroxyl group is 10% by mass or more and up to 50% by mass with respect to 100% by mass of the resin composition (B).

9. The acrylic resin laminate according to claim 1, wherein the monomer unit having the secondary hydroxyl group is selected from the group consisting of hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate.

10. The acrylic resin laminate film according to claim 1, wherein the resin composition (B) comprises 5% to 60% by mass of the second acrylic resin (B-2) other than the first acrylic resin (B-1) with respect to 100% by mass of the first acrylic resin (B-1) and the second acrylic resin (B-2) in total.

11. The acrylic resin laminate film according to claim 1, wherein the resin composition (B) comprises 0.1 to 50 parts by mass the additive (C) other than the first acrylic resin (B-1) and the second acrylic resin (B-2) with respect to 100% by mass of the first acrylic resin (B-1) and the second acrylic resin (B-2) in total.

12. A method for manufacturing the acrylic resin laminate film according to claim 1, the method utilizing a co-extrusion method in manufacturing of the acrylic resin laminate film.

13. A method for manufacturing the acrylic resin laminate film according to claim 1, the method utilizing a coating method in manufacturing of the acrylic resin laminate film.

14. A method, comprising applying the acrylic resin laminate film according to claim 1 as a protective film to a base material.

15. A method of protecting a surface of a melamine decorative board comprising applying the acrylic resin laminate film according to claim 1 as a film.

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

17. An acrylic resin laminate film comprising: a first acrylic resin layer (I) composed of an acrylic resin composition (A) containing acrylic rubber particles (A-1) having a multilayer structure of two or more layers in which a layer containing a hard polymer (a-2) as an outer layer is formed on a layer containing an elastic copolymer (a-1) as an inner layer; and a second acrylic resin layer (II) composed of a resin composition (B) containing 40 to 100% by mass of a first acrylic resin (B-1) containing a monomer unit having a secondary hydroxyl group in an amount of 5% by mass or more and up to 50% by mass with respect to 100% by mass of the resin composition (B), wherein the first acrylic resin composition (B-1) has a glass-transition temperature of 15 C. to 80 C.; 0 to 60% by mass of a second acrylic resin (B-2) other than the first acrylic resin (B-1) with respect to 100% by mass of the first acrylic resin (B-1) and the second acrylic resin (B-2) in total; and 0 to 50 parts by mass of an additive (C) other than the first acrylic resin (B-1) and the second acrylic resin (B-2) with respect to 100 parts by mass of the first acrylic resin (B-1) and the second acrylic resin (B-2) in total, and a hydroxyl value of the resin composition (B) is 15 mgKOH/g to 300 mgKOH/g.

18. The acrylic resin laminate film according to claim 17, wherein the hydroxyl value of the resin composition (B) is 20 mgKOH/g to 120 mgKOH/g.

19. The acrylic resin laminate film according to claim 17, wherein the hydroxyl value of the resin composition (B) is 25 mgKOH/g to 180 mgKOH/g.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in more detail by means of Examples, but the present invention is not limited to these Examples. In Examples, part(s) represents part(s) by mass. Further, abbreviations in Examples are as described below.

(2) MMA: methyl methacrylate

(3) MAA: methacrylic acid

(4) BMA: butyl methacrylate

(5) MA: methyl acrylate

(6) BA: butyl acrylate

(7) St: styrene

(8) HEMA: 2-hydroxyethyl methacrylate

(9) HPMA: 2-hydroxypropyl methacrylate

(10) AMA: allyl methacrylate

(11) 1,3BD: 1,3-butylene glycol dimethacrylate

(12) CHP: cumene hydroperoxide

(13) t-BH: t-butyl hydroperoxide

(14) t-HH: t-hexyl hydroperoxide

(15) LPO: lauryl peroxide

(16) n-OM: n-octylmercaptan

(17) RS-610NA: sodium mono-n-dodecyloxytetraoxyethylene phosphate (trade name: PHOSPHANOL RS-610NA, manufactured by TOHO CHEMICAL INDUSTRY Co., Ltd.)

(18) LA-31: Adekastab LA-31RG (trade name) manufactured by ADEKA CORPORATION

(19) LA-57: Adekastab LA-57 (trade name) manufactured by ADEKA CORPORATION

(20) TV234: TINUVIN 234 (trade name) manufactured by BASF

(21) TV1600: TINUVIN 1600 (trade name) manufactured by BASF

(22) Irg1076: Irganox 1076 (trade name) manufactured by BASF

(23) VH: ACRYPET VH (trade name) manufactured by MITSUBISHI RAYON CO., LTD.

(24) MD: ACRYPET MD (trade name) manufactured by MITSUBISHI RAYON CO., LTD.

(25) Various physical properties in Examples were measured according to the following methods.

(26) (1) Mass Average Molecular Weight (Mw) and Molecular Weight Distribution

(27) 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 at 40 C. for a sample obtained by dissolving the polymer in tetrahydrofuran by using a gel permeation chromatography (model name: HLC-8200, manufactured by Tosoh Corporation), a column (trade name: TSK-GEL SUPER MULTIPORE HZ-H, manufactured by Tosoh Corporation, 4.6 mm inner diameter15 cm length2 pieces), and an eluent (tetrahydrofuran). The mass average molecular weight (Mw) and the number average molecular weight were obtained from a calibration curve using standard polystyrenes. Furthermore, the molecular weight distribution was calculated by the following equation.
Molecular weight distribution=(mass average molecular weight)/(number average molecular weight)

(28) (2) Glass-Transition Temperature (Tg)

(29) The glass-transition temperature was calculated by the FOX equation using values described in a polymer handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)].

(30) (3) Average Particle Diameter

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

(32) (4) Gel Content of Resin Composition

(33) An acrylic resin pellet before being formed in a film shape was dissolved in chloroform to prepare a solution of 1% by mass chloroform, and the solution was left at 25 C. for a whole day and night. Thereafter, centrifuge separation was performed thereon at 16000 r.p.m for 90 minutes, % by mass of the insoluble matter after the supernatant solution thereof was removed and dried was considered as the gel content.

(34) (5) Total Light Transmittance, Haze, Yellow Index, and White Index

(35) The total light transmittance was evaluated according to JIS K7361-1, the haze was evaluated according to JIS K7136, the yellow index was evaluated according to JIS K7373, and the white index was evaluated according to JIS Z8715.

(36) (6) Melamine Base Material Curing Temperature

(37) An endothermic peak temperature when the temperature of the melamine base material was raised from 25 C. to 200 C. at a rate of 10 C./min under nitrogen stream was measured by using DSC6200 (product name, manufactured by SII Nano Technology Inc.) and the endothermic peak temperature was considered as a melamine base material curing temperature.

(38) (7) Water Whitening Resistance Evaluation

(39) The boiling test was performed at 100 C. for 2 hours according to CEN (European Committee for Standardization) standards, EN438-2, and a change in white indexes before and after the boiling test was measured.

(40) (8) Adhesion Evaluation

(41) The melamine decorative board in a state of room temperature was scored in grids of 100 squares at an interval of 1 mm by using a cutter knife, and then the peeling property was confirmed with a cellophane tape (manufactured by Nichiban Co., Ltd.). This test was performed before and after the boiling test. A case where squares were not peeled at all was evaluated as , a case where one or more but nine or less squares were peeled was evaluated as , and a case where ten or more squares were peeled was evaluated as x.

(42) (9) Thickness of Acrylic Resin Layer (II)

(43) The acrylic resin laminate film was cut into a proper size, the cut piece was immersed in an aqueous solution of 0.5% by mass ruthenium tetroxide at room temperature for 15 hours so as to be dyed. Further, a sample was cut to have a thickness of about 70 nm such that a cross-section layer thereof could be observed by using a microtome and then the cross-section layer was photographed by a transmission electron microscope. The thickness of a portion where the acrylic rubber particles (A-1) did not exist was obtained from this photograph and was considered as the thickness of the acrylic resin layer (II).

(44) (10) Weather Resistance Evaluation

(45) The test was performed on the melamine decorative board by using Super Xenon Weather Meter SX75 (trade name, manufactured by Suga Test Instruments Co., Ltd.) at an irradiation intensity 60 W/m.sup.2 (300 to 400 nm) with a filter #275 for one cycle including irradiation (63 C., 50% RH) 102 minutes and irradiation+spraying (95% RH) 18 minutes (120 minutes in total). The adhesion and the white index before and after the test were evaluated in the same manner as described above.

(46) (11) Hydroxyl Value

(47) First, an acid value of the sample was obtained by the following method. The sample was dissolved in acetone, phenolphthalein was used as an indicator, and then titration was performed using 0.1 mol/L of an ethanolic potassium hydroxide solution. In addition, the blank test was performed on other cases not using the sample by the same operation, and the acid value was obtained by the following equation.
Acid value=(AB)f56.10.1/S

(48) f: titer of 0.1 mol/L ethanolic potassium hydroxide

(49) S: sample amount (g)

(50) A: amount (ml) of ethanolic potassium hydroxide used in the titration

(51) B: amount (ml) of ethanolic potassium hydroxide used in the blank test

(52) Next, after the sample was dissolved in acetic anhydride and pyridine and subjected to acetylation, phenolphthalein was used as an indicator and then titration was performed using 0.5 mol/L of an ethanolic potassium hydroxide solution. In addition, the blank test was performed on other cases not using the sample by the same operation, and the hydroxyl value was obtained by the following equation.
Hydroxyl value=(BA)f56.10.5/S+acid value

(53) f: titer of 0.5 mol/L ethanolic potassium hydroxide

(54) S: sample amount (g)

(55) A: amount (ml) of ethanolic potassium hydroxide used in the titration

(56) B: amount (ml) of ethanolic potassium hydroxide used in the blank test

(57) The value obtained by the above method is considered as a measured value of the hydroxyl value. The hydroxyl value in the present invention indicates the measured value of the hydroxyl value. Incidentally, a calculated value in Tables 1 and 4 is a value obtained when the introduction rate of the hydroxyl group monomer is assumed to be 100% and the acid value is assumed to be 0 (zero). The measured value of the hydroxyl value can be speculated from the calculated value of the hydroxyl value.

(58) (12) Film Appearance

(59) The film appearance was visually observed and the number of foreign materials per 100 cm.sup.2 was counted.

(60) : 0 to 1 piece/100 cm.sup.2

(61) : 2 to 10 piece/100 cm.sup.2

(62) (13) Pencil Hardness

(63) The pencil hardness was evaluated according to JIS K5600-5-4.

Production Example 1

Production of Acrylic Rubber Particles (A-1A)

(64) Into a reaction container equipped with a reflux condenser, 206 parts of deionized water was charged under a nitrogen atmosphere, and the temperature was raised to 80 C. Components (i) to be described below were added thereto, and 1/10 of raw materials (ii) to be described below (some of raw materials for the elastic copolymer (a-1)) were supplied thereto with stirring, followed by being maintained for 15 minutes. Subsequently, 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 resultant mixture was maintained for 1 hour and then polymerization was performed to thereby obtain a polymer latex. Subsequently, 0.2 part of sodium formaldehyde sulfoxylate was added to the polymer latex. Thereafter, the resultant mixture was maintained for 15 minutes, and raw materials (iii) to be described below (some of raw materials for the elastic copolymer (a-1)) were continuously added thereto while stirring was performed 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 resultant mixture was maintained for 2 hours and then polymerization was performed to thereby obtain a latex of the elastic copolymer (a-1).

(65) To this latex of the elastic copolymer (a-1), 0.2 part by mass of sodium formaldehyde sulfoxylate was added. Thereafter, the resultant mixture was maintained for 15 minutes, and raw materials (iv) to be described below (raw materials for the hard polymer (a-2)) was continuously added thereto while stirring was performed 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 resultant mixture was maintained for 1 hour and then polymerization was performed to thereby obtain a latex of acrylic rubber particles (A-1A). The average particle diameter of the acrylic rubber particles (A-1A) was 0.28 m.

(66) This latex of the acrylic rubber particles (A-1A) was filtrated with a filter having an aperture of 50 m. Subsequently, coagulation, aggregation, and solidification reaction were performed using calcium acetate, and then filtration, washing with water, and drying were performed to thereby obtain acrylic rubber particles (A-1A).

(67) (i)

(68) Sodium formaldehyde sulfoxylate 0.4 part

(69) Ferrous sulfate 0.00004 part

(70) Disodium ethylenediamine tetraacetate 0.00012 part

(71) (ii)

(72) MMA 11.25 parts

(73) BA 12.5 parts

(74) St 1.25 parts

(75) AMA 0.094 part

(76) 1,3BD 0.75 part

(77) t-BH 0.044 part

(78) RS-610NA 0.75 part

(79) (iii)

(80) BA 30.9 parts

(81) St 6.6 parts

(82) AMA 0.66 part

(83) 1,3BD 0.09 part

(84) CHP 0.11 part

(85) RS-610NA 0.6 part

(86) (iv)

(87) MMA 35.6 parts

(88) MA 1.9 parts

(89) n-OM 0.11 part

(90) t-BH 0.06 part

Production Example 2

Production of Acrylic Rubber Particles (A-1B)

(91) After 8.5 parts of deionized water was supplied to a container equipped with a stirrer, raw materials (ii) to be described below (some of raw materials for the elastic copolymer (a-1)) were added thereto with stirring, and stirring was carried out for 20 minutes to prepare an emulsified liquid.

(92) Then, into a polymerization container equipped with a condenser, 191.5 parts of deionized water and components (i) to be described below were charged, and the temperature was raised to 70 C. Subsequently, the prepared emulsified liquid was added dropwise to the polymerization container for 8 minutes with stirring under nitrogen and then the reaction was continued for 15 minutes.

(93) Subsequently, raw materials (iii) to be described below (some of raw materials for the elastic copolymer (a-1)) were added dropwise to the polymerization container for 90 minutes, and then the reaction was continued for 60 minutes to thereby obtain a latex of the elastic copolymer (a-1). Incidentally, the Tg of only the elastic copolymer (a-1) was 48 C.

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

(95) Subsequently, raw materials (v) to be described below were added dropwise to the polymerization container for 140 minutes, and then the reaction was continued for 60 minutes to form the hard 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, the Tg of only the hard polymer (a-2) was 84 C. Further, the average particle diameter of the acrylic rubber particles (A-1B) measured after polymerization was 0.12 m.

(96) This latex of the acrylic rubber particles (A-1B) was filtrated with a filter having an aperture of 50 m. Subsequently, coagulation, aggregation, and solidification reaction were performed using calcium acetate, and then filtration, washing with water, and drying were performed to thereby obtain the acrylic rubber particles (A-1B).

(97) (i)

(98) Sodium formaldehyde sulfoxylate 0.2 part

(99) Ferrous sulfate 0.0001 part

(100) Disodium ethylenediamine tetraacetate 0.0003 part

(101) (ii)

(102) MMA 0.3 part

(103) BA 4.5 parts

(104) AMA 0.05 part

(105) 1,3BD 0.2 part

(106) CHP 0.025 part

(107) RS-610NA 1.1 parts

(108) (iii)

(109) MMA 1.5 parts

(110) BA 22.5 parts

(111) AMA 0.25 part

(112) 1,3BD 1.0 part

(113) CHP 0.016 part

(114) (iv)

(115) MMA 6.0 parts

(116) BA 4.0 parts

(117) AMA 0.075 part

(118) CHP 0.013 part

(119) (v)

(120) MMA 55.2 parts

(121) BA 4.8 parts

(122) n-OM 0.22 part

(123) t-BH 0.075 part

Production Example 3

Production of Acrylic Rubber Particles (A-1C)

(124) After 8.5 parts of deionized water was supplied to a container equipped with a stirrer, raw materials (ii) to be described below (some of raw materials for the elastic copolymer (a-1)) were added thereto with stirring, and stirring was carried out for 20 minutes to prepare an emulsified liquid.

(125) Then, into a polymerization container equipped with a condenser, 191.5 parts of deionized water and components (i) to be described below were charged, and the temperature was raised to 70 C. Subsequently, the prepared emulsified liquid was added dropwise to the polymerization container for 8 minutes with stirring under nitrogen and then the reaction was continued for 15 minutes.

(126) Subsequently, raw materials (iii) to be described below (some of raw materials for the elastic copolymer (a-1)) were added dropwise to the polymerization container for 90 minutes, and then the reaction was continued for 60 minutes to thereby obtain a latex of the elastic copolymer (a-1). Incidentally, the Tg of only the elastic copolymer (a-1) was 20 C.

(127) Subsequently, raw materials (iv) to be described below were added dropwise to the polymerization container for 45 minutes, and then the reaction was continued for 60 minutes to form the intermediate polymer (a-3) on the elastic copolymer (a-1). Incidentally, the Tg of only the intermediate polymer (a-3) was 60 C.

(128) Subsequently, raw materials (v) to be described below were added dropwise to the polymerization container for 140 minutes, and then the reaction was continued for 60 minutes to form the hard polymer (a-2) on the intermediate polymer (a-3). According to the above processes, a latex containing 100 parts of acrylic rubber particles (A-1C) was obtained. Incidentally, the Tg of only the hard polymer (a-2) was 99 C. Further, the average particle diameter of the acrylic rubber particles (A-1C) measured after polymerization was 0.12 m.

(129) This latex of the acrylic rubber particles (A-1C) was filtrated with a filter having an aperture of 50 m. Subsequently, coagulation, aggregation, and solidification reaction were performed using calcium acetate, and then filtration, washing with water, and drying were performed to thereby obtain the acrylic rubber particles (A-1C).

(130) (i)

(131) Sodium formaldehyde sulfoxylate 0.2 part

(132) Ferrous sulfate 0.0001 part

(133) Disodium ethylenediamine tetraacetate 0.0003 part

(134) (ii)

(135) MMA 0.3 part

(136) BA 4.5 parts

(137) AMA 0.05 part

(138) 1,3BD 0.2 part

(139) CHP 0.025 part

(140) RS-610NA 1.3

(141) (iii)

(142) MMA 9.6 parts

(143) BA 14.4 parts

(144) AMA 0.25 part

(145) 1,3BD 1.0 part

(146) CHP 0.016 part

(147) (iv)

(148) MMA 6.0 parts

(149) MA 4.0 parts

(150) AMA 0.075 part

(151) CHP 0.013 part

(152) (v)

(153) MMA 57 parts

(154) MA 3 parts

(155) n-OM 0.26 part

(156) t-BH 0.075 part

Production Example 4

Production of Acrylic Rubber Particles (A-1D)

(157) Into a reaction container equipped with a reflux condenser, 153 parts of deionized water was charged under a nitrogen atmosphere, and the temperature was raised to 80 C. Components (i) to be described below were added thereto, and raw materials (ii) to be described below (some of raw materials for the elastic copolymer (a-1)) were added thereto with stirring. Thereafter, the resultant mixture was maintained for 1 hour and then polymerization was performed to thereby obtain a polymer latex. Subsequently, 0.1 part of sodium formaldehyde sulfoxylate was added to the polymer latex. Thereafter, the resultant mixture was maintained for 15 minutes, and raw materials (iii) to be described below (raw materials for the hard polymer (a-2)) were added while stirring was performed at 80 C. under a nitrogen atmosphere. Thereafter, the resultant mixture was maintained for 1 hour and then polymerization was performed to thereby obtain a latex of acrylic rubber particles (A-1D). The average particle diameter of the acrylic rubber particles (A-1D) was 0.12 m.

(158) This latex of the acrylic rubber particles (A-1D) was filtrated with a filter having an aperture of 50 m. Subsequently, coagulation, aggregation, and solidification reaction were performed using calcium acetate, and then filtration, washing with water, and drying were performed to thereby obtain the acrylic rubber particles (A-1D).

(159) (i)

(160) Sodium formaldehyde sulfoxylate 0.4 part

(161) Ferrous sulfate 0.00004 part

(162) Disodium ethylenediamine tetraacetate 0.00012 part

(163) (ii)

(164) BA 50.9 parts

(165) St 11.6 parts

(166) AMA 0.56 part

(167) t-BH 0.19 part

(168) RS-610NA 1.0 part

(169) (iii)

(170) MMA 35.6 parts

(171) MA 1.9 parts

(172) t-BH 0.056 part

(173) n-OM 0.16 part

(174) RS-610NA 0.25 part

Production Example 5

Production of Thermoplastic Polymer (C1)

(175) Into a reaction container, 200 parts of ion-exchange water substituted with nitrogen was supplied, and 1 part of potassium oleate and 0.3 part of potassium persulfate were supplied thereto as an emulsifier. Subsequently, 40 parts of MMA, 10 parts of BA, and 0.005 part of n-OM were supplied thereto, and stirring was performed at 65 C. for 3 hours under a nitrogen atmosphere, thereby completing polymerization. Subsequently, a monomer mixture composed of 48 parts of MMA and 2 parts of BA was added dropwise for 2 hours and then maintained for 2 hours after the dropwise addition was completed, thereby completing polymerization. The obtained latex was added to an aqueous solution of 0.25% by mass sulfuric acid and the polymer was subjected to acid coagulation. Thereafter, dehydration, washing with water, and drying were performed so as to recover the polymer in a powder form. The mass average molecular weight of the obtained copolymer was 1,000,000.

Production Examples 6 to 16

Production of Reactive Group-Containing Acrylic Resins (B-1A) to (B-1K)

(176) In Production Example 6, the following mixtures were supplied to a reaction container with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

(177) MMA 75 parts

(178) BA 10 parts

(179) HEMA 15 parts

(180) n-OM 0.25 part

(181) LPO 0.4 part

(182) Copolymer of methyl methacrylate/methacrylic acid salt/salt of sulfoethyl methacrylate

(183) 0.02 part

(184) Sodium sulfate 0.3 part

(185) Ion-exchange water 145 parts

(186) The inside of the container was sufficiently replaced with nitrogen gas, then heated up to 75 C. with stirring, and polymerization reaction was allowed to advance in the nitrogen gas stream. After 2 hours, the temperature thereof was raised to 95 C. and further maintained for 60 minutes, thereby completing polymerization. A polymer bead thus obtained was dehydrated and dried to thereby obtain a reactive group-containing acrylic resin (B-1A).

(187) Further, in Production Examples 7 to 16, reactive group-containing acrylic resins (B-1B) to (B-1K) were obtained in the same manner as the above procedures, except that raw materials to be used (MMA, BA, HEMA, and n-OH) were changed as presented in Table 1.

(188) TABLE-US-00001 TABLE 1 Hydroxyl value Reactive [mgKOH/g] group-containing MMA MA BA HEMA HPMA n-OM Molecular Tg Calculated Measured acrylic resin [part] [part] [part] [part] [part] [part] weight [ C.] value value Production B-1A 75 0 10 15 0 0.25 96,000 72 65 Example 6 Production B-1B 70 0 15 15 0 0.25 97,000 61 65 Example 7 Production B-1C 80 0 15 0 5 0.15 131,000 64 19 Example 8 Production B-1D 75 0 15 0 10 0.12 162,000 60 39 39 Example 9 Production B-1E 70 0 15 0 15 0.15 146,000 56 58 53 Example 10 Production B-1F 70 20 0 10 0 0.25 98,000 76 43 Example 11 Production B-1G 65 20 0 15 0 0.25 102,000 74 65 Example 12 Production B-1H 60 10 0 30 0 0.12 173,000 77 129 127 Example 13 Production B-1I 60 0 10 0 30 0.25 104,000 55 117 Example 14 Production B-1J 45 0 10 0 45 0.25 117,000 44 175 Example 15 Production B-1K 70 0 15 0 15 0.25 98,000 56 58 52 Example 16

Production Examples 17 to 19

Production of Reactive Group-Containing Acrylic Resins (B-1L) to (B-1N)

(189) Reactive group-containing acrylic resins (B-1L) to (B-1N) were obtained in the same manner as in Production Example 2, except that raw materials as presented in Table 2 were used instead of MMA and BA (60 parts in total) among the raw materials (v) in Production Example 2.

(190) TABLE-US-00002 TABLE 2 Acrylic MMA BA HEMA HPMA resin [part] [part] [part] [part] Production A-1B 55.2 4.8 Example 2 Production B-1L 52.44 4.56 3 Example 17 Production B-1M 49.68 4.32 6 Example 18 Production B-1N 52.44 4.56 3 Example 19

Production Examples 20 to 27

Production of Acrylic Resin Compositions (A1) to (A8)

(191) In Production Example 20, 1 part of the thermoplastic polymer (C1) of Production Example 5, 2 parts of LA-31, 0.1 part of LA-57, and 0.1 part of Irg1076 were added to 100 parts of a polymer mixture obtained by mixing 16 parts of the acrylic rubber particles (A-1A) of Production Example 1 as the acrylic rubber particles (A-1) and 84 parts of VH as the thermoplastic polymer (A-2) and mixed by using a Henschel mixer. Then, this resultant mixture was melt-kneaded by using a 35-mm screw type biaxial extruder (L/D=26) under the conditions including a cylinder temperature of 200 C. to 240 C. and a die temperature of 240 C. so as to be pelletized, thereby obtaining an acrylic resin composition (A1) for the acrylic resin layer (I).

(192) Further, in Production Examples 21 to 27, acrylic resin compositions (A2) to (A8) for the acrylic resin layer (I) were obtained in the same manner as the above procedures, except that raw materials as presented in Table 3 were used as the acrylic rubber particles (A-1), the thermoplastic polymer (A-2), and the additive (C).

(193) TABLE-US-00003 TABLE 3 A-1 A-2 C Acrylic resin A-1A A-1B A-1C VH MD C1 LA-31 TV 1600 LA-57 Stearic acid Irg 1076 composition [part] [part] [part] [part] [part] [part] [part] [part] [part] [part] [part] Production A1 16 84 1 2.1 0.15 0.1 Example 20 Production A2 24 76 1 2.1 0.15 0.1 Example 21 Production A3 45 55 2.1 0.15 0.1 Example 22 Production A4 75 25 2.1 0.15 0.1 Example 23 Production A5 10 80 10 2.1 0.15 0.1 Example 24 Production A6 100 2 2.1 0.15 0.1 Example 25 Production A7 100 4 2.4 0.45 0.25 0.1 Example 26 Production A8 16 84 1 2.1 0.15 0.1 Example 27

Production Examples 28 to 49

Production of Resin Compositions (B1) to (B22)

(194) In Production Example 28, 100 parts of the reactive group-containing acrylic resin (B-1A) of Production Example 5 as the reactive group-containing acrylic resin (B-1) and 0.1 part of Irg1076 were used and mixed with a Henschel mixer. Then, this resultant mixture was melt-kneaded by using a 35-mm screw type biaxial extruder (L/D=26) under the conditions including a cylinder temperature of 200 C. to 240 C. and a die temperature of 240 C. so as to be pelletized, thereby obtaining a resin composition (B1) for the acrylic resin layer (II).

(195) In Production Examples 29 to 49, resin compositions (B2) to (B22) for the acrylic resin layer (II) were obtained in the same manner as the above procedures, except that raw materials as presented in Table 4 were used as the reactive group-containing acrylic resin (B-1), the acrylic resin (B-2) other than (B-1), and the additive (C).

(196) TABLE-US-00004 TABLE 4 Hydroxyl value B-1 B-2 C [mgKOH/g] Resin Used amount Used amount LA-31 LA-57 C1 Irg1076 Calculated Measured composition Type [part] Type [part] [part] [part] [part] [part] value value Production B1 B-1A 100 0.1 65 Example 28 Production B2 B-1B 100 0.1 65 Example 29 Production B3 B-1C 100 0.1 19 Example 30 Production B4 B-1D 100 0.1 39 Example 31 Production B5 B-1E 100 0.1 58 52 Example 32 Production B6 B-1F 100 0.1 43 Example 33 Production B7 B-1G 100 0.1 65 Example 34 Production B8 B-1I 10 A-1B 90 0.1 12 Example 35 Production B9 B-1I 20 A-1B 80 0.1 23 Example 36 Production B10 B-1I 40 A-1B 60 0.1 47 Example 37 Production B11 B-1I 60 A-1B 40 0.1 70 Example 38 Production B12 B-1I 80 A-1B 20 0.1 94 Example 39 Production B13 B-1J 20 A-1B 80 0.1 35 Example 40 Production B14 B-1J 40 A-1B 60 0.1 70 Example 41 Production B15 B-1J 60 A-1B 40 0.1 105 Example 42 Production B16 B-1K 95 A-1A 5 0.1 55 Example 43 Production B17 B-1K 90 A-1A 10 0.1 52 Example 44 Production B18 B-1K 80 A-1A 20 0.1 46 Example 45 Production B19 B-1K 60 A-1D 40 0.1 35 Example 46 Production B20 B-1E 80 A-1A 20 2 0.3 2 0.1 46 Example 47 Production B21 B-1H 10 A-1B 90 0.1 13 Example 48 Production B22 B-1H 9 A-1B 91 0.1 12 Example 49

Production Example 50

Production of Resin Composition (B23)

(197) Into a flask provided with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer, 47 parts of i-butyl acetate and 18 parts of ethyl acetate were put under a nitrogen atmosphere. The inner temperature of the flask was raised to 95 C. while the inside thereof was stirred. Thereafter, the following monomer mixture was added dropwise into the flask for 3 hours and then maintained at 95 C. for 1 hour.

(198) (Monomer Mixture)

(199) MAA 0.3 part

(200) MMA 22.7 parts

(201) St 30 parts

(202) BMA 21 parts

(203) HEMA 26 parts

(204) 2,2-Azobis-2-methylbutyronitrile 0.7 part

(205) Ethyl acetate 10 parts

(206) Furthermore, a dropping solution obtained by mixing 20 parts of ethyl acetate and 0.6 part of 2,2-azobis-2-methylbutyronitrile was added dropwise for 60 minutes and maintained at 95 C. for 90 minutes. After the solution was cooled, 200 parts of ethyl acetate was mixed therewith to thereby obtain a resin composition (B23) having a glass-transition temperature of 70 C. and a mass average molecular weight of 30,000.

Production Example 51

Production of Resin Composition (B24)

(207) 22.5 parts of the acrylic rubber particles (A-1B) and 260 parts of ethyl acetate were mixed with 100 parts of the resin composition (B23) to thereby obtain a resin composition (B24).

Examples 1 to 33

Manufacturing of Acrylic Resin Laminate Film and Melamine Decorative Board

(208) In Example 1, the acrylic resin composition (A1) for the acrylic resin layer (I) obtained in Production Example 20 and the resin composition (B1) for the acrylic resin layer (II) obtained in Production Example 28 were dried at 80 C. for a whole day and night. The resin composition (B1) was plasticized by a 30-mm extruder having a cylinder temperature set to 240 C. Further, the acrylic resin composition (A1) was plasticized by a 40-mm extruder having a cylinder temperature set to 240 C. and equipped with a screen mesh of 400 meshes. Subsequently, the acrylic resin composition (A1) and the resin composition (B1) were formed into an acrylic resin laminate film having a thickness of 50 m by using a feedblock die for two kinds and two layers having a temperature set to 250 C. while the acrylic resin layer (I) side was in contact with a mirror-finished cooling roll. The thicknesses of the acrylic resin layers (I) and (II) were 45 m and 5 m, respectively.

(209) Further, a melamine base material was laminated on the surface side of the acrylic resin layer (II) of this acrylic resin laminate film, followed by being pressed under the conditions including a temperature of 140 C., a pressure of 4 MPa, and a time of 20 minutes to thereby manufacture a melamine decorative board. The evaluation results of the obtained melamine decorative board are shown in Table 5 and Table 7. The curing temperature of the used melamine base material was 94 C.

(210) Further, in Examples 2 to 33, an acrylic resin laminate film and a melamine decorative board were manufactured by the same operation as in Example 1, except that materials as presented in Table 5 were used as the acrylic resin composition (A) for the acrylic resin layer (I) and the resin composition (B) for the acrylic resin layer (II) and the thicknesses of the acrylic resin layers (I) and (II) were set as presented in Table 5. The evaluation results of the obtained melamine decorative board are shown in Table 5 and Table 7. Incidentally, in Table 5, an amount of a monomer having a reactive substituent contained, as a copolymer component, in the reactive group-containing acrylic resin (B-1) with respect to 100% by mass of the resin composition (B) is referred to as a functional group content. The functional group content is a value calculated from the supplied amount of the raw materials. The same is applied to Table 6.

Examples 34 and 35

Manufacturing of Acrylic Resin Laminate Film and Melamine Decorative Board

(211) In Example 34, the acrylic resin composition (A4) for the acrylic resin layer (I) obtained in Production Example 23 was dried at 80 C. for a whole day and night. This dried pellet was supplied to a 40-mm non-vent screw extruder (L/D=26) equipped with a T die having a width of 300 mm to manufacture an acrylic resin film having a thickness of 50 m. As the conditions at this time, a cylinder temperature was 200 to 240 C., a T die temperature was 240 C., and a cooling roll temperature was 80 C.

(212) The resin composition (B23) was coated on 200 mm square of the acrylic resin film by a bar coater. Subsequently, the obtained product was left at 80 C. for 10 minutes in a hot air dryer and thus a solvent was volatilized to thereby obtain an acrylic resin laminate film. The thickness of the acrylic resin laminate film was 52 m and the thickness of the acrylic resin layer (II) was 2 m.

(213) Further, a melamine base material was laminated on the surface side of the acrylic resin layer (II) of this acrylic resin laminate film, followed by being pressed under the conditions including a temperature of 140 C., a pressure of 4 MPa, and a time of 20 minutes to thereby manufacture a melamine decorative board. The evaluation results of the obtained melamine decorative board are shown in Table 6. The curing temperature of the used melamine base material was 94 C.

(214) Further, in Example 35, an acrylic resin laminate film and a melamine decorative board were manufactured by the same operation as in Example 34, except that the resin composition (B24) was used instead of the resin composition (B23) as the resin composition (B) for the acrylic resin layer (II). The evaluation results of the obtained melamine decorative board are shown in Table 6.

Comparative Examples 1 to 3

(215) An acrylic resin laminate film and a melamine decorative board were manufactured in the same manner as in Example 1, except that materials as presented in Table 5 were used as the acrylic resin composition (A) for the acrylic resin layer (I) and the resin composition (B) for the acrylic resin layer (II) and the thicknesses of the acrylic resin layers (I) and (II) were set as presented in Table 5. The evaluation results of the obtained melamine decorative board are shown in Table 5 and Table 7. A case where the layer (I) or the layer (II) is not described is a single layer film.

(216) TABLE-US-00005 TABLE 5 Layer (II) Initial After Layer (I) Monomer unit Functional group Total light state boiling test Acrylic Resin Thickness Resin having reactive content Thickness Film Pencil transmittance Yellow White White composition A [m] composition B substituent [% by mass] [m] appearance hardness [%] Haze index Adhesion index Adhesion index Example 1 A1 45 B1 HEMA 15 5 3H 91.7 6.3 1.7 10 25 Example 2 A2 45 B1 HEMA 15 5 2H 91.9 5.7 2.0 10 22 Example 3 A3 45 B1 HEMA 15 5 H 91.8 5.1 1.8 10 24 Example 4 A4 45 B1 HEMA 15 5 H 91.6 5.3 1.5 10 26 Example 5 A5 45 B1 HEMA 15 5 F 91.6 5.3 1.6 10 32 Example 6 A6 45 B1 HEMA 15 5 4B 92.0 3.5 1.4 10 31 Example 7 A3 45 B2 HEMA 15 5 92.0 3.5 1.3 10 23 Example 8 A6 45 B3 HPMA 5 5 92.3 0.6 1.0 10 25 Example 9 A6 45 B4 HPMA 10 5 92.4 0.8 1.0 11 26 Example 10 A6 45 B5 HPMA 15 5 93.0 0.6 1.0 10 28 Example 11 A6 90 B5 HPMA 15 10 92.3 1.1 1.3 10 29 Example 12 A6 27 B5 HPMA 15 3 92.5 0.9 1.0 10 32 Example 13 A6 70 B5 HPMA 15 30 92.0 1.1 1.2 10 27 Example 14 A6 35 B5 HPMA 15 15 92.2 0.9 1.0 10 38 Example 15 A6 47 B5 HPMA 15 3 92.4 0.8 1.1 10 33 Example 16 A3 45 B6 HEMA 10 5 92.3 0.6 0.9 10 25 Example 17 A3 45 B7 HEMA 15 5 92.4 0.5 0.9 10 24 Example 18 A1 45 B8 HPMA 3 5 91.1 28.0 4.3 10 21 Example 19 A1 45 B9 HPMA 6 5 91.5 10.0 2.2 10 21 Example 20 A1 45 B10 HPMA 12 5 92.4 1.9 1.4 10 19 Example 21 A1 45 B11 HPMA 18 5 92.2 2.2 1.3 10 21 Example 22 A1 45 B12 HPMA 24 5 92.5 0.8 0.9 10 22 Example 23 A1 45 B13 HPMA 9 5 92.2 3.6 1.7 10 22 Example 24 A1 45 B14 HPMA 18 5 92.2 2.3 1.5 10 23 Example 25 A1 45 B15 HPMA 27 5 92.3 2.0 1.5 10 20 Example 26 A1 45 B16 HPMA 14.3 5 92.4 1.0 0.9 10 19 Example 27 A1 45 B17 HPMA 13.5 5 92.4 1.7 1.3 10 19 Example 28 A1 45 B18 HPMA 12 5 92.4 2.1 1.4 10 21 Example 29 A7 45 B5 HPMA 15 5 4B 92.5 0.7 1.1 10 25 Example 30 A1 45 B5 HPMA 15 5 92.5 1.5 1.2 10 16 Example 31 A8 45 B5 HPMA 15 5 92.4 1.8 1.4 10 23 Example 32 A7 45 B19 HPMA 9 5 92.5 2.3 1.4 10 18 Example 33 A7 45 B20 HPMA 12 5 92.5 2.0 1.5 10 30 Comparative A6 50 93.0 0.6 1.0 11 x 30 Example 1 Comparative B21 HEMA 3 50 91.0 62.0 6.2 11 x 40 Example 2 Comparative A6 45 B22 HEMA 2.7 5 91.3 44.3 6.5 11 x 46 Example 3

(217) TABLE-US-00006 TABLE 6 Layer (I) Layer (II) After Acrylic Functional Initial boiling resin Resin group state test composition Thickness composition content Thickness White White A [m] B [% by mass] [m] Adhesion index Adhesion index Example 34 A4 50 B23 26.3 2 14 30 Example 35 A4 50 B24 14.1 2 14 30

(218) TABLE-US-00007 TABLE 7 Comparative Comparative Comparative Example 1 Example 10 Example 1 Example 2 Example 3 Functional group content 15 15 0 3 [% by mass] Weather Adhesion/ 0 resistance test time 1000 x evaluation [hr] 2000 x 3000 x x White index/ 0 11 10 10 10 10 test time 1000 12 11 12 11 30 [hr] 2000 12 12 18 13 44 3000 13 14 18 16 48

(219) Based on Examples and Production Examples described above, the following matters were clarified. The acrylic resin laminate films obtained in Examples 1 to 35 were excellent in adhesiveness with the melamine base material, and in the melamine decorative boards using these acrylic resin laminate films, a case where ten or more squares were peeled did not occur in the adhesion evaluation. Further, these melamine decorative boards had small change in white index after the boiling test and the remarkable deterioration of appearance was suppressed. These acrylic resin laminate films and melamine decorative boards have favorable adhesiveness and stability with respect hot water, and have a high industrial utility value. In particular, in Examples 1 to 7, 9 to 11, 14, 16, 17, 19 to 21, 23, 24, 28, 29, and 31 to 33, high adhesiveness can be secured even after the boiling test, and the melamine decorative boards using these acrylic resin laminate films have particularly favorable stability with respect hot water and have a higher industrial utility value.

(220) On the other hand, in the acrylic resin laminate film obtained in Comparative Example 3, the content of the monomer unit having a reactive substituent in the resin composition (B) was less than 3% by mass and the hydroxyl value of the resin composition (B) was less than 15 mgKOH/g. For this reason, adhesiveness with the melamine base material was low and ten or more squares were peeled in the adhesion evaluation. The acrylic resin laminate film was easily peeled when being used in the melamine decorative board, and the melamine decorative board with favorable quality could not be obtained. Further, since the acrylic resin laminate film obtained in each of Comparative Examples 1 and 2 did not have the acrylic resin layer (I) or (II), it was inferior in the water resistance and ten or more squares were peeled in the adhesion evaluation.

(221) This application claims priority based on Japanese Patent Application No. 2013-110816 filed in Japan on May 27, 2013, all of which disclosure is incorporated herein by reference.

(222) Hereinbefore, the present invention has been described with reference to embodiments and Examples, but the present invention is not intended to be limited to the above embodiments and Examples. It should be understood by those skilled in the art that various modifications could be made to the configuration and details of the present invention without departing from the scope of the present invention.