VINYL CHLORIDE SOL-BASED ULTRAVIOLET CURABLE SEALING MATERIAL

Abstract

Provided is a UV curable sealing material containing a vinyl chloride sol as a main ingredient, the film strength of the sealing material being not reduced even in a thin film, the sealing material thus having high resistant pressure against a hem blister. Provided is a vinyl chloride sol composition containing a vinyl chloride-based resin, a UV curable resin having a polar group (functional group), a blocked isocyanate resin, and a filler, the vinyl chloride sol composition being characterized by containing the UV curable resin having a polar group (functional group) in an amount of 20 to 100 parts by weight, the blocked isocyanate resin in an amount of 10 to 50 parts by weight, and the filler in an amount of 50 to 160 parts by weight, relative to 100 parts by weight of the vinyl chloride-based resin.

Claims

1. A vinyl chloride sol composition comprising a vinyl chloride-based resin, a UV curable resin having a polar group (functional group), a blocked isocyanate resin, and a filler, the vinyl chloride sol composition containing the UV curable resin having a polar group (functional group) in an amount of 20 to 100 parts by weight, the blocked isocyanate resin in an amount of 10 to 50 parts by weight, and the filler in an amount of 50 to 160 parts by weight, relative to 100 parts by weight of the vinyl chloride-based resin.

2. The vinyl chloride sol composition according to claim 1, further comprising a urethane acrylate-based UV curable resin in an amount of 20 to 100 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

3. The vinyl chloride sol composition according to claim 1, comprising, as the filler, a silica in an amount of 0 to 100 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

4. The vinyl chloride sol composition according to claim 1, comprising, as the filler, a hydrophobically surface-treated silica in an amount of 0 to 100 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

5. The vinyl chloride sol composition according to claim 1, comprising, as the filler, in addition to the silica and/or the hydrophobically surface-treated silica, a surface-treated calcium carbonate in an amount of 0 to 90 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

6. The vinyl chloride sol composition according to claim 1, comprising a polymerization initiator in an amount of 0.5 to 10 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

7. The vinyl chloride sol composition according to claim 1, comprising a latent curing agent in an amount of 0 to 5 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

8. The vinyl chloride sol composition according to claim 1, comprising, as the vinyl chloride-based resin, two or more vinyl chloride-based resins in mixture.

9. The vinyl chloride sol composition according to claim 1, comprising, as the blocked isocyanate resin, two or more blocked isocyanate resins in mixture.

10. The vinyl chloride sol composition according to claim 1, further comprising a polymer-based plasticizer in an amount of 60 to 210 parts by weight relative to 100 parts by weight of the vinyl chloride-based resin.

11. The vinyl chloride sol composition according to claim 10, comprising, as the polymer-based plasticizer, two or more polymer-based plasticizers in mixture.

Description

EXAMPLES

[0053] The vinyl chloride sol composition according to the present invention will be more specifically described below with reference to examples, but the present invention is not to be limited to the examples as long as the aspect is not beyond the gist of the invention.

[0054] The following materials were used to produce vinyl chloride sol compositions of Examples 1 to 29 and Comparative Examples 1 to 5 according to the formulations shown in Tables 1 to 2.

Formulated Materials

[0055] (1) Vinyl chloride-based resin

[0056] A: Copolymer having a polar group in the molecule (MH-100, manufactured by KANEKA CORPORATION)

[0057] B: Copolymer with vinyl acetate (PCH-175, manufactured by KANEKA CORPORATION)

(2) Acrylic resin

[0058] General purpose acrylic resin (LP-3106, manufactured by MITSUBISHI RAYON CO., LTD.)

(3) UV curable resin

[0059] E: UV curable resin having a polar group (functional group) (M-5700, manufactured by TOAGOSEI CO., LTD.)

[0060] F: Urethane acrylate-based UV curable resin (CN978, manufactured by Arkema)

(4) Polymerization initiator: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (acylphosphine oxide-based) (IRGACURE 819, manufactured by BASF SE)
(5) Latent curing agent (powder) : polyamine-based (EH3731S, manufactured by ADEKA CORPORATION)
(6) Adhesion agent

[0061] G: Amine-based blocked isocyanate-containing urethane prepolymer (XMN3030, manufactured by The Dow Chemical Company)

[0062] H: Oxime-based blocked isocyanate-containing urethane prepolymer (QR9401-1, manufactured by ADEKA CORPORATION)

(7) Filler: Silica (REOLOSIL, manufactured by Tokuyama Corporation)

[0063] Hydrophobically surface-treated silica (RY200S, manufactured by NIPPON AEROSIL Co., Ltd.)

[0064] Surface-treated calcium carbonate (NEOLIGHT SP, manufactured by Takehara Kagaku Kogyo Co., Ltd.)

(8) Plasticizer:

[0065] General purpose plasticizer: DINP (manufactured by J-PLUS Co., Ltd.)

[0066] I: Polymer-based plasticizer :(MESAMOLL, manufactured by LANXESS)

[0067] J: Polymer-based plasticizer :(PN-350N, manufactured by ADEKA CORPORATION)

Methods of Testing and Evaluation

[0068] For Examples and Comparative Examples, evaluation was performed under the following conditions. The results are shown in Table 1.

(1) Viscosity

[0069] The viscosity was measured using a BH viscometer.

[0070] Evaluation criteria: a viscosity of 150 to 190 Pa.Math.s was acceptable.

(2) Evaluation of resistant pressure

[0071] a) Evaluation of adhesion force to electrodeposition paint (after ultraviolet ray curing)

[0072] The composition of each example was applied on a 70 mm×70 mm steel sheet test piece into a thickness of 0.5 mm and was irradiated with an ultraviolet ray (irradiation condition: 2000 mJ/cm.sup.2). Then, the test piece was set in a pressure tester.

[0073] The air pressure in the pressure tester was gradually increased, and while keeping a constant pressure for 30 seconds, occurrence of air leakage was checked. The air pressure (kPa) when air leakage occurred was taken as a value of blister resistant pressure.

[0074] Evaluation criteria: a resistant pressure of 35 kPa or more was acceptable.

(3) Evaluation of coating suitability

[0075] a) Elongation percentage

[0076] The composition of each example was applied on a release paper into a thickness of 2 mm and was irradiated with an ultraviolet ray (irradiation condition: 1000 mJ/cm.sup.2), followed by baking at 140° C. for 25 minutes. Then, the resultant was stamped out with a No. 2 dumbbell, was pulled at a tensile rate of 50 mm/min, and the elongation percentage at break was calculated.

[0077] Evaluation criteria: an elongation percentage of 150% or more was acceptable.

[0078] b) Tensile strength

[0079] The composition of each example was applied on a release paper into a thickness of 2 mm and was irradiated with an ultraviolet ray (irradiation condition: 1000 mJ/cm.sup.2), followed by baking at 140° C. for 25 minutes. Then, the resultant was stamped out with a No. 2 dumbbell, was pulled at a tensile rate of 50 mm/min, and the maximum strength at break was calculated.

[0080] Evaluation criteria: a tensile strength of 0.8 MPa or more was acceptable.

[0081] c) Hardness

[0082] The composition of each example was applied on a release paper into a thickness of 2 mm and was irradiated with an ultraviolet ray (irradiation condition: 1000 mJ/cm.sup.2), followed by baking at 140° C. for 25 minutes. The sheets were stacked and the hardness at a thickness of 10 mm was calculated with a type A hardness tester.

[0083] Evaluation criteria: a hardness of 50 to 90 was acceptable.

[0084] d) Adhesive property to electrodeposition paint

[0085] The composition of each example was applied on a 70 mm×150 mm steel sheet test piece with an electrodeposition coating into a thickness of 2 mm, a width of 10 mm, and a length of 100 mm, and was irradiated with an ultraviolet ray (irradiation condition: 1000 mJ/cm.sup.2), followed by baking at 130° C. for 12 minutes. Then, the adhesiveness with the electrodeposited steel sheet was checked by scraping off with a fingernail.

[0086] Evaluation was performed in terms of which of cohesive failure (Cf), interface failure (adhesive failure (Af)), and cohesive failure with partial interface failure (mixed of Af and Cf) occurred.

[0087] Evaluation criteria: interface failure and cohesive failure with interface failure (cases where interface failure occurred even partially) were unacceptable.

e) Adhesion to paint

[0088] The composition of each example was applied on a 70 mm×150 mm steel sheet test piece with an electrodeposition coating into a thickness of 2 mm, a width of 50 mm, and a length of 100 mm, and was irradiated with an ultraviolet ray (irradiation condition: 1000 mJ/cm.sup.2). Then, an intermediate paint, a top-coating paint, and a clear coat were applied, followed by baking at 130° C. for 12 minutes. Subsequently, the resulting test piece was placed in a thermostatic water bath at 40° C. and was kept for 10 days, and then a cross-cut adhesion test was performed.

[0089] Evaluation criteria: No peeling off (0/100) was acceptable.

[0090] Note that “UVX-T3-405” manufactured by EYE GRAPHICS Co., Ltd. was used in the irradiation with an ultraviolet ray with a distance to the object of 50 mm.

[0091] The results of the above evaluations for Examples 1 to 29 and Comparative Examples 1 to 5 are shown in Tables 1 to 2.

TABLE-US-00001 TABLE 1 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Component 1 2 3 4 5 6 7 8 Vinyl chloride- A: Copolymer having a polar 50 100 75 25 — 50 50 50 based resin group in the molecule B: Copolymer with vinyl acetate 50 — 25 75 100 50 50 50 Acrylic resin — — — — — — — — UV curable resin E: UV curable resin having a 53 53 63 53 53 25 80 20 polar group (Functional group) F: Urethane acrylate-based 53 53 63 53 53 25 26 86 UV curable resin Polymerization initiator 2 2 2 2 2 3 2 2 Latent curing agent — — — — — — — — Adhesion agent G: Amine-based blocked isocyanate- 12 12 12 12 12 12 12 12 containing urethane prepolymer H: Oximer-based blocked isocyanate- 12 12 12 12 12 12 12 12 containing urethane prepolymer Filler Silica 36 36 36 36 36 36 36 36 Silica (hydrophobically 47 47 47 47 47 47 47 47 surface-treated) Surface-treated calcium 37 37 37 37 37 37 37 37 carbonate Plasticizer General purpose 44 44 44 44 44 44 44 44 I: Polymer-based 112 112 112 1122 112 112 112 112 J: Polymer-based 47 47 47 47 47 47 47 47 Additive 8 8 8 8 8 8 8 8 Viscosity BH viscometer 150-190 170 164 157 174 181 185 153 162 Pa .Math. s Adhesion force to electrodeposition t 0.5 mm 35 kPa or more 45 45 45 45 45 35 66 35 paint (after UV ray curing) Elongation percentage 150% or more 140° C. × 25 min. 160% 150% 155% 165% 165% 165% 150% 165% Tensile strength 0.8 MPa or more 1.8 1.8 1.8 1.7 1.8 1.7 1.9 1.7 Hardness 50 to 90 52 52 51 51 50 54 55 51 Adhesive property to electrodeposition 130° C. × 12 min. Cf Cf Cf Cf Cf Cf Cf Cf paint Cohesion failure Cf Adhesion to paint No peeling (0/100) 0/ 1/ 0/ 0/ 0/ 0/ 0/ 0/ 100 100 100 100 100 100 100 100 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 9 10 11 12 13 14 15 16 17 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 — — — — — — — — — 53 53 53 53 53 53 53 53 53 53 53 53 53 53 53 53 53 53 2 2 2 2 2 2 2 2 2 — — — — — — — — — 10 24 40 — 12 12 12 12 12 — — — 24 12 12 12 12 12 36 36 36 36 30 53 — 36 36 47 47 47 47 — 30 83 47 47 37 37 37 37 37 37 37 — 70 44 44 44 44 44 44 44 44 44 112 112 112 112 112 112 112 112 112 47 47 47 47 47 47 47 47 47 8 8 8 8 8 8 8 8 8 186 171 162 166 150 179 158 160 180 45 45 40 40 35 45 45 45 35 160% 155% 160% 165% 180% 150% 200% 165% 160% 1.8 1.9 2.0 1.7 1.3 2.3 1.7 1.7 1.9 53 53 52 50 50 66 52 50 55 Cf Cf Cf Cf Cf Cf Cf Cf Cf 0/ 0/ 0/ 0/ 0/ 0/ 0/ 0/ 0/ 100 100 100 100 100 100 100 100 100

TABLE-US-00002 Ex. Ex. Ex. Ex. Ex. Ex. Component 18 19 20 21 22 23 Vinyl chloride- A: Copolymer having a polar 50 50 50 50 50 50 based resin group in the molecule B: Copolymer with vinyl acetate 50 50 50 50 50 50 Acrylic resin — — — — — — UV curable resin E: UV curable resin having a 53 53 53 53 53 53 polar group (Functional group) F: Urethane acrylate-based 53 53 53 53 53 53 UV curable resin Polymerization initiator 0.5 10 2 2 2 2 Latent curing agent — — 5 — — — Adhesion agent G: Amine-based blocked isocyanate- 12 12 12 12 12 12 containing urethane prepolymer H: Oximer-based blocked isocyanate- 12 12 12 12 12 12 containing urethane prepolymer Silica 36 36 36 36 36 36 Filler Silica (hydrophobically 47 47 47 47 47 47 surface-treated) Surface-treated calcium 37 37 37 37 37 37 carbonate Plasticizer General purpose 44 44 44 44 113 — I: Polymer-based 112 112 112 144 57 156 J: Polymer-based 47 47 47 15 33 47 Additive 8 8 8 8 8 8 Viscosity BH viscometer 150-190 170 171 172 165 150 188 Pa .Math. s Adhesion force to electrodeposition t 0.5 mm 35 kPa or more 40 45 45 45 45 45 paint (after UV ray curing) Elongation percentage 150% or more 140° C. × 25 min. 160% 160% 150% 150% 150% 180% Tensile strength 0.8 MPa or more 1.7 1.8 2.1 1.6 1.5 2.1 Hardness 50 to 90 50 53 55 51 50 57 Adhesive property to electrodeposition 130° C. × 12 min. Cf Cf Cf Cf Cf Cf paint Cohesion failure Cf Adhesion to paint No peeling (0/100) 0/ 0/ 0/ 0/ 0/ 0/ 100 100 100 100 100 100 Ex. Ex. Ex. Ex. Ex. Ex. Component 24 25 26 27 28 29 Vinyl chloride- A: Copolymer having a polar 50 50 50 50 50 50 based resin group in the molecule B: Copolymer with vinyl acetate 50 50 50 50 50 50 Acrylic resin — — — — — — UV curable resin E: UV curable resin having a 53 53 53 53 53 53 polar group (Functional group) F: Urethane acrylate-based 53 53 53 53 53 53 UV curable resin Polymarization initiator 2 2 2 2 2 2 Latent curing agent — — 10 — — — Adhesion agent G: Amine-based blocked isocyanate- 12 12 12 12 12 12 containing urethane prepolymer H: Oximer-based blocked isocyanate- 12 12 12 12 12 12 containing urethane prepolymer Silica 36 83 36 36 36 36 Filler Silica (hydrophobically 47 — 47 47 47 47 surface-treated) Surface-treated calcium 37 37 37 37 37 37 carbonate Plasticizer General purpose 44 44 44 44 136 44 I: Polymer-based 59 112 112 159 47 — J: Polymer-based 100 47 47 — 20 159 Additive 8 8 8 8 8 8 Viscosity BH viscometer 150-190 190 190 175 159 143 212 Pa .Math. s Adhesion force to electrodeposition t 0.5 mm 35 kPa or more 45 45 45 45 45 45 paint (after UV ray curing) Elongation percentage 150% or more 140° C. × 25 min. 175% 100% 140% 145% 130% 180% Tensile strength 0.8 MPa or more 2.0 2.5 1.8 1.6 1.4 2.1 Hardness 50 to 90 55 58 57 50 50 56 Adhesive property to electrodeposition 130° C. × 12 min. Cf Cf Cf Cf Cf Cf paint Cohesion failure Cf Adhesion to paint No peeling (0/100) 0/ 0/ 0/ 0/ 0/ 0/ 100 100 100 100 100 100 Comp. Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 — 50 50 50 50 — 50 50 50 50 100 — — — — — 106 — 53 53 105 — 105 53 53 3 2 2 2 2 42 — — — — 32 12 12 5 12 32 12 12 — 12 175 36 36 36 36 — 47 47 47 47 87 37 37 37 100 112 44 44 44 44 229 112 112 112 112 — 47 47 47 47 8 8 8 8 8 171 144 190 190 190 25 60 20 50 20 150% 100% 190% 130% 130% 1.3 1.0 1.6 1.6 2.2 49 60 49 52 58 Cf Cf Af Af Cf 1/ 0/ 17/ 0/ 0/ 100 100 100 100 100

[0092] As can be seen in the test results of Examples 1 to 29 and Comparative Examples 1 to 5 shown in Tables 1 to 2, the vinyl chloride sol compositions of Examples show good results in each of the items (1) viscosity, (2) evaluation of resistant pressure, and (3) evaluation of coating suitability. Thus, it was found that a UV curable sealing material that contains a vinyl chloride sol as a main ingredient and that has high resistant pressure against a hem blister can be provided without reduction in the film strength of the sealing material.