Two-component-type primer, primer coating film, layered antifouling coating film, and method for preventing base material from being fouled

Abstract

Provided is a two-component-type primer having good adhesive property with a base material, particularly a nonferrous metal, and excellent curability, without containing any chromium compound. The two-component-type primer comprises an epoxy resin, an MXDA (meta-xylenediamine) Mannich modified curing agent, a gypsum (excluding crystal gypsum), and a pigment (excluding gypsum), wherein the volume concentration of a gypsum and a pigment in a dry coating film formed with the primer is 40 to 50%.

Claims

1. A two-component primer, comprising: a base agent component comprising an epoxy resin, and a curing agent component comprising a meta-xylenediamine Mannich modified curing agent, said two-component primer further comprising: a gypsum, excluding crystal gypsum, and a pigment, excluding gypsum, wherein a volume concentration of the gypsum and the pigment in a dry coating film formed with the two-component primer is from 43 to 50%.

2. The two-component primer according to claim 1, wherein said base agent component further comprises at least a part of said gypsum and at least a part of said pigment.

3. A layered antifouling coating film, comprising: a primer coating film obtained from a two-component primer and an antifouling coating film formed on a surface of the primer coating film, wherein the two-component primer comprises a base agent component comprising an epoxy resin, and a curing agent component comprising a meta-xylenediamine Mannich modified curing agent, said two-component primer further comprising: a gypsum, excluding crystal gypsum, and a pigment, excluding gypsum, wherein a volume concentration of the gypsum and the pigment in the primer coating film is from 43 to 50%, and wherein the antifouling coating film comprises a coating film obtained from a silicone resin-comprising composition.

4. The layered antifouling coating film according to claim 3, wherein the epoxy resin comprises a bisphenol epoxy resin.

5. The layered antifouling coating film according to claim 4, wherein the epoxy resin further comprises a novolac epoxy resin.

6. The layered antifouling coating film according to claim 3, wherein a reaction ratio between the epoxy resin and the curing agent is from 0.5 to 1.0.

7. The layered antifouling coating film according to claim 3, wherein a content of the gypsum in the primer is 5 to 300 parts by weight based on 100 parts by weight of the epoxy resin.

8. The layered antifouling coating film according to claim 3, wherein the primer further comprises a curing accelerator.

9. The layered antifouling coating film according to claim 3, wherein the primer further comprises a petroleum resin.

10. A ship propeller, comprising thereon the layered antifouling coating film according to claim 3, wherein said ship propeller is a nonferrous metal ship propeller.

11. A method for preventing a base material from being fouled, the method comprising: covering a surface of the base material with the layered antifouling coating film according to claim 3 in order of the base material, the primer coating film, and the antifouling coating film.

12. The method according to claim 11, wherein the base material is a nonferrous ship propeller.

13. The layered antifouling coating film according to claim 3, wherein the volume concentration of the gypsum and the pigment in the primer coating film is from 45 to 50%.

14. The layered antifouling coating film according to claim 13, wherein the gypsum is hemihydrate gypsum.

15. The layered antifouling coating film according to claim 14, wherein the hemihydrate gypsum is type hemihydrate gypsum.

16. The layered antifouling coating film according to claim 13, wherein the gypsum is anhydrous gypsum.

17. The layered antifouling coating film according to claim 3, wherein the primer comprises (i) a bisphenol A epoxy resin or a bisphenol F epoxy resin and (ii) a novolac type epoxy resin, wherein a rate thereof (i):(ii) is, by mass ratio, 300:100 to 100:300.

18. The layered antifouling coating film according to claim 3, wherein the meta-xylenediamine Mannich modified curing agent comprises a curing agent that is solid at 25 C. and a curing agent that is liquid at 25 C.

19. The layered antifouling coating film according to claim 3, wherein the silicone resin-containing composition is a composition comprising an organopolysiloxane having at least condensation-reactive functional groups.

20. The layered antifouling coating film according to claim 3, wherein said base agent component further comprises at least a part of said gypsum and at least a part of said pigment.

Description

EXAMPLES

(1) The present invention will be more specifically described below referring to examples, but the present invention is not limited to the examples described below. Unless otherwise specified, part(s) in the examples and comparative examples described below refers to part(s) by weight.

(2) Raw materials used in the examples and comparative examples described below are listed in Table 1 below.

(3) TABLE-US-00001 TABLE 1 Heating Kind Product name Manufacturer Substance Remarks residue Epoxy resin EPIROTE Mitsubishi Semisolid bisphenol A Epoxy equivalent weight 394 85% 834 X-85 Chemical type epoxy resin Corporation EPICLON Dainippon Novolac modified epoxy resin Epoxy equivalent weight 457 70% 3100-70 Ink And Chemicals, Inc. Gypsum CALCINED NORITAKE CO, Hemihydrate gypsum 100% PLASTER LIMITED FT-2 (hemihydrate gypsum) AS GYPSUM SAN ESU Anhydrous gypsum 100% (anhydrous GYPSUM gypsum) CO., LTD. Pigment TTK TALC Takehua Extender pigment 100% kaguku kogyo Co., Ltd. TAROXIL-XLO Takn Kogyo Ltd. Coloring pigment 100% MICA Fukuoka Extender pigment 100% POWDER Talc Co., Ltd. 325 MESH Curing M-CURE 400 Seatomer Company Poly functional actyl ester 100% accelerator Coupling KBM-400 Shin-Etsu Silane coupling agent 100% agent Chemical Co., Ltd. Anti- DISPARLON Kusumoto Thixotropic agent 100% sagging 6650 Chemicals, Ltd. agent Plasticizer HIRENOL KOLON Petrolum resin (C9 hydrocarbon) 100% PL-10096 MXDA MAD-204 (A) OHTAKE MXDA Mannich modified amine Active hydrogen equivalent weight: 202 (liquid) 65% Mannich MEISHIN modified CHEMICAL, curing CO. LTD. agent LUCKAMIDE Dainippon MXDA Mannich modified amine Active hydrogen equivalent weight: 80 (liquid) 100% VS-221 Ink And Chemicals, Inc. Curing LUCKAMIDE Dainippon Aliphate modified amine Active hydrogen equivalent weight: 327 60% agent TD-966 Ink And Chemicals, Inc. ANCAMINE Air Products Isophorone diamine Active hydrogen equivalent weight: 92 100% 2074 and Chemicals, modified amine Inc. ANCAMINE Air Products Phenalkamine Active hydrogen equivalent weight: 255 80% 2724 and Chemicals, Inc. IETAMINE Huntsman Polyether amine Active hydrogen equivalent weight: 60 100% D-230 International LLC CARDOLITE Cardolite Ethylene diamine Mannich Active hydrogen equivalent weight: 125 100% NC541LY Corporation modified amine Curing VERSAMINE KOGNIS Tertiary amine 100% accelerator 8830 Remark: The epoxy equivalent weights and active hydrogen equivalent weight described are representation values.

Example 1

(4) (Base Agent Component)

(5) In a 1000 mL plastic container, EPIKOTE 834 X-85 (6.5 parts), EPICLON 5300-70 (6.5 parts), M-CURE 400 (2 parts), HiRENOL PL-1000S (2 parts), xylene (15 parts), n-butyl alcohol (7 parts), TTK TALC (29 parts), CALCINED PLASTER FT-2 (6 parts), MICA POWDER 325-MESH (7 parts), DISPARLON 6650 (1 part), TAROX LL-XLO (2 parts), and KBM-403 (1 part) were blended as listed in Tables 2A and 2B below, and glass beads (200 parts) were added thereto, followed by dispersing the resultant in a paint shaker for 1 hour. The obtained dispersion was filtrated through a 60-mesh filter screen to prepare a base agent component (filtrate).

(6) (Curing Agent Component)

(7) In a 250 mL plastic container, MAD-204 (A) (10 parts), VERSAMINE EH30 (0.1 part), xylene (2.9 parts), and n-butyl alcohol (2 parts) were blended and dispersed in a paint shaker for 10 minutes until being homogeneous. The obtained dispersion was filtrated through a 60-mesh filter screen to prepare a curing agent component (filtrate).

Examples 2 to 9 and Comparative Examples 1 to 10

(8) In each example, a base agent component and a curing agent component were prepared in the same manner as in Example 1 except that the kinds and amounts of the components blended into the base agent component and the curing agent component in Example 1 were changed as listed in Tables 2A and 2B below.

(9) TABLE-US-00002 TABLE 2 Examples Comparative Examples 1 2 3 4 5 6 7 8 9 1 2 3 Base agent EPIKOTE 834 X-85 6.5 13 6.5 8 5 6.5 6.5 6.5 6.5 6.5 6.5 13 component EPICLON 5300-70 6.5 6.5 5 8 6.5 6.5 6.5 6.5 6.5 6.5 13 CALCINED PLASTER FT-2 6 6 6 6 6 10 15 6 6 6 (hemihydrate gypsum) AS GYPSUM 6 (anhydrous gypsum TTK Talc 29 29 29 29 29 25 20 29 29 35 41 23 TAROX LL-XLO 2 2 2 2 2 2 2 2 2 2 2 2 Xylene 15 15 15 15 15 15 15 15 15 15 3 8 n-Butyl alcohol 7 7 7 7 7 7 7 7 7 7 7 7 MICA POWDER 325-MESH 7 7 7 7 7 7 7 7 7 7 7 7 M-CURE 400 2 2 2 2 2 2 2 2 2 2 2 2 KBM-403 1 1 1 1 1 1 1 1 1 1 1 1 DISPARLON 6650 1 1 1 1 1 1 1 1 1 1 1 1 HiRENOL PL-1000S 2 2 2 2 2 2 2 2 2 2 2 2 (Subtotal) 85 85 85 85 85 85 85 85 85 85 85 85 Curing agent MAD-204(a) 10 10 4 4 4 4 4 2 2 4 4 6 component LUCKAMIDE V6-221 3 3 3 3 3 4 4 3 3 5 LUCKAMIDE TD-966 ANCAMINE 2074 ANCAMINE 2724 JEFFAMINE D-230 CARDOLITE NC541LV VERSAMINE EH30 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Xylene 2.9 2.9 5.9 5.9 5.9 5.9 5.9 6.9 6.9 5.9 5.9 1.9 n-Butyl alcohol 2 2 2 2 2 2 2 2 2 2 2 2 (Subtotal) 15 15 15 15 15 15 15 15 15 15 15 15 [Total] 100 100 100 100 100 100 100 100 100 100 100 100 PVC 48 46 48 48 49 49 49 49 49 48 54 33 Reaction ratio 0.8 0.8 0.9 0.9 0.9 0.8 0.8 0.9 0.9 0.9 0.9 0.9 Pencil hardness After drying at 23 C. B 2B HB 2B H HB HB HB HB HB 4B 6B or less for 24 hours After drying at 5 C. 4B 5B 3B 5B 2B 3B 3B 3B 3B 4B 6B or less 6B or less for 24 hours Electrolytic Anti- Appearance Good Good Good Good Good Good Good Good Good Blister Blister Blister protection fouling Adhesive property 0 0 0 0 0 0 0 0 0 6D 6F 6F test coating A (cross-cut test 3 3 3 evaluation) Detachment area None None None None None None None None None Base Base Base material material material surface surface surface Anti- Appearance Good Good Good Good Good Good Good Good Good Blister Blister Blister fouling Adhesive property 0 0 0 0 0 0 0 0 0 6F 6F 6D coating B (cross-aid test 3 3 3 evaluation) Detachment area None None None None None None None None None Base Base Base material material material surface surface surface Comparative Examples 4 5 6 7 8 9 10 Base agent EPIKOTE 834 X-85 12 4 6.5 4 6.5 6.5 6.5 component EPICLON 5300-70 12 4 6.5 4 6.5 6.5 6.5 CALCINED PLASTER FT-2 6 6 6 6 6 6 6 (hemihydrate gypsum) AS GYPSUM (anhydrous gypsum) TTK Talc 29 29 29 29 29 29 29 TAROX LL-XLO 2 2 2 2 2 2 2 Xylene 6 15 15 15 15 15 15 n-Butyl alcohol 5 7 7 7 7 7 7 MICA POWDER 325-MESH 7 7 7 7 7 7 7 M-CURE 400 2 2 2 2 2 2 2 KBM-403 1 1 1 1 1 1 1 DISPARLON 6650 1 1 1 1 1 1 1 HiRENOL PL-1000S 2 2 2 2 2 2 2 (Subtotal) 85 80 85 80 85 85 85 Curing agent MAD-204(a) 5 2 component LUCKAMIDE V6-221 5 1 LUCKAMIDE TD-966 17 ANCAMINE 2074 5 ANCAMINE 2724 11.5 JEFFAMINE D-230 3.7 CARDOLITE NC541LV 7 VERSAMINE EH30 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Xylene 2.9 0.9 7.9 6.4 9.2 5.9 9.9 n-Butyl alcohol 2 2 2 2 2 2 2 (Subtotal) 15 15 15 15 15 15 15 [Total] 100 100 100 100 100 100 100 PVC 38 48 48 48 49 46 53 Reaction ratio 0.9 0.9 0.9 0.9 0.9 0.9 0.4 Pencil hardness After drying at 23 C. 5B 6B or less 6B or less 5B 6B or less 6B or less 5B for 24 hours After drying at 5 C. 5B 6B or less 6B or less 6B or less 6B or less 6B or less 6B or less for 24 hours Electrolytic Anti- Appearance Blister Blister Blister Blister Blister Blister Blister protection fouling 6F 6D 6D 6D 6D 6D 6D test coating A Adhesive property 3 3 3 3 3 3 3 (cross-cut test evaluation) Base Base Base Base Base Base Base Detachment area material material material material material material material surface surface surface surface surface surface surface Anti- Appearance Blister Blister Blister Blister Blister Blister Blister fouling 6D 6D 6D 6D 6D 6D 6D coating B Adhesive property 3 3 3 3 3 3 3 (cross-aid test) evaluation) Base Base Base Base Base Base Base Detachment area material material material material material material material surface surface surface surface surface surface surface

(10) (Measurement of Pencil Hardness in Low-Temperature Drying)

(11) The base agent component and the curing agent component obtained in each example and comparative example were mixed and applied to a glass plate with a film applicator so that the thickness of the dried film was 100 m, and the pencil hardness of the coating film dried at 23 C. or 5 C. for 24 hours was measured to confirm coating film strength.

(12) (Electric Anticorrosion Adhesion Test for Layered Antifouling Coating Film)

(13) The base agent component and the curing agent component obtained in each example and comparative example described above were mixed to obtain a composition.

(14) The obtained composition was spray-coated on a brass plate (150 mm70 mm10 mm) manufactured by Nippon Testpanel Co., Ltd., to which columnar anticorrosion zinc of 2 cm (diameter)1 cm (height) was attached with a lead wire (copper), so that the thickness of the dried film was 100 m, and was dried at 23 C. for 24 hours, and an antifouling coating A or an antifouling coating B was thereafter spray-coated, so that the thickness of the dried film was 100 m, and was dried at 23 C. for 24 hours to obtain a substrate with a layered antifouling coating film. The obtained substrate with the layered antifouling coating film was dipped in 3% salt water at 40 C. to conduct an electric anticorrosion test. The appearance and adhesive property after 60-day dipping were confirmed. The results are listed in Tables 2A and 2B.

(15) For the appearance, the presence or absence of a blister, a crack, and detachment was evaluated by visual observation. The blister was evaluated based on ASTM D-714.

(16) For the adhesive property, a knife test (cross cut test) was conducted to evaluate the presence or absence of a spot with deteriorated adhesive property and to evaluate a detachment area. The evaluation was conducted in four stages by cross-cut test evaluation points represented in Table 3 below.

(17) TABLE-US-00003 TABLE 3 Evaluation point (RN) 0 1 2 3 Detachment area: 50% or more

(18) The antifouling coating A (silicon type antifouling coating) was prepared by mixing 100 parts of organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., 20000 cs/25 C.) represented by the following formula (1), 30 parts of silicone oil SH550 (manufactured by Dow Corning Toray Co., Ltd.), and 30 parts of xylene.

(19) ##STR00005##

(20) The antifouling coating B (hydration decomposition type antifouling coating) was prepared by mixing blending components listed in Table 4 below in blending amounts listed in Table 4 below.

(21) TABLE-US-00004 TABLE 4 Kind Product name Manufacturer Substance Blending amount Resin LAROFLEX MP-25 BASP Poly vinyl chloride/poly- 7 weight parts vinyl acetate copolymer ROSIN Made in China Rosin 7 weight parts Anti-settling agent DISPARLON 4200-20X Kusumoto Chemicals, Ltd. Anti-settling agent 2 weight parts Coloring pigment BENGALA 404 MORISHITA BENGARA KOGYO CO., LTD. Coloring pigment 1 weight part Antifoulant CUPROUS OXIDE NC-301 NISSIN CHEMCO Co., Ltd. Cuprous oxide 45 weight parts COPPER OMADINE Arch Chemicals Copper pyrithione 1 weight part Extender pigment TALC FC-1 Fukuoka Talc Co., Ltd. Extender pigment 3 weight parts Anti-sagging agent DISPARLON 630-20X Kusumoto Chemicals, Ltd. Thixotropic agent 2 weight parts Solvent XYLENE Mitsui Chemicals, Inc. Solvent 27 weight parts METHYL ISOBUTYL KETONE Mitsui Chemicals, Inc. Solvent 5 weight parts