CN107022273A - Epoxy resin anticorrosive coating composition and anticorrosion film, stacking antifouling coat, antifouling base material and its manufacture method - Google Patents

Epoxy resin anticorrosive coating composition and anticorrosion film, stacking antifouling coat, antifouling base material and its manufacture method Download PDF

Info

Publication number
CN107022273A
CN107022273A CN201710059821.6A CN201710059821A CN107022273A CN 107022273 A CN107022273 A CN 107022273A CN 201710059821 A CN201710059821 A CN 201710059821A CN 107022273 A CN107022273 A CN 107022273A
Authority
CN
China
Prior art keywords
epoxy resin
antifouling
anticorrosive coating
film
coating composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710059821.6A
Other languages
Chinese (zh)
Other versions
CN107022273B (en
Inventor
仁井本顺治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chugoku Marine Paints Ltd
Original Assignee
Chugoku Marine Paints Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=59503500&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN107022273(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Chugoku Marine Paints Ltd filed Critical Chugoku Marine Paints Ltd
Publication of CN107022273A publication Critical patent/CN107022273A/en
Application granted granted Critical
Publication of CN107022273B publication Critical patent/CN107022273B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides stacking antifouling coat, the film is obtained by the way that epoxy resin anticorrosion film and antifouling coat are laminated, the reduction of antifouling property can also be inhibited in the case that the epoxy resin not sufficiently cured stage forms antifouling coat on anticorrosion film and traumatic resistance is excellent, and provide for forming this epoxy resin anticorrosive coating, epoxy resin anticorrosion film and its manufacture method for being laminated antifouling coat etc..Epoxy resin anticorrosive coating composition, be for formed substrate surface from the substrate side stack gradually anticorrosion film, antifouling coat and set stacking antifouling coat in the anticorrosion film epoxy resin anticorrosive coating composition, wherein, contain epoxy resin, solid thermoplastic resin and amine curing agent, the solid thermoplastic resin is solid at normal temperatures, relative to the mass parts of solid constituent 100 of the epoxy resin, the content of the solid thermoplastic resin is more than 50 mass parts.

Description

Epoxy resin anticorrosive coating composition and anticorrosion film, stacking antifouling coat, Antifouling base material and its manufacture method
Technical field
The present invention relates to epoxy resin anticorrosive coating composition, epoxy resin anticorrosion film, by the anticorrosion Stacking antifouling coat that film and the antifouling coat that is laminated thereon are constituted, the antifouling base material with the stacking antifouling coat with And their manufacture method.
Background technology
The boat bottom for submerging seawater for ship carries out regularly Repair Coatings.Common application mode is to implement It will become rusty, film owes the surface treatment (Japanese such as damage portion removing：Handle lowerly) afterwards painting anticorrosion erosion coating, then application it is antifouling apply Material, so as to prevent corrosion and the attachment of marine organisms.In Repair Coatings, it is desirable to which anticorrosion film is attached well with antifouling paint , and the soil resistance for being laminated film for the antifouling paint for requiring anticorrosive coating and being formed on is good.
As the anticorrosive coating, usually using epoxy resin anticorrosive coating.
Exist to have recorded in the substantial amounts of document on epoxy resin anticorrosive coating, such as patent document 1~3 and contain The epoxy resin anticorrosive coating composition of vinyl chloride copolymer thing etc., and using water-disintegrable antifouling paint to by the coating The anticorrosion film of composition formation carries out application.
Recorded in further patent document 2 and 3 and application is carried out to anticorrosion film with antifouling paint, have rated dynamic anti- Dirt and consumption degree.
Prior art literature
Patent document
Patent document 1:International Publication No. 2006/016625
Patent document 2:Japanese Patent Laid-Open 10-259351 publications
Patent document 3:Japanese Patent Laid-Open 11-333374 publications
The content of the invention
The technical problems to be solved by the invention
In the repairerment painting operation process of ship, due to ship shipping schedule adjustment or painting operation when meteorological bar Part etc. and the situation that causes the overlay painting interval of anticorrosive coating and antifouling paint to shorten is more.This shorter overlay painting interval is sometimes Problem can be caused.
Epoxy resin anticorrosive coating is by the reaction of the curing agent such as epoxy resin and amine, solidification and this dry mechanism Form anticorrosion film.It is antifouling in application in the case that the overlay painting interval of epoxy resin anticorrosive coating and antifouling paint is short During coating, anticorrosion film is in reacting insufficient and remaining unreacted epoxy resin for the curing agent such as epoxy resin and amine State.If confirming the coating anti-pollution coating on this anticorrosion film, unreacted epoxy resin oozes out (transfer) extremely Antifouling paint, the under its influence expendable of antifouling coat and soil resistance reduction.Confirm and particularly applied at low temperature In the case of dress, the residual quantity that is slack-off and making unreacted epoxy resin ingredient in film of reacting of epoxy resin and curing agent increases Plus, this influence can further be strengthened.
Further confirm that, the film for being laminated anticorrosion film and antifouling coat described in patent document 2 and 3 Although dynamic soil resistance is excellent, in the evaluation of more strict standing soil resistance, also there is room for improvement.
In addition, by the film of the ship of repairerment application be difficult cause the property of plastic deformation and destruction (following by external pressure Referred to as " traumatic resistance ") it is considered as important.Nearly all it is in application according to loading schedule in the repairerment application of ship The rapid situation sailed and pulled in shore in bulkhead wall after the end of job, if ship pulls in shore and deforms the film after repairerment and be covered with damage Wound, the then painting operation specially carried out is futile.Therefore, the rapid painting that traumatic resistance is presented very preferably after application Film.
But, in the case of carrying out application when waiting low temperature in the winter time, the reactivity of epoxy resin and curing agent is reduced and made The coating strength reduction of anticorrosive coating, the result is that the traumatic resistance of stacking film is also reduced.
It is used as the resolution policy of these problems, it is contemplated that the epoxy in simple reduction epoxy resin anticorrosive coating composition The methods such as resin content, but the coating of this composition is excessive and application operability is poor due to pigment composition, planarization is bad, sets Fat part is short of and can not be continuously formed film, and the outward appearance of gained film, water resistance and anticorrosive property are poor.
In view of this problem of the prior art, it is an object of the invention to provide the ring for forming stacking antifouling coat The epoxy resin anticorrosive coating of oxygen tree lipid anticorrosion film, the stacking antifouling coat is by by epoxy resin anti-corrosion Erosion film and antifouling coat are laminated and obtained, and form antifouling on anticorrosion film even in the epoxy resin not sufficiently cured stage The reduction of antifouling property (particularly standing soil resistance) can also be inhibited in the case of film and traumatic resistance is excellent, and The epoxy resin anticorrosion film used as the anticorrosion film of above-mentioned stacking antifouling coat, the antifouling painting of above-mentioned stacking are provided Film and its manufacture method and antifouling coat and its manufacture method with above-mentioned stacking antifouling coat.
Solve the technical scheme that technical problem is used
To solve the above problems, present inventor is conscientiously studied, find by epoxy resin anticorrosive coating The thermoplastic resin at normal temperatures for solid is more applied in combination while middle use epoxy resin, antifouling property can be formed The reduction of (particularly standing soil resistance), which is inhibited, and traumatic resistance is also excellent has anticorrosion film and antifouling coat Antifouling coat is laminated, so as to complete the present invention.
Think that the mechanism that the effect of the present invention is presented is as follows：
In the anticorrosion film formed by epoxy resin anticorrosive coating, if epoxy resin be not with the curing agent such as amine The unreacted state of reaction, then exist with liquid or semi-solid state.If the coated face on the anticorrosion film of this state Coating is applied, then the solvent-saturated of painting coating is in anticorrosion film, the softening of anticorrosion film, unreacted epoxy infiltration (transfer) to face applies film.On the other hand, even if the solvent-saturated of painting coating is in anticorrosion film, in anticorrosion film The resin for solid is not easy to be transferred to face painting film at normal temperatures.Based on this reason, it is believed that if by solid thermoplastic tree Fat is used with epoxy composite, then the amount of epoxy resin is relative is reduced, therefore, it is possible to by the infiltration of unreacted epoxy resin into Divide and reduce, thereby making the antifouling property (particularly standing soil resistance) for the antifouling coat being layered on anticorrosion film does not reduce, And improve the traumatic resistance of stacking film.
The present invention relates to following [1]~[23].
[1] epoxy resin anticorrosive coating composition, it be used for formed substrate surface from the substrate side successively The epoxy resin anti-corrosion of stacking anticorrosion film, antifouling coat and the anticorrosion film in the stacking antifouling coat that sets Corrosion-inhibiting coating composition, wherein,
Containing epoxy resin (A), solid thermoplastic resin (B) and amine curing agent (C),
The solid thermoplastic resin (B) is solid at normal temperatures,
Relative to the mass parts of solid constituent 100 of the epoxy resin (A), the content of the solid thermoplastic resin (B) More than 50 mass parts.
[2] the epoxy resin anticorrosive coating composition as described in [1], wherein, the epoxy resin (A) is to be selected from It is more than one or both of bisphenol-A, bisphenol-A D and Bisphenol F.
[3] the epoxy resin anticorrosive coating composition as described in [1] or [2], it is further arbitrarily to contain silane The epoxy resin anticorrosive coating composition of coupling agent, wherein, the reaction shown in following formula (1) during without silane coupler Than, containing to the amine curing agent (C) have reactivity silane coupler when following formula (2) shown in reaction ratio, contain The reaction ratio respectively 0.3~0.8 shown in following formula (3) when there is the silane coupler of reactivity to the epoxy resin (A).
[number 1]
(in above formula (1)~(3), the unit of incorporation and equivalent is respectively g and g/eq.)
[4] the epoxy resin anticorrosive coating composition as any one of [1]~[3], wherein, also contain pigment (E)。
[5] the epoxy resin anticorrosive coating composition as described in [4], wherein, the pigment volume concentration shown in following formula (4) is dense It is 25~50% to spend (PVC).
The volume of pigment in pigment volume concentration (PVC) (%)=anticorrosive coating composition/(in anticorrosive coating composition Resinae volume+anticorrosive coating composition in pigment volume) × 100 ... formula (4)
[6] the epoxy resin anticorrosive coating composition as any one of [1]~[5], wherein, the solid thermal Plastic resin (B), which contains, is selected from Petropols, chloridized polyolefin, acrylic resin, butyl acetate resinoid, styrene resin At least one of and vinyl chloride resin.
[7] the epoxy resin anticorrosive coating composition as described in [6], wherein, the vinyl chloride resin is chloroethene Alkene/ethene isobutyl ether copolymer.
[8] the epoxy resin anticorrosive coating composition as any one of [1]~[7], wherein, also contain tertiary amine It is used as curing accelerator (D).
[9] the epoxy resin anticorrosive coating composition as any one of [1]~[8], wherein, also containing attachment Hardening agent (F).
[10] the epoxy resin anticorrosive coating composition as described in [9], wherein, the attachment hardening agent (F) is silicon Alkane coupling agent.
[11] the epoxy resin anticorrosive coating composition as described in [10], wherein, the silane coupler is γ-ring Oxygen propoxypropyl trimethoxy silane.
[12] the epoxy resin anticorrosive coating composition as any one of [1]~[11], wherein, it is described antifouling Film is hydrolysis-type antifouling coat.
[13] epoxy resin anticorrosion film, it is used as stacking gradually anticorrosion from the substrate side in substrate surface Film, antifouling coat and set stacking antifouling coat in the anticorrosion film epoxy resin anticorrosion film, its In,
The epoxy resin anticorrosion film is the epoxy resin anticorrosive coating any one of [1]~[12] The solidfied material of composition.
[14] epoxy resin anticorrosion film, it is used as stacking gradually anticorrosion from the substrate side in substrate surface Film, antifouling coat and set stacking antifouling coat in the anticorrosion film epoxy resin anticorrosion film, its In,
The epoxy resin anticorrosion film is by comprising containing epoxy resin cured product and solid thermoplastic resin (B) Formed by matrix constitute,
The solid thermoplastic resin (B) is solid at normal temperatures,
The content of the solid thermoplastic resin (B) is 7~80 mass %.
[15] the epoxy resin anticorrosion film as described in [14], wherein, also containing epoxy resin (A).
[16] manufacture method of epoxy resin anticorrosion film, it be used as substrate surface from the substrate side successively The epoxy resin anti-corrosion of stacking anticorrosion film, antifouling coat and the anticorrosion film in the stacking antifouling coat that sets The manufacture method of film is lost,
The manufacture method, which is included, to be made as the epoxy resin anticorrosive coating composition any one of [1]~[12] The process of the film solidification of formation.
[17] antifouling coat is laminated, it is from the substrate side to stack gradually anticorrosion film, antifouling painting in substrate surface Film and the stacking antifouling coat set, the anticorrosion film is the epoxy resin anti-corrosion any one of [13]~[15] Lose film.
[18] the stacking antifouling coat as described in [17], wherein, the antifouling coat is hydrolysis-type antifouling coat.
[19] manufacture method of antifouling coat is laminated, it is to stack gradually anticorrosion from the substrate side in substrate surface to apply Film, antifouling coat and set stacking antifouling coat manufacture method,
The manufacture method includes the work for forming the epoxy resin anticorrosion film any one of [13]~[15] Sequence and the process for forming the antifouling coat on the surface of the epoxy resin anticorrosion film.
[20] antifouling base material, wherein, in substrate surface to stack gradually the anticorrosion film from the substrate side, it is described The mode of antifouling coat forms the stacking antifouling coat described in [17] or [18] and constitutes the antifouling base material.
[21] with the antifouling base material described in [20] of seawater or fresh water into contact.
[22] the antifouling base material as described in [20] or [21], wherein, the base material is to be selected from ship, marine structure and land At least one of upper works.
[23] manufacture method of antifouling base material in the stacking described in substrate surface formation [17] or [18] comprising prevent The process of dirty film.
Invention effect
In substrate surface anticorrosion film, antifouling coat and the stacking antifouling coat set are stacked gradually from the substrate side In, if forming anticorrosion film, the solidification of the anticorrosion film of gained by the epoxy resin anticorrosive coating of the present invention Property and drying property during containing solvent are excellent, can suppress unreacted epoxy resin ingredient in anticorrosion film to antifouling coat Infiltration, therefore, it is possible to the reduction for the antifouling property (particularly standing soil resistance) for suppressing to be laminated antifouling coat, and can improve stacking The traumatic resistance of antifouling coat.
Brief description of the drawings
Fig. 1 is the figure for the evaluation criterion for representing traumatic resistance, wherein,
5：Film is undeformed, shows most good state；
4：If confirming the deformation of dry coating film, good state is shown；
3rd, 2,1 is to confirm the state that largely deformation, part steel plate expose.The degree of (deformation) is damaged according to 3,2,1 Order become big successively.
Embodiment
Hereinafter, the present invention will be described in more detail.
[epoxy resin anticorrosive coating composition]
The present invention epoxy resin anticorrosive coating composition (hereinafter also referred to as " anticorrosive coating composition ") be For being formed in substrate surface anticorrosion film, antifouling coat and the stacking antifouling coat set are stacked gradually from the substrate side In the anticorrosion film epoxy resin anticorrosive coating composition, contain epoxy resin (A), solid thermoplastic resin And curing agent (C) (B).
Below, each composition contained in composition is illustrated, described on stacking antifouling coat after.
Epoxy resin (A)
As the epoxy resin (A), can enumerate 1 intramolecular has the polymer or oligomer of two or more epoxy radicals, And the polymer or oligomer generated by the part ring-opening reaction of the epoxy radicals.
As the epoxy resin (A), bisphenol-type epoxy resin, such as epichlorohydrin-bisphenol A epoxy resin can be specifically enumerated Deng bisphenol A type epoxy resin；The bisphenol-A D-ring oxygen tree fat such as epichlorohydrin-bisphenol AD epoxy resin；By epichlorohydrin and Bisphenol F (4, 4'- methylene bis-phenol) bisphenol f type epoxy resin such as epoxy phenolics of structure obtained by reaction；3,4- epoxies phenoxy group- The aromatic epoxy resins such as 3', 4'- epoxy-phenyl carboxyl methane；The hydrogen combined in epichlorohydrin-bisphenol A epoxy resin with phenyl ring is former The brominated epoxy resin for the structure that at least a portion in son is replaced by bromine atoms；By epichlorohydrin and aliphatic dihydroxy alcohol reaction and The aliphatic epoxy resin of the structure obtained；The multifunction group epoxy of structure obtained by epichlorohydrin and three (hydroxy phenyl) methane reactions Resin etc..
Preferred epoxy resin (A) is selected from bisphenol A type epoxy resin, bisphenol-A D-ring oxygen tree fat and double in these resins At least one of phenol F epoxy resin epoxy resin.
The epoxy resin (A) a kind of can be used alone or be used in combination of two or more.
(condition determination is aftermentioned reality to the weight average molecular weight by GPC (gel permeation chromatography) measure of the epoxy resin (A) Apply the condition or condition equal therewith during the weight average molecular weight that copolymer (a3) is obtained in a column) prevent with the epoxy resin The coated solidified condition of anticorrosive coating composition is (for example：Air drying application or sintering application etc.) etc. it is also relevant, though can not one In general, but preferably 350~20000.In addition, the viscosity (25 DEG C) of the epoxy resin (A) is preferably in below 12000cPs, Further preferably in below 10000cPs.
The epoxide equivalent (according to JIS K7236) of the epoxy resin (A) is preferably 150~1000g/eq.
As the epoxy resin (A), preferably epoxide equivalent is 150~700g/eq bisphenol A type epoxy resin.
In addition, when two or more epoxy resin are applied in combination, the weight average molecular weight and epoxy of the epoxy resin (A) are worked as Amount is two or more epoxy resin as overall weight average molecular weight and epoxide equivalent.
As representational bisphenol A type epoxy resin, " jER828 " (Mitsubishi Chemical's strain formula for liquid under normal temperature can be enumerated Commercial firm's (Mitsubishi Chemical (strain)) makes, 180~190g/eq of epoxide equivalent, 12000~15000cPs/25 DEG C of viscosity), " E-028- 90X " (big bamboo Ming Xin KCCs (big bamboo is bright new chemical (strain)) system, 828 type epoxy resin (dimethylbenzene is free of, NV90%), epoxide equivalent about 210g/eq), " AER260 " (bisphenol A type epoxy resin, (Asahi Chemical Industry of epoxy Co., Ltd. of Asahi Chemical Industry エ Port キ シ (strain)), epoxide equivalent 190g/eq, NV100%) etc.,
Can enumerate under normal temperature for semisolid " jER-834-X90 " (Mitsubishi chemical Co., Ltd's system, epoxide equivalent 230~ 270g/eq, without dimethylbenzene NV100%), " E-834-85X " (big bamboo Ming Xin KCCs system, epoxide equivalent about 290~ 310g/eq, without dimethylbenzene NV85%) etc.,
" jER1001-X75 " (Mitsubishi chemical Co., Ltd, 600~650g/ of epoxide equivalent for solid-state under normal temperature can be enumerated Eq, without dimethylbenzene NV75%), " E-001-75X " (big bamboo Ming Xin KCCs, epoxide equivalent about 610~650g/eq, Without dimethylbenzene NV75%) etc.,
Content of the epoxy resin (A) in the anticorrosive coating composition preferably 5~80 mass %, more preferably 10 ~50 mass %.
Solid thermoplastic resin (B)
The resin that it is solid under normal temperature (23 DEG C) that the solid thermoplastic resin (B), which is,.Refer at normal temperatures for solid, Shape can also be kept in 1 day by being placed under normal temperature and pressure (23 DEG C, 1 atmospheric pressure).
If containing the solid thermoplastic resin (B), then can suppress, even prevent in the anticorrosive coating composition Only the unreacted epoxy resin (A) is permeated and caused to the antifouling coat being layered on anticorrosion film in anticorrosion film Its antifouling property (particularly standing soil resistance) reduction.
The solid thermoplastic resin (B) by GPC determine (detailed measuring conditions are recorded in the column of aftermentioned embodiment In) weight average molecular weight is preferably 5000~100000, more preferably 20000~80000.
It is used as the solid thermoplastic resin (B), more preferably resin of the glass transition temperature more than 30 DEG C.
As the solid thermoplastic resin (B), can enumerate chloridized polyolefin, acrylic resin, butyl acetate resinoid, Styrene resin, vinyl chloride resin etc..
In these solid thermoplastic resins, ダ イ ア ナ ー Le BR106 (three can be enumerated as the commercially available product of acrylic resin Ling Liyang Co., Ltd. (Mitsubishi's レ イ ヨ Application (strain)) system, Mw=60000), パ ラ ロ イ De B66 (Dow Chemical (ダ ウ ケ ミ カ Le) system, Mw=70000) etc. solid propenoic acid resin, methyl-prop obtained by acrylic acid and its ester or derivatives thereof copolymerization Olefin(e) acid and its ester or derivatives thereof solid methyl acrylic resin etc. obtained by copolymerization.
As the solid thermoplastic resin (B), particularly from the tack with antifouling paint, the traumatic resistance of film, Influence to soil resistance, which is especially lacked, angularly to be considered, preferred vinyl chloride resin in the resin.
It is used as the vinyl chloride resin, further preferred vinyl chloride/ethene isobutyl ether copolymer, more preferably vitrifying Resin of the temperature more than 30 DEG C.As the commercially available product of this vinyl chloride/ethene isobutyl ether copolymer, BASF can be enumerated public Department (BASF societies) system " ラ ロ Off レ ッ Network ス LR8829 ", " ラ ロ Off レ ッ Network ス MP-25 " (Mw=28000~30000), " ラ ロ Off レ ッ Network ス MP-35 ", " ラ ロ Off レ ッ Network ス MP-45 " etc..In addition, the vinyl chloride/ethene isobutyl ether copolymer In " rising of ラ ロ Off レ ッ Network ス MP-25 " its dope viscosity when preparing epoxy resin anticorrosive coating composition is few, Application operability is excellent, therefore preferably.
These solid thermoplastic resins a kind of can be used alone or be used in combination of two or more.
The unreacted epoxy resin (A) is to being layered in anticorrosion film from suppressing, even preventing anticorrosion film On antifouling coat infiltration caused by its antifouling property (particularly standing soil resistance) reduction from the point of view of, relative to institute The amount of the solid thermoplastic resin (B) in the mass parts of epoxy resin (A) 100, the anticorrosive coating composition is stated 50 More than mass parts, preferably more than 60 mass parts, play excellent anticorrosive property, face from anticorrosion film and apply property, drying property Angle considers that its upper limit is preferably 100 mass parts, more preferably 80 mass parts.
Amine hardener (C)
The amine curing agent (C) is reacted containing reactive hydrogen and with the epoxy resin (A), is not particularly limited, excellent Select aliphatic amine, ester ring type amine, aromatic amine and heterocyclic amine.
Specifically, as the aliphatic category amine, ethylenediamine, diethylenetriamines, trien, four can be enumerated (2- aminoethylaminomethyls) methane, 1,3- double (2'- aminoethylaminos) propane, triethylenes-bis- (trimethylene) six Amine, double (3- amino-ethyls) amine, bis hexamethylene triamine [H2N(CH2)6NH(CH2)6NH2], double (cyano ethyl) diethylidenes three Amine etc..
As the ester ring type amine, Isosorbide-5-Nitrae-cyclohexanediamine, 4,4'- methylenebiscyclohexylamines, 4,4'- isopropylidenes can be enumerated Dicyclohexylamine, norbornane diamines (NBDA/2,5- and double (amino methyl)-bicyclic [2,2,1] heptane of 2,6-), double (amino Methyl) hexamethylene, diamino-dicyclohexyl methane, IPD (IPDA/3- amino methyl -3,5,5- 3-methyl cyclohexanols Amine), menthene diamines etc..
As the aromatic amine, can enumerate O-phthalic amine, m-xylene diamine (MXDA), p dimethylamine, phenylenediamine, Naphthylene diamine, diaminodiphenyl-methane, diaminourea diethylbenzene methane, 2,2- double (4- aminophenyls) propane, 4,4'- bis- Aminodiphenyl base ether, 4,4'- diaminourea benzophenone, 4,4'- diamino diphenyl sulfones, 2,2'- dimethyl -4,4'- diaminourea two Phenylmethane, 2,4- benzidines, 2,3'- dimethyl -4,4'- benzidines, 3,3'- dimethoxy-4 's, 4'- diaminos Base biphenyl, double (amino methyl) naphthalenes, double (amino-ethyl) naphthalenes and 2,4,6- tri- (3- aminomethyl phenyls Methylaminomethyl) benzene Phenol etc..
As the heterocyclic amine, N methyl piperazine, morpholine, Isosorbide-5-Nitrae-bis--(3- aminopropyls)-piperazine, piperazine -1 can be enumerated, 4- Diazesuberanes, 1- (2'- aminoethylpiperazines), 1- [2'- (2 "-aminoethylamino) ethyl] piperazine, 1,11- phenodiazines Heterocycle eicosane, 1,15- diazacyclo octacosanes etc..
Further, can be by the polyamide and its modifier of these amine, epoxy resin adduction modifier, Mannich modifier As the amine curing agent (C).
Ahew (amine equivalent) preferably 50~1000g/eq, more preferably 70~500g/ of the amine curing agent (C) eq。
As the amine curing agent (C), commercially available product can enumerate ラ ッ カ マ イ De TD966 (Dainippon Ink Chemicals (DIC (strain)) system, polyamide, Ahew 377g/eq), PA-66 (big bamboo Ming Xin KCCs system, polyamide, reactive hydrogen Equivalent 377g/eq), PA-290 (A) (big bamboo Ming Xin KCCs system, Ahew 277g/eq), ア Application カ マ イ De 2050 (air products Co., Ltd., polyamide adducts, Ahew 150g/eq), NX-4918 (Ka Delai companies (カ ー De ラ イ ト societies) system, aminotoluene base alcohol the Mannich modifier of amine (karr moral phenol (カ Le ダ ノ ー Le) with) adduct, activity Hydrogen equivalent 255g/eq) etc..
The amount of the amine curing agent (C) in the anticorrosive coating composition is relative to the epoxy resin (A) 100 Mass parts, preferably 10~100 mass parts, more preferably 20~100 mass parts.From the curability of anticorrosion film and contain From the point of view of drying property, the traumatic resistance of stacking anticorrosion film during solvent, the amount of preferably described amine curing agent (C) exists In above range.
(other compositions)
It is usually prepared for by the host composition containing the epoxy resin (A) and the solid thermoplastic resin (B), containing State amine curing agent (C) curing agent component composition anticorrosive coating, i.e. by application before mix the host composition and The curing agent component prepares the epoxy resin anticorrosive coating composition.
In the host composition, curing accelerator can be mixed as needed in the range of the purpose of the present invention is not damaged (D), pigment (E), attachment hardening agent (F), solvent (G), resist sagging sedimentation agent (H), dehydrating agent (stabilizer) (I) or other Film forming component (dispersant, defoamer, smoothing agent (Japanese：レ べ リ Application グ drug) etc.) etc., can also it not damage the present invention's Curing accelerator (D) or solvent (G) etc. are mixed in the range of purpose in the curing agent component.
[curing accelerator (D)]
As the curing accelerator (D), such as tertiary amines can be enumerated, triethanolamine (N can be specifically enumerated as tertiary amine (C2H5OH)3), dialkylamino ethanol ([CH3(CH2)n]2NCH2OH、n：Repeat number), triethylenediamine (1,4- diazacyclos (2,2,2) octane), (dimethylaminomethyl) phenol of 2,4,6- tri- (C6H5-CH2N(CH3)2), " バ ー サ ミ Application EH30 " (Henkel Plain boiled water Co., Ltd. (ヘ Application ケ Le plain boiled waters (strain)) make), " ア Application カ ミ Application K-54 " (air products Co., Ltd. (エ ア ー プ ロ ダ クツ societies) system) etc..
As the curing accelerator (D), esters of acrylic acid curing accelerator can be also enumerated.
It is improved, prevents from the curing rate that can obtain the leading epoxy resin (A) of the amine curing agent (C) Corrode film and face apply film, i.e. with the tack of antifouling coat is excellent, anticorrosion film excellent flexibility anticorrosion painting From the point of view of film, counted by 100 mass % of the amount of the nonvolatile component of anticorrosive coating composition, then the anticorrosive coating The amount of the curing accelerator (D) in composition is preferably 0.1~5.0 mass %.
In addition, in the present invention, " nonvolatile component of anticorrosive coating composition (or antifouling paint compositions) " refers to, this Standard (the heating temperature according to JIS K56011-2 of the anticorrosive coating composition (or antifouling paint compositions described later) of invention Degree:125 DEG C, heat time:60 minutes) determine heating residual component.
Pigment (E)
As the pigment (E), filler pigment, coloring pigment and rust resisting pigment etc. can be enumerated.
As filler pigment, barium sulfate, potassium feldspar, blanc fixe, silica, calcium carbonate, talcum, cloud can be specifically enumerated Female, glass flake (Japanese：ガ ラ ス フ レ ー Network), aluminum stearate etc..
As coloring pigment, titanium white, iron oxide red, iron oxide yellow (Japanese can be specifically enumerated：Yellow ベ Application ガ ラ), carbon black Deng.
As rust resisting pigment, aluminium thickener, zinc chromate, trbasic zinc phosphate etc. can be enumerated.From the side of Physical properties of coating film (traumatic resistance etc.) Face consideration, preferably the aluminium thickener of flakey.
Counted by 100 mass % of the amount of the nonvolatile component of anticorrosive coating composition, then the anticorrosive coating combination The amount of the filler pigment in thing is preferably 0.1~80 mass %.
Counted by 100 mass % of the amount of the nonvolatile component of anticorrosive coating composition, then the amount of the coloring pigment is excellent Elect 0.1~50 mass % as.
Counted by 100 mass % of the amount of the nonvolatile component of anticorrosive coating composition, then the amount of the rust resisting pigment is excellent Elect 0.1~50 mass % as.
Adhere to hardening agent (F)
As the attachment hardening agent (F), organic acid, chelating agent, silane coupler etc. can be enumerated, wherein, from anti-corrosion From the point of view of the storage stability of corrosion-inhibiting coating composition, preferred silane coupler.
Silane coupler generally has Liang Zhong functional groups in an intramolecular, can play raising anticorrosion film to inanimate matter The effect such as the bonding force of base material and the viscosity of reduction anticorrosive coating composition.Silane coupler is to such as Formula X-Si (OR)3[X Represent the functional group that can be reacted with organic material (for example：Amino, vinyl, epoxy radicals, sulfydryl, halogen group and tool Have the alkyl (alkyl can have ehter bond etc.) of these groups), OR represents hydrolization group (such as methoxyl group, ethyoxyl)] institute The composition shown has reactivity, and epoxy resin (A) described in preferred pair or the amine curing agent (C) have reactivity.
As the specific example of this silane coupler, if commercially available product, then " KBM403 " (γ-epoxy third can be enumerated Epoxide propyl trimethoxy silicane, Shin-Etsu Chemial Co., Ltd's (SHIN-ETSU HANTOTAI's chemical industry (strain)) system), " シ ラ Application S-510 " (Chisso Corp (チ ッ ソ (strain)) system) etc..
In the case where mixing the silane coupler, if using the amount of the nonvolatile component of anticorrosive coating composition as 100 mass % are counted, then the amount of the silane coupler in the anticorrosive coating composition preferably 0.1~10 mass %, more preferably 0.5~5 mass %.If silane coupler is used for into anticorrosive coating composition with the amount, the anticorrosion film of gained The performances such as tack are improved, and the viscosity reduction of anticorrosive coating composition, and application operability increases.
Solvent (G)
As the solvent (G), such as dimethylbenzene, toluene, methylisobutylketone (MIBK), methoxypropanol, first can be enumerated Ethyl ketone (MEK), butyl acetate, n-butanol, isobutanol, isopropanol (IPA) etc..
These solvents a kind of can be used alone or be used in combination of two or more.
The content of the solvent (G) in host composition is, for example, described molten in 0.1~80 mass %, curing agent component The content of agent (G) is, for example, 0.1~80 mass %.
Resist sagging sagging inhibitor (H)
As the resist sagging sagging inhibitor (thixotropic agent) (H), polyamide wax, Tissuemat E, swelling can be specifically enumerated Great soil group, the nano-particle (aerosil (Japanese containing OH：エ ロ ジ ー Le), resin balls) etc. thixotropic agent.
As this resist sagging sagging inhibitor, " the デ ィ of this chemical conversion of nanmu Co., Ltd. (this chemical conversion of nanmu (strain)) system can be enumerated ス パ ロ Application 4200-20 ", " デ ィ ス パ ロ Application 6650 ", Itoh Oil Mfg (Yi Teng System oil (strain)) system " ASAT- 250F " etc..
Counted by 100 mass % of the amount of the nonvolatile component of anticorrosive coating composition, then the anticorrosive coating combination The amount of the nonvolatile component of the resist sagging sagging inhibitor (H) in thing is preferably 0.1~30 mass %.
Dehydrating agent (stabilizer) (I)
The anticorrosive coating composition of the present invention is resulted in more by being added as needed on dehydrating agent (stabilizer) (I) For excellent extended storage stability.
As dehydrating agent (I), inorganic dehydrating agent and organic dehydrating agent can be enumerated.As the inorganic dehydrating agent, Preferably synthetic zeolite, anhydrous gypsum or semi-hydrated gypsum, are used as organic dehydrating agent, preferably tetramethoxy-silicane, tetraethoxy-silicane Alkane, four butoxy silanes, tetraphenoxy-silicane alkane, MTES, dimethyldiethoxysilane and trimethyl second The alkoxyl silicone such as TMOS alkanes or the polyalkoxysilane class and original acid A ester and orthoformic acid as its condensation product The alkyl orthoformate class such as ethyl ester.
The amount of the dehydrating agent (I) in the anticorrosive coating composition relative to the mass parts of epoxy resin (A) 100, Preferably 0.1~50 mass parts.
(anticorrosive coating composition)
By containing above-mentioned epoxy resin (A), solid thermoplastic resin (B) and amine curing agent (C), and according to common Method mixes these compositions, can prepare the anticorrosive coating composition of the present invention.
(the reaction ratio of epoxy resin (A) and amine curing agent (C))
The epoxy resin (A) is reacted with the amine curing agent (C), forms film.
The present invention anticorrosive coating composition in be free of silane coupler when following formula (1) shown in reaction ratio, contain To the amine curing agent (C) have reactivity silane coupler when following formula (2) shown in reaction ratio, containing to the ring There is oxygen tree fat (A) the reaction ratio shown in the following formula (3) during the silane coupler of reactivity to be respectively preferably 0.3~0.8, more excellent Elect as 0.4~0.7 scope.
[number 2]
(in above formula (1)~(3), the unit of incorporation and equivalent is respectively g and g/eq.)
It is above-mentioned it is various in " reactive group equivalent of silane coupler " refer to, the quality of 1 mole of silane coupler (g) the contained functional group that can be reacted with organic material is (following also referred to as in (i.e. molecular weight) divided by 1 molecule silane coupler For " reactive group ") number obtained by be worth.As silane coupler, as described above, can use containing amino or epoxy radicals It is used as the silane coupler of reactive group.Judge whether to use silane coupler, in a situation of use where, it is necessary to according to reaction Property group species judge silane coupler to epoxy resin (A) whether have reactivity and whether have to amine curing agent (C) There is reactivity, the appropriate formula of selection, obtains the reactive group equivalent of silane coupler, calculate respectively from above formula (1)~(3) Reaction ratio.
If the reaction is than more than the lower limit, the epoxy resin (A) is crosslinked in multiple positions, therefore not The epoxy resin ingredient of reaction is difficult residual, and the curability of the anticorrosion film of gained and drying property during containing solvent are excellent, The reduction degree for being laminated the soil resistance (particularly standing soil resistance) of antifouling coat is small, and traumatic resistance is excellent.
If the reaction is than below the higher limit, obtained by the unreacted amine curing agent (C) in film Residual is difficult, the unreacted amine curing agent (C) takes away moisture, can prevent reduction and discoloration of water-resistance property of coating etc. Problem.
(PVC)
The present invention anticorrosive coating composition nonvolatile component defined with following formula (4) pigment volume concentration (PVC) (with Preferably 25~50%, more preferably 30~45% down also referred to as " PVC ").
The volume of pigment in pigment volume concentration (PVC) (%)=anticorrosive coating composition/(in anticorrosive coating composition Resinae volume+anticorrosive coating composition in pigment volume) × 100 ... formula (4)
In addition, " volume of resinae " described in the denominator of formula (4) refers to, epoxy resin (A), solid thermoplastic resin (B), total volume of amine curing agent (C) and curing accelerator (D).
If PVC is more than the lower limit, the drying property and traumatic resistance of gained film are excellent.
If PVC is below the higher limit, the viscosity of anticorrosive coating composition is significantly improved, and it can be prevented to apply The unfavorable condition of the reduction of operability is filled, or prevents the reduction of the planarization of film or occurs perforation and cause anticorrosive property to reduce Unfavorable condition.
[epoxy resin anticorrosion film]
The epoxy resin anticorrosion film (hereinafter also referred to as " anticorrosion film ") of the present invention is used as in base material table Face from the substrate side stack gradually anticorrosion film, antifouling coat and set stacking antifouling coat the anticorrosion film Anticorrosion film, by comprising containing epoxy resin cured product, the solid thermoplastic resin (B) (still, the asphalt mixtures modified by epoxy resin Except the solidfied material of fat (A)) formed by matrix constitute.
The anticorrosion film of the present invention is the solidfied material of above-mentioned anticorrosive coating composition of the invention.
The content ratio of solid thermoplastic resin (B) described in the anticorrosion film is usually 7~80 mass %, preferably For 7~50 mass %, more preferably 7~30 mass %.The anticorrosion film of the present invention contains the solid thermoplastic with the ratio Property resin (B), therefore as described above, the unreacted epoxy resin (A) can be suppressed to being layered in the anticorrosion film On antifouling coat transfer and cause the reduction of the antifouling property (particularly standing soil resistance) of antifouling coat.
Make in addition, the manufacture method of the anticorrosion film of the present invention is included by the anticorrosive coating composition of the present invention The process of the film solidification of composition.In addition to using anticorrosive coating composition of the invention as anticorrosive coating, Neng Goutong The manufacture method identical method with past epoxy resin anticorrosion film is crossed to manufacture the anticorrosion film of the present invention.
The thickness (dry film thickness) of the anticorrosion film is usually 50~800 μm or so.
[stacking antifouling coat, antifouling base material etc.]
The stacking antifouling coat of the present invention is from the substrate side to stack gradually anticorrosion film, antifouling painting in substrate surface Film and the stacking antifouling coat set, the anticorrosion film is above-mentioned epoxy resin anticorrosion film of the invention.
In addition, the antifouling base material of the present invention is to be applied in substrate surface with stacking gradually the anticorrosion from the substrate side Film, the mode of the antifouling coat form antifouling base material obtained by the stacking antifouling coat of the present invention.
(antifouling paint compositions)
As for forming the antifouling paint compositions of antifouling coat to anticorrosion film implementation face painting, it can enumerate Known antifouling paint compositions, from can effectively suppress the unreacted epoxy resin from anticorrosion film (A) from the point of view of being transferred to antifouling coat and causing the reduction of the antifouling property of antifouling coat, selective hydrolysis type antifouling paint Composition.
As the film formation resin of hydrolysis-type antifouling paint, for example, it can enumerate
Logical formula (I):
COO-M-O-COR1……(I)
[in formula (I), M represents zinc or copper, R1Represent organic group.] shown in the metalline with side chain terminal group Copolymer,
Contain logical formula (II):
CH2=C (R2)-COO-M-O-CO-C(R2)=CH2…(II)
[in formula (II), M represents zinc or copper, R2Represent hydrogen atom or methyl.] shown in monomer derived obtained by structure list Member, metalline copolymer that can be with construction unit obtained by other unsaturated monomers derivative of the monomer copolymerization, and
Contain logical formula (III):
R3- CH=C (R4)-COO-SiR5R6R7…(III)
[in formula (III), R4Represent hydrogen atom or methyl, R5、R6And R7Separately represent there can be heteroatomic carbon 1 valency organic group of number 1~20, R3Represent hydrogen atom or R8- O-CO (still, R8Independently represent there can be heteroatomic carbon number 1~20 1 valency organic group or with SiR9R10R11The silicyl of expression, R9、R10And R11Separately expression can have miscellaneous 1 valency organic group of the carbon number 1~20 of atom.)] shown in monomer derived obtained by construction unit, can be common with the monomer The copolymer containing silyl ester of construction unit obtained by poly- other unsaturated monomers derivative.
Use long-term soil resistance, the long-term Physical properties of coating film of the antifouling paint compositions of these hydrolysis-type resins stable, because This is preferred.
, can example as other unsaturated monomers that can be with the monomer copolymerization shown in the logical formula (II) or logical formula (III) Lift the half ester (monoesters) and diester, vinyl esters, benzene of (methyl) esters of acrylic acid, monocarboxylic acid class, omega-dicarboxylic acids or these compositions Vinyl.
As above-mentioned unsaturated monomer, it can enumerate such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third Olefin(e) acid butyl ester, (methyl) 2-EHA, (methyl) lauryl acrylate, three last of the ten Heavenly stems of (methyl) acrylic acid ester, (methyl) Octadecyl ester, (methyl) allyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) Isobornyl acrylate, (methyl) acrylic acid methoxyethoxy ester, (methyl) acrylic acid ethoxy ester, (methyl) glycidyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl Base butyl ester etc. (methyl) esters of acrylic acid；The monocarboxylic acid classes such as (methyl) acrylic acid；The dicarboxylic acids such as itaconic acid, maleic acid, butanedioic acid The half ester (simple substance) and dibasic acid esters of class or these compositions；The phenylethylenes such as styrene, α-methylstyrene；Vinyl acetate, propionic acid The vinyl esters such as vinyl acetate；Deng can be used more than one or both of these compositions.
From the point of view of Physical properties of coating film, counted by 100 mass % of the amount of the nonvolatile component of antifouling paint compositions, then Film formation in the antifouling paint compositions is preferably 5~50 mass %, more preferably 5~30 matter with the amount of resin Measure %.
The antifouling paint compositions can also contain as needed is selected from rosin and/or monocarboxylic acid compound, copper or copper Compound, organic anti-fouling agent, coloring pigment, filler pigment, dehydrating agent, plasticizer, pigment dispersing agent, anti-sagging agent, anti-settling The composition of agent and solvent etc..
Rosin and/or monocarboxylic acid compound
As rosin, the rosin such as gum rosin, wood rosin, toll oil rosin can be enumerated, the pine such as hydrogenated rosin, disproportionated rosin Fragrant derivative etc..Rosin is the residue that will be remained after the rosin distillation as the resin of pinaceae plant, is with rosin acid (fir Acid, palustric acid (Japanese：パ ラ ス ト リ Application acid), isodextropimaric acid (Japanese：イ ソ ピ マ ー Le acid) etc.) it is the natural of principal component Resin.
As monocarboxylic acid compound, aliphatic or ester ring type monocarboxylic acid, their monocarboxylic acid derivative or metal can be enumerated Salt etc..As the specific example of monocarboxylic acid compound, can enumerate aphthenic acids, cyclenes yl carboxylic acid, bicycloenyl carboxylic acid, versatic acid, Trimethyl isobutenyl cyclohexenyl group carboxylic acid, stearic acid, hydroxy stearic acid, salicylic acid and their metal salt etc..
Film formation resin contain quality (WA) and rosin and/or monocarboxylic acid compound contain quality (WB) Contain mass ratio (WA/WB) it is preferably 99.9/0.1~30/70, more preferably 95/5~35/65, more preferably 90/10 ~40/60.If it is above-mentioned containing mass ratio in the scope, with improve antifouling coat cleaning (Japanese：Grind Sweep Property) (film expendable) effect, it is possible to increase soil resistance (particularly stands soil resistance).
Copper or copper compound
As copper compound, it can be organic or any copper compound of inorganic, for example, can enumerate powdered copper (copper powder), cuprous oxide, cuprous sulfocyanide, copper-nickel alloy, copper pyrithione etc..
From the point of view of long-term soil resistance, if using the amount of the nonvolatile component of antifouling paint compositions as 100 matter % meters are measured, then the amount (total amount of copper and copper compound) of the copper in the antifouling paint compositions or copper compound is preferably 0.1~90 mass %, more preferably 0.5~80 mass %.
Organic anti-fouling agent
As organic anti-fouling agent, the pyrithione metal class (except copper pyrithione) such as can enumerate ZPT, The bromo- 2- of DCOIT, 4- (4- chlorphenyls) -5- (trifluoromethyl) -1H- pyrroles -3- Nitrile, triphenylboron pyridine, 4- isopropyl pyridine diphenyl methyls boron, N, N- dimethyl-N '-(3,4- dichlorophenyls) urea, N- (2,4,6- trichlorophenyls) maleimide, 2,4,5,6- daconil Ms, 2- methyl mercapto -4- tert-butylamino -6- rings third Base amino -1,3,5- triazines, dexmedetomidine (Japanese：メ デ ト ミ ジ Application), double (DMDS is for carbamoyl) zinc ethene Double (dithiocarbamate) (Japaneses：ビスジメチルジチオカルバモイルジンクエチレンビスジ チ オ カ ー バ メ ー ト), chloromethyl-n-octyl disulfide (Japanese：Network ロ ロ メ チ Le-n- オ Network チ Le ジ ス Le Off ィ De), N ', N '-dimethyl-N- phenyl-(N- fluorine dichloros methyl mercapto) sulfonamide, tetraalkylthiuram disulfide, DMDS For carbaminate, ethene bisdithiocarbamic zinc, 2,3- bis- chloro- N- (2 ', 6 '-diethyl phenyl) maleimide, The chloro- N- of 2,3- bis- (2 '-ethyl -6 '-aminomethyl phenyl) maleimide etc..
From the point of view of long-term soil resistance, maintenance water-resistance property of coating (maintenance mechanical property), with antifouling paint compositions Nonvolatile component amount be 100 mass % meter, then the amount of organic anti-fouling agent in the antifouling paint compositions is preferably 0.1 ~90 mass %, more preferably 0.5~80 mass %.
Coloring pigment
As coloring pigment, known organic or the various coloring pigments of inorganic can be enumerated.As organic Color pigment, can enumerate carbon black, naphthol reds, phthalocyanine blue etc..In addition, as the coloring pigment of inorganic, iron oxide red, again can be enumerated Spar powder, titanium white, yellow iron oxide etc..
The antifouling paint compositions, can also be containing dyestuff etc. in addition to coloring pigment while containing coloring pigment Colouring agent, or colouring agent containing dyestuff etc. in addition to coloring pigment is to substitute coloring pigment.
From the point of view of coloring, disguise, exposure discolouration, soil resistance, water-resistance property of coating (mechanical property), to prevent The amount of the nonvolatile component of dirty coating composition is 100 mass % meters, then coloring pigment in the antifouling paint compositions Amount is preferably 0.01~50 mass %, more preferably 0.1~30 mass %.
Filler pigment
As filler pigment, can enumerate for example talcum, silica, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, Kaolin, aluminum oxide are white, white carbon, aluminium hydroxide, magnesium carbonate, barium carbonate, barium sulfate etc..Wherein, preferably talc, titanium dioxide Silicon, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar, zinc oxide.In addition, calcium carbonate and white carbon also respectively as Sagging inhibitor described later is used.
From the point of view of water-resistance property of coating (mechanical property), soil resistance, film water-disintegrable (expendable), with antifouling paint The amount of the nonvolatile component of composition is counted for 100 mass %, then the amount of the filler pigment in the antifouling paint compositions is preferred For 0.1~80 mass %, more preferably 0.5~70 mass %.
Dehydrating agent
As dehydrating agent, known gypsum, tetraethoxysilane etc. can be used.
From prevent storage during viscosity rise effect from the aspect of, with the nonvolatile component of antifouling paint compositions Measure and counted for 100 mass %, then the amount of the dehydrating agent in the antifouling paint compositions is preferably 0.01~30 mass %, more preferably For 0.1~20 mass %.
Plasticizer
As plasticizer, chlorinated paraffin, Petropols class, ketone resin, TCP (tricresyl phosphate), polyethylene can be enumerated Ether, bialkyl ortho phthalate etc., are examined from the angle of water-resistance property of coating (mechanical property), film water-disintegrable (expendable) Consider, wherein it is preferred that chlorinated paraffin, Petropols class or ketone resin.
As the specific example of chlorinated paraffin, can enumerate " ト ヨ パ ラ ッ Network ス 150 " and " ト ヨ パ ラ ッ Network ス A-70 " ( For TOSOH Co., Ltd (East ソ ー (strain)) system) etc..In addition, as Petropols class, can enumerate C5 classes, C9 classes, phenylethylene, Dichloro pentadiene class and their hydride etc..As the specific example of Petropols class, " Network イ Application ト Application can be enumerated 1500 " and " Network イ Application ト Application 1700 " (be Zeon Corp's (Japanese ゼ オ Application (strain)) system) etc..
Film hydrolysis when from soil resistance, water-resistance property of coating (mechanical property), film formation with resin being hydrolysis-type resin From the point of view of property (expendable), counted by 100 mass % of the amount of the nonvolatile component of antifouling paint compositions, then it is described antifouling The amount of plasticizer in coating composition is preferably 0.1~80 mass %, more preferably 0.5~70 mass %.
Pigment dispersing agent
As pigment dispersing agent, known organic or the various pigment dispersing agents of inorganic can be enumerated, for example, can be enumerated Aliphatic amine or organic acid (for example, " デ ュ オ ミ Application TDO " (Lion Corporation's (LIO N (strain)) system), " Disperbyk101 " (BYK companies (BYK (strain)) system).
From the aspect of the effect for reducing dope viscosity, the effect for preventing color separation, with the non-volatile of antifouling paint compositions The amount of composition is counted for 100 mass %, then the amount of the pigment dispersing agent in the antifouling paint compositions is preferably 0.01~20 matter Measure %, more preferably 0.1~10 mass %.
Anti-sagging agent
As anti-sagging agent, the mixture of amide waxe, rilanit special wax, polyamide wax and these compositions can be enumerated, closed Into fine particle silica etc..Wherein, from the point of view of storage stability, the repetition coating of of the same race/xenogenesis coating, resist sagging Agent is preferably amide waxe or synthesis fine particle silica.
As the commercially available product of anti-sagging agent, " デ ィ ス パ ロ Application A630-20X " (this chemical conversion of nanmu Co., Ltd. (nanmus can be enumerated This chemical conversion (strain)) system), " ASAT-250F " (Itoh Oil Mfg (Yi Teng System oil (strain)) system).
From the point of view of storage stability, the repetition coating of of the same race/xenogenesis coating, with antifouling paint compositions not The amount of volatile ingredient is counted for 100 mass %, then the amount of the anti-sagging agent in the antifouling paint compositions is preferably 0.1~50 matter Measure %, more preferably 0.5~30 mass %.
Anti- sinking agent
As sagging inhibitor, Al, Ca or Zn ammonium salt, polyethylene kind wax, oxidic polyethylene class wax etc. can be enumerated, wherein excellent Select oxidic polyethylene class wax.As the commercially available product of oxidic polyethylene class wax, " デ ィ ス パ ロ Application 4200-20X " (nanmu sheets can be enumerated It is melted into Co. Ltd. system).
From the point of view of storage stability, the repetition coating of of the same race/xenogenesis coating, with antifouling paint compositions not The amount of volatile ingredient is counted for 100 mass %, then the amount of the sagging inhibitor in the antifouling paint compositions is preferably 0.1~50 matter Measure %, more preferably 0.5~30 mass %.
Solvent
To improve the dispersiveness of antifouling paint compositions and the viscosity of adjustment said composition, antifouling paint compositions are according to need Water or organic solvent equal solvent can be contained.
As organic solvent, fragrant same clan's organic solvent such as dimethylbenzene, toluene, ethylbenzene can be enumerated；MEK, methyl tert-butyl The ketones such as ketone, cyclohexanone；The aliphatic such as ethanol, isopropanol, n-butanol, isobutanol (carbon number 1~10, preferably 2~5 or so) Unary alcohol；The esters solvents such as ethyl acetate, butyl acetate；Deng.The amount of solvent in the antifouling paint compositions, antifouling In the case that the amount of coating composition is 100 mass %, usually 5~80 mass %, preferably 10~70 mass %.
(manufacture method of stacking antifouling coat etc.)
The manufacture method of the stacking antifouling coat of the present invention, which is included, forms epoxy resin anticorrosion film of the invention Process and the process for forming the antifouling coat on the surface of the epoxy resin anticorrosion film.In addition, the present invention The manufacture method of antifouling base material is included in the process that substrate surface forms the stacking antifouling coat of the present invention.
Therefore, except use the present invention epoxy resin anticorrosion film as epoxy resin anticorrosion film it Outside, the stacking antifouling coat and antifouling base material of the present invention can be manufactured by method as in the past.That is, by the past public The method known is coated with the epoxy resin anticorrosive coating of the present invention in substrate surface and is allowed to solidification to form epoxy resin Anticorrosion film, then on the surface of the epoxy resin anticorrosion film it is coated with the antifouling paint group with known method Compound simultaneously is allowed to solidify, and can manufacture the stacking antifouling coat and antifouling base material of the present invention.
As the base material, preferably require that there is anticorrosive property and the base material of soil resistance in water, ship (ship can be enumerated Bottom etc.), fishery goods, materials and equipments, the aouatic structure thing, gulf bank road, seabed tunnel, bay such as the discharge mouth of a river of nuclear power plant of thermal power plant Sludge nonproliferation film of the various ocean earthworks such as equipment, canal or water route etc., as the material of base material, can enumerate steel, Aluminium, wood, FRP etc..The stacking antifouling coat of the invention formed on the surface of these base materials prevents sea lettuce, barnacle, green grass or young crops for a long time Sea sedge, Hai Mango (Japaneses：セ Le プ ラ), oyster, the attachment of aquatile such as careless tongue worm characteristic (soil resistance, it is particularly quiet Put soil resistance) aspect it is excellent.
The thickness (dry film thickness) of the antifouling coat is not particularly limited, but in the feelings that base material is ship and aouatic structure thing Under condition, for example, 50~2000 μm or so.
Embodiment
Carry out more specific description to the present invention below based on embodiment and comparative example, but the present invention be not only restricted to it is following Embodiment.
<The hydrolysis-type antifouling paint S1 of metalline, the hydrolysis-type antifouling paint S2 containing silyl ester preparation>
(manufacture of copolymer (a2) solution of metalline)
[Production Example 1]
The third of 85.4 mass parts are added to being provided with the four-hole boiling flask of cooler, thermometer, dropping funel and mixer The zinc oxide of glycol monomethyl ether (PGM) and 40.7 mass parts, warming while stirring is to 75 DEG C.
Then, as dropping funel with being at the uniform velocity added dropwise by 50.0 mass parts in three hours opalescent mixtures obtained by The mixture that methacrylic acid (MAA), 36.1 mass parts acrylic acid (AA) and 5 mass parts water are constituted.After completion of dropwise addition, reaction Solution is changed into transparent.After further stirring 2 hours, the propylene glycol monomethyl ether (PGM) of 36 mass parts is added, transparent contain has been obtained The monomer solution (a1) of metal salt.The solid constituent of metalline monomer (a1) solution of gained is 44.8 mass %.
[table 1]
The manufacture of the monomer (a1) of the metalline of table 1
[Production Example 2]
The third the two of 15 mass parts are added in the four-hole boiling flask of cooler, thermometer, dropping funel and mixer to being provided with The ethyl acrylate of alcohol monomethyl ether (PGM), the dimethylbenzene of 57 mass parts and 4 mass parts, warming while stirring is to 100 DEG C.
Then, with 6 hours as being at the uniform velocity added dropwise in dropping funel mixture obtained by by 1 mass parts methyl methacrylate (MAA), 70.2 mass parts ethyl acrylates (EA), 5.4 mass parts acrylic acid 2- methoxy acrylates (2-MEA), 52 mass parts by Monomer (a1) solution of metalline obtained by Production Example 1,10 mass parts dimethylbenzene, (the Japanese grease strain of 1 mass parts chain-transferring agent Formula commercial firm (day oil (strain)) system " ノ フ マ ー MSD "), 2.5 mass parts azodiisobutyronitriles (AIBN, Japanese fine chemistry industry strain Formula commercial firm (Japan of Co., Ltd. Off ァ イ Application ケ system (Japanese ヒ De ラ ジ Application industrial (strain)))) and 7 mass parts 2,2 '-it is even The transparent mixture of nitrogen double (2- methylbutyronitriles) (AMBN) formation.(it is following, also the dropwise addition process is referred to as and " process 1 " is added dropwise.)
After completion of dropwise addition, 0.5 mass parts tert-butyl hydroperoxide caprylate (TBPO) and 7 mass parts diformazans was added dropwise with 30 minutes Benzene, further stirring adds 4.4 mass parts dimethylbenzene after 30 minutes 1 hour, has obtained the metalline copolymerization of pale yellow transparent Thing (a2) solution.Raw material and characteristic of metalline copolymer (a2) etc. are shown in table 2.
[table 2]
The manufacture (Production Example 2) of the copolymer (a2) of the metalline of table 2
(manufacture of copolymer (a3) solution containing silyl ester)
[Production Example 3]
Add being provided with the reaction vessel of mixer, circulation cooler, thermometer, nitrogen ingress pipe and dropping funel Enter 53 mass parts dimethylbenzene, in a nitrogen atmosphere with mixer stir dimethylbenzene while, under normal pressure by reaction vessel Dimethylbenzene is heated to 85 DEG C.While the temperature of dimethylbenzene in reaction vessel is maintained into 85 DEG C, two are used by dropping funel Hour will be by TIPSMA (methacrylic acid triisopropylsilyl ester) 50 mass parts, MEMA (methacrylic acid 2- methoxyl groups Ethyl ester) 30 mass parts and the mass parts of MMA (methyl methacrylate) 10, mass parts of BA (butyl acrylate) 10 and 2,2 '- The monomer mixture of double (2- methylbutyronitriles) the 1 mass parts formation of azo is made an addition in reaction vessel.
Then, the mass parts of the peroxidation acid tert-butyl ester 0.5 further being added in reaction vessel, being held in will be reacted under normal pressure While liquid temperature in device is maintained at 85 DEG C, using mixer by the liquid continuous stirring two hours in reaction vessel.Then, will Liquid temperature in reaction vessel rises to 110 DEG C from 85 DEG C, and after heating 1 hour, the dimethylbenzene of 14 mass parts is added into reaction vessel, The liquid temperature in reaction vessel is reduced, stirring is stopped when liquid temperature is 40 DEG C.Thereby, prepared and contained the copolymerization containing silyl ester The solution of thing (a3).Raw material and characteristic containing silyl ester copolymer (a3) etc. are shown in table 3.
[table 3]
The manufacture (Production Example 3) of copolymer (a3) of the table 3 containing silyl ester
(copolymer (a2) of metalline, the evaluating characteristics of the copolymer (a3) containing silyl ester)
The above-mentioned various characteristics of the copolymer (a2) of metalline and the copolymer (a3) containing silyl ester are pressed with lower section Method is determined.
(1) containing ratio of residual component is heated in copolymer solution
With 1 atmospheric pressure, 108 DEG C of condition by copolymer solution 1.5g (X in thermostat1(g)) kept for 3 hours, removed Remove volatile ingredient and obtain heating residual component (nonvolatile component).Then, determine it is remaining heating residual component (it is non-volatile into Point) amount (X2(g) containing ratio of heating residual component contained in polymer (copolymer) solution), is calculated based on following formula (%).
Heat containing ratio (%)=X of residual component2/X1×100
(2) mean molecule quantity of copolymer
Mean molecule quantity (the number-average molecular weight of copolymer is determined using GPC (gel permeation chromatography) with following conditions (Mn) or weight average molecular weight (Mw)).Condition determination is as described below.
GPC conditions
Device：" HLC-8120GPC " (TOSOH Co., Ltd (East ソ ー (strain)) makes)
Post：" SuperH2000+H4000 " (TOSOH Co., Ltd's system, 6mm (internal diameter), each 15cm (length))
Eluent：Tetrahydrofuran (THF)
Flow velocity：0.500ml/ minutes
Detector：RI
Post thermostat temperature：40℃
Standard substance：Polystyrene
Sample compound method：Add after a small amount of calcium chloride is dehydrated, will be filtered by filter membrane device into copolymer solution Obtained by filtrate be used as GPC determine sample.
(3) viscosity of copolymer solution
Brookfield viscometer (Tokyo Keiki Inc. (East capital Meter devices (strain)) is used to make) determine the copolymer of 25 DEG C of liquid temperature Viscosity (the unit of solution：mPa·s).
(the hydrolysis-type antifouling paint S1 of metalline, the manufacture of the hydrolysis-type antifouling paint S2 containing silyl ester)
[Production Example 4]
Dimethylbenzene (16g), metalline copolymer (a2) solution (37g), oxidation are added into 1000ml plastic containers Zinc (20g), TTK talcums (10g), iron oxide red 404 (1.5g), ノ バ パ ー system レ ッ De F5RK (0.5g), ジ Application Network オ マ ジ Application (8g), エ U ネ ア (4g), add 200g beades, carry out 1 hour scattered.Afterwards, addition デ ィ ス パ ロ Application A630- 20X (3.0g), further disperses 15 minutes.Filtered using the screen pack of 60 mesh, the hydrolysis-type for having prepared metalline is prevented Dirty coating S1.In addition, raw material guide look is shown in table 5.
[Production Example 5]
In addition to changing incorporation composition as shown in table 4, the antifouling painting of the hydrolysis-type containing silyl ester has similarly been prepared Expect S2.
[table 4]
Composition (the unit of the antifouling paint of table 4：g)
<The preparation of anticorrosive coating composition>
[embodiment 1]
Anticorrosive coating composition has been prepared by as described below.
(host composition)
MIBK (3g), n-butanol (3g), dimethylbenzene (17g), jER1001-X75 are added into 1000ml plastic containers (16g), ラ ロ Off レ ッ Network ス MP-25 (6g), TTK talcums (25g), バ リ Us 300W (8g), the mesh of mica powder 325 (5g), oxidation Iron oxide red 404 (2g), デ ィ ス パ ロ Application 6650 (1.5g), KBM403 (0.5g), add 200g beades, carry out point of 1 hour Dissipate.In addition, raw material guide look is shown in table 5.Dispersion liquid is filtered using the screen pack of 60 mesh, anticorrosive coating has been prepared Host composition.
(curing agent component)
Dimethylbenzene (5.7g), ラ ッ カ マ イ De TD-966 (7g), ア Application カ ミ Application K- are added into 200ml plastic containers 54 (0.3g), disperse within 10 minutes.In addition, raw material guide look is shown in table 5.Dispersion liquid is carried out using the screen pack of 60 mesh Filtering, has prepared the curing agent component of anticorrosive coating.
(anticorrosive coating composition)
As conventional method, host composition and curing agent component by obtained by are mixed before i.e. by application, have prepared anticorrosion painting Feed composition.
[embodiment 2~7, comparative example 1~7]
In addition to by the proportioning of host composition and curing agent component by being changed table 6 Suo Shi, similarly to Example 1 Anticorrosive coating composition is prepared.
[table 5]
The raw material of the antifouling paint of table 5 and anticorrosive coating
[table 6]
<It is laminated the making and evaluation of antifouling coat>
(1) it is laminated the expendable of antifouling coat
Using coating machine on 50mm × 50mm × 1.5mm hard ethlyene dichloride plate coating Examples 1~7 and comparative example Each anticorrosive coating composition prepared in 1~7, it is respectively 150 μm to make dry film thickness, and overlay painting interval uses coating machine after 1 day The hydrolysis-type antifouling paint S1 and hydrolysis-type antifouling paint S2 containing silyl ester of metalline are coated with, makes the dry film thickness be 100 μm, it is dried at 23 DEG C 7 days, has made the breadboard with stacking antifouling coat.
Above-mentioned breadboard is installed in the side of the rotating drum set in the thermostat equipped with 25 DEG C of seawater, with rotating speed 15 The speed rotation of section, the accumulation consumption (thickness decrement (μm)) that every 1 month determines an antifouling coat from setting.
(2) it is laminated the standing soil resistance of antifouling coat；
Using aerial spraying machine on 100 × 300 × 3.2mm blasting treatment steel plate coating Examples 1~7 and comparative example Each anticorrosive coating composition prepared in 1~7, it is respectively 150 μm to make dry film thickness, and overlay painting interval is sprayed after 1 day using air The hydrolysis-type antifouling paint S1 of the painting machine coating metalline and hydrolysis-type antifouling paint S2 containing silyl ester, makes dry film thickness For 100 μm, it is dried at 23 DEG C 7 days, has made the breadboard with stacking antifouling coat.
Above-mentioned breadboard is stood and is impregnated in the gulf of Nagasaki,Japan Nagasaki, each moon is visually to determine since dipping The bond area of aquatile is (relative to the part for being attached with aquatile of the gross area 100% of the antifouling coat of breadboard Area ratio (%)), evaluated according to following evaluation criterions.
0：Attachment without aquatile
0.5：The bond area of aquatile is more than 0% and below 10%
1：The bond area of aquatile is more than 10% and below 20%
2：The bond area of aquatile is more than 20% and below 30%
3：The bond area of aquatile is more than 30% and below 40%
4：The bond area of aquatile is more than 40% and below 50%
5：The bond area of aquatile is more than 50%
(3) it is laminated the traumatic resistance of antifouling coat
Coating Examples 1~7 and compared on 70mm × 150mm × 1.6mm blasting treatment steel plate with aerial spraying machine Each anticorrosive coating composition prepared in example 1~7, it is respectively 150 μm to make dry film thickness, places 1 day, forms at 5 DEG C Anticorrosion film.After overlay painting interval 1 day, the hydrolysis of metalline is coated with the surface of the anticorrosion film using aerial spraying machine The type antifouling paint S1 or hydrolysis-type antifouling paint S2 containing silyl ester, the dry film thickness for making antifouling coat is 150 μm, 5 Dried at DEG C, made the breadboard with stacking antifouling coat.Antifouling coat starts after drying 1 day, after 2 days and after 3 days, Middle body on antifouling coat places 30mm × 30mm × 10mm wood chip, vertically applies on the wood chip 20 minutes 40kgf/cm2The pressure of (3.9MPa), observes the state (degree of deformation for determining film) of film coated surface, is evaluated by following Standard is evaluated (reference picture 1).
5：Film is undeformed, shows most good state.
4：If confirming the deformation of dry coating film, good state is shown.
3rd, 2,1 is to confirm the state that largely deformation, part steel plate expose.Damage the degree of (deformation) according to 3, 2nd, 1 order becomes big successively.
[comparison reference example]
To hydrolysis-type antifouling paint S2 shapes respectively by the hydrolysis-type antifouling paint S1 of metalline and containing silyl ester Into single antifouling coat implement tests below.
(1) expendable of antifouling coat；
The hydrolysis-type for being coated with metalline on 50mm × 50mm × 1.5mm hard ethlyene dichloride plate with coating machine is antifouling The coating S1 or hydrolysis-type antifouling paint S2 containing silyl ester, it is 100 μm to make dry film thickness, is dried at 23 DEG C 7 days, The breadboard of the single film without anticorrosion film is made.
Above-mentioned breadboard is installed in the side of the rotating drum set in the thermostat equipped with 25 DEG C of seawater, with rotating speed 15 The speed rotation of section, the accumulation consumption (thickness decrement (μm)) for determining an antifouling coat in every 1 month.
(2) the standing soil resistance of antifouling coat；
The hydrolysis-type for being coated with metalline on 100 × 300 × 3.2mm hard ethlyene dichloride plate with aerial spraying machine is prevented Dirty coating S1, the hydrolysis-type antifouling paint S2 containing silyl ester, it is 100 μm to make dry film thickness, and 7 are dried at 23 DEG C My god, make the breadboard with single antifouling coat without anticorrosion film.
Using with the single antifouling coat breadboard substitute with stacking antifouling coat breadboard, carried out with it is upper State the evaluation of the standing soil resistance of stacking antifouling coat equally.
(3) traumatic resistance of antifouling coat；
The hydrolysis of metalline is coated with 70mm × 150mm × 1.6mm hard ethlyene dichloride plate with aerial spraying machine The type antifouling paint S1 or hydrolysis-type antifouling paint S2 containing silyl ester, it is 150 μm to make dry film thickness, is dried at 5 DEG C, is made The breadboard with single antifouling coat without anticorrosion film is made.Using this there is the breadboard of single antifouling coat to substitute Breadboard with stacking antifouling coat, has carried out the evaluation same with the traumatic resistance of above-mentioned stacking antifouling coat.
[table 8]
[table 9]
Table 9

Claims (23)

1. epoxy resin anticorrosive coating composition, it be used to be formed stacked gradually in substrate surface from the substrate side it is anti- Corrosion film, antifouling coat and set stacking antifouling coat in the anticorrosion film epoxy resin anticorrosive coating Composition, it is characterised in that
Containing epoxy resin (A), solid thermoplastic resin (B) and amine curing agent (C),
The solid thermoplastic resin (B) is solid at normal temperatures,
Relative to the mass parts of solid constituent 100 of the epoxy resin (A), the content of the solid thermoplastic resin (B) is 50 It is more than mass parts.
2. epoxy resin anticorrosive coating composition as claimed in claim 1, it is characterised in that the epoxy resin (A) It is more than one or both of bisphenol-A, bisphenol-A D and Bisphenol F.
3. epoxy resin anticorrosive coating composition as claimed in claim 1, it is characterised in that also arbitrarily even containing silane Join agent, the reaction ratio shown in following formula (1) during without silane coupler, containing there is reactivity to the amine curing agent (C) Silane coupler when following formula (2) shown in reaction ratio, containing to the epoxy resin (A) have reactivity it is silane coupled The reaction ratio respectively 0.3~0.8 shown in following formula (3) during agent,
[number 3]
(in above formula (1)~(3), the unit of incorporation and equivalent is respectively g and g/eq.)
4. epoxy resin anticorrosive coating composition as claimed in claim 1, it is characterised in that also containing pigment (E).
5. epoxy resin anticorrosive coating composition as claimed in claim 4, it is characterised in that the face shown in following formula (4) It is 25~50% to expect volumetric concentration (PVC),
The volume of pigment in pigment volume concentration (PVC) (the %)=anticorrosive coating composition/(tree in anticorrosive coating composition The volume of pigment in volume+anticorrosive coating composition of lipid) × 100 ... formula (4).
6. epoxy resin anticorrosive coating composition as claimed in claim 1, it is characterised in that the solid thermoplastic tree Fat (B), which contains, is selected from Petropols, chloridized polyolefin, acrylic resin, butyl acetate resinoid, styrene resin and chlorine At least one of vinyl resins.
7. epoxy resin anticorrosive coating composition as claimed in claim 6, it is characterised in that the vinyl chloride resin For vinyl chloride/ethene isobutyl ether copolymer.
8. epoxy resin anticorrosive coating composition as claimed in claim 1, it is characterised in that also contain tertiary amine as solid Change accelerator (D).
9. epoxy resin anticorrosive coating composition as claimed in claim 1, it is characterised in that also containing attachment hardening agent (F)。
10. epoxy resin anticorrosive coating composition as claimed in claim 9, it is characterised in that the attachment hardening agent (F) it is silane coupler.
11. epoxy resin anticorrosive coating composition as claimed in claim 10, it is characterised in that the silane coupler For γ-glycidoxypropyltrime,hoxysilane.
12. the epoxy resin anticorrosive coating composition as any one of claim 1~11, it is characterised in that institute Antifouling coat is stated for hydrolysis-type antifouling coat.
13. epoxy resin anticorrosion film, it be used as substrate surface from the substrate side stack gradually anticorrosion film, The epoxy resin anticorrosion film of antifouling coat and the anticorrosion film in the stacking antifouling coat that sets, its feature exists In,
The epoxy resin anticorrosion film is the epoxy resin anticorrosive coating any one of claim 1~12 The solidfied material of composition.
14. epoxy resin anticorrosion film, it be used as substrate surface from the substrate side stack gradually anticorrosion film, The epoxy resin anticorrosion film of antifouling coat and the anticorrosion film in the stacking antifouling coat that sets, its feature exists In,
The epoxy resin anticorrosion film is by including the shape containing epoxy resin cured product and solid thermoplastic resin (B) Into matrix constitute,
The solid thermoplastic resin (B) is solid at normal temperatures,
The content of the solid thermoplastic resin (B) is 7~80 mass %.
15. epoxy resin anticorrosion film as claimed in claim 14, it is characterised in that also containing epoxy resin (A).
16. the manufacture method of epoxy resin anticorrosion film, it is used as stacking gradually from the substrate side in substrate surface Anticorrosion film, antifouling coat and set stacking antifouling coat in the anticorrosion film epoxy resin anticorrosion apply The manufacture method of film, it is characterised in that
Include the film solidification for making to be formed as the epoxy resin anticorrosive coating composition any one of claim 1~12 Process.
17. be laminated antifouling coat, it be substrate surface from the substrate side stack gradually anticorrosion film, antifouling coat and set The stacking antifouling coat put, it is characterised in that the anticorrosion film is the epoxy any one of claim 13~15 Resinae anticorrosion film.
18. antifouling coat is laminated as claimed in claim 17, it is characterised in that the antifouling coat, which is that hydrolysis-type is antifouling, to be applied Film.
19. be laminated the manufacture method of antifouling coat, it be from the substrate side stack gradually anticorrosion film in substrate surface, it is anti- Dirty film and set stacking antifouling coat manufacture method, it is characterised in that
Comprising the process for forming the epoxy resin anticorrosion film any one of claim 13~15 and described The process that the surface of epoxy resin anticorrosion film forms the antifouling coat.
20. antifouling base material, it is characterised in that by being applied in substrate surface with stacking gradually the anticorrosion from the substrate side Film, the mode of the antifouling coat form the stacking antifouling coat described in claim 17 or 18 and constituted.
21. antifouling base material as claimed in claim 20, it is characterised in that with seawater or fresh water into contact.
22. antifouling base material as claimed in claim 21, it is characterised in that the base material be selected from ship, marine structure and At least one of land-based structure thing.
23. the manufacture method of antifouling base material, it is characterised in that included in the layer described in substrate surface formation claim 17 or 18 The process of folded antifouling coat.
CN201710059821.6A 2016-01-29 2017-01-24 Epoxy resin anticorrosive coating composition, anticorrosive coating film, laminated antifouling coating film, antifouling substrate, and method for producing same Active CN107022273B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-016164 2016-01-29
JP2016016164A JP6814541B2 (en) 2016-01-29 2016-01-29 Epoxy resin-based anticorrosion coating composition, epoxy resin-based anticorrosion coating film, laminated antifouling coating film, antifouling base material, and methods for producing these.

Publications (2)

Publication Number Publication Date
CN107022273A true CN107022273A (en) 2017-08-08
CN107022273B CN107022273B (en) 2020-06-23

Family

ID=59503500

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710059821.6A Active CN107022273B (en) 2016-01-29 2017-01-24 Epoxy resin anticorrosive coating composition, anticorrosive coating film, laminated antifouling coating film, antifouling substrate, and method for producing same

Country Status (4)

Country Link
JP (1) JP6814541B2 (en)
KR (1) KR102075434B1 (en)
CN (1) CN107022273B (en)
SG (1) SG10201700592VA (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107541117A (en) * 2017-08-30 2018-01-05 深圳先进技术研究院 Nanometer fishing net waterborne anti-fouling coatings and its preparation method and application
CN107581129A (en) * 2017-08-31 2018-01-16 浦江县酉泽水产科技有限公司 Keep hanging formula ecology crab farming equipment
CN108727545A (en) * 2018-06-13 2018-11-02 鲁东大学 A kind of anticorrosion and antifouling type coating resin and preparation method thereof
CN112876938A (en) * 2021-01-18 2021-06-01 徐松波 Antifouling corrosion-resistant epoxy coating and preparation method thereof
CN113574124A (en) * 2019-04-12 2021-10-29 中国涂料株式会社 Anticorrosive coating composition
CN114106666A (en) * 2020-08-26 2022-03-01 中国涂料株式会社 Coating composition
CN115368802A (en) * 2021-05-20 2022-11-22 株式会社Kcc Water-based heavy-duty coating composition
CN116134100A (en) * 2020-07-30 2023-05-16 中国涂料株式会社 Epoxy resin anticorrosive coating composition, anticorrosive coating film, laminated antifouling coating film, antifouling substrate, and method for producing antifouling substrate

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108948969A (en) * 2018-09-03 2018-12-07 广西南宁维防腐科技有限公司 A kind of marine paints and its production method
KR102391000B1 (en) * 2020-03-06 2022-04-27 한국조선해양 주식회사 Epoxy type paint composition and offshore structure comprising coating film of thereof
KR102177185B1 (en) * 2020-05-14 2020-11-10 대화페인트공업주식회사 Thermoplastic road marking paint with high cold check resistance, stain resistance and abrasion resistance
KR102188761B1 (en) * 2020-06-16 2020-12-08 김나영 Anticorrosive coating composition for improving function of paint film crack prevention and coating method using the same
JPWO2022202897A1 (en) * 2021-03-26 2022-09-29

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1185468A (en) * 1996-11-29 1998-06-24 中国涂料株式会社 NOn-tar type epoxy-resin coating composite, coating method for ship outer casing and ship body coated by same
JP2010024408A (en) * 2008-07-24 2010-02-04 Nippon Paint Marine Kk Anticorrosive coating material composition, double-layered coating film formed by using the same and vessel and marine structure equipped with double-layered coating film
CN103360904A (en) * 2013-07-22 2013-10-23 天长市开林化工有限公司 Tar-free epoxy resin coating and its preparation method
CN105026506A (en) * 2013-03-08 2015-11-04 中国涂料株式会社 Anticorrosive coating composition, anticorrosive coating film, and method for preventing corrosion of base material

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10211464A (en) * 1996-11-29 1998-08-11 Chugoku Marine Paints Ltd Coating method for vessel outer board and coated vessel
JP3917279B2 (en) 1997-01-17 2007-05-23 中国塗料株式会社 Non-tar epoxy resin coating composition and heavy anticorrosion coating film formed therefrom
JP3492224B2 (en) * 1997-12-26 2004-02-03 日本ペイント株式会社 Epoxy paint composition and anticorrosion coating method
JP4271280B2 (en) 1998-05-28 2009-06-03 中国塗料株式会社 Painting method and painting ship outside the ship
JP4350182B2 (en) * 1998-10-26 2009-10-21 中国塗料株式会社 Anticorrosion paint composition, anticorrosion coating film, and method for anticorrosion of metal substrate surface
JP4550259B2 (en) * 2000-12-01 2010-09-22 日本ペイントマリン株式会社 Epoxy coating composition, anticorrosion coating method and article to be coated
US20090226729A1 (en) * 2004-08-10 2009-09-10 Chugoku Marine Paints, Ltd. High-solid anticorrosive coating composition, high-solid rapidly-curable anticorrosive coating composition, method of coating ship or the like, high-solid anticorrosive film and rapidly cured high- anticorrosive film obtained, and coated ship and underwater structure coated with these coating films
CN101076573B (en) * 2004-12-14 2010-09-15 中国涂料株式会社 Epoxy anticorrosive coating composition, anticorrosive coating film, antifouling organopolysiloxane composite coating film, and ship and underwater structure covered by such composite coating film
JP5993799B2 (en) * 2013-05-20 2016-09-14 新日鐵住金株式会社 High corrosion resistance coating composition using Sn ions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1185468A (en) * 1996-11-29 1998-06-24 中国涂料株式会社 NOn-tar type epoxy-resin coating composite, coating method for ship outer casing and ship body coated by same
JP2010024408A (en) * 2008-07-24 2010-02-04 Nippon Paint Marine Kk Anticorrosive coating material composition, double-layered coating film formed by using the same and vessel and marine structure equipped with double-layered coating film
CN105026506A (en) * 2013-03-08 2015-11-04 中国涂料株式会社 Anticorrosive coating composition, anticorrosive coating film, and method for preventing corrosion of base material
CN103360904A (en) * 2013-07-22 2013-10-23 天长市开林化工有限公司 Tar-free epoxy resin coating and its preparation method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107541117A (en) * 2017-08-30 2018-01-05 深圳先进技术研究院 Nanometer fishing net waterborne anti-fouling coatings and its preparation method and application
CN107581129A (en) * 2017-08-31 2018-01-16 浦江县酉泽水产科技有限公司 Keep hanging formula ecology crab farming equipment
CN108727545A (en) * 2018-06-13 2018-11-02 鲁东大学 A kind of anticorrosion and antifouling type coating resin and preparation method thereof
CN108727545B (en) * 2018-06-13 2021-07-06 鲁东大学 Anticorrosive antifouling coating resin and preparation method thereof
CN113574124A (en) * 2019-04-12 2021-10-29 中国涂料株式会社 Anticorrosive coating composition
CN116134100A (en) * 2020-07-30 2023-05-16 中国涂料株式会社 Epoxy resin anticorrosive coating composition, anticorrosive coating film, laminated antifouling coating film, antifouling substrate, and method for producing antifouling substrate
CN114106666A (en) * 2020-08-26 2022-03-01 中国涂料株式会社 Coating composition
CN114106666B (en) * 2020-08-26 2024-03-08 中国涂料株式会社 Coating composition
CN112876938A (en) * 2021-01-18 2021-06-01 徐松波 Antifouling corrosion-resistant epoxy coating and preparation method thereof
CN115368802A (en) * 2021-05-20 2022-11-22 株式会社Kcc Water-based heavy-duty coating composition
CN115368802B (en) * 2021-05-20 2024-03-08 株式会社Kcc Aqueous heavy duty coating composition

Also Published As

Publication number Publication date
KR102075434B1 (en) 2020-02-10
SG10201700592VA (en) 2017-08-30
CN107022273B (en) 2020-06-23
KR102075434B9 (en) 2022-05-02
JP2017132960A (en) 2017-08-03
KR20170091034A (en) 2017-08-08
JP6814541B2 (en) 2021-01-20

Similar Documents

Publication Publication Date Title
CN107022273A (en) Epoxy resin anticorrosive coating composition and anticorrosion film, stacking antifouling coat, antifouling base material and its manufacture method
CN104968738B (en) 2 into parting priming paint, primer coating film, lamination antifouling coat and base material anti-fouling method
CN105143368B (en) Antifouling paint compositions, antifouling coat, the manufacture method of antifouling base material and antifouling base material
CN108307625B (en) Antifouling composite coating film, antifouling substrate, and method for producing antifouling substrate
WO2006016625A1 (en) High-solid anticorrosive coating composition, high-solid rapidly-curable anticorrosive coating composition, method of coating ship or the like, high-solid anticorrosive film and rapidly cured high-solid anticorrosive film obtained, and coated ship and underwater structure coated with these coating films
CN106939132A (en) Antifouling paint compositions and application thereof
US20200317932A1 (en) Anticorrosion coating composition, anticorrosion coating film, substrate with anticorrosion coating film, and method of manufacturing same
CN103282447A (en) Antifouling coating composition
CN107109082B (en) The manufacturing method of two-liquid type antifouling paint compositions, antifouling coat, antifouling substrate and antifouling substrate
KR20150033669A (en) Antifouling coating composition
CN108368376B (en) Antifouling coating composition, antifouling coating film, antifouling substrate, and method for producing antifouling substrate
CN107406712A (en) Antifouling paint compositions, antifouling coat, antifouling base material, the storage practice of the manufacture method of antifouling base material and antifouling paint compositions
KR20190114952A (en) Coating composition and coating film formed from this
JP6990241B2 (en) Epoxy resin-based anticorrosion paint composition, anticorrosion coating film, laminated antifouling coating film, antifouling base material, and manufacturing method thereof.
JP7440642B2 (en) Epoxy resin anticorrosive paint composition, anticorrosive coating, laminated antifouling coating, antifouling base material, and method for producing the antifouling base material
KR20190114953A (en) Coating composition and coating film formed from this
KR102680739B1 (en) Antifouling composite coating film, antifouling substrate, and method for manufacturing antifouling substrate
JP6976495B1 (en) Antifouling paint composition
JP2024017095A (en) Primer composition for nonferrous metal base material
CN110691826A (en) Laminated antifouling coating film, substrate with laminated antifouling coating film and method for producing same, coating kit for forming laminated antifouling coating film, upper antifouling coating composition, and antifouling method
TWI385223B (en) An antifouling paint composition, a method for producing the composition, an antifouling coating film formed using the same, a coating material having a coating film on its surface, and a antifouling treatment method for forming the coating film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant