VINYL CHLORIDE-BASED RESIN COMPOSITION FOR POWDER MOLDING, AND VINYL CHLORIDE-BASED RESIN-MOLDED BODY AND LAMINATE

Abstract

A composition of polyvinyl chloride for powder molding may include a polyvinyl chloride (A), a polyvinyl chloride (B), and a phosphate, among others. The polyvinyl chloride (A) may have an average particle diameter of 50 to 500 and the polyvinyl chloride (B) may have an average particle diameter of 0.01 μm or more and less than 50 An average polymerization degree of the polyvinyl chloride (A) may be 1350 or more, and the phosphate may comprise a polyoxyalkylene alkyl phosphate.

Claims

1. A polyvinyl chloride composition for powder molding, comprising: a polyvinyl chloride (A) having an average particle diameter of 50 to 500 μm or less; a polyvinyl chloride (B) having an average particle diameter of 0.01 μm or more and less than 50 μm; a plasticizer; and a phosphate, wherein an average polymerization degree of the polyvinyl chloride (A) is 1350 or more, the phosphate is a polyoxyalkylene alkyl phosphate, and the polyvinyl composition contains the polyvinyl chloride (B) in an amount of 5 to 40 parts by mass, the plasticizer in an amount of 120 to 150 parts by mass, and the polyoxyalkylene alkyl phosphate in an amount of 0.1 to 3.0 parts by mass, with respect to 100 parts by mass of the polyvinyl chloride (A).

2. The polyvinyl chloride composition for powder molding according to claim 1, wherein the plasticizer comprises a trimellitic acid-based plasticizer.

3. The polyvinyl chloride composition for powder molding according to claim 1, wherein the polyoxyalkylene alkyl phosphate is a polyoxyethylene alkyl phosphate.

4. The polyvinyl chloride composition for powder molding according to claim 3, wherein the polyoxyethylene alkyl phosphate has a structure represented by General Formula (1) below:
[R—(CH.sub.2CH.sub.2O).sub.m—O].sub.n—P(═O)(OH).sub.3-n]  (1) where R is an alkyl group with 1 to 20 carbon atoms, m is an integer of 1 to 10, and n is an integer of 1 to 3.

5. The polyvinyl chloride composition for powder molding according to claim 1, to be used in powder slush molding.

6. A polyvinyl chloride molded body obtained by molding a polyvinyl chloride composition for powder molding through powder slush molding, wherein the polyvinyl chloride composition for powder molding comprises: a polyvinyl chloride (A) having an average particle diameter of 50 to 500 μm; a polyvinyl chloride (B) having an average particle diameter of 0.01 μm or more and less than 50 μm; a plasticizer, and a phosphate, wherein an average polymerization degree of the polyvinyl chloride (A) is 1350 or more, wherein the phosphate is a polyoxyalkylene alkyl phosphate, and wherein the polyvinyl chloride composition contains the polyvinyl chloride (B) in an amount of 5 to 40 parts by mass, the plasticizer in an amount of 120 to 150 parts by mass, and the polyoxyalkylene alkyl phosphate in an amount of 0.1 to 3.0 parts by mass, with respect to 100 parts by mass of the polyvinyl chloride (A).

7. A vehicle facing material, comprising the polyvinyl chloride molded body according to claim 6.

8. A laminate obtained by laminating a polyurethane foam layer and a polyvinyl chloride molded body, wherein the polyvinyl chloride molded body is obtained by molding a polyvinyl chloride composition for powder molding through powder slush molding, wherein the polyvinyl chloride composition for powder molding comprises: a polyvinyl chloride (A) having an average particle diameter of 50 to 500 μm; a polyvinyl chloride (B) having an average particle diameter of 0.01 μm or more and less than 50 μm; a plasticizer; and a phosphate, wherein an average polymerization degree of the polyvinyl chloride (A) is 1350 or more, wherein the phosphate is a polyoxyalkylene alkyl phosphate, and wherein the polyvinyl chloride composition contains the polyvinyl chloride (B) in an amount of 5 to 40 parts by mass, the plasticizer in an amount of 120 to 150 parts by mass, and the polyoxyalkylene alkyl phosphate in an amount of 0.1 to 3.0 parts by mass, with respect to 100 parts by mass of the polyvinyl chloride (A).

9. A vehicle interior material, comprising the laminate according to claim 8.

10. The polyvinyl chloride composition for powder molding according to claim 4, wherein in General Formula (1), R is an alkyl group with 4 to 16 carbon atoms, m is an integer of 2 to 10, and n is 2.

11. The polyvinyl chloride composition for powder molding according to claim 1, wherein the average polymerization degree of the polyvinyl chloride (A) is 3800 or less.

12. The polyvinyl chloride molded body according to claim 6, wherein the plasticizer comprises a trimellitic acid-based plasticizer.

13. The polyvinyl chloride molded body according to claim 6, wherein the polyoxyalkylene alkyl phosphate is a polyoxyethylene alkyl phosphate.

14. The polyvinyl chloride molded body according to claim 13, wherein the polyoxyethylene alkyl phosphate has a structure represented by General Formula (1) below:
[R—(CH.sub.2CH.sub.2O).sub.m—O].sub.n—P(═O)(OH).sub.3-n]  (1) where R is an alkyl group with 1 to 20 carbon atoms, m is an integer of 1 to 10, and n is an integer of 1 to 3.

15. The polyvinyl chloride molded body according to claim 14, wherein in General Formula (1), R is an alkyl group with 4 to 16 carbon atoms, m is an integer of 2 to 10, and n is 2.

16. The polyvinyl chloride molded body according to claim 6, wherein the average polymerization degree of the polyvinyl chloride (A) is 3800 or less.

17. The laminate according to claim 8, wherein the plasticizer comprises a trimellitic acid-based plasticizer.

18. The laminate according to claim 8, wherein the polyoxyalkylene alkyl phosphate is a polyoxyethylene alkyl phosphate.

19. The laminate according to claim 18, wherein the polyoxyethylene alkyl phosphate has a structure represented by General Formula (1) below:
[R—(CH.sub.2CH.sub.2O).sub.m—O].sub.n—P(═O)(OH).sub.3-n]  (1) where R is an alkyl group with 1 to 20 carbon atoms, m is an integer of 1 to 10, and n is an integer of 1 to 3.

20. The laminate according to claim 19, wherein in General Formula (1), R is an alkyl group with 4 to 16 carbon atoms, m is an integer of 2 to 10, and n is 2.

Description

EXAMPLES

[0055] Hereinafter, the present invention will be described further specifically by way of examples. However, the present invention is not limited to the following examples.

[0056] Raw materials listed in Table 1 below were used in Examples and Comparative Examples.

[0057] <Polyvinyl Chloride>

[0058] (1) Vinyl chloride homopolymer “S1004D” manufactured by KANEKA CORPORATION, average polymerization degree: 1400, average particle diameter: 159 μm

[0059] (2) Vinyl chloride homopolymer “KS-3000” manufactured KANEKA CORPORAIION, average polymerization degree: 3000, average particle diameter: 170 μm

[0060] (3) Vinyl chloride homopolymer “TH-3800” manufactured by TAIYO VINYL CORPORATION, average polymerization degree: 3800, average particle diameter: 175 μm

[0061] (4) Vinyl chloride homopolymer “S1001T” manufactured by KANEKA CORPORATION, average polymerization degree: 1000, average particle diameter: 210 μm

[0062] (5) Vinyl chloride homopolymer “PSM-31” manufactured by KANEKA CORPORATION, average polymerization degree: 1300, average particle diameter: 10 μm

[0063] <Plasticizer>

[0064] (1) Tri(n-octyl) trimellitate “C-8L” manufactured by ADEKA CORPORATION

[0065] (2) Tri(2-ethylhexyl) trimellitate “C-8” manufactured by ADEKA CORPORATION

[0066] (3) Diisononyl phthalate “DINP” manufactured by CG ESTER CORPORAIION

[0067] <Phosphate>

[0068] (1) Polyoxyethylene alkyl (12-15) ether phosphate (2E.O.) “DDP-2” manufactured by Nikko Chemicals Co., Ltd., diester, wax

[0069] (2) Polyoxyethylene alkyl (12-15) ether phosphate (6E.O.) “DDP-6” manufactured by Nikko Chemicals Co., Ltd., diester, wax

[0070] (3) Polyoxyethylene alkyl (12-15) ether phosphate (10E.O.) “DDP-10” manufactured by Nikko Chemicals Co., Ltd., diester, wax

[0071] (4) Di(2-ethylhexyl) phosphate manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD., liquid

[0072] <Stabilizer>

[0073] (1) Zinc stearate

[0074] (2) Sodium perchlorate

[0075] (3) Hindered amine light stabilizer (HALS)

[0076] (4) Epoxidized soybean oil

[0077] Lubricant (fatty add ester): 1,2-hydroxystearic acid “LS-12” manufactured by ADEKA CORPORATION, semi-wax

Example 1

[0078] <Production of Polyvinyl Chloride Composition for Powder Molding>

[0079] Into a 100 L super mixer (manufactured by KAWATA MFG. Co., Ltd.), 100 parts by mass of the polyvinyl chloride (1), 125 parts by mass of the plasticizer (1), 0.6 parts by mass of the phosphate (1), 5 parts by mass of the stabilizer (1), 1.5 parts by mass of the stabilizer (2), 0.3 parts by mass of the stabilizer (3), 5 parts by mass of the stabilizer (4) and 3 parts by mass of a pigment (black) were introduced and mixed at 70° C. Next, the mixture thus obtained was dried and then cooled to a temperature of 50° C. or lower. Then, 25 parts by mass of the polyvinyl chloride (5) was added thereto and mixed to produce a polyvinyl chloride composition for powder molding (powder).

[0080] <Production of Polyvinyl Chloride Molded Body>

[0081] Powder slush molding using the polyvinyl chloride composition for powder molding obtained as described above was performed using a box-type slush molding machine including a mold for slush molding provided with an embossed flat plate (with a length of 22 cm and a width of 31 cm) and a powder box (with a length of 22 cm, a width of 31 cm, and a depth of 16 cm). Specifically, first, 2 kg of the polyvinyl chloride composition for powder molding was introduced into the powder box, and the mold for slush molding heated to 280° C. was set in the slush molding machine. Next, when the temperature of the mold reached 260° C., the slush molding machine was inverted and the polyvinyl chloride composition for powder molding was held in the mold for about 10 to 12 seconds such that a polyvinyl chloride sheet (also referred to as “PVC sheet”) would have a thickness of 1.0 mm. Then, the slush molding machine was inverted. After 60 seconds, the mold was cooled to 50° C. using cooling water. Next, the PVC sheet was removed from the mold, and a polyvinyl chloride molded body was obtained. The mold release resistance of the PVC sheet when the sheet was removed from the mold was measured in the manner described below.

[0082] <Production of Laminate>

[0083] The PVC sheet obtained as described above was placed on the bottom of a mold for foaming (190 mm×240 mm×11 mm). Next, a raw material solution prepared by mixing 36 g of liquid A containing 4,4′-diphenylmethane-diisocyanate and 78 g of liquid B containing polyether polyol (containing 1.0 mass % of triethylenediamine and 1.6 mass % of water) was poured onto the PVC sheet, and the mold was sealed. After a predetermined period of time, a laminate including the PVC sheet (facing) with a thickness of about 1 mm and a polyurethane foam layer (backing material) with a thickness of about 9 mm laminated on the PVC sheet was collected from the mold.

Examples 2-4

[0084] Polyvinyl chloride compositions for powder molding, polyvinyl chloride molded bodies and laminates of Examples 2-4 were produced in the same manner as in Example 1 except for the kind of the phosphate as indicated in Table 1 and the blending amount of the phosphate as indicated in Table 1.

Example 5

[0085] A polyvinyl chloride composition for powder molding, a polyvinyl chloride molded body and a laminate of Example 5 were produced in the same manner as in Example 2 except for the use of the polyvinyl chloride (2) in place of the polyvinyl chloride (1).

Example 6

[0086] A polyvinyl chloride composition for powder molding, a polyvinyl chloride molded body and a laminate of Example 6 were produced in the same manner as m Example 2 except for the blending amount of the plasticizer as indicated in Table 1.

Examples 7-8

[0087] Polyvinyl chloride compositions for powder molding, polyvinyl chloride molded bodies and laminates of Examples 7-8 were produced in the same manner as in Example 2 except for the kind of the plasticizer as indicated in Table 1.

Example 9

[0088] A polyvinyl chloride composition for powder molding, a polyvinyl chloride molded body and a laminate of Example 9 were produced in the same manner as in Example 1 except for the kind of the phosphate as indicated in Table 1.

Example 10

[0089] A polyvinyl chloride composition for powder molding, a polyvinyl chloride molded body and a laminate of Example 10 were produced in the same manner as in Example 2 except for the use of the polyvinyl chloride (3) in place of the polyvinyl chloride (1).

Comparative Examples 1-2

[0090] Polyvinyl chloride compositions for powder molding, polyvinyl chloride molded bodies and laminates of Comparative Examples 1-2 were produced in the same manner as in Example 2 except for the blending amount of the phosphate as indicated in Table 2 below.

Comparative Examples 3-4

[0091] Polyvinyl chloride compositions for powder molding, polyvinyl chloride molded bodies and laminates of Comparative Examples 3-4 were produced in the same manner as in Example 2 except for the blending amount of the plasticizer as indicated in Table 2 and the use of 1,2-hydroxystearic add in place of phosphate.

Comparative Example 5

[0092] A polyvinyl chloride composition fur powder molding, a polyvinyl chloride molded body and a laminate of Comparative Example 5 were produced in the same manner as in Example 2 except for the blending amount of the plasticizer as indicated in Table 2.

Comparative Example 6

[0093] A polyvinyl chloride composition for powder molding, a polyvinyl chloride molded body and a laminate of Comparative Example 6 were produced in the same manner as in Example 2 except for the kind of the phosphate as indicated in Table 2.

Comparative Example 7

[0094] A polyvinyl chloride composition for powder molding of Comparative Example 7 was produced in the same manner as in Example 2 except for the use of the polyvinyl chloride (4) in place of the polyvinyl chloride (1). The resultant could not be powdered.

Comparative Example 8

[0095] A polyvinyl chloride composition for powder molding, a polyvinyl chloride molded body and a laminate of Comparative Example 8 were produced in the same manner as in Example 10 except for the blending amount of the plasticizer as indicated in Table 2.

[0096] In Examples and Comparative Examples, the average particle diameter and the powder yield of each polyvinyl chloride composition for powder molding were measured as below. Moreover, in Examples and. Comparative Examples, the mold. release resistance, the odor, the tensile elongation at break after heat aging, and the adhesiveness to urethane of each polyvinyl chloride molded body were measured and evaluated as below. Tables 1 and 2 show the results.

[0097] (Powder Yield)

[0098] The powder yield of each polyvinyl chloride composition for powder molding was determined in the following manner The polyvinyl chloride composition for powder molding was passed through a sieve with a mesh (mesh size 42: 355 μm), a mass (Wa) of the composition before passing through the sieve and a mass (Wb) of the composition after passing therethrough were measured, and the measured values were substituted into the formula below

Powder yield (%)=Wb/Wa×100

[0099] (Average Particle Diameter)

[0100] The average particle diameter of each polyvinyl chloride composition for powder molding was measured in accordance with JIS K 7369:2009.

[0101] (Mold Release Resistance)

[0102] In Examples and Comparative Examples, in the removal of the PVC sheet from the mold, the mold was placed on a platform scale such that the vertical surface would face downward. The mold release resistance was determined by measuring a maximum load applied when the PVC sheet was removed from the top to the bottom for a distance of 20 cm at a speed of 0.25 sec/cm. The PVC sheet having a molding stress of 1.3 kg or less was judged to have easy releasability from a slush mold.

[0103] (Odor Evaluation)

[0104] The PVC sheet was cut into 10 cm×15 cm, rolled in a cylindrical shape, and placed in a wide-mouthed 500 mL reagent bottle (made of glass with a fit lid). Then, the bottle was lidded and heated in an oven at 100° C. for 30 minutes. Odor in the reagent bottle was evaluated in a sensory test by three each of men and women (all evaluators were nonsmokers and sensitive to odor). The degree of the odor was measured in accordance with the following criteria. An odor evaluation value is an arithmetic mean (rounded to the first decimal place) of scores given by the evaluators. The value of 3 or higher was judged as acceptable.

[0105] 5: No pungent odor

[0106] 4: Slight pungent odor

[0107] 3: Weak pungent odor

[0108] 2: Pungent odor

[0109] 1: Strong pungent odor

[0110] (Adhesiveness to Urethane)

[0111] The adhesiveness to urethane was evaluated as follows. After a lapse of 12 hours or more at room temperature after production of a laminate, the PVC sheet was peeled off from the polyurethane foam layer. If the polyurethane foam layer adhering to the PVC sheet was completely destroyed, the PVC sheet was judged to have good adhesiveness to urethane. If interfacial peeling was observed even in one part, the PVC sheet was judged to have poor adhesiveness to urethane.

[0112] (Tensile Elongation at Break after Heat Aging)

[0113] The laminate was placed into an oven and heated at 125° C. for 200 hours for heat aging. Thereafter, the PVC sheet was removed from the laminate. The removed PVC sheet was punched into a No. 3 dumbbell shape to obtain a No. 3 dumbbell-shaped sample. Next, the two ends of the sample were held by two chucks (the distance between the chucks was 40 mm). After the sample was kept in a chamber at −10° C. for 3 minutes, the tensile elongation at break (tensile elongation (%) at break after heat aging) of the sample was measured at a tension speed of 200 mm/minute. The PVC sheet having a tensile elongation at break after heat aging of 140% or more was judged as acceptable.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 Polyvinyl chloride 1 (average polymerization degree: 1400; 100 100 100 100 — 100 100 100 100 — (parts by mass) average particle diameter: 159 μm) 2 (average polymerization degree: 3000; — — — — 100 — — — — — average particle diameter: 170 μm) 3 (average polymerization degree: 3800; — — — — — — — — — 100 average particle diameter: 175 μm) 5 (average polymerization degree: 1300; 25 25 25 25 25 25 25 25 25 25 average particle diameter: 10 μm) Plasticizer Tri(n-octyl) trimellitate 125 125 125 125 125 120 — — 125 125 (parts by mass) Tri(2-ethylhexyl) trimellitate — — — — — — 125 — — — Diisononyl phthalate — — — — — — — 125 — — Phosphate Polyoxyethylene alkyl (12-15) ether phosphate 0.6 — — — — — — — — — (parts by mass) (2E.O.) Polyoxyethylene alkyl (12-15) ether phosphate — 0.6 0.2 2.9 0.6 0.6 0.6 0.6 — 0.6 (6E.O.) Polyoxyethylene alkyl (12-15) ether phosphate — — — — — — — — 0.6 — (10E.O.) Polyvinyl chloride Average particle diameter (μm) 197 201 190 191 181 180 203 201 210 190 composition Powder yield (%) 94 97 96 95 99 99 94 95 90 99 (powder) Polyvinyl chloride Mold release resistance (kg) 0.7 0,7 0,8 0.4 0.8 1.0 0.8 0.6 0.8 0.6 molded body Tensile elongation at break after heat aging (%) 200 198 201 203 224 190 201 141 197 142 Adhesiveness to urethane Good Good Good Good Good Good Good Good Good Good Odor 3 3 3 3 3 3 3 3 3 3

TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 4 5 6 7 8 Polyvinyl chloride 1 (average polymerization degree: 1400; 100 100 100 100 100 100 — — (parts by mass) average particle diameter: 159 μm) 3 (average polymerization degree: 3800; — — — — — — — 100 average particle diameter: 175 μm) 4 (average polymerization degree: 1000; — — — — — — 100 — average particle diameter: 210 μm) 5 (average polymerization degree: 1300; 25 25 25 25 25 25 25 25 average particle diameter: 10 μm) Plasticizer Tri(n-octyl) trimellitate 125 125 125 110 110 125 125 160 (parts by mass) Phosphate Polyoxyethylene alkyl (12-15) ether phosphate 0.05 3.2 — — 0.6 — 0.6 0.6 (parts by mass) (6E.O.) Di(2-ethylhexyl) phosphate — — — — — 0.6 — — 1,2-Hydroxystearic acid (parts by mass) — — 0.6 0.6 — — — — Polyvinyl chloride Average particle diameter (μm) 209 190 224 189 182 202 Could 215 composition Powder yield (%) 90 98 85 99 99 94 not be 88 (powder) powdered Polyvinyl chloride Mold release resistance (kg) 1.5 0.4 1.2 1.4 1.6 1.4 0.4 molded body Tensile elongation at break after heat aging (%) 205 200 192 173 176 198 268 Adhesiveness to urethane Good Good Poor Poor Good Good Good Odor 3 2 3 3 3 1 1

[0114] The results of Table 1 indicate that the polyvinyl chloride molded bodies of Examples 1-10, which were produced using the polyvinyl chloride compositions each prepared by blending: 5 parts by mass or more and 40 parts by mass or less of the polyvinyl chloride (B) having an average particle diameter of 0.01 μm or more and less than 50 μm; 120 parts by mass or more and 150 parts by mass or less of the plasticizer; and 0.1 parts by mass or more and 3.0 parts by mass or less of the polyoxyalkylene alkyl phosphate, with respect to 100 parts by mass of the polyvinyl chloride (A) having an average particle diameter of 50 μm or more and 500 μm or less and an average polymerization degree of 1350 or more, had easy releasability from a mold for slush molding, high tensile elongation at break after heat aging, i.e., high heat aging resistance, and high adhesiveness to a polyurethane foam layer, with weak pungent odor. The comparisons between Examples 1, 2, 5, 7, 9 and Example 8 indicate that the use of the trimellitic acid-based plasticizer as a plasticizer further improved the tensile elongation at break after heat aging and resulted in higher heat aging resistance. The comparisons between Examples 2, 5 and Example 10 indicate that the use of the polyvinyl chloride (A) having an average polymerization degree of 3500 or less further improved the tensile elongation at break after heat aging and resulted in higher heat aging resistance.

[0115] On the other hand, the results of Table 2 indicate that the polyvinyl chloride molded body of Comparative Example 1 in which the blending amount of the polyoxyalkylene alkyl phosphate was less than 0.1 parts by mass resulted in the mold release resistance exceeding 1.3 kg, and thus was difficult to be released from a mold for slush molding. The polyvinyl chloride molded body of Comparative Example 2 in which the blending amount of the polyoxyalkylene alkyl phosphate exceeded 3 parts by mass resulted in an odor evaluation value of 2 or lower and had pungent odor. The polyvinyl chloride molded bodies of Comparative Examples 3 and 4 in which the polyoxyalkylene alkyl phosphate was not used and 1,2-hydroxystearic acid was used as a lubricant resulted in poor adhesiveness to the poly urethane foam layer. The polyvinyl chloride molded body of Comparative Example 4 in which the content of the plasticizer was less than 120 parts by mass resulted in the mold release resistance exceeding 1.3 kg and thus was difficult to be released from a mold for slush molding. The polyvinyl chloride molded body of Comparative Example 5 in which the polyoxyalkylene alkyl phosphate was used but the content of the plasticizer was less than 120 parts by mass resulted in the mold release resistance exceeding 1.3 kg, and thus was difficult to be released from a mold for slush molding. The polyvinyl chloride molded body of Comparative Example 6 in which di(2-ethylhexyl) phosphate was used as a phosphate resulted in the mold release resistance exceeding 1.3 kg, and thus was difficult to be released from a mold for slush molding; besides, it resulted in an odor evaluation value of 1 and had strong pungent odor. Comparative Example 7 in which the polyvinyl chloride used had an average particle diameter of 50 μm or more and 500 μm or less but had an average polymerization degree of less than 1350 failed to obtain a powdered polyvinyl chloride composition. The polyvinyl chloride molded body of Comparative Example 8 in which the blending amount of the plasticizer exceeded 150 parts by mass resulted in an odor evaluation value of 1 and had strong pungent odor.