WO2002008348A1 - Composition de revetement durcissant a froid - Google Patents

Composition de revetement durcissant a froid Download PDF

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Publication number
WO2002008348A1
WO2002008348A1 PCT/JP2001/005186 JP0105186W WO0208348A1 WO 2002008348 A1 WO2002008348 A1 WO 2002008348A1 JP 0105186 W JP0105186 W JP 0105186W WO 0208348 A1 WO0208348 A1 WO 0208348A1
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Prior art keywords
coating composition
weight
cold
solution
silicone oligomer
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PCT/JP2001/005186
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English (en)
Japanese (ja)
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WO2002008348A8 (fr
Inventor
Zuyi Zhang
Hajimu Wakabayashi
Akio Konishi
Kazuhiro Kawabe
Satoshi Kumano
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Nihon Yamamura Glass Co., Ltd.
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Publication of WO2002008348A1 publication Critical patent/WO2002008348A1/fr
Publication of WO2002008348A8 publication Critical patent/WO2002008348A8/fr

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    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to a cold-setting coating composition. More specifically, the present invention relates to a room temperature-curable coating composition which forms an organopolysiloxane coating film having excellent chemical durability, which can be cured at room temperature and has a short dry time to the touch, and which can be applied on site. I do. Background art
  • Japanese Patent Application Laid-Open No. 9-19977-17 discloses a method for forming a smooth, dense, and transparent independent film containing organosiloxane having flexibility as a main component by using ammonia gas or amine gas.
  • a method for accelerating the curing of a methyl group-containing polysiloxane film has been proposed. It has also been reported that the contact with an aqueous ammonia solution can accelerate the curing of polysiloxane (Z. Zhang et al., J. Phys. Chem, m., Vol. 28, 1997).
  • a basic compound is directly added to a silicone resin solution as a curing agent, there is a problem that rapid gelation occurs.
  • Japanese Unexamined Patent Publication (Kokai) No. 63-191868 describes that an organic amine compound is used as a coating agent having excellent adhesion to a substrate, and capable of forming a tough and heat-resistant coating film.
  • Carboxylate Coating agents using as a curing accelerator component of a ladder type silicone oligomer have been proposed.
  • Japanese Unexamined Patent Publication No. 59-136363 describes a sodium acetate and benzyltrimethylammonium acetate catalyst as an aqueous composition effective for preventing or suppressing corrosion of a metal substrate.
  • Alumina colloid-containing organic silicon resins have been proposed. Such a catalyst promotes crosslinking of the silicone oligomer, but cures insufficiently at room temperature, requiring heat treatment, and cannot be used as a room temperature curing type coating agent.
  • Japanese Patent Application Laid-Open No. 63-117174 discloses a coating composition having excellent storage stability that forms a coating film having high hardness on the surface of metal, ceramics, glass, and the like and excellent physical properties.
  • a coating composition containing a condensate of an organotrialkoxysilane, colloidal silica, water and a hydrophilic organic solvent, and, if necessary, an amine silane coupling agent as a curing agent for room temperature curing has been proposed.
  • Japanese Patent Application Laid-Open No. 63-1377972 discloses that a coating film having a transparent and glossy appearance and having excellent alkali resistance and water resistance is formed on a surface of metal, glass, plastic, or the like.
  • the coating composition examples include a coating composition containing a condensate of an organotrialkoxysilane, colloidal silica, water, a hydrophilic organic solvent, and an aluminum alkoxide or an aluminum diketone chelate compound as a curing agent. Proposed. These coating compositions require a separate addition of an acid in order to maintain the stability of the coating solution, and have a problem that the preparation of the coating solution is complicated. In addition, to apply these coating compositions on site, it is necessary to reduce the touch drying time. Furthermore, the coating composition proposed in JP-A-63-137792 is difficult to cure at room temperature.
  • silicone oligomers obtained by hydrolysis and polycondensation of alkoxysilanes are used, have a long pot life, have a short touch-drying time when forming coatings, and are cured at room temperature to be applied on site. It has been desired to develop a coating composition for forming a coating film having excellent chemical durability and capable of forming a coating film.
  • the present invention provides an organopolysiloxane coating film having a long pot life, a short drying time to the touch, and curing at room temperature to be applied in the field, and having excellent chemical durability.
  • the purpose of the present invention is to provide a curable coating composition. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when forming a coating film on a silicone oligomer solution obtained by hydrolysis and condensation polymerization of alkoxysilane, a specific organometallic compound, By adding and mixing a solution containing a water-soluble acid and an amine-based silane coupling agent, the pot life is long, the touch drying time is short, it cures at room temperature, and it can be installed on site, and has chemical durability
  • the present inventors have found that a coating composition that forms an excellent organopolysiloxane coating film can be obtained, and based on this finding, have completed the present invention.
  • M 1 is, A +, G a 3 + , I n 3 +, L a 3 +, F e 3 +, Y 3 +, Eu 3 +, T i 4+, either Z r 4+
  • the room-temperature-curable coating composition of the present invention is a solution in which the main component (A) contains a silicone oligomer having an average structural unit of RS i O x / 2 (OH) y (OR 2 ) z , B) is a coating composition that is a solution containing M ⁇ Ch) P (OR 3 ) q or a partial hydrolyzate thereof, a volatile acid, and an amine-based silane coupling agent.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, a vinyl group or a phenyl group, which may be the same or different
  • R 2 is an alkyl group having 1 to 3 carbon atoms, and all are the same.
  • M 1 is a metal having three or more valences
  • Che is a chelating agent
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • the average structural unit is a structural unit averaged for one Si atom in the silicone oligomer.
  • the average structural unit! TnS i Ox / 2 used as the main agent (A) In a solution containing a silicone oligomer having (OH) y (OR 2 ) z , if n is less than 0.8, stress is not easily relieved at the stage of drying the coating film, and the coating film may be cracked. If n exceeds 1.7, it becomes difficult to form a three-dimensional network structure, and the mechanical properties of the coating film may be reduced. When X is 2 or less, it is difficult to form a linear polymer, and the volatile component may increase. If X is 3.2 or more, it is difficult to relieve stress in the drying stage of the coating film, and the coating film may be cracked.
  • a curing agent for room-temperature curing is added before coating.
  • the hydroxyl group OH of the silicone oligomer forms a cross-linking point bridged by the action of the curing agent for room-temperature curing. It is essential that a hydroxyl group be present, ie y> 0.
  • the alkoxyl group OR 2 must have an alkoxyl group, that is, z> 0, in order to improve the storage stability of the solution before adding a curing agent for room-temperature curing.
  • alkoxysilane used in the production of the main agent (A) there is no particular limitation on the alkoxysilane used in the production of the main agent (A).
  • tetraalkoxysilane such as tetramethoxysilane (TMOS) and tetraethoxyquinsilane (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) ), Ethyltrimethoxysilane (ETMS), phenylinoletriethoxysilane (PhTES), vinyltriethoxysilane (VTES), n-propynoletrimethoxysilane (n-PrTMS), trialkoxy such as isopropylbenzenemethoxysilane (iso-PrTMS)
  • Examples thereof include silane, dialkoxysilanes such as dimethyljetoxirane (DMDE), diphenyldimethoxysilane (DPhDM), and
  • the composition, water and alkoxysilane were mixed so that the H 2 0 ZS i power from 1.4 to 4.0 (mole ratio), hydrolysis, is possible to perform polycondensation reaction preferably, mixed and hydrolyzed as an H 2 0 / S i power 1.5 to 2.5 (molar ratio), it is more preferable to carry out the polycondensation reaction.
  • H 2 OZS i is less than 1.4 (molar ratio)
  • unreacted alcohol in the production of silicone oligomer solution Many xyl groups remain and the oligomerization rate of the oligomer decreases, which may adversely affect the mechanical properties of the coating film.
  • H 20 / S i exceeds 4.0 (molar ratio) the stability of the silicone oligomer solution may be reduced.
  • dew condensation tends to occur during spraying, and it may be difficult to form a uniform coating film during film formation.
  • a metal chelate compound or an acid can be used as a hydrolysis catalyst when producing the main agent (A).
  • the metal chelate compound not only exerts a catalytic effect on the hydrolysis of the alkoxysilane, but also suppresses the precipitation of crystals when a large amount of methyltrialkoxysilane is used as a raw material.
  • the metal chelate compound not only acts as a hydrolysis catalyst, but also promotes the deprotonation of silanol and promotes the condensation polymerization reaction in a more linear manner. Has a long gelation time, is excellent in long-term storage stability of the solution, and is advantageous for forming a coating film.
  • a metal chelate compound is preferably used in combination.
  • the metal chelate compound to be used is not particularly limited, but a metal chelate compound having an S-diketone having a 1,3-dioxopropylene chain or a macrocyclic polyether as a ligand can be suitably used.
  • the kind of metal ion is not particularly limited, but a metal having a large complex formation constant with a ligand can be suitably used.
  • metal chelate compounds include, for example, tris (acetylacetonato) aluminum (111), tris (ethylacetylacetonato) aluminum (111), tris (getylmalonato) aluminum (111), bis (acetylacetato) aluminum (111) (Cetonato) copper (11), tetrakis (acetylacetonato) zirconium (IV), tris (acetylacetonato) chromium (111), tris (acetylacetonato) cobalt (111), titanium oxide (II) acetylacetone S_diketon metal chelates such as [(CH 3 COCHCOCH 3 ) 2 T i 0], / 8-diketone metal chelates of rare earth metals, 18-crown 16-force lithium chelate compound salts, 1 2 —Crown 1 41 lithium lithium compound Macrocyclic polyether compound metal salts such as a salt of 15-c
  • the amount of the metal chelate compound catalyst to be added is not particularly limited, and the force can be selected according to the catalytic effect. Usually, it is preferably 0.001 to 5 mol% with respect to alkoxysilane, More preferably, it is 0.05 to 1 mol%. If the amount of the metal chelate compound catalyst is less than 0.01 mol% based on the alkoxysilane, the catalytic effect of hydrolysis may not be sufficiently exhibited. If the amount of the metal chelate compound catalyst exceeds 5 mol% with respect to the alkoxysilane, the metal chelate compound will precipitate during the formation of the coating film, which may adversely affect the properties of the coating film. When an autocatalyst is used, the amount of the metal chelate compound added includes that derived from the autocatalyst.
  • the silicone oligomer of the main agent (A) has an average structural unit of R 4 a S i
  • it can also be produced by hydrolyzing and condensing an alkoxysilane with a solution containing a gay compound which is soluble in a hydrophilic organic solvent as an autocatalyst.
  • R 4 is an alkyl group having 1 to 3 carbon atoms, a vinyl group or a phenyl group, which may be the same or different
  • R 5 is an alkyl group having 1 to 3 carbon atoms
  • the average structural unit is a structural unit averaged for one Si atom in a gayne compound. When a is 3 or more, the above-mentioned gay compound is likely to volatilize, and may be condensed and deactivated.
  • the resulting silicone oligomer—Silicone oligomer in the solution can also be a gay compound having the above average structural unit R 4 a S i O b / 2 (OH) c (OR 5 ) d.
  • the addition amount of the autocatalyst is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, based on the alkoxysilane.
  • the autocatalyst solution is prepared from alkoxysilane, it is preferable to add at least one of an acid and a metal chelate compound as a catalyst.
  • an acid an inorganic acid such as nitric acid or hydrochloric acid and an organic acid such as acetic acid which are used in a usual sol-gel reaction can be used.
  • an acid catalyst here may reduce the storage stability of the solution. It is preferable to use a compound catalyst.
  • a new autocatalyst solution can be prepared by further hydrolyzing and condensing the alkoxysilane with the autocatalyst solution thus obtained as a catalyst.
  • alkoxysilane used to prepare the autocatalyst solution there is no particular limitation on the alkoxysilane used to prepare the autocatalyst solution.
  • tetraalkoxysilanes such as tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), and methyltriethoxysilane (MTMS)
  • Trialkoxy such as (MTES), ethyltrimethoxysilane (ETMS), phenyltriethoxysilane (PhTES), vinyltriethoxysilane (VTES), n-propyltrimethoxysilane (n_PrTMS), and isopropyltrimethoxysilane (iso-PrTMS)
  • Examples thereof include dialkoxysilanes such as silane, dimethyldiethoxysilane (DMDE), diphenyldimethoxysilane (DPh
  • metal chelate compound catalyst used in preparing the autocatalyst solution, but a metal chelate compound containing a / 9 diketone or macrocyclic polyether as a ligand is preferably used.
  • a metal chelate compound containing a / 9 diketone or macrocyclic polyether as a ligand is preferably used.
  • the type of metal ion is not particularly limited, but a metal having a large complex formation constant with a ligand can be suitably used.
  • Such metal chelate compounds include, for example, tris (acetylethylacetonato) aluminum (111), tris (ethyl ethylacetonato) aluminum (111), tris (ethyl malonato) aluminum (111) , Bis (acetylacetonato) copper (11), tetrakis (acetylacetonato) zirconium (IV), tris (acetylacetonato) chromium (I ⁇ ), tris (acetylacetonato) cobalt ⁇ -), titanium oxide ( ⁇ ) acetyl acetate [(CH 3 COCHCOCH 3 ) 2 T i 0], etc .; S-diketone metal chelates, rare earth metal S-diketone metal chelates, 18-crown Macrocyclic polyether compounds such as 1-6-rhodium chelate salt, 12-crown-14-lithium chelate compound salt, 15-crown-15-so
  • the amount of the metal chelate compound catalyst to be added when preparing the autocatalyst solution is not particularly limited, and can be selected according to the catalytic effect. However, usually, the amount is not less than 0.01 mol% based on the alkoxysilane. Preferably, it is at least 0.05 mol%, more preferably at least 0.05 mol%. If the amount of the metal chelate compound catalyst is less than 0.001 mol% with respect to the alkoxysilane, the catalytic effect of hydrolysis may not be sufficiently exhibited. There is no particular upper limit on the amount of the metal chelate compound catalyst to be added to the alkoxysilane, as long as the metal chelate compound is uniformly dissolved.
  • the solvent of the solution containing the silicone oligomer as the main agent (A) is an alcohol formed by hydrolysis of alkoxysilane.
  • the alcohol produced by hydrolysis as a solvent without adding another solvent, it is possible to prepare a silicone oligomer solution that is stable and has a high solid content.
  • the molecular weight of the silicone oligomer is not particularly limited, and the silicone oligomer produced by the hydrolysis and condensation polymerization of the alkoxysilane is dissolved in the alcohol produced at the same time and becomes uniform. Higher molecular weight silicone oligomers can be used as long as a solution is formed.
  • M ⁇ C he) P (OR 3 ) q used as the curing agent (B) (where M 1 is a trivalent or higher-valent metal, and Che is a chelating agent , R 3 is an alkyl group having 1 to 4 carbon atoms, and P ⁇ l and q ⁇ 2.) or a partially hydrolyzed product thereof, a volatile acid and an amine silane coupling agent.
  • the solution is a curing agent for curing at room temperature. It is added to and mixed with the solution containing the silicone oligomer, which is the main component (A), to promote the formation of a siloxane network and gradually increase the catalytic effect after film formation.
  • the curing agent is MC he) P (OR 3 ) q (including partial hydrolyzate), a complex salt composed of a volatile acid and an amine silane coupling agent, or M ⁇ C he) P (OR 3 ) q (including partial hydrolyzate), a complex salt composed of a volatile acid and an amine-based silane coupling agent, and a volatile acid or an amine-based silane coupling agent can also be prepared.
  • the composition prepared as described above is also included in the curing agent (B) of the composition of the present invention.
  • the curing agent (B) When the curing agent (B) is added to and mixed with the main agent (A), when M 1 —OR 3 in the curing agent (B) undergoes a dealcoholization reaction with the silanol group of the silicone oligomer in the main agent (A) Both have a catalytic effect on the dehydration reaction between the silicone oligomers and promote the formation of siloxane crystals. On the other hand, it is considered that the curing agent (B) contains a complex salt formed by the reaction between the volatile acid and the amine-based silane coupling agent.
  • the amine-based silane coupling agent reacts with the alcohol as in the case of MC he) P (OR 3 ) q (including partial hydrolyzate). As a result, they enter the polysiloxane network by themselves, but due to these actions, the touch drying during the formation of the coating film is accelerated. The amino group and imino group in the form of a complex salt are hardly maintained as they are. Trifle is longer. After the formation of the film, the volatile acid is gradually released from the coating film, and the amino group and imino group in the form of a complex salt are returned to the free amino group and imino group.
  • the polycondensation of hydroxyl is further promoted, and the hydroxyl group is reduced.
  • Amine silane cutlet Since the coupling agent itself enters the polysiloxane network, the catalytic effect of the amino group or imino group functions for a long time, and as a result, the polysiloxane with the developed network can be obtained at room temperature.
  • the trivalent or higher valent metal ion represented by M 1 is not particularly limited, In order to avoid rapid gelation of the coating composition after being added to and mixed with (A), it is preferable that the metal ion be a metal ion which forms a stable complex. Examples of such metal ions, e.g., A 1 3+, G a 3+ , I n 3+, L a 3+, F e 3+, Y 3+, E u 3+, Ti 4+, Z r 4+ and the like.
  • T i 4+ and Z r 4+ are more preferred, and T i 4+ is most preferred from the viewpoint of crack resistance of the coating film.
  • the partial hydrolyzate can simply part of OR 3 are not human Dorokishiru group converted partial hydrolyzate to OH only, fused also used Natsuta partial hydrolyzate and polynuclear complex. M 1 in the polynuclear complex may be all the same or different.
  • the alkoxyl group OR 3 is a reactive functional group, for example, main butoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, sec- butoxy group, and the like tert- butoxy Can be.
  • M 1 (C he) p ( ⁇ R 3 ) q by setting q ⁇ 2, that is, by setting the number of alkoxyl groups OR 3 as reactive functional groups to 2 or more, M ⁇ Ch e) P (OR 3 )
  • q promotes crosslinking by catalysis of the dehydration reaction
  • the effect of itself as a crosslinking agent in the silicone oligomer solution or in the formed coating film is exhibited.
  • p ⁇ 1 that is, the presence of the chelating agent represented by Ch e enhances the stability of the curing agent for room temperature curing, and its handling is improved. It will be easier.
  • the chelating agent is not particularly limited, but 3-diketones can be suitably used. Examples of 8-diketones include acetylacetone, ethyl acetate, and getyl malonate.
  • the volatile acid in the curing agent (B) is not particularly limited, and examples thereof include volatile inorganic acids such as hydrochloric acid and nitric acid, and organic acids having a boiling point of 200 ° C or less, preferably 170 ° C or less.
  • organic acids include, for example, formic acid, acetic acid, propionic acid, butyric acid.
  • Examples thereof include carboxylic acids such as acid, isobutyric acid, valeric acid, isovaleric acid, acrylolic acid, isocrotonic acid, and methacrylic acid.
  • One of these volatile acids can be used alone, or two or more can be used in combination.
  • One of these amine-based silane coupling agents can be used alone, or two or more can be used in combination.
  • the mixing ratio of the curing agent (B) M ⁇ C he formulated as) P ( ⁇ _R 3) q, or a partial hydrolyzate thereof and an amine silane cutlet coupling agent is 1: 9 To 9: 1 (molar ratio), and more preferably 3: 7 to 7: 3 (molar ratio). If the amount of the amine-based silane coupling agent is larger than this mixing ratio, the organic groups derived from the amine-based silane coupling agent remaining in the coating film will increase, and the weather resistance of the coating film may be reduced. If the amount of the amine-based silane coupling agent is smaller than this mixing ratio, the curing rate after film formation may be reduced.
  • the mixing ratio of the volatile acid to the amine silane coupling agent is preferably 1: 4 to 3: 1 (molar ratio), more preferably 1: 3 to 2: 1 (molar ratio). I like it. If the acid content is less than this mixing ratio, the free amino groups or free imino groups present in the coating solution become too large, and the pot life may be shortened. When the acid is higher than this mixing ratio, M ⁇ including C he) P (OR 3) q ( partial hydrolyzate) and ligand exchange, the curing property is lowered, possibly touch dry time is longer is there.
  • the addition amount of the curing agent (B) in terms of solid content is preferably 0.1 to 20 parts by weight based on 100 parts by weight of solid content of the base material (A).
  • the amount of the hardener (B) added to the base material (A) on a solid basis basis of less than 0.1 part by weight relative to 100 parts by weight of the base agent (A) is less than 0.1 part by weight, the effect as a curing agent for room temperature curing becomes insufficient.
  • the amount of the curing agent (B) added to the solid content of 100 parts by weight of the base agent (A) in terms of the solid content is 20 parts by weight.
  • the amount of alkoxyl groups derived from M ⁇ CheCO R 3 ) (including partial hydrolyzate) and the amine-based silane coupling agent increases, and the crosslinking effect of the polysiloxane decreases, and the properties of the coating film decrease. May decrease.
  • a solution containing the silicone oligomer of the main agent (A) is added to a solution containing an organic solvent as a dispersion medium, and a sol.
  • Oxide sols such as antimony sol and alumina sol can be added.
  • an inorganic pigment having high weather resistance can be used by dispersing it in a solution containing the silicone oligomer of the main agent (A).
  • the inorganic pigment include, for example, titanium oxide, iron oxide, alumina, zinc oxide, titanium yellow, cobanolette, kaolin, and the like.
  • a needle-like substance such as glass fiber or whiskers, or a powder-like substance such as carbon black may be added.
  • the silicone oligomer of the main agent (A) When a large amount of pigment is added to the solution containing the silicone oligomer of the main agent (A), 100 parts by weight of alkoxysilane used as a raw material, in addition to the generated alcohol and the dispersion medium in the oxide sol, is added. Less than 50 parts by weight of a hydrophilic organic solvent can be added. If the amount of the hydrophilic organic solvent to be added is more than 50 parts by weight based on 100 parts by weight of the alkoxysilane, the volatile component may increase and the economic efficiency may be impaired.
  • the addition amount of the hydrophilic organic solvent is more preferably 20 parts by weight or less based on 100 parts by weight of the alkoxysilane used as the raw material.
  • the hydrophilic organic solvent to be added is not particularly limited, but a volatile solvent having a low boiling point such as methanol, ethanol, propyl alcohol, isopyl propyl alcohol, and acetone can be suitably used.
  • the hydrophilic organic solvent refers to an organic solvent which is mixed uniformly with water at an arbitrary ratio at ordinary temperature.
  • the coating method for forming the organopolysiloxane coating film from the coating composition of the present invention is not particularly limited, and any known coating method may be used according to the shape of the object to be coated, the purpose of the coating, and the like. You can select the construction method. For example, various coating methods such as a spray method, an immersion method, a flow method, and a roll method can be selected.
  • the coating thickness is Can be appropriately selected according to the purpose of the above, but usually it is preferably 1 to 50 ⁇ .
  • Coating an inorganic substrate such as metal, glass, ceramic, concrete, or an organic substrate such as acrylic resin, ABS resin, wood, or paper to form an organopolysiloxane coating film, It can protect and enhance aesthetics. Further, it can be suitably used as an intermediate layer between the photocatalytic film and the substrate.
  • Example 1 Coating an inorganic substrate such as metal, glass, ceramic, concrete, or an organic substrate such as acrylic resin, ABS resin, wood, or paper to form an organopolys
  • the pot life of the coating composition was measured by placing the coating composition in a glass container, sealing the container, storing it in a constant temperature room at 20 ° C, and observing the condition every 6 hours until 48 hours. The longest time to maintain fluidity without gelling was defined as the pot life.
  • the dry time to the touch was measured according to JIS 540.6.5, and the pencil grip value was measured according to JIS 540.8.4.2.
  • a mixture of 126 parts by weight of methyltriethoxysilane [Shin-Etsu Chemical Co., Ltd., LS-1890] and 45 parts by weight of phenyltrimethoxysilane [Shin-Etsu Chemical Co., Ltd., LS-2750] was used as an autocatalyst.
  • 1 part by weight of the silicone oligomer solution A-2 was added, and 0.1 part by weight of tris (acetylacetonato) aluminum ( ⁇ ) [Dohjin Chemical Laboratory Co., Ltd.] was added.
  • This solution was stirred at room temperature for 30 minutes to dissolve tris (acetylacetonato) aluminum ( ⁇ ), and then 33 parts by weight of distilled water was added thereto with stirring for 1 hour.
  • the mixture was allowed to stand at room temperature to obtain a transparent silicone solution A-3.
  • the solids content of the silicone oligomer solution is about 36% by weight.
  • a mixed solution of 130 parts by weight of methyltriethoxysilane [Shin-Etsu Chemical Co., Ltd., LS-1890] and 42 parts by weight of dimethyl ethoxysilane [Shin-Etsu Chemical Co., Ltd., LS-1370] was mixed with an autocatalyst.
  • 50 parts by weight of the silicone oligomer solution A-12 were added, and 0.1 part by weight of tris (acetylacetonato) aluminum (III) [Dohjin Chemical Laboratory Co., Ltd.] was added.
  • This solution was stirred at room temperature for 30 minutes to dissolve tris (acetylacetonato) aluminum (III), and then 29 parts by weight of distilled water was added thereto with stirring for 1 hour. After standing at room temperature for 1 day, a clear silicone oligomer solution A-4 was obtained.
  • the solids content of this silicone oligomer solution is about 35% by weight.
  • Production Example 6 (Production of curing agent for room temperature curing) After adding 50 parts by weight of aluminum tri-n-butoxide to 500 parts by weight of isopropyl alcohol, 20 parts by weight of acetyl acetone was reacted. To this solution was added 35 parts by weight of y-aminopropyltriethoxysilane [Shin-Etsu Chemical Co., Ltd., KBE903], mixed, and allowed to react with 12 parts by weight of acetic acid. A curing agent B-2 was obtained.
  • Production Example 8 (Production of curing agent for room temperature curing)
  • Example 2 100 parts by weight of a room temperature curing hardener B-1 was added to 100 parts by weight of the silicone oligomer solution A-2 to obtain a coating composition.
  • the pot life of the obtained coating composition was 30 hours.
  • This coating composition was applied to a glass substrate (2 mm thick) by a spray method. The touch dry time was within 30 minutes. After drying at room temperature for one month, the film thickness of the obtained coating film was measured and found to be 15 ⁇ m.
  • the pencil-pull value of this coating film was 2H.
  • the coating film was rubbed 50 times with absorbent cotton impregnated with xylene and absorbent cotton impregnated with ethanol, respectively, and the appearance was observed with the naked eye. As a result, no abnormality was found in any case.
  • a room temperature curing hardener B-2 100 parts by weight of a room temperature curing hardener B-2 was added to 100 parts by weight of the silicone oligomer solution A-2 to obtain a coating composition.
  • the pot life of the obtained coating composition was 48 hours or more.
  • This coating composition was applied to a glass substrate (2 mm thick) using a spray method. The touch dry time was within 30 minutes. After drying at room temperature for one month, the thickness of the obtained coating film was measured and found to be 7 ⁇ m.
  • the pencil-pull value of this coating film was 4H. Furthermore, the coated film was rubbed 50 times with absorbent cotton impregnated with xylene and absorbent cotton impregnated with ethanol, respectively, and the appearance was visually observed.
  • a room temperature curing hardener B-4 100 parts by weight of a room temperature curing hardener B-4 was added to 100 parts by weight of the silicone oligomer solution A-2 to obtain a coating composition.
  • the pot life of the obtained coating composition was 48 hours or more.
  • This coating composition was applied to a glass substrate (thickness: 2 imn) using a spray method. The touch dry time was within 30 minutes. After drying for one month at room temperature, the film thickness of the obtained coating film was measured. The pencil-pull value of this coating film was 2H. Further, the coating film was rubbed 50 times with absorbent cotton impregnated with Kinren and ethanol-impregnated cotton, respectively. After observing the appearance with the naked eye, no abnormality was found in any case.
  • a room temperature curing hardener B-1 100 parts by weight of a room temperature curing hardener B-1 was added to 100 parts by weight of the silicone oligomer solution A-3 to obtain a coating composition.
  • the pot life of the obtained coating composition was 18 hours.
  • the coating composition was applied to a glass substrate (thickness: 2) using a spray method. The touch dry time was within 30 minutes. After drying at room temperature for one month, the thickness of the obtained coating film was measured and found to be 16 m.
  • the pencil-pull value of this coating film was 3H. Further, the coating film was rubbed 50 times each with absorbent cotton impregnated with xylene and absorbent cotton impregnated with ethanol, and the appearance was visually observed. As a result, no abnormality was found in any case.
  • an organometallic compound of a trivalent or higher-valent metal, a volatile acid, and an amine-based silane coupling agent are compounded into the silicone oligomer solution as a curing agent for room temperature curing. Since the solution is added and mixed, the drying time to the touch is short, it cures at room temperature and can be applied on site, and it is possible to form an organopolysiloxane coating film with excellent chemical durability.

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Abstract

Composition de revêtement durcissant à froid contenant: un ingrédient principal (A) consistant en une solution d'un oligomère de silicone possédant une unité structurale moyenne R1nSiOx/2(OH)y(OR2)z dans laquelle R1 représente alkyle C¿1-3?, vinyle ou phényle, R?2¿ représente alkyle C¿1-3? et 0,8 ≤ n ≤ 1,7, 2 < x < 3,2, y > 0 et z > 0, étant donné que y + z = 4 - n- X; un durcissant (B) consistant en une solution obtenue par mélangeage de M?1(Che)¿p(OR3)q, dans laquelle M1 représente un métal dont la valence est égale ou supérieure à 3, Che représente un agent séquestrant, R3 représente alkyle C¿1-4?, p ≥ 1 et q ≥ 2, ou un de ses hydrolysats partiels avec un acide volatil et un agent de copulation de silane de type amine. Cette composition possède une durée de conservation prolongée et une durée limitée sans propriété adhésive. Elle durcit à température ordinaire et peut être appliquée sur place. Elle constitue une pellicule de revêtement d'organopolysiloxane possédant une durée chimique excellente.
PCT/JP2001/005186 2000-07-25 2001-06-18 Composition de revetement durcissant a froid WO2002008348A1 (fr)

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JP2000-223335 2000-07-25
JP2000223335A JP3499811B2 (ja) 2000-07-25 2000-07-25 常温硬化型コーティング組成物

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WO2002008348A8 WO2002008348A8 (fr) 2002-02-28

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06299073A (ja) * 1993-04-14 1994-10-25 Toshiba Silicone Co Ltd 水分散シリコーン樹脂組成物
JPH08151552A (ja) * 1994-11-29 1996-06-11 Japan Synthetic Rubber Co Ltd ハードコートフィルム
JPH1060375A (ja) * 1996-08-22 1998-03-03 Toshiba Silicone Co Ltd 防錆用コーティング剤組成物および基材の防錆方法
JPH1147688A (ja) * 1997-08-07 1999-02-23 Jsr Corp 樹脂成形品
JPH11256041A (ja) * 1998-03-12 1999-09-21 Tsb:Kk 無機系樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06299073A (ja) * 1993-04-14 1994-10-25 Toshiba Silicone Co Ltd 水分散シリコーン樹脂組成物
JPH08151552A (ja) * 1994-11-29 1996-06-11 Japan Synthetic Rubber Co Ltd ハードコートフィルム
JPH1060375A (ja) * 1996-08-22 1998-03-03 Toshiba Silicone Co Ltd 防錆用コーティング剤組成物および基材の防錆方法
JPH1147688A (ja) * 1997-08-07 1999-02-23 Jsr Corp 樹脂成形品
JPH11256041A (ja) * 1998-03-12 1999-09-21 Tsb:Kk 無機系樹脂組成物

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JP3499811B2 (ja) 2004-02-23
JP2002038088A (ja) 2002-02-06
WO2002008348A8 (fr) 2002-02-28

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