ACRYLIC RESIN COMPOSITION, ACRYLIC RESIN FILM, AND MOLDED BODY

Abstract

The present invention addresses the issue of providing an acrylic resin composition having high weather resistance, flexibility, heat resistance, transparency, and stress-whitening resistance. This issue is solved by an acrylic resin composition containing a rubber-containing multi-stage polymer (I) containing at least 30% by mass of an elastic polymer (A).

Claims

1. An acrylic resin composition comprising a rubber-containing multistage polymer (I) comprising an elastic polymer (A) at 30% by mass or more, wherein: (1) a value of a total light transmittance of a molded body which has a thickness of 1 mm and is obtained by melting a powdery acrylic resin composition through heating, pressurizing a melted acrylic resin composition for 5 minutes at a temperature of 200 C. and a pressure of 5 MPa, and then cooling the resultant for 5 minutes while applying a pressure of 2 MPa to the resultant is 90% or more, and (2) a difference in whiteness degree W before and after stretching when: a test piece 1 obtained from the molded body and having a length of 80 mm and a width of 15 mm; or a test piece 2 obtained by forming the acrylic resin composition into a film by a T-die method and having a thickness of from 0.05 to 0.1 mm, a length of 80 mm, and a width of 15 mm; is stretched by 10 mm from an initial distance between chucks of 25 mm to a final distance between chucks of 35 mm at a temperature of 23 C. and a tension rate of 500 mm/min in conformity to ISO 527 is 1 or less.

2. The acrylic resin composition according to claim 1, wherein a haze value of the molded body is 2% or less.

3. The acrylic resin composition according to claim 1, wherein a test piece 3, obtained by forming the acrylic resin composition into a film by a T-die method, having a thickness of from 0.05 to 0.1 mm, a length of 150 mm, and a width of 15 mm satisfies the following conditions (3) and (4); (3): a rupture elongation is from 20 to 300% when the test piece 3 is stretched at a temperature of 0 C. and a tension rate of 50 mm/min and (4): a rupture elongation is from 100 to 500% when the test piece 3 is stretched at a temperature of 23 C. and a tension rate of 50 mm/min.

4. The acrylic resin composition according to claim 1, wherein the rubber-containing multistage polymer (I) is a polymer comprising: an elastic polymer (A) obtained by polymerizing a monomer (a) comprising one or more kinds of monomers selected from the group consisting of an alkyl acrylate (a1) having an alkyl group having from 1 to 8 carbon atoms and an alkyl methacrylate (a2) having an alkyl group having from 1 to 4 carbon atoms and a crosslinkable monomer (a4), and a hard polymer (B) obtained by polymerizing a monomer (b) comprising an alkyl methacrylate having an alkyl group having from 1 to 4 carbon atoms in the presence of the elastic polymer (A).

5. The acrylic resin composition according to claim 4, wherein Tg of the hard polymer (B) is 85 C. or higher.

6. The acrylic resin composition according to claim 1, wherein the elastic polymer (A) is a graft polymer obtained from a grafting agent, wherein a content of a grafting agent unit in 100% by mass of the elastic polymer (A) is 1.3% by mass or more.

7. The acrylic resin composition according to claim 1, further comprising an elastic modulus in bending of a test piece having a thickness of 4 mm calculated from a bending stress measured in conformity to ISO 178 is 400 MPa or more.

8. The acrylic resin composition according to claim 1, further comprising a MFR value under conditions of a temperature of 230 C. and a load of 5.0 kg measured in conformity to ASTM D-1238 is 1 g/10 min or more.

9. The acrylic resin composition according to claim 1, wherein a content of the sum of a monomer (a1) unit and a monomer (a2) unit in the elastic polymer (A) is 80% by mass or more.

10. The acrylic resin composition according to claim 1, wherein a mass ratio of monomer (a1) unit: monomer (a2) unit is from 50:50 to 100:0 when a total mass of the monomer (a1) unit and the monomer (a2) unit in the elastic polymer (A) is 100.

11. The acrylic resin composition according to claim 4, wherein a content of a monomer (b) unit in a hard polymer (B) is 70% by mass or more.

12. The acrylic resin composition according to claim 1, wherein 2-[2-hydroxy-3,5-bis(,-dimethylbenzyl)phenyl]-2H-benzotriazole and/or 2-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol is present in the rubber-containing multistage polymer (I).

13. The acrylic resin composition according to claim 1, comprising: a thermoplastic polymer (II) comprising a polymer comprising a methyl methacrylate unit at from 50 to 100% by mass and a unit of one or more kinds of other vinyl monomers copolymerizable with methyl methacrylate at a range from 0 to 50% by mass and having a reduced viscosity of from 0.2 to 2 dL/g and the rubber-containing multistage polymer (I).

14. A method for manufacturing a rubber-containing multistage polymer (I) comprising an elastic polymer (A) and a hard polymer (B), the method comprising: obtaining the elastic polymer (A) by polymerizing a monomer (a) containing one or more kinds of monomers selected from the group consisting of an alkyl acrylate (a1) having an alkyl group having from 1 to 8 carbon atoms and an alkyl methacrylate (a2) having an alkyl group having from 1 to 4 carbon atoms and a crosslinkable monomer (a4), and then obtaining the hard polymer (B) by polymerizing a monomer (b) comprising an alkyl methacrylate having an alkyl group having from 1 to 4 carbon atoms in the presence of the elastic polymer (A), wherein a content of a grafting agent unit in 100% by mass of the elastic polymer (A) is 1.3% by mass or more, and a content of the elastic polymer (A) in 100% by mass of the rubber-containing multistage polymer (I) is 30% by mass or more.

15. The method for manufacturing a rubber-containing multistage polymer (I) according to claim 14, wherein the method satisfies the following (5) to (7); (5) a content of a sum of a monomer (a1) unit and a monomer (a2) unit in the elastic polymer (A) is 80% by mass or more, (6) a ratio of monomer (a1) unit/monomer (a2) unit in the elastic polymer (A) is from 50 to 100% by mass/from 0 to 50% by mass, and (7) a content of a monomer (b) unit in the hard polymer (B) is 70% by mass or more.

16. A rubber-containing multistage polymer (I) obtained by the manufacturing method according to claim 14.

17. An acrylic resin composition comprising the rubber-containing multistage polymer (I) according to claim 16.

18. A molded body obtained by molding the acrylic resin composition according to claim 1.

19. An acrylic resin film obtained by molding the acrylic resin composition according to claim 1.

20. A method for manufacturing an acrylic resin film comprising: forming the acrylic resin composition according to claim 1 into a film through calendering.

21. A laminate formed by laminating the acrylic resin film according to claim 19 on a substrate.

22. A laminate formed by laminating the acrylic resin film according to claim 19 on a metal member.

Description

EXAMPLES

[0182] Hereinafter, the invention will be more specifically described with reference to Examples, but the invention is not limited thereto. The term parts in the following description denotes parts by mass.

[0183] Abbreviations in Examples mean materials presented in Table 1.

TABLE-US-00001 TABLE 1 Abbreviation Material MMA Methyl methacrylate nBA n-Butyl acrylate AMA Allyl methacrylate BDMA 1,3-Butylene glycol dimethacrylate OTP Sodium di-2-ethylhexylsulfosuccinate (trade name: PELEX OT-P manufactured by Kao Corporation) RS610 Sodium mono-n-dodecyloxytetraoxyethylene phosphate (trade name: PHOSPHANOL RS-610NA manufactured by TOHO CHEMICAL INDUSTRY Co., Ltd.) nOM n-Octyl mercaptan t BH t-Butyl hydroperoxide CHP Cumene hydroperoxide EDTA Ethylenediaminetetraacetic acid disodium salt

[0184] First, Examples of the first group will be described.

Example 1

[0185] [Production of Rubber-Containing Multistage Polymer (I)-1]

[0186] Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 195 parts of deionized water was introduced, a mixture prepared by premixing monomer components of 0.3 part of MMA, 4.7 parts of nBA, and 0.08 part of AMA, 1 part of OTP, and 0.025 part of tBH was then introduced thereinto, and the temperature thereof was raised to 75 C.

[0187] After the temperature was raised, a mixture of 5 parts of deionized water, 0.2 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate, and 0.0003 part of EDTA was introduced thereinto at one time to initiate the polymerization. The reaction was continued for 15 minutes after the peak temperature was confirmed to complete the polymerization of the first elastic polymer (A1).

[0188] Subsequently, monomer components of 3.0 parts of MMA, 47.0 parts of nBA, and 0.82 part of AMA, and 0.25 part of tBH were added dropwise into the polymerization vessel over 120 minutes. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the second elastic polymer (A2).

[0189] Subsequently, monomer components (components for hard polymer (B)) of 40.5 parts of MMA, 4.5 parts of nBA, 0.061 part of tBH, and 0.3 part of nOM were added dropwise into the polymerization vessel over 120 minutes, and the reaction was continued for 60 minutes, thereby obtaining the latex-like rubber-containing multistage polymer (I)-1.

Examples 2 to 9 and Comparative Examples 1 to 3

[0190] [Production of rubber-containing multistage polymers (I)-2 to 9 and (I)-101 to 103]

[0191] The latex-like rubber-containing multistage polymers (I)-2 to 9 and (1)-101 to 103 were obtained in the same manner as in Example 1 except that the amounts of components added were as presented in Table 2-1, Table 2-2, and Table 2-5.

Comparative Example 4

[0192] [Production of Rubber-Containing Multistage Polymer (I)-104]

[0193] The latex-like rubber-containing multistage polymer (I)-104 was obtained in the same manner as in Example 1 except that components of the monomer of the intermediate polymer (C) and the like presented in Table 2-5 were added dropwise into the polymerization vessel over 45 minutes in the middle of manufacture and the reaction was then maintained for 60 minutes, and the amounts of components added were as presented in Table 2-5.

[0194] [Production of Powdery Acrylic Resin Composition]

[0195] The latex-like rubber-containing multistage polymers (I)-1 to 9 and (I)-101 to 104 were added dropwise into 100 parts of hot water containing 0.8 part of calcium acetate at 70 C. to coagulate the latex. Furthermore, the temperature of the resultants was raised to 95 C. and held for 5 minutes so as to solidify the resultants. The coagulated products thus obtained were separated, washed, and dried for 24 hours at 70 C., thereby obtaining powdery acrylic resin compositions.

[0196] [Evaluation on Physical Properties]

[0197] The powdery acrylic resin compositions thus obtained were subjected to the following respective evaluations, and the results thereof are presented in Table 3 and Table 4.

[0198] [1. Total Light Transmittance]

[0199] The powdery acrylic resin composition was sandwiched between SUS plates, heat-melted for 10 minutes at a temperature of 200 C. and a pressure of 0 MPa and then pressurized for 5 minutes at a temperature of 200 C. and a pressure of 5 MPa by using the press molding machine manufactured by Shoji Tekko Co., Ltd. Thereafter, the resultant was cooled for 5 minutes while applying a pressure of 2 MPa thereto, thereby obtaining a molded body having a thickness of 1 mm.

[0200] The total light transmittance was measured by using this as a test piece and the haze meter (HR-100) manufactured by MURAKAMI COLOR RESEARCH LABORATORY CO., Ltd. in conformity to ISO 13468.

[0201] [1. Haze]

[0202] A molded body having a thickness of 1 mm was obtained in the same manner as in the case of [1. Total light transmittance]. The haze was measured by using this as a test piece and the haze meter (HR-100) manufactured by MURAKAMI COLOR RESEARCH LABORATORY CO., Ltd. in conformity to ISO 14782.

[0203] [1. Whiteness Degree (W)]

[0204] A molded body having a thickness of 1 mm was obtained in the same manner as in the case of [1. Total light transmittance]. This molded body was cut so as to have a length of 80 mm and a width of 15 mm, thereby producing the test piece 1.

[0205] The value of whiteness degree W1 of the test piece 1 was measured by using the spectroscopic color-difference meter SE-2000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.

[0206] Next, the test piece 1 was pulled from the initial distance between chucks of 25 mm to the final distance between chucks of 35 mm at a tension rate of 500 mm/min and a temperature of 23 C. by using the Strograph T manufactured by Toyo Seiki Seisaku-Sho, Ltd. in conformity to ISO 527, and the value of whiteness degree W2 of the test piece 1 was measured by using the spectroscopic color-difference meter SE-2000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.

[0207] The difference W (=W2W1) in whiteness degree before and after the tension test was determined.

[0208] [1. Tg]

[0209] A molded body having a thickness of 1 mm was obtained in the same manner as in the case of [1. Total light transmittance]. This molded body was cut so as to have a width of 6 mm, thereby producing a test piece.

[0210] The value of tan (loss tangent) at each temperature was calculated by the equation tan =E/E using the values of the storage elastic modulus (E) and loss elastic modulus (E) measured in a tension mode under the conditions of an initial distance between chucks of 20 mm, a measurement frequency of 0.1 Hz, a measurement temperature range of from 90 to 150 C., a temperature increase rate of 2 C./min, a nitrogen stream of 200 mL/min by using the dynamic viscoelasticity measuring apparatus EXSTAR DMS6100 manufactured by Seiko Instruments Inc. in conformity to ISO 6721-4.

[0211] Next, the value of tan was plotted with respect to the temperature to have two peaks. The temperature corresponding to the peak which appeared on the lower temperature side between the two peaks was adopted as the Tg of the elastic polymer. In addition, the temperature corresponding to the peak which appeared on the higher temperature side was adopted as the Tg of the hard polymer (B).

[0212] [1. Elastic Modulus in Bending]

[0213] A molded body was obtained in the same manner as in the case of [1. Total light transmittance], but the thickness thereof was 4 mm. This molded body was cut so as to have a length of 80 mm and a width of 10 mm, thereby producing a test piece.

[0214] A bending test was conducted at a temperature of 23 C., a distance between supporting points of 64 mm, and a test speed of 2 mm/min by using the Strograph T manufactured by Toyo Seiki Seisaku-Sho, Ltd. in conformity to ISO 178, and the elastic modulus in bending was calculated from the bending stress measured in the amount of deflection of 0.088 mm and 0.44 mm.

[0215] Next, Examples of the second group will be described.

Example 11

[0216] [Production of Rubber-Containing Multistage Polymer (I)-11]

[0217] Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 195 parts of deionized water was introduced, a mixture prepared by premixing components of the monomer of the first elastic polymer (A1) and the like presented in Table 2-3 was then introduced thereinto, and the temperature thereof was raised to 75 C.

[0218] After the temperature was raised, a mixture of 5 parts of deionized water, 0.2 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate, and 0.0003 part of EDTA was introduced into the polymerization vessel at one time to initiate the polymerization. The reaction was continued for 15 minutes after the peak temperature was confirmed to complete the polymerization of the first elastic polymer (A1).

[0219] Subsequently, components of the monomer of the second elastic polymer (A2) and the like presented in Table 2-3 were added dropwise into the polymerization vessel over 150 minutes. Thereafter, the reaction was then continued for 60 minutes to complete the polymerization of the second elastic polymer (A2).

[0220] Subsequently, components of the monomer of the hard polymer (B) and the like presented in Table 2-3 were added dropwise into the polymerization vessel over 120 minutes, and the reaction was continued for 60 minutes, thereby obtaining the latex-like rubber-containing multistage polymer (I)-11.

[0221] Through a filter having a mesh of 50 m, 100 parts of the latex-like rubber-containing multistage polymer (I)-11 thus obtained was filtered and added dropwise into 100 parts of hot water containing 2.5 parts of calcium acetate at 80 C. to coagulate the latex. Furthermore, the temperature of the resultant was raised to 95 C. and held for 5 minutes so as to solidify the resultant. The coagulated product thus obtained was separated, washed, and dried for 24 hours at 75 C., thereby obtaining a powdery acrylic resin composition.

Examples 12 to 14

[0222] [Production of Rubber-Containing Multistage Polymers (I)-12 to 14]

[0223] The rubber-containing multistage polymers (I)-12 to 14 were produced in the same manner as in Example 11 except that the amounts of components added were as presented in Table 2-3.

[0224] Thereafter, powdery acrylic resin compositions were obtained in the same manner as in Example 11.

Examples 15 to 17 and Comparative Example 11

[0225] [Production of rubber-containing multistage polymers (I)-15 to 17 and (I)-111]

[0226] The rubber-containing multistage polymers (I)-15 to 17 and (I)-111 were obtained in the same manner as in Example 11 except that components of the monomer of the intermediate polymer (C) and the like presented in Table 2-3 and Table 2-5 were added dropwise into the polymerization vessel over 45 minutes in the middle of manufacture and the reaction was then maintained for 60 minutes, and the amounts of components added were as presented in Table 2-3 and Table 2-5.

[0227] Thereafter, powdery acrylic resin compositions were obtained in the same manner as in Example 11.

Blending Examples 11 to 17 and Comparative Blending Example 11

[0228] The powdery acrylic resin composition thus obtained was mixed with various kinds of aids such as an ultraviolet absorber, a light stabilizer, and an antioxidant in the blending ratio presented in Table 5 by using the Henschel mixer, this powder mixture was melt-kneaded at a cylinder temperature of from 100 to 240 C. and a die temperature of 240 C. by using the de-airing extruder (TEM-35: manufactured by TOSHIBA MACHINE CO., LTD.) to obtain a pellet.

[0229] Subsequently, the pellets were dried for a whole day and night at 80 C. and molded into a film having a thickness of from 0.05 to 0.1 mm at a cylinder temperature of from 200 to 240 C., a T die temperature of 250 C., and a cooling roll temperature of 80 C. by using a non-bent screw type extruder (L/D=26) which had a diameter of 40 mm and to which a T-die having a width of 300 mm was mounted.

[0230] The various kinds of aids presented in Table 5 are as follows.

[0231] LA-31RG: ultraviolet absorber (manufactured by ADEKA PALMAROLE)

[0232] Tinuvin 234: ultraviolet absorber (manufactured by BASF Japan Ltd.)

[0233] LA-57G: light stabilizer (manufactured by ADEKA PALMAROLE)

[0234] Chimassorb 2020: light stabilizer (manufactured by BASF Japan Ltd.)

[0235] Thermoplastic polymer (II)-1: the details will be described later

[0236] Thermoplastic polymer (II)-2: the details will be described later

[0237] Aerosil R976: antiblocking agent (manufactured by NIPPON AEROSIL CO., LTD.)

[0238] Irganox 1076: antioxidant (manufactured by BASF Japan Ltd.)

[0239] [Production of Thermoplastic Polymer (II)-1]

[0240] Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 222 parts of deionized water, 3.9 parts of dipotassium alkenylsuccinate, 80 parts of MMA, 20 parts of nBA, and 0.0008 part of nOM were introduced at one time, and the temperature thereof was raised to 45 C.

[0241] Furthermore, 6 parts of deionized water and 0.15 part of potassium persulfate were added thereto at one time, and the temperature thereof was raised to 55 C. Thereafter, the reaction was continued for 2.5 hours, thereby obtaining the latex-like thermoplastic polymer (II)-1.

[0242] This latex was added dropwise into hot water containing calcium acetate so as to be coagulated. The coagulated product was separated, washed, and dried, thereby obtaining the thermoplastic polymer (II)-1.

[0243] The reduced viscosity of the thermoplastic polymer (II)-1 was 0.82 dL/g.

[0244] [Production of Thermoplastic Polymer (II)-2]

[0245] Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 143 parts of deionized water, 1.1 parts of dipotassium alkenylsuccinate, 40 parts of MMA, 2 parts of nBA, and 0.0026 part of nOM were introduced at one time, and the temperature thereof was raised to 50 C.

[0246] Furthermore, 6 parts of deionized water and 0.15 part of potassium persulfate were added thereto at one time, and the temperature thereof was raised to 60 C. Thereafter, the reaction was continued, 44 parts of MMA, 14 parts of nBA, and 0.0087 part of nOM were added thereto dropwise over 90 minutes when the temperature thereof was once raised and then dropped to 70 C., and the reaction was continued for 2 hours, thereby obtaining the latex-like thermoplastic polymer (II)-2.

[0247] This latex was added dropwise into hot water containing calcium acetate so as to be coagulated. The coagulated product was separated, washed, and dried, thereby obtaining the thermoplastic polymer (II)-2.

[0248] The reduced viscosity of the thermoplastic polymer (II)-2 was 0.38 dL/g.

[0249] [Evaluation on Physical Properties]

[0250] The following respective evaluations were conducted, and the results thereof are presented in Table 6 and Table 7.

[0251] [2. Total Light Transmittance]

[0252] The total light transmittance was measured by using the powder mixtures prepared in Blending Examples 11 to 17 and Comparative Blending Example 11 in the same manner as in the [1. Total light transmittance].

[0253] [2. Haze]

[0254] The haze was measured by using the powder mixtures prepared in Blending Examples 11 to 17 and Comparative Blending Example 11 in the same manner as in the [1. Haze].

[0255] [2. Whiteness Degree (W)]

[0256] A film which had a thickness of from 0.05 to 0.1 mm and was formed by a T-die method was cut so as to have a width of 15 mm, thereby producing the test piece 2.

[0257] The difference in whiteness degree W (=W2 W1) was determined by using the test piece 2 in the same manner as in the [1. Whiteness degree (W)].

[0258] [2. Tensile Rupture Elongation]

[0259] Films formed by using the powder mixtures prepared in Blending Examples 11 to 17 and Comparative Blending Example 11 by a T-die method were molded so as to have a thickness of from 0.05 to 0.1 mm and a width of 15 mm in conformity to ISO 527-3, and these were used as the test piece 3.

[0260] Condition (1): the rupture elongation when the test piece 3 is stretched under the conditions of a tension rate of 50 mm/min and a temperature of 0 C. is presented in the column for rupture elongation % MD/TD (0 C.) in Table 7

[0261] Condition (2): the rupture elongation when the test piece 3 is stretched under the conditions of a tension rate of 50 mm/min and a temperature of 23 C. is presented in the column for rupture elongation % MD/TD (23 C.) in Table 7.

[0262] [2. Fluidity (MFR)]

[0263] The MFR value was measured by using the powder mixtures prepared in Blending Examples 11 to 17 and Comparative Blending Example 11 under the conditions of a temperature of 230 C. and a load of 5.0 kg in conformity to ASTM D-1238.

[0264] Next, Examples of the third group will be described.

Blending Examples 21 to 25 and Blending Example 11

[0265] The powdery acrylic resin composition of the rubber-containing multistage polymer (I)-11 was mixed with various kinds of aids such as an ultraviolet absorber, a light stabilizer, and an antioxidant in the blending ratio presented in Table 5 by using the Henschel mixer, this powder mixture was melt-kneaded at a cylinder temperature of from 100 to 240 C. and a die temperature of 240 C. by using the de-airing extruder (TEM-35: manufactured by TOSHIBA MACHINE CO., LTD.) to obtain a pellet.

[0266] Subsequently, the pellets were dried for a whole day and night at 80 C. and molded into a film having a thickness of 0.05 mm at a cylinder temperature of from 220 to 250 C., a T die temperature of 250 C., and a cooling roll temperature of 80 C. by using a non-bent screw type extruder (L/D=26) which had a diameter of 40 mm and to which a T-die having a width of 300 mm was mounted.

[0267] The various kinds of aids presented in Table 8 are as follows.

[0268] LA-31RG: ultraviolet absorber (manufactured by ADEKA PALMAROLE)

[0269] Tinuvin 234: ultraviolet absorber (manufactured by BASF Japan Ltd.)

[0270] Tinuvin 1600: ultraviolet absorber (manufactured by BASF Japan Ltd.)

[0271] Tinuvin 1577: ultraviolet absorber (manufactured by BASF Japan Ltd.)

[0272] Thermoplastic polymer (II)-2: described above

[0273] LA-57G: light stabilizer (manufactured by ADEKA PALMAROLE)

[0274] Irganox 1076: antioxidant (manufactured by BASF Japan Ltd.)

[0275] [Evaluation on Physical Properties]

[0276] The following respective evaluations were conducted, and the results thereof are presented in Table 9.

[0277] [3. Total Light Transmittance]

[0278] The total light transmittance was measured by using the powder mixtures thus obtained in the same manner as in the [1. Total light transmittance].

[0279] The measurement results of the total light transmittance were the same as that in Blending Example 11 since the rubber-containing multistage polymer (I)-11 was used in the evaluation as in Blending Example 11.

[0280] [3. Haze]

[0281] The haze was measured by using the powder mixtures thus obtained in the same manner as in the [1. Haze].

[0282] The measurement results of the haze were the same as that in Blending Example 11 since the rubber-containing multistage polymer (I)-11 was used in the evaluation as in Blending Example 11.

[0283] [3. Whiteness Degree (W)]

[0284] The difference in whiteness degree (W) was determined by using the powder mixtures thus obtained in the same manner as in the [1. Whiteness degree (W)]. The measurement results of the whiteness degree W were the same as that in Blending Example 11 since the rubber-containing multistage polymer (I)-11 was used in the evaluation as in Blending Example 11.

[0285] [3. Resistance to Bleed Out]

[0286] A film formed by a T-die method was humidified and heated for 10 hours at 80 C. and 90 RH %, and the presence or absence of bleed out was visually evaluated.

[0287] : bleeding out is not observed and film is not clouded.

[0288] x: bleeding out is observed and film is clouded in white.

[0289] The acrylic resin compositions of Blending Examples 21 to 24 have favorable weathering resistance and favorable resistance to bleed out as it is blended with an ultraviolet absorber. Hence, it is possible to obtain a molded body suitable for a processing at room temperature even in applications which require high design property. In addition, the additives and the like do not bleed out, and thus deterioration in appearance is not observed even when the molded body is stored for a long period of time.

[0290] Cracking does not occur at the curved portion when the molded bodies obtained from the acrylic resin compositions of Blending Examples 21 to 24 are bonded to a substrate such as a steel plate and this substrate is then bent at room temperature so as to be fit to the shape of various kinds of members such as a window frame. Hence, it does not occur that the substrate exposed by cracking is exposed to sunlight and decomposed.

[0291] Bleeding out of the additive is observed in the acrylic resin compositions of Blending Example 25 and Blending Example 11, and thus the appearance of the molded bodies formed therefrom is poor. In addition, it is difficult to apply the molded bodies to a member required to exhibit high design property since the appearance of the molded bodies deteriorates due to bleeding of the additive even when the molded bodies are stored for a long period of time.

[0292] Next, Examples of the fourth group will be described.

Example 31

[0293] [Production of Rubber-Containing Multistage Polymer (I)-31]

[0294] Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 195 parts of deionized water was introduced, a mixture prepared by premixing monomer components of 0.3 part of MMA, 4.7 parts of nBA, and 0.03 part of AMA, 1 part of OTP, and 0.013 part of tBH was then introduced thereinto, and the temperature thereof was raised to 75 C. After the temperature was raised, a mixture of 5 parts of deionized water, 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate, and 0.0003 part of EDTA was introduced thereinto at one time to initiate the polymerization. The reaction was continued for 15 minutes after the peak temperature was confirmed to complete the polymerization of the first elastic polymer (A1).

[0295] Subsequently, monomer components of 3.0 parts of MMA, 47.0 parts of nBA, 0.27 part of AMA, and 0.13 part of tBH were added dropwise into the polymerization vessel over 120 minutes. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the second elastic polymer (A2).

[0296] Subsequently, monomer components (components for hard polymer (B)) of 40.5 parts of MMA, 4.5 parts of nBA, 0.061 part of tBH, and 0.3 part of nOM were added dropwise into the polymerization vessel over 120 minutes, and the reaction was continued for 60 minutes, thereby obtaining the latex-like rubber-containing multistage polymer (I)-31.

Examples 32 and 33

[0297] [Production of Rubber-Containing Multistage Polymers (I)-32 and 33]

[0298] The latex-like rubber-containing multistage polymers (I)-32 and 33 were obtained in the same manner as in Example 31 except that the amounts of components added were as presented in Table 2.

[0299] [Production of Powdery Acrylic Resin Composition]

[0300] The latex-like rubber-containing multistage polymer (I) was added dropwise into 100 parts of hot water containing 0.8 part of calcium acetate at 70 C. to coagulate the latex. Furthermore, the temperature of the resultant was raised to 95 C. and held for 5 minutes so as to solidify the resultant. The coagulated product thus obtained was separated, washed, and dried for 24 hours at 70 C., thereby obtaining a powdery acrylic resin composition.

[0301] [Evaluation on Physical Properties]

[0302] The following respective evaluations were conducted, and the results thereof are presented in Table 10.

[0303] [4. Total Light Transmittance]

[0304] The total light transmittance was measured in the same manner as in the [1. Total light transmittance].

[0305] [4. Whiteness Degree (W)]

[0306] The whiteness degree (W) was determined in the same manner as in the [1. Whiteness degree (W)].

[0307] [4. Molecular Weight]

[0308] The mass average molecular weight of the acetone-soluble matter in the rubber-containing multistage polymer (I) was measured.

[0309] The measuring method is as described in the text.

[0310] [4. Elastic Modulus in Bending]

[0311] The elastic modulus in bending was measured in the same manner as in the [1. Elastic modulus in bending].

TABLE-US-00002 TABLE 2-1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Rubber-containing (I)-1 (I)-2 (I)-3 (I)-4 (I)-5 (I)-6 multistage polymer First elastic MMA 0.3 0.3 0.3 0.3 0.3 0.3 polymer (A1) nBA 4.7 4.7 4.7 4.7 4.7 4.7 [parts] AMA 0.08 0.11 0.14 0.27 0.08 0.08 BDMA 0 0 0 0 0.05 0.05 t BH 0.025 0.025 0.025 0.025 0.025 0.025 CHP 0 0 0 0 0 0 OTP 1 1 1 1 1 1 RS610 0 0 0 0 0 0 Second elastic MMA 3.0 3.0 3.0 3.0 3.0 3.6 polymer (A2) nBA 47.0 47.0 47.0 47.0 46.7 56.0 [parts] AMA 0.82 0.82 0.82 0.82 0.82 0.98 BDMA 0 0 0 0 0.5 0.6 t BH 0.25 0.25 0.25 0.25 0.25 0.30 CHP 0 0 0 0 0 0 Grafting agent in 1.64 1.69 1.74 1.98 1.63 1.63 A1 and A2 Intermediate MMA 0 0 0 0 0 0 polymer (C) nBA 0 0 0 0 0 0 [parts] AMA 0 0 0 0 0 0 CHP 0 0 0 0 0 0 Hard MMA 40.5 40.5 40.5 40.5 40.3 31.3 polymer (B) nBA 4.5 4.5 4.5 4.5 4.5 3.5 [parts] tBH 0.061 0.061 0.061 0.061 0.063 0.048 nOM 0.30 0.30 0.30 0.30 0.30 0.23

TABLE-US-00003 TABLE 2-2 Example 7 Example 8 Example 9 Rubber-containing multistage (I)-7 (I)-8 (I)-9 polymer First elastic polymer MMA 0.3 0.3 0.3 (A1) [parts] nBA 4.6 5.1 4.3 AMA 0.08 0.24 0.07 BDMA 0.02 0 0 t BH 0.025 0.028 0.023 CHP 0 0 0 OTP 1 1 1 RS610 0 0 0 Second elastic polymer MMA 3.6 3.3 2.7 (A2) [parts] nBA 55.7 51.3 42.8 AMA 0.98 2.38 0.74 BDMA 1.2 0 0 t BH 0.30 0.28 0.23 CHP 0 0 0 Grafting agent in A1 and A2 [%] 1.62 4.37 1.64 Intermediate polymer MMA 0 0 0 (C) [parts] nBA 0 0 0 AMA 0 0 0 CHP 0 0 0 Hard polymer (B) MMA 31.1 36.0 45.0 [parts] nBA 3.5 4.0 5.0 tBH 0.048 0.056 0.069 nOM 0.23 0.27 0.34

TABLE-US-00004 TABLE 2-3 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Rubber-containing (I)-11 (I)-12 (I)-13 (I)-14 (I)-15 (I)-16 (I)-17 multistage polymer First elastic MMA 0.3 0.3 0.3 0.3 0.2 0.2 0.3 polymer (A1) nBA 4.7 4.7 4.7 4.7 4.5 4.5 4.5 [parts] AMA 0.08 0.08 0.08 0.08 0.05 0.05 0.15 BDMA 0 0 0 0 0.30 0.30 0.20 t BH 0.010 0.025 0.025 0 0 0 0 CHP 0 0 0 0.025 0.025 0.025 0.025 OTP 1 1 1 0 0 0 0 RS610 0 0 0 1.1 1.1 1.1 1.1 Second elastic MMA 3.0 3.0 3.0 3.0 1.0 1.0 1.5 polymer (A2) nBA 47.0 47.0 47.0 47.0 22.5 22.5 22.5 [parts] AMA 0.80 0.80 0.80 0.80 0.75 0.75 0.75 BDMA 0 0 0 0 1.5 1.5 1.0 t BH 0.10 0.25 0.25 0 0 0 0 CHP 0 0 0 0.04 0.02 0.02 0.02 Grafting agent in 1.60 1.60 1.60 1.60 2.67 2.67 3.00 A1 and A2 [%] Intermediate MMA 0 0 0 0 6.0 6.0 6.0 polymer (C) nBA 0 0 0 0 4.0 4.0 4.0 [parts] AMA 0 0 0 0 0.075 0.075 0.075 CHP 0 0 0 0 0.0125 0.0125 0.0125 Hard MMA 40.5 40.5 40.5 40.5 55.2 55.2 55.2 polymer (B) nBA 4.5 4.5 4.5 4.5 4.8 4.8 4.8 [parts] tBH 0.063 0.063 0.063 0.063 0.075 0.075 0.075 nOM 0.30 0.30 0.20 0.30 0.22 0.24 0.20

TABLE-US-00005 TABLE 2-4 Example Example Example 31 32 33 Rubber-containing multistage (I)-31 (I)-32 (I)-33 polymer First elastic polymer (A1) MMA 0.3 0.3 0.3 [parts] nBA 4.7 4.7 4.7 AMA 0.03 0.03 0.03 BDMA 0 0 0 t BH 0.013 0.025 0.025 CHP 0 0 0 OTP 1 1 1 RS610 0 0 0 Second elastic polymer MMA 3.0 3.0 3.0 (A2) [parts] nBA 47.0 47.0 47.0 AMA 0.27 0.27 0.27 BDMA 0 0 0 t BH 0.13 0.25 0.25 CHP 0 0 0 Grafting agent in A1 and A2 [%] 0.55 0.55 0.55 Intermediate polymer (C) MMA 0 0 0 [parts] nBA 0 0 0 AMA 0 0 0 CHP 0 0 0 Hard polymer (B) [parts] MMA 40.5 40.5 40.5 nBA 4.5 4.5 4.5 tBH 0.061 0.061 0.310 nOM 0.15 0.15 0.15

TABLE-US-00006 TABLE 2-5 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 11 Rubber-containing (I)-101 (I)-102 (I)-103 (I)-104 (I)-111 multistage polymer First elastic MMA 0.3 0.3 0.3 0.3 0.3 polymer (A1) nBA 4.7 5.1 5.0 4.6 4.5 [parts] AMA 0.03 0.03 0.06 0.03 0.05 BDMA 0 0 0.22 0 0.20 t BH 0.025 0 0 0 0 CHP 0 0.028 0.028 0.025 0.025 OTP 1 0 0 0 0 RS610 0 1.2 1.2 1.1 1.1 Second elastic MMA 3.0 1.7 1.7 1.5 1.5 polymer (A2) nBA 47.0 25.3 25.0 22.8 22.5 [parts AMA 0.27 0.15 0.28 0.08 0.25 BDMA 0 0 1.1 0 1.0 t BH 0.25 0 0 0 0 CHP 0 0.02 0.02 0.02 0.02 Grafting agent in 0.55 0.55 1.00 0.35 1.00 A1 and A2 [%] Intermediate MMA 0 0 0 6.1 6.0 polymer (C) nBA 0 0 0 4.0 4.0 [parts] AMA 0 0 0 0.076 0.075 CHP 0 0 0 0.0132 0.0125 Hard MMA 40.5 62.2 61.3 55.9 55.2 polymer (B) nBA 4.5 5.4 5.3 4.9 4.8 [parts] tBH 0.061 0.084 0.083 0.076 0.075 nOM 0.30 0.25 0.33 0.22 0.22

TABLE-US-00007 TABLE 3 Elastic polymer in Total light rubber-containing transmittance Test polymer (I) [%] [%] Haze [%] W piece Example 1 55 92 1.5 0.5 1 Example 2 55 92 1 0 1 Example 3 55 92 1.9 0.9 1 Example 4 55 92 1.3 0.3 1 Example 5 55 92 1.8 0 1 Example 6 65 92 1.1 0 1 Example 7 65 92 1.1 0 1 Example 8 60 92 1.1 0 1 Example 9 50 91 1.6 0 1 Comparative 55 79 43 10 1 Example 1 Comparative 32 90 2.7 7.3 1 Example 2 Comparative 33 91 2.6 6.2 1 Example 3 Comparative 29 92 1.9 4.9 1 Example 4

TABLE-US-00008 TABLE 4 Tg [ C.] Elastic modulus in bending [MPa] Example 1 96 450 Example 2 95 460 Example 3 97 490 Example 4 96 450 Example 5 92 560 Example 6 93 200 Example 7 93 210 Example 8 91 400 Example 9 96 510 Comparative Example 1 100 100 Comparative Example 2 Comparative Example 3 104 1100 Comparative Example 4 101

TABLE-US-00009 TABLE 5 Comparative Blending Blending Blending Blending Blending Blending Blending Blending Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 11 Rubber- (I)-11 100.sup. containing (I)-12 100.sup. multistage (I)-13 100.sup. polymer (I)-14 100.sup. (I)-15 100.sup. (I)-16 100.sup. (I)-17 100.sup. (I)-111 100.sup. Additive LA-31RG 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Tinuvin 234 2.1 LA-57G 0.3 0.3 0.3 0.3 0.3 0.3 Chimassorb 0.3 0.34 2020 Thermoplastic 3.sup. polymer (II)-1 Thermoplastic 2.sup. 2.sup. polymer (II)-2 Aerosil R976 0.3 Irganox 1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

TABLE-US-00010 TABLE 6 Elastic polymer in rubber- containing Total light polymer transmittance Haze Test (I) [%] [%] [%] W piece Blending Example 11 55 92 1 0 2 Blending Example 12 55 92 0.9 0.1 2 Blending Example 13 55 90 1.8 0.1 2 Blending Example 14 55 92 1.1 0 2 Blending Example 15 30 91 1.9 0.8 2 Blending Example 16 30 92 1.5 0.3 2 Blending Example 17 30 92 0.7 0.2 2 Comparative Blending 30 92 1.7 1.2 2 Example 11

TABLE-US-00011 TABLE 7 Tensile rupture Tensile rupture elongation elongation [MPa] 0 C. [MPa] 23 C. MD/TD MD/TD MFR [g/10 min] Blending Example 11 76/120 130/140 3.2 Blending Example 12 112/124 137/134 0.5 Blending Example 13 102/112 167/139 0.1 Blending Example 14 110/70 150/130 1.6 Blending Example 15 66/55 108/104 1.0 Blending Example 16 75/86 111/132 1.6 Blending Example 17 60/60 100/70 0.4 Comparative Blending 12/14 137/132 2.9 Example 11

TABLE-US-00012 TABLE 8 Blending Blending Blending Blending Blending Blending Example 11 Example 21 Example 22 Example 23 Example 24 Example 25 (Example 11) Rubber- (I)-11 100.sup. 100.sup. 100.sup. 100.sup. 100.sup. 100.sup. containing multistage polymer Additive LA-31RG 2.1 Tinuvin 234 2.1 2.1 Tinuvin 1600 2.1 2.1 Tinuvin 1577 2.1 Thermoplastic 2.sup. 2.sup. polymer (II)-2 LA-57G 0.3 0.3 0.3 0.3 0.3 0.3 Irganox 1076 0.1 0.1 0.1 0.1 0.1 0.1

TABLE-US-00013 TABLE 9 Resistance to bleed out Blending Example 21 Blending Example 22 Blending Example 23 Blending Example 24 Blending Example 25 X Blending Example 11 X

TABLE-US-00014 TABLE 10 Total light Elastic modulus in W Mw transmittance [%] bending [MPa] Example 31 0 69000 91 210 Example 32 0 68000 91 180 Example 33 0.5 69000 90 240 Example 1 0.5 35000 92 450 Comparative 10 35000 79 100 Example 1

[0312] The following facts have been demonstrated by Examples and Comparative Examples described above.

[0313] The acrylic resin composition of the invention exhibits excellent transparency as the total light transmittance is 90% or more in the case of being molded into a molded body having a thickness of 1 mm, and also the molded body or a film formed by a T-die method exhibits excellent resistance to stress whitening as the difference in whiteness degree W before and after stretching thereof is small to be 1 or less (Examples 1 to 9).

[0314] In addition, the acrylic resin composition of the invention has low haze of 2% and further a favorable rupture elongation value at room temperature and a low temperature. Furthermore, the acrylic resin composition of the invention exhibits excellent flexibility as Tg thereof is 85 C. or higher and the elastic modulus in bending is 400 MPa or more in both directions.

[0315] The acrylic resin composition (blended product) of the invention to which various additives are added also exhibits excellent transparency and resistance to stress whitening, and further, has low haze, a favorable elastic modulus in bending, and a favorable rupture elongation value at room temperature and a low temperature (Blending Examples 11 to 17) in the same manner as the above.

[0316] In addition, the acrylic resin composition (blended product) of the invention to which a certain additive is added exhibits excellent resistance to bleed out as well (Blending Examples 21 to 23).

[0317] Accordingly, by using the acrylic resin composition of the invention, it is possible to manufacture an acrylic resin molded body such as a film to which a problem such as cracking or peeling off and whitening is not caused even when a decorative sheet or the like is bonded to a metal substrate and this substrate is bent at room temperature or a low temperature so as to be fit to the shape of various kinds of members such as an entrance door so as to exhibit high design property.

[0318] Cracking does not occur at the curved portion when this molded body is bonded to a substrate such as a steel plate and this substrate is then bent at room temperature so as to be fit to the shape of various kinds of members such as a window frame, and thus it does not occur that the substrate exposed by cracking is exposed to sunlight and decomposed. In addition, the molded body to be obtained exhibits high heat resistance. Hence, it has a high mechanical strength at a high temperature and is suitable for use in a region where the temperature is high and the sunlight is strong.

[0319] On the other hand, the acrylic resin compositions of Comparative Examples 1 to 4 have a low total light transmittance, high haze, and stress whitening since phase rupture is caused at the time of melt molding due to weak crosslink between the grafts, and thus it is difficult to apply the acrylic resin compositions of Comparative Examples 1 to 4 to a member required to exhibit high design property.

INDUSTRIAL APPLICABILITY

[0320] The molded body obtained by molding the acrylic resin composition of the invention can be used as outer wall building materials such as an agricultural vinyl house, a marking film, a poster, a wallpaper, a foam sheet, an outdoor fabric-backed PVC film, a roofing material of a PVC steel plate, and a siding material, automotive interior and exterior, a coating alternative of furniture and the like, elevator interior, guttering, flooring, corrugated plate, a cosmetic pillar, lighting, and a coating material of a water-related member in a bathroom or a kitchen. In addition, the molded body can also be used in an insulating film, a polarizing film-protecting film to be used in a polarizing plate such as a liquid crystal display, and a retardation film to be used in a retardation plate for viewing angle compensation and retardation compensation.