WO2019073698A1 - Method for forming surface protective coating film for floor surfaces - Google Patents

Method for forming surface protective coating film for floor surfaces Download PDF

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Publication number
WO2019073698A1
WO2019073698A1 PCT/JP2018/031007 JP2018031007W WO2019073698A1 WO 2019073698 A1 WO2019073698 A1 WO 2019073698A1 JP 2018031007 W JP2018031007 W JP 2018031007W WO 2019073698 A1 WO2019073698 A1 WO 2019073698A1
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WIPO (PCT)
Prior art keywords
forming
coating
floor
coat layer
hard coat
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PCT/JP2018/031007
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French (fr)
Japanese (ja)
Inventor
井上　剛
亮史 樋口
勇也 平本
永野　裕幸
Original Assignee
関西ペイント株式会社
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Application filed by 関西ペイント株式会社 filed Critical 関西ペイント株式会社
Priority to JP2019547936A priority Critical patent/JP7060609B2/en
Priority to MYPI2020001746A priority patent/MY195486A/en
Publication of WO2019073698A1 publication Critical patent/WO2019073698A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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

Definitions

  • the present invention can form a coating excellent in abrasion resistance, water resistance and glossiness by maintaining the floor surface of an office building, a commercial facility, a convenience store, etc., and can maintain the aesthetic appearance of the floor surface for a long time
  • the present invention relates to a method for forming a surface protective coating on a floor surface.
  • an aqueous floor polish is used for the purpose of protecting floor materials from scratches and dirt, etc., as well as providing gloss and improving the appearance.
  • these aqueous floor polishes having a resin emulsion as a main component have a problem that scratches and dirt easily accumulate due to walking of a person or transportation of a carriage, and the gloss (aesthetic appearance) is reduced early.
  • no improvement is found in the maintenance for cleaning, it is necessary to peel off the coating on the floor surface, and there is an inherent problem that the wastewater generated at that time becomes an industrial waste.
  • Patent Document 1 discloses a floor coating agent comprising an aqueous urethane resin, water, and 1- (2-methoxy-2-methylethoxy) -2-propanol. .
  • the floor coating agent described in Patent Document 1 is excellent in durability, adhesion, gloss and the like because a film is formed of an aqueous urethane resin, but a lacquer type (a volatilization-drying type coating formed by evaporating a solvent) Since the crosslink density is low, abrasions occur early and there is a problem that the appearance can not be maintained for a long time.
  • Patent Document 2 a polyorgan having an average of 0.9 to 1.1 hydrocarbon groups bonded to a silicon atom per silicon atom, and at least two hydroxyl groups bonded to a silicon atom per molecule.
  • a room temperature curable floor coating composition containing a siloxane resin and having a slip resistance of 0.10 kgf or greater is disclosed.
  • the floor coating agent described in Patent Document 2 can obtain a film excellent in drying property and curability by a polyorganosiloxane resin having a silanol group, but since the polarity of the resin is low, adhesion may not be obtained depending on the type of floor material. It might have been enough.
  • Patent Document 3 a floor surface on-site coating curing method is applied in which various cold setting drying type coating compositions are applied to a floor surface, a primer layer is applied, and then an ultraviolet curing middle coat and / or a top coat is cured.
  • a primer layer is applied to a floor surface
  • an ultraviolet curing middle coat and / or a top coat is cured.
  • the invention described in Patent Document 3 requires a large-scale apparatus for curing the top coat with ultraviolet light
  • the primer disclosed in Patent Document 3 has a problem in drying property, and coating workability, the process film obtained The water resistance, finish and adhesion were not always satisfactory.
  • the present invention has been made in view of the above-mentioned circumstances, and the construction can be carried out simply and in a short time, and the adhesion, finish, tear resistance, scratch resistance and glossiness of the obtained surface protective film are excellent.
  • a method of forming a surface protective film on a surface is provided.
  • the inventors of the present invention conducted intensive studies and found that when forming a hard coat layer by a coating agent for forming a hard coat layer on a floor surface, a cured coating layer by a specific room temperature curing urethane primer composition in advance. It has been found that the above problems can be solved by including the step of forming
  • the present invention provides a method of forming a surface protective coating on a floor surface, which includes the following aspects: (Aspect 1) A step of coating a room temperature curing type urethane primer composition (A) on a floor surface to form a cured coating layer (I) by the composition, and then applying a coating agent for forming a hard coat layer (B), A method of forming a surface protective film on a floor surface comprising the step of forming one hard coat layer (II), wherein the cold-curable urethane primer composition (A) is The main component containing a hydroxyl group-containing acrylic resin (a) and a curing agent containing a polyisocyanate compound (b), and the isocyanate group of the polyisocyanate compound (b) contained in the curing agent and the hydroxyl group contained in the main component A method of forming a surface protective film on a floor surface, wherein the ratio (NCO / OH) of the contained acrylic resin (a) to the hydroxyl group is in the range
  • Aspect 2 Aspect 1 in which the hard coat layer-forming coating agent (B) contains an epoxysilane oligomer (c), colloidal silica (d) having an average particle diameter in the range of 1 to 100 nm, and a curing catalyst (e) The surface protective film formation method of the floor surface as described in-.
  • a room temperature curing type urethane primer composition forms a film even at normal temperature, so It can be easily constructed, the coating time in the painting process is short, and the construction period can be shortened.
  • the multilayer film (it may be abbreviated as a process film) formed by this method is excellent in adhesion with the floor material, and has a coating film such as finish, resistance to rubbing, scratch resistance and gloss. Physical properties can be maintained for a long time.
  • a floor surface is coated with a specific cold-curable urethane primer composition (A) to form a cured coating layer (I) of the composition, and then a hard coat is formed on the cured coating layer. Applying a layer forming coating agent (B) to form at least one hard coat layer (II).
  • the object to which this method is applied is a floor surface.
  • the floor surface is constituted by a general floor material, for example, ceramic floor materials such as porcelain and porcelain tiles; metal floor materials such as iron and aluminum; and wood floors such as natural wood and plywood Materials: Synthetic resin flooring such as vinyl chloride resin; Stone flooring such as granite and marble; flooring made of composites of these materials, etc .; and protective seal and old paint film provided on the surface It may also be one.
  • the shape and size of the floor material are not particularly limited. It may be either a new floor or an existing floor.
  • a vinyl chloride resin-based floor material is preferable as a substrate to which the present method is applied.
  • This method uses a specific cold-curable urethane primer composition (A).
  • the said room temperature curing type urethane primer composition (A) can be coated by publicly known means, such as mop coating, spray coating, roller coating, brush coating, flow coating, for example. It can be appropriately selected and used according to the site where the material is applied.
  • the number of times of coating is not particularly limited, and may be applied one or more times.
  • the dry film thickness varies depending on the condition of the object to be coated and the surrounding environment, but can generally be in the range of 3 to 50 ⁇ m, preferably 7 to 30 ⁇ m at one time.
  • a drying method normal temperature drying is adopted, and a coating film can be obtained by drying, but there is no particular problem even if it is dried by heating or forced drying depending on the coating environment and the like. You may use wind drying together using a blower etc. as needed.
  • a coating can be obtained by drying under an environment of 5 to 45.degree.
  • the relative humidity (hereinafter sometimes abbreviated as RH) at the time of coating is preferably 80% or less, particularly 70% or less.
  • a circulator or the like When wind drying is used in combination, for example, a circulator or the like is installed in a normal temperature environment, and ventilation is performed for 10 to 60 minutes, preferably 15 to 55 minutes, thereby promoting drying and a coating film having a uniform curing state. You can get
  • the drying time after coating of the room temperature curing type urethane primer composition (A) used in the present method is to dry until the cured state becomes a semi cured dry state or more, the finish of the process film obtained and the hard coat described later It is preferable from the point of the crack resistance at the time of forming a layer.
  • the semi-cured and dried state means the semi-cured and dried state defined in JIS K 5600-1-1 (2004), that is, the center of the coated surface is gently rubbed with a fingertip and coated. It is a coating film in a state where no marks are formed on the surface.
  • a cured coating film less than the semi-cured and dried state is a state in which the coating film has not reached the cured and dried state, and refers to the non-touch-dried state specified in JIS K 5600-1-1 (2004). .
  • the room temperature curing type urethane primer composition (A) of the present method is excellent in finishability and adhesion when a coating agent (B) for forming a hard coat layer described later is applied repeatedly if it is at least the above-mentioned semicured and dried state.
  • a surface protective coating can be formed on the floor surface.
  • the initial drying property means the time until the coated film state reaches the cured and dried state, and the shorter the better, the better the drying property and the quick drying property.
  • the room temperature curing type urethane primer composition (A) used in the present method is brought into the semi-cured dry state, but for example, when the dry film thickness is 50 ⁇ m or less It may be less than 3 hours, and may be 1 to 2 hours.
  • This method using a room temperature curing type urethane primer composition (A) as a primer (primer) can coat a coating agent (B) for forming a hard coat layer described later in a relatively short time, and is excellent in working efficiency .
  • a coating agent (B) for forming a hard coat layer described later in a relatively short time, and is excellent in working efficiency .
  • this method there is no particular problem even if it takes a long time such as 3 hours or more until the time of overpainting.
  • a cured coating layer (I) is formed by the cold-curable urethane primer composition (A).
  • the cured coating layer (I) preferably has a Martens hardness of 30 N / mm 2 or more, particularly preferably 50 to 300 N / mm 2 under the following conditions from the viewpoint of the warpage resistance of the step film. is there.
  • Martens hardness is a test plate obtained by applying a sample to a glass plate using an applicator so that the dry film thickness is 20 ⁇ m and drying for 24 hours under an atmosphere of 23 ° C. and 50% relative humidity. It is a value measured using an ultra-microhardness tester.
  • ultra-micro hardness tester examples include Fisher Scope HM-2000 (trade name) manufactured by Fisher Instruments Co., Ltd., etc., using a Vickers indenter under an atmosphere of 23 ° C. and 50% relative humidity. The load shall be measured under the condition of 20 mN / 25 seconds.
  • the hard coat layer-forming coating agent (B) is applied on the cured coating layer (I) of the room temperature curing type urethane primer composition (A) to form at least one hard coat layer (II). Do.
  • the coating agent (B) for hard-coat layer formation As a coating method at the time of coating the coating agent (B) for hard-coat layer formation, it can be coated by publicly known means, such as mop coating, spray coating, roller coating, brush coating, flow coating, for example. It can be appropriately selected and used according to the site where the material is applied. Furthermore, it is also possible to wipe off the excess after painting if necessary.
  • publicly known means such as mop coating, spray coating, roller coating, brush coating, flow coating, for example. It can be appropriately selected and used according to the site where the material is applied. Furthermore, it is also possible to wipe off the excess after painting if necessary.
  • the number of times of coating is not particularly limited, and may be applied one or more times.
  • the dry film thickness per one time can be in the range of 2 to 50 ⁇ m, preferably 3 to 30 ⁇ m, from the viewpoint of finishability and resistance to cracking.
  • Drying of the formed coating film can be carried out by normal temperature drying, but depending on the coating environment etc., heat drying or forced drying may be carried out. Moreover, you may use wind drying together using a blower etc. as needed.
  • a coating can be obtained by drying under an environment of 5 to 45.degree.
  • the relative humidity (hereinafter sometimes abbreviated as RH) at the time of coating is preferably 80% or less, particularly 70% or less.
  • a circulator or the like may be installed in a normal temperature environment to promote drying by ventilating during drying.
  • a cured coating layer (I) is formed on a floor surface by a specific room temperature curing type urethane primer composition (A), and a hard coating layer to be described later is formed on the coating layer (I).
  • A room temperature curing type urethane primer composition
  • a hard coating layer to be described later is formed on the coating layer (I).
  • the room temperature curing type urethane primer composition (A) applied to the present method is to form a coating film having a urethane bond in a coating film after curing, and a main agent containing a hydroxyl group-containing acrylic resin (a) and a polyisocyanate
  • a ratio of the isocyanate group of the polyisocyanate compound (b) contained in the curing agent to the curing agent containing the compound (b) and the hydroxyl group of the hydroxyl group-containing acrylic resin (a) contained in the main agent (NCO / OH) is characterized in that it is in the range of 0.7 to 2.0.
  • the coating agent (B) for forming a hard coat layer can be coated in a short time, and at the same time, the finishability, cracking resistance and scratch resistance are achieved.
  • An excellent surface protective film can be formed.
  • the NCO / OH is preferably in the range of 0.8 to 1.8, more preferably in the range of 0.9 to 1.6, from the viewpoint of the finish and the pot life of the room temperature curing type urethane primer composition (A).
  • a range of more than 1.0 and less than 1.6 is more preferable.
  • the room temperature curing type urethane primer composition (A) applied to this method may be any form of water-based paint and organic solvent type paint, as long as it can be cured at normal temperature and forms a polyurethane cross-linked coating film. Good.
  • the composition applied to the present method is preferably an aqueous coating composition from the viewpoint of reducing the environmental impact and the point of odor.
  • the hydroxyl group-containing acrylic resin (a) contained in the main agent is a component to be a polyurethane cross-linked film-forming component together with the later-described polyisocyanate compound (b).
  • the glass transition temperature (hereinafter sometimes abbreviated as Tg) of the hydroxyl group-containing acrylic resin (a) is preferably in the range of 20 to 90 ° C. from the viewpoint of the initial drying property and the warpage resistance of the surface protective film. From the viewpoint of durability, the range of 25 to 80 ° C. is more preferable, and the range of 30 to 70 ° C. is more preferable.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin (a) is preferably in the range of 15 to 200 mg KOH / g, more preferably in the range of 30 to 180 mg KOH / g, from the viewpoint of the balance between initial drying and pot life. More preferably, it is in the range of ⁇ 160 mg KOH / g.
  • the glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin is a value calculated by the following equation.
  • W 1 , W 2 ,... W n are mass fractions of respective monomers
  • T 1 , T 2 ... T n are glass transition temperatures Tg (K) of homopolymers of respective monomers .
  • the glass transition temperature of the homopolymer of each monomer is described in POLYMER HANDBOOK Fourth Edition, J. Org. Brandrup, E. h. Immergut, E., et al. A.
  • the glass transition temperature of a monomer which is a value according to Grulke (1999) and which is not described in the literature is static when a homopolymer of the monomer is synthesized to have a weight average molecular weight of about 50,000. Let it be the glass transition temperature.
  • the static glass transition temperature is obtained, for example, by taking a sample in a measuring cup and vacuum suction to completely remove the solvent, and then using a differential scanning calorimeter “DSC-50Q type” (trade name, manufactured by Shimadzu Corporation), It can be measured by measuring the heat change in the range of -100 ° C. to 150 ° C. at a heating rate of 3 ° C./min, and using the initial baseline change point on the low temperature side as the static glass transition temperature. .
  • DSC-50Q type trade name, manufactured by Shimadzu Corporation
  • hydroxyl group-containing acrylic resin (a) usually, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer can be obtained by a conventionally known method, for example, It can be produced by copolymerization by a method such as a solution polymerization method in an organic solvent or an emulsion polymerization method in water.
  • hydroxyl group-containing polymerizable unsaturated monomer examples include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid and monoester of dihydric alcohol of 2 to 8 carbon atoms; ⁇ -caprolactone modified product of monoester of (meth) acrylic acid and dihydric alcohol of 2 to 8 carbon atoms; allyl alcohol Etc. can be mentioned.
  • polymerizable unsaturated monomers copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer for example, methyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert- Alkyl or cycloalkyl (meth) acrylates such as butyl (meth) acrylate and cyclohexyl (meth) acrylate; polymerizable unsaturated monomers having an isobornyl group; polymerizable unsaturated monomers having an adamantyl group; vinyl aromatic compounds; alkoxysilyl groups Perfluoroalkyl (meth) acrylate; polymerizable unsaturated monomer having a fluorinated alkyl group; polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group; vinyl compound; ) Acrylic acid, maleic acid, black Carbox
  • hydroxyl group-containing acrylic resin (a) may be modified, and examples thereof include urethane modification, epoxy modification, silicone modification and the like.
  • the form of the hydroxyl group-containing acrylic resin (a) may be any of water dispersion type, water solubility, and organic solvent type, but from the viewpoint of safety and health of the coating environment and odor, water dispersion type or water solubility
  • the water dispersion type is preferable from the viewpoint of water resistance.
  • a conventionally known method can be used as a method for producing a water dispersion of a hydroxyl group-containing acrylic resin.
  • a method of emulsion-polymerizing a polymerizable unsaturated monomer in the presence of an emulsifier, or a part or all of an anionic group such as a carboxyl group contained in a resin produced by the solution polymerization method is a basic compound such as an amine
  • an emulsifying agent or surfactant may be used, and excess organic solvent may be removed before addition of the neutralizing agent or after water dispersion.
  • the above-mentioned water-dispersed hydroxyl group-containing acrylic resin may be copolymerized by dividing the polymerizable unsaturated monomer components having different compositions into multiple steps, and it is not only a single layer but also a multilayer structure called core-shell type. It may be
  • the hydroxyl group-containing acrylic resin (a) When the hydroxyl group-containing acrylic resin (a) is dispersed in water, it is preferable to contain a carboxyl group-containing polymerizable unsaturated monomer from the viewpoint of the stability of the aqueous dispersion.
  • the carboxyl group-containing polymerizable unsaturated monomer is not particularly limited, but those exemplified for the carboxyl group-containing polymerizable unsaturated monomer can be used. Among them, acrylic acid and methacrylic acid are preferable.
  • a neutralizing agent may be added to the hydroxyl group-containing acrylic resin (a) to neutralize at least a part of the carboxyl groups.
  • the neutralizing agent is not particularly limited, and examples thereof include: ammonia; organic amines such as monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine and dimethylethanolamine; and inorganic bases such as sodium hydroxide and potassium hydroxide And the like. These neutralizing agents may be used alone or in combination of two or more.
  • the acid value of the hydroxyl group-containing acrylic resin (a) before neutralization is preferably 50 mg KOH / g or less from the viewpoint of the water dispersion stability of the acrylic resin, the storage stability and the water resistance of the coating film.
  • the weight average molecular weight of the hydroxyl group-containing acrylic resin (a) described above can be generally adjusted in the range of 3,000 to 2,000,000, and from the viewpoint of coating workability and initial drying property, 5 A range of from 1,000 to 1,000,000 is preferable.
  • the hydroxyl group-containing acrylic resin (a) is a resin produced by a solution polymerization method
  • the weight average molecular weight of the resin (a) is 3,000 to 100,000, and further 5,000 to 60.
  • the range of 1,000 is more preferable.
  • the acid value of the hydroxyl group-containing acrylic resin (a) produced by the solution polymerization method is preferably in the range of 0 to 50 mg KOH / g, from the viewpoint of production stability, storage stability, and water resistance of the coating film. It is more preferably in the range of ⁇ 48 mg KOH / g.
  • the weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) based on standard polystyrene.
  • the measurement in the following production examples etc. is “HLC8120GPC” (trade name, manufactured by Tosoh Corp.) as a GPC apparatus, “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” as a column, Using four “TSKgel G-2000HXL” (all manufactured by Tosoh Corp., trade name): Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: performed under RI conditions.
  • the average particle diameter of the dispersion resin is preferably in the range of 0.05 to 1.0 ⁇ m, and more preferably in the range of 0.08 to 0.8 ⁇ m. preferable.
  • a sample is diluted with deionized water to a concentration suitable for measurement with Coulter Counter N4 (trade name, manufactured by Beckman Coulter, Inc., particle size distribution measuring apparatus), The value is measured at about 20 ° C.
  • the resin solid content of the hydroxyl group-containing acrylic resin (a) is preferably about 35 to 65% by mass from the viewpoint of the dispersion stability of the hydroxyl group-containing acrylic resin (a).
  • resin solid content is a value calculated by collecting about 2.0 g of a sample in an aluminum foil cup having a diameter of about 5 cm and measuring the residual content (g) after heating at 110 ° C. for 1 hour It is.
  • polyisocyanate compound (b) contained in the curing agent used in the present invention is a compound having two or more free isocyanate groups in one molecule, and has conventionally been used for the production of polyurethane Can be used.
  • aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like; alicyclic diisocyanates such as 4,4'-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate; Aromatic diisocyanates such as diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane diisocyanate (hereinafter referred to as polymeric MDI); and derivative compounds such as these isocyanurates and burettes.
  • polymeric MDI polymeric MDI
  • aliphatic diisocyanates, alicyclic diisocyanates and derivative compounds thereof are preferably used for at least a part of the components, and specifically, hexamethylene diisocyanate (HMDI), hexamethylene Derivative compounds of diisocyanate (HMDI), isophorone diisocyanate (IPDI), derivatives of isophorone diisocyanate (IPDI), and the like are preferably used.
  • HMDI hexamethylene diisocyanate
  • HMDI hexamethylene Derivative compounds of diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI derivatives of isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • hydrophilicized polyisocyanate compound in which a hydrophilic group such as a polyether group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or a betaine structure-containing group is introduced into the polyisocyanate compound, or a polyisocyanate using a surfactant.
  • a hydrophilic group such as a polyether group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or a betaine structure-containing group is introduced into the polyisocyanate compound, or a polyisocyanate using a surfactant.
  • polyisocyanate compounds for aqueous coatings such as water-dispersible polyisocyanate compounds, which allow the compounds to be dispersed in water.
  • the above polyisocyanate compounds can be used alone or in combination of two or more.
  • the room temperature curing type urethane primer composition (A) is an aqueous paint
  • the polyisocyanate compound (b) a polyisocyanate compound modified for an aqueous paint which can be mixed with water immediately before coating.
  • anionic group-containing polyisocyanate compounds are preferable from the viewpoint of the smoothness of the obtained coating film and the like.
  • the anionic group-containing polyisocyanate polyisocyanate compounds having a sulfonic acid group and / or a phosphoric acid group are particularly preferred.
  • the isocyanate group content of the polyisocyanate compound (b) is preferably in the range of 6 to 25% by mass from the viewpoint of interlayer adhesion and cracking resistance.
  • the isocyanate group content refers to the mass fraction of the amount of isocyanate groups contained in the compound.
  • the measurement of the amount of the isocyanate group can be performed in accordance with JIS K 1603-1 (2007). Specifically, it is a value determined by back titration of unreacted dibutylamine with a hydrochloric acid standard solution after adding an excess of dibutylamine to the sample to cause a reaction sufficiently.
  • the content of the polyisocyanate compound (b) contained in the curing agent is more preferably adjusted in the range of 10 to 99.9% by mass and 30 to 80% by mass based on the total mass of the curing agent.
  • the organic solvent for diluting the curing agent conventionally known ones can be used, but since they may react with the above-mentioned polyisocyanate compound (b), among the water-soluble solvents having no hydroxyl group It is preferable to select suitably.
  • an acetate type, a ketone type, an ester type, an ether type, a glycol ether type may be mentioned, and an acetate type water soluble solvent having no hydroxyl group, a glycol ether type having no hydroxyl group, from the viewpoint of safety and health and finishability. At least one selected from water-soluble solvents is preferred.
  • Examples of acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate (alias: n-butyl cellosolve acetate), diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate And 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (alias: methoxypropyl acetate), 1-methoxypropyl-2-acetate and the like.
  • ketone system As a ketone system, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone etc. are mentioned, for example.
  • esters examples include ethyl acetate (alias: ethyl acetate), butyl acetate (alias: butyl acetate), isobutyl acetate (alias: isobutyl acetate), methyl benzoate (alias: methyl benzoate), ethyl ethoxypropionate, propion Ethyl acid, methyl propionate and the like can be mentioned.
  • ether group examples include tetrahydrofuran, dioxane, dimethoxyethane, aromatic hydrocarbons, aliphatic hydrocarbons and the like.
  • glycol ethers include ethylene glycol diethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol divinyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether and the like Diethylene glycol diether; triethylene glycol diether such as triethylene glycol dimethyl ether, triethylene glycol divinyl ether; tetraethylene glycol diether such as tetraethylene glycol diethyl ether; propylene glycol dimethyl ether, pro Propylene glycol diethers such as propylene glycol diether, propylene glycol di-n-propyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether,
  • the content in the case of containing the organic solvent is 10% by mass or more, particularly 20 to 70% by mass from the viewpoint of the miscibility with the polyisocyanate compound (b), that is, the finish based on the total mass of the curing agent. It is preferable to adjust in the range of
  • urethane curing catalyst conventionally known ones can be used.
  • tin octylate dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin Diacetate, dioctyltin di (2-ethylhexanoate), dibutyltin oxide, dibutyltin sulfite, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zinc
  • bismuth octanoate bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobal
  • the content of the curing catalyst is room temperature curing, from the viewpoint of the balance between the drying property and the pot life (working life) and the water resistance of the coating film obtained and the finish of the step film. It is preferably in the range of 0.0001 to 1.0% by mass, more preferably in the range of 0.0005 to 0.5% by mass, relative to the total amount of solids in the urethane primer composition (A) .
  • the total solid content of the room temperature curing type urethane primer composition (A) refers to the resin solid content of the hydroxyl group-containing acrylic resin (a), the resin solid content of the polyisocyanate compound (b) and other additives to be blended It refers to the total mass of the active ingredient.
  • the active ingredient means the total mass of the residue obtained by removing the solvent such as water and organic solvent from the sample.
  • the room temperature curing type urethane primer composition (A) used in the present invention is a two-component type primer composition comprising a main agent containing the above-mentioned hydroxyl group-containing acrylic resin (a) and a curing agent, It can be easily prepared by mixing it with
  • the room temperature curing type urethane primer composition (A) is a resin other than the hydroxyl group-containing acrylic resin (a) (for example, polyurethane resin), a surface control agent, an extender pigment, a color pigment, if necessary, in addition to the above components.
  • Fillers eg, talc, glass beads, mica etc.
  • dyes eg, talc, glass beads, mica etc.
  • dispersion stabilizers e.g., viscosity modifiers
  • UV absorbers e.g., UV absorbers
  • light stabilizers e.g., UV absorbers
  • polymer particles e.g., polyethylene glycol
  • film forming aids e.g., film forming aids
  • preservatives e.g., antifoaming agents
  • neutralizing agents e.g., talc, glass beads, mica etc.
  • additives such as a leveling agent, a silane coupling agent, a plasticizer, an antifreeze agent, a fragrance, a pH adjuster, a flame retardant, and a dilution solvent.
  • additives such as a leveling agent, a silane coupling agent, a plasticizer, an antifreeze agent, a fragrance, a pH adjuster, a
  • talc is preferably 0.3 to 15% by mass with respect to the total solid content in the room temperature curing type urethane primer composition (A).
  • the amount of the polyurethane resin added is preferably 0.3 to 15% by mass, more preferably 1.0 to 10%, as the solid content of the polyurethane resin, based on the total solid content in the room temperature curing type urethane primer composition (A). It is mass%.
  • anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycol Surfactants and nonionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; silicone surfactants; fluorosurfactants and the like It can be mentioned.
  • silicone surfactants or fluorosurfactants are preferable from the viewpoint of the wettability to the floor material of the room temperature curing type urethane primer composition (A).
  • colloidal silica may be contained from the viewpoint of the warpage resistance of the multilayer film formed by the present method, and as the colloidal silica, those mentioned in the coating agent (B) for forming a hard coat layer described later are particularly mentioned It can be used suitably.
  • the room temperature curing type urethane primer composition (A) used in the present invention has a solid content of usually 15 to 15 in view of finish, ease of spreading on a floor surface and formation of a uniform crosslinked coating during coating.
  • the content is preferably 70% by mass, and more preferably 20 to 60% by mass.
  • the viscosity of the room temperature curing type urethane primer composition (A) is preferably 25 Pa ⁇ s or less from the viewpoint of coating workability.
  • the viscosity is a value measured by mixing a main agent and a curing agent under conditions of 23 ° C. and 50% RH for 1 minute, leaving it to stand for 1 minute, and using a B-type viscometer at 60 rpm.
  • the coating agent (B) for forming a hard coat layer applied to the present method is suitably used one that forms a coating having a siloxane bond in the coating after curing. can do.
  • the hydrolyzable group and the silanol group in the coating agent composition may be reacted to form a siloxane bond to form a three-dimensional glassy cured film.
  • a silica, a hydrolysable silane, and / or its condensate are mentioned, for example, Furthermore, a silane coupling agent etc. are mentioned, These are used individually or in combination suitably Can.
  • the coating agent (B) for forming the hard coat layer comprises an epoxysilane oligomer (c) as a hydrolyzable silane, colloidal silica (d) having an average particle diameter in the range of 1 to 100 nm, and a curing catalyst (e It is particularly preferable from the viewpoint of drying property, cracking resistance and scratch resistance that the ink composition contains
  • epoxysilane Oligomer (c) is a compound having an epoxy group and a siloxane bond in the molecule, and, for example, hydrolysis of an epoxy group-containing hydrolyzable silane represented by the following general formula (I) Hydrolyzed condensate (c2) of a condensate (c1) and / or a mixture of the epoxy group-containing hydrolyzable silane and a hydrolyzable silane represented by the following general formula (II) having no epoxy group Can be.
  • general formula (I) Hydrolyzed condensate (c2) of a condensate (c1) and / or a mixture of the epoxy group-containing hydrolyzable silane and a hydrolyzable silane represented by the following general formula (II) having no epoxy group Can be.
  • R 1 is an epoxy-containing organic group
  • X is a hydrolyzable group
  • a is an integer of 1 to 3.
  • the above-mentioned X is a hydrolyzable group, and examples thereof include an alkoxy group, an acetoxy group, an oxime group, an aminoxy group, a halogen atom and the like, and an alkoxy group having 1 to 6 carbon atoms which is easily available is preferable. From the viewpoint of reaction rate, a methoxy group is preferred.
  • organic group containing an epoxy group of R 1 include glycidoxy groups such as glycidoxypropyl group, (3,4-epoxycyclohexyl) methyl group, (3,4-epoxycyclohexyl) ethyl group And 3,4-epoxycyclohexyl groups.
  • hydrolyzable silane represented by the above general formula (I) examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane and the like can be mentioned.
  • R 2 is an organic group having no epoxy group
  • X is a hydrolyzable group which may be the same or different
  • a represents an integer of 0 to 3].
  • the organic group having no epoxy group is preferably a monovalent organic group having 1 to 18 carbon atoms in view of scratch resistance, and may be linear or branched, and urethane bond, ester bond, ether bond And may be substituted by halogen such as fluorine.
  • hydrolyzable silane represented by the above general formula (II) for example, a monofunctional, bifunctional, trifunctional or tetrafunctional hydrolysis wherein the a is an integer of 0 to 3
  • Degradable silanes can be mentioned.
  • trifunctional hydrolyzable silanes where a 1, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, partially hydrolyzed condensate of methyltrimethoxysilane (trade name “KC-89S”, Shin-Etsu Chemical Co., Ltd.), p-styryltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Triethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysi
  • difunctional hydrolyzable silanes where a 2, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyl Dimethoxysilane, methylpropyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldisilane
  • Ethoxysilanes and organohalosilanes such as dimethyldichlorosilane and trimethylchlorosilane can be mentioned.
  • tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraphenoxysilane, and the like; tetrahalosilanes such as tetrachlorosilane; It can be mentioned.
  • the monofunctional, bifunctional, trifunctional or tetrafunctional hydrolyzable silanes may be used in combination of two or more, if necessary.
  • the weight average molecular weight of the epoxysilane oligomer (c) is preferably adjusted to be in the range of 500 to 20,000, and more preferably in the range of 800 to 10,000, from the viewpoint of improving the drying property and the cracking resistance. It is preferable to be adjusted to be inside.
  • the epoxy equivalent of the epoxysilane oligomer (c) is preferably in the range of 150 to 1,000 (g / eq), and in the range of 200 to 800 (g / eq), from the viewpoint of water dilution stability and curability. Is more preferred.
  • the epoxy equivalent is the number of grams of a resin containing one gram equivalent of an epoxy group measured by the method according to JIS K7236.
  • the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene of known molecular weight, which is measured under the same conditions as the retention time (retention capacity) measured using gel permeation chromatography (GPC) It is the value calculated by converting it into the molecular weight of polystyrene.
  • GPC gel permeation chromatography
  • G2000HXL trade names, all manufactured by Tosoh Corporation
  • a differential refractometer is used as a detector
  • mobile phase tetrahydrofuran
  • measurement temperature 40 ° C.
  • flow rate 1 mL / min. It can be measured below.
  • the epoxy silane oligomer (c) can be obtained by combining a production method used for producing a general organosilane oligomer with a conventionally known chemical reaction. For example, it can manufacture using the following manufacturing methods.
  • a hydrolyzable silane having no epoxy group-containing hydrolyzable silane represented by the formula (I) and optionally an epoxy group represented by the formula (II) as a starting material And hydrolytic condensation reaction in the presence of water and a catalyst to produce an epoxysilane oligomer (c).
  • the epoxysilane oligomer (c) is a hydrolysis condensate (a1) of an epoxy group-containing hydrolyzable silane represented by the above general formula (I), particularly from the viewpoint of scratch resistance, the epoxysilane oligomer (c) And / or a hydrolytic condensate (a2) of a mixture of the epoxy group-containing hydrolyzable silane and the epoxy group-free hydrolyzable silane represented by the general formula (II) is preferred, and in particular The hydrolytic condensate (a2) of a mixture of the epoxy group-containing hydrolyzable silane represented by the formula (I) and the hydrolyzable silane having no epoxy group represented by the general formula (II) is preferred.
  • the epoxysilane oligomer (c) is the hydrolysis compound (a2), it is represented by the epoxy group-containing hydrolyzable silane represented by the formula (I) and the formula (II)
  • the ratio to the hydrolyzable silane having no epoxy group is preferably in the range of 99/1 to 55/45 as the former / the latter (molar ratio), and is in the range of 85/15 to 60/40. It is further preferred that the
  • the epoxysilane oligomer (c) may be used in combination with the hydrolysis condensate (a1) and the hydrolysis condensate (a2).
  • the hydrolysis condensation reaction in the method for producing the epoxysilane oligomer (c) used in the present invention may employ, for example, conditions of pH 1 to 7.5, preferably pH 2 to 7 in the presence of the catalyst. . By reacting in the above-mentioned pH range, it is possible to suppress gelation and generation of aggregates during synthesis.
  • the catalyst is not particularly limited as long as it can be adjusted to the above-mentioned pH range, and for example, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, Organic acids such as toluene sulfonic acid or inorganic acids such as hydrogen fluoride, hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, or solid acid catalysts such as cation exchange resin having carboxylic acid group and sulfonic acid group on the surface .
  • the amount of the catalyst used is not particularly limited. However, if the amount is too large, there are problems such as cost increase, gelation during synthesis or storage, etc., and if less, reaction may be delayed.
  • the amount of the catalyst used is suitably in the range of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compounded as the starting material.
  • An organic solvent may be used in the hydrolysis and condensation reaction. It is preferable to use an organic solvent from the viewpoint of preventing gelation and in that the viscosity at the time of production can be adjusted.
  • organic solvent examples include alcohols such as methanol, ethanol and isopropanol, aromatic compounds such as toluene and xylene, ketones such as acetone, and esters such as ethyl acetate.
  • the reaction temperature at the time of hydrolysis and condensation is generally 0 to 200 ° C., preferably 10 to 190 ° C., and more preferably 10 to 120 ° C.
  • the reaction can be carried out regardless of the pressure, but a pressure range of 0.02 to 0.2 MPa is preferable, and a pressure range of 0.08 to 0.15 MPa is particularly preferable.
  • the reaction usually completes in about 1 to 15 hours.
  • the alcohol, the solvent and the catalyst produced in the reaction may be removed by a known method.
  • the product obtained may be further purified according to the purpose by removing the catalyst by various purification methods such as washing, column separation, adsorption by a solid adsorbent, and the like. From the point of efficiency, it is preferable to remove the alcohol and catalyst generated in the reaction by washing with water.
  • the structure of the epoxysilane oligomer changes depending on the condensation ratio of the hydrolyzable group of the hydrolyzable silane in the hydrolytic condensation reaction, but the product obtained by the present production method has a Si-OH group of 100 In some cases, it may include an epoxysilane oligomer of a fully caged structure, a linear, branched, ladder structure, an incomplete caged structure and / or a random condensation product in which a fully caged structure, a Si-OH group remains.
  • the epoxysilane oligomer which is the component (c) obtained by the present production method may be any one of the complete cage structure, linear, branched, ladder structure, incomplete cage structure and / or random condensation product. Good.
  • the content of the epoxysilane oligomer in the coating agent (B) for forming a hard coat layer is the total amount of the active ingredients of the coating agent (B) for forming a hard coat layer from the viewpoint of the hardness and abrasion resistance of the obtained film
  • the range of 20 to 80% by mass is preferable, and the range of 35 to 75% by mass is more preferable.
  • colloidal Silica A commercially available product of colloidal silica includes colloidal silica fine particles.
  • Colloidal silica is obtained by dispersing ultrafine particles of silica in a dispersion medium.
  • the dispersion medium for example, water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol and n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol mono Examples thereof include polyhydric alcohol derivatives such as butyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; and monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and tetrahydrofurfuryl acrylate.
  • a water-soluble solvent such as water, methanol, ethanol or the like, particularly water as a dispersion medium, from the viewpoint of stability when applied to the coating agent.
  • colloidal silica which makes water a dispersion medium
  • acidic colloidal silica As colloidal silica which makes water a dispersion medium, acidic colloidal silica, basic colloidal silica, etc. are mentioned, for example.
  • the acidic colloidal silica is not particularly limited.
  • Snowtex AK, Snowtex O, Snowtex O-40, Snowtex OL, Snowtex OUP, Snowtex OXS, Snowtex OYL all trade names
  • Snowtex is a registered trademark
  • Adelite AT-20Q trade name, manufactured by ADEKA, Adelite is a registered trademark
  • the basic colloidal silica is not particularly limited.
  • Snowtex C, Snowtex N, Snowtex NXS trade names, manufactured by Nissan Chemical Industries, Ltd., Snowtex is a registered trademark
  • Adelite AT- 20 trade names, manufactured by ADEKA, Adelite is a registered trademark
  • ADEKA ADEKA
  • Adelite is a registered trademark
  • the colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited.
  • commercially available products such as MA-ST-M, IPA-ST, EG-ST, PGM-ST (all trade names, Nissan Chemical Industries, Ltd.) And the like.
  • colloidal silicas may be used alone or in combination of two or more.
  • a method of using two or more types of colloidal silica in combination specifically, for example, the mass ratio of acidic colloidal silica having an average primary particle size of 10 to 15 nm and acidic colloidal silica having an average primary particle size of 20 to 25 nm Acidic colloidal silica having an average primary particle size of 20 to 25 nm and an acid colloidal having an average primary particle size of 50 to 80 nm, preferably used in combination such that the former / latter) is preferably in the range of 10/90 to 70/30.
  • a method of using silica and a mass ratio (the former / the latter) preferably in the range of 10/90 to 60/40 can be mentioned.
  • inorganic fine particles other than silica fine particles such as alumina sol, titania sol, ceria sol can also be contained in the colloidal silica.
  • the average particle diameter of the colloidal silica (d) is preferably in the range of 1 to 100 nm, and more preferably in the range of 8 to 50 nm, from the viewpoint of the transparency and hardness of the cured coating.
  • acidic colloidal silica can be suitably used as the colloidal silica from the viewpoint of the stability of the hard coat layer-forming coating agent (B) and the appearance of the coating film.
  • the average particle size is an average particle size of primary particles of colloidal silica particles.
  • the average particle size of colloidal silica refers to the average particle size calculated by the nitrogen adsorption method (BET method) unless otherwise specified.
  • the content of the colloidal silica (d) is in the range of 20 to 80% by mass based on the total amount of the active ingredients of the coating agent (B) for forming a hard coat layer from the viewpoint of the hardness and abrasion resistance of the obtained film.
  • the content is preferably in the range of 35 to 75% by mass.
  • the curing catalyst is not particularly limited as long as it can accelerate the curing by hydrolytic condensation of a compound having a hydrolyzable group, and the method for producing the epoxysilane oligomer (c) is not particularly limited.
  • organotin compounds such as diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octoate, dibutyltin diacetate, dibutyltin dioctyrate;
  • phosphoric acid compounds and organic tin compounds are preferable in view of drying property, scuff resistance, and water dilution stability.
  • examples of the above phosphoric acid compounds include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphinic acid And alkali metal salts or ammonium salts of these phosphoric acid compounds.
  • the content of the curing catalyst (e) is preferably in the range of 0.1 to 30 parts by mass with respect to the total amount of the active ingredients of the coating agent (B) for forming the hard coat layer, and more preferably 0.5 to 20 It is desirable to adjust in the range which becomes a mass part.
  • the coating agent (B) for hard-coat layer formation used for this invention can mix
  • the functional group is not particularly limited as long as it is functional, and specific examples thereof include epoxy group, hydroxyl group, amino group, ureido group, mercapto group, vinyl group, (meth) acryloyl group and isocyanate group.
  • glycidoxy group-containing silane cups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.
  • the content thereof is the active ingredient of the hard coat layer-forming coating agent (B) from the viewpoint of the coating film appearance and the scratch resistance. It is preferably in the range of 1 to 70% by mass, more preferably in the range of 5 to 50% by mass, based on the total amount of
  • the coating agent (B) for forming a hard coat layer used in the present invention is, in addition, a dilution solvent, RTV rubber, color pigment, extender pigment, dye, matting agent, aggregate, resin particles, surface conditioner, viscosity modifier, Antifoaming agent, antibacterial agent, antifungal agent, flame retardant, antifogging agent, plasticizer, slip agent, dehydrating agent, ultraviolet absorber, light stabilizer, metal oxide fine particles, metal powder, antioxidant, surfactant Agents, film forming aids, thickeners, antistatic agents, water repellent agents, additives such as fibers; crosslinking agents such as isocyanate compounds and melamine resins; resin components such as resin emulsions and wax emulsions; acrylic resins, Modifiers such as fluorocarbon resins and various organically modified silicone oils can be appropriately blended.
  • a dilution solvent RTV rubber, color pigment, extender pigment, dye, matting agent, aggregate, resin particles, surface conditioner, viscosity modifier,
  • the coating agent (B) for hard-coat layer formation used for this invention may be a non-solvent, or may contain the organic solvent.
  • an organic solvent By containing an organic solvent, the compatibility between the hydrolyzable silane and the silica can be improved, which is particularly preferable. Any appropriate organic solvent may be used as long as it dissolves the hydrolyzable silane compound and can be dissolved even after the hydrolysis condensation reaction proceeds.
  • organic solvent examples include alcohol solvents such as methanol, ethanol, butanol, methyl isobutyl carbinol, 2-ethylhexanol and benzyl alcohol; ketone solvents such as acetone and methyl isobutyl ketone; ethyl acetate, butyl acetate and benzoic acid Ester solvents such as methyl and methyl propionate; Ether solvents such as cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether and isopropyl glycol; diethylene glycol monomethyl Ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3 Glycol ether solvents such as methoxy-3-methyl-1-butanol, aromatic hydrocarbon solvents include
  • the solubility (20 ° C.) of the organic solvent in water is preferably 5 g / 100 g or more, and from the viewpoint of the finish and the improvement of the compatibility between the hydrolyzable silane and the silica, 20 g / water 100 g or more is preferable. Preferably it is 50 g / 100 g or more of water.
  • organic solvents it is selected from among butanol, 3-methoxy-3-methyl-1-butanol and ethylene glycol monotertiary butyl ether from the viewpoint of coating workability and compatibility.
  • at least one is used.
  • the content thereof is the total amount of the active ingredients of the coating agent for forming hard coat (B) from the viewpoint of coating appearance and coating workability.
  • the amount is, for example, 5 to 200 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass.
  • the coating agent for forming a hard coat layer (B) is a hydrolyzable silane, It may contain at least one hydrolyzable silane selected from hydrofunctional silanes having 1 to 4 functions and / or its hydrolytic condensate (f).
  • a hydrolysis condensate of the hydrolyzable silane represented by the general formula (II) can be suitably used.
  • hydrolyzable silane having no 1 to 4 functional epoxy group represented by the above general formula (II) are mentioned, and among them, methyltrimethoxysilane is preferable in particular from the viewpoint of drying property.
  • the content thereof can be appropriately adjusted from the viewpoint of the balance between the abrasion resistance and the crack resistance etc., but the content is based on the total amount of the active ingredients of the hard coat layer forming coating agent (B). And 1 to 40% by mass, preferably 35 to 30% by mass.
  • a coating agent (B) for forming a hard coat layer is tetrafunctional in at least a part of the components (f) among the components (f). It may contain a hydrolyzable silane and / or its hydrolytic condensate (g).
  • component (g) examples include hydrolyzable silanes represented by the following general formula (III) and / or hydrolytic condensates thereof.
  • the general formula (III) is a tetrafunctional hydrolyzable silane, and specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraphenoxysilane, etc .; Halosilane etc. can be mentioned.
  • hydrolytic condensate of the above-mentioned tetrafunctional hydrolyzable silane one having an average degree of condensation of 2 to 15 is preferable, and the silica remaining as silica when the organosilicate compound is calcined at 900 ° C.
  • Condensates condensed to a weight fraction of 20 to 60% by mass are preferred.
  • the hydrolytic condensate may contain a condensate of a branched or cyclic structure.
  • the average degree of condensation can be determined using the molecular weight obtained from gel permeation chromatography (GPC) of a condensation compound of a tetrafunctional hydrolyzable silane.
  • the content of the tetrafunctional hydrolyzable silane represented by the general formula (III) and / or its content in the case of containing the hydrolytic condensate (G) is the scratch resistance, the drying property, and the crack resistance. From the viewpoint of balance, the content is preferably in the range of 1 to 20% by mass, and more preferably 1.5 to 15% by mass, with respect to the total amount of the active ingredients of the hard coat layer forming coating agent (B).
  • the active ingredient means a residue obtained by removing a solvent such as water and an organic solvent from a sample.
  • the amount of the active ingredient can be determined, for example, from the heating residue when the solvent, etc. is volatilized by drying the mixture, composition, etc. containing water, organic solvent etc. in a hot air drier at 105 ° C. for 3 hours .
  • silicon compounds such as hydrolyzable silanes and silane coupling agents are included in the active ingredients.
  • the coating agent (B) for hard coat layer formation may contain water (h). By containing water, drying can be promoted at the time of film formation. Moreover, the viscosity of the coating agent (B) for hard-coat layer formation can be suitably adjusted by diluting with water at the time of coating later, and coating workability can be prepared.
  • the coating agent (B) for hard coat layer formation can contain water, and water can be used instead of the organic solvent in the dilution operation of the coating step. There is little risk of damaging the surrounding sanitation environment and safety is high.
  • water (h) arbitrary things can be used, for example, tap water, ion exchange water, and a pure water are used preferably.
  • the content of the water (h) can be appropriately adjusted within the range in which the finishing properties of the hard coat layer forming coating agent (B) and the repelling properties at the time of coating are considered.
  • the addition amount thereof can be, for example, in the range of 1 to 30% by mass with respect to the total amount of the active ingredients of the coating agent (B) for hard coat layer formation before dilution.
  • the coating agent (B) for forming a hard coat layer is a curing catalyst other than the curing catalyst, a RTV rubber, a coloring pigment, an extender pigment, a pigment such as a luster pigment, a dye, and a matting agent as long as the performance is not impaired.
  • the form and preparation method of the coating agent (B) for hard-coat layer formation applied to this method may be a one-pack type composition, and two or more multi-packs It may be a mold composition.
  • a method of using a hydrolyzable silane as the first component, a curing catalyst (e) as the second component, and distributing the other components to any or third components may be mentioned. it can.
  • the third solution containing silica (d) can be individually prepared, and the entire solution can be mixed and used immediately before use.
  • the above-mentioned silane coupling agent, organic solvent, components (f) to (h) and other various additives such as pigment dispersant, anti-settling agent, anti-foaming agent, anti-oxidant, ultraviolet absorber etc. It can be suitably contained in any of the solutions.
  • the compatibility may be improved by mixing the colloidal silica (d) with the curing catalyst (e) in advance, which is preferable in some cases.
  • the coating agent (B) for hard-coat layer formation applied to this method may be a non-solvent, and may contain a dilution solvent.
  • a dilution solvent water and an organic solvent may be mentioned, and from the viewpoint of odor and compatibility, those exemplified in the section of the organic solvent for diluting the above-mentioned curing agent can be suitably used.
  • the coating agent (B) for hard coat layer formation used in the present invention has a content of the active ingredient of usually 15% by mass or more, particularly in the range of 20 to 60% by mass from the viewpoint of workability and finish during coating. It is preferable to
  • the hard coat layer (II) has a Martens hardness in the range of 100 to 300 N / mm 2 , particularly 120 to 300 N / mm 2 from the viewpoint of scratch resistance and cracking resistance of the process film. ing.
  • a mixture consisting of the following monomer blend was added to form an emulsion, and the emulsion was dropped at a constant speed over 4 hours into a glass four-necked flask kept at 82 ° C. After completion of the dropwise addition, the mixture is further stirred at 82 ° C. for 2 hours, cooled to 40 ° C., and adjusted to pH 7.5 with ammonia to obtain a hydroxyl group-containing acrylic resin having an average particle diameter of 150 nm and a resin solid content of 50% (a An aqueous dispersion of -1) was obtained.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin (a-1) was 103 mg KOH / g, and the glass transition temperature was 41 ° C.
  • a hydroxyl group-containing acrylic resin having an average particle diameter of 150 nm and a resin solid content of 50% (a A core-shell type aqueous dispersion of -2) was obtained.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin was 103 mg KOH / g, and the glass transition temperature was 40 ° C.
  • a solution of 4 parts of azobisisobutyronitrile dissolved in 80 parts of "Swazol 1000" is added dropwise over 1 hour, and stirring is further continued at 90 ° C for 1 hour, and then cooled to 40 ° C.
  • a 50% solution of hydroxyl group-containing acrylic resin (a-4) was obtained.
  • the acrylic resin had a hydroxyl value of 103 mg KOH / g, a glass transition temperature of 39 ° C., and a weight average molecular weight of 15,000.
  • the dispersion of the hydroxyl group-containing acrylic resin had a hydroxyl value of 103 mg KOH / g, a glass transition temperature of 43 ° C., and a weight average molecular weight of 30,000.
  • Production Example 6 Comparative Resin (a'-1) In Production Example 1, except that the composition of the monomer mixture is as shown in the column of acrylic resin (a'-1) in Table 1, it is hydroxyl-free in the same manner as in Production Example 1 and diacetone as a crosslinking functional group monomer. An aqueous dispersion of an acrylic resin (a'-1) obtained by copolymerizing acrylamide was obtained.
  • the resin solid content, average particle diameter, hydroxyl value, acid value and glass transition temperature of the hydroxyl group-containing acrylic resin or acrylic resin obtained in Production Examples 1 to 6 are shown in Table 2.
  • the solid content and NCO / OH ratio of the room temperature curing type urethane primer composition (A-1) are shown in Table 3.
  • the results of the initial drying evaluation of the room temperature curing type urethane primer composition (A-1) and the value of Martens hardness are also shown in Table 3.
  • test methods and evaluation criteria of the test items in the table are as follows.
  • Martens hardness It measured according to the method of a statement statement.
  • Epoxysilane oligomer (c-1) 236 parts (1.0 mol) of KBM-403 (Note 7) and methanol in a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube 32 parts (1.0 mol) were added and mixed and stirred at room temperature.
  • 10 parts of 0.05 N hydrochloric acid water was added dropwise over 30 minutes while stirring, and the mixture was further stirred for 30 minutes. Thereafter, the temperature was raised to 75 ° C. using a mantle heater, and reflux was performed for 2 hours while simultaneously removing by-produced methanol.
  • an epoxysilane oligomer (c-1) After cooling to room temperature, filtration was performed to obtain an epoxysilane oligomer (c-1). As a result of heating the product (c-1) at 120 ° C. for 1 hour, the heating residue (active ingredient) was 80%. Moreover, the weight average molecular weight was 1,100 and the epoxy equivalent was 220 g / eq.
  • KBM-403 trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, molecular weight 236.34.
  • KBM-13 trade name, manufactured by Shin-Etsu Chemical, methyltrimethoxysilane.
  • each room temperature curing type urethane primer composition described in Table 4 The paint was applied using a floor mop and dried for 2 hours under conditions of a temperature of 23 ° C. and a humidity of 50% RH to form each primer cured coating layer (I).
  • the dry film thickness was as shown in Table 4. The interval until the over-coating of the next process at this time was 2 hours of drying time.
  • a coating agent (B-1) or (B-3) for hard coat layer formation is applied once on this to a dry film thickness of 15 ⁇ m using a floor mop, air temperature 23 ° C., humidity 50% RH The coated film was dried for 4 days under the following conditions to form a hard coat layer (II) to obtain each painted tile.
  • Example 10 Each room temperature curing type urethane primer composition (A shown in Table 4) on a 305 ⁇ 305 ⁇ 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material) -1) was painted using a floor mop and dried for 24 hours under conditions of an air temperature of 23 ° C. and a humidity of 50% RH to form a primer cured coating layer (I).
  • the dry film thickness was as shown in Table 4. The interval until the over-coating of the next process at this time was 24 hours of the drying time.
  • the coating agent (B-1) for hard-coat layer formation is once coated so that it may become dry film thickness 25micrometer using a floor mop on this, and it is 4 days on condition of temperature 23 ° C, humidity 50% RH. After drying, a hard coat layer (II) was formed to obtain a painted tile.
  • each room temperature curing type urethane primer composition described in Table 4 was applied using a floor mop and dried for 2 hours under conditions of a temperature of 23 ° C. and a humidity of 50% RH to form each primer cured coating layer (I).
  • the dry film thickness was as shown in Table 4. The interval until the over-coating of the next process at this time was 2 hours of drying time.
  • the coating described in the first column of the hard coat layer forming coating in Table 4 is applied once on this to a dry film thickness of 15 ⁇ m using a floor mop, air temperature 23 ° C., humidity 50% RH Let stand for 18 hours under the following conditions, and then further coat the coating agent described in the second column of the hard coat layer forming coating once with a floor mop to a dry film thickness of 15 ⁇ m, It dried under the same conditions for 4 days, and obtained the coated tile in which two-layer hard-coat layer (II) was formed on primer cured coating layer (I).
  • the interval to over-coating before applying the second layer hard coating agent is 18 hours of drying time.
  • Example 12 to 14 The same steps as in Example 1 are carried out except that the room temperature curing type primer composition, the coating agent for forming a hard coat layer, and the coating interval (time: h) are as shown in Table 4 in Example 11, and each primer On the layer (I), a painted tile in which two hard coat layers (II) were formed was obtained.
  • Example 3 The same steps as in Example 1 are carried out in Example 1 except that the room temperature curing type primer composition, the coating agent for forming a hard coat layer, and the overlapping coating interval (time: h) are as shown in Table 4; A painted tile having a hard coat layer (II) formed thereon was obtained on (I).
  • a hard coat is not coated on a 305 ⁇ 305 ⁇ 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), and the room temperature curing type urethane primer composition is not coated.
  • the layer forming coating agent (B-1) was coated once using a floor mop to a dry film thickness of 15 ⁇ m, dried at a temperature of 23 ° C. and a humidity of 50% RH for 4 days, and a hard coat layer To obtain a coated tile having no primer cured coating layer (I).
  • a hard coat is not coated on a 305 ⁇ 305 ⁇ 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), and the room temperature curing type urethane primer composition is not coated.
  • the layer forming coating agent (B-2) was coated once using a floor mop to a dry film thickness of 15 ⁇ m, allowed to stand for 18 hours under conditions of temperature 23 ° C., humidity 50% RH, and then further The coating agent (B-2) for hard-coat layer formation is once coated so that it may become a dry film thickness of 15 micrometers using a floor mop, and it is made to dry under the same conditions for 4 days.
  • (I) There was obtained a painted tile in which two hard coat layers (II) were formed. The interval to over-coating before applying the second layer hard coating agent is 18 hours of drying time.
  • Each painted tile obtained as described above was used as a test plate and subjected to various tests.
  • test item 4. Finishing property [coating film appearance (visual)]: The coating film appearance of each test plate was visually confirmed and evaluated according to the following criteria. :: Smooth and uniform gloss feeling is observed ⁇ : Smooth but very slight gloss unevenness is observed ⁇ : Yuzu skin and gloss unevenness are slightly observed ⁇ : Remarkable Yuz skin and gloss unevenness are recognized Be
  • Adhesion The coated film on each test plate is cross-cut to reach the substrate, and the coated cell surface after sticking adhesive cellophane tape on the coated surface and peeling strongly is checked visually, and the following criteria for peeling from the tile It evaluated. In addition, all interfaces when the coating film was peeled were the vinyl chloride resin material / primer interlayer. :: Peeling not observed ⁇ : Peeling slightly observed on the crosscut line ⁇ : Peeling partially observed along the crosscut area ⁇ : Peeling all over the crosscut area Is recognized.
  • Test item 8. Water resistance: The test boards obtained were left for 4 days under conditions of a temperature of 23 ° C. and a humidity of 50% RH for 4 days, and then immersed in water at 20 ° C. for 24 hours, and then the appearance of the test boards washed in water was evaluated according to the following criteria.
  • X Significant whitening is observed for the coating before the test.

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Abstract

The present invention addresses the problem of providing a method for forming a surface protective coating film for floor surfaces, which is able to be performed easily and in a short time, while providing a surface protective coating film formed thereby with excellent adhesion, finish properties, cracking resistance, scratch resistance and gloss. The present invention relates to a method for forming a surface protective coating film for floor surfaces, which comprises: a step wherein a normal temperature-curable urethane primer composition (A) is applied to a floor surface, thereby forming a cured coating film layer (I) of the composition; and a subsequent step wherein a coating agent (B) for hard coat layer formation is applied, thereby forming at least one hard coat layer (II). This method for forming a surface protective coating film for floor surfaces is characterized in that the ratio of the isocyanate groups of a polyisocyanate compound (b) contained in a curing agent to the hydroxyl groups of a hydroxyl group-containing acrylic resin (a) contained in the base material in the normal temperature-curable urethane primer composition (A), namely the ratio NCO/OH is within the range of 0.7 to 2.0.

Description

床面の表面保護被膜形成方法Method of forming surface protective coating on floor surface
　本発明は、オフィスビルや商業施設、コンビニエンスストア等の床面に施工することにより、耐擦り傷性、耐水性及び艶感に優れる被膜を形成し、床面の美観を長期間維持することができる床面の表面保護被膜形成方法に関する。 INDUSTRIAL APPLICABILITY The present invention can form a coating excellent in abrasion resistance, water resistance and glossiness by maintaining the floor surface of an office building, a commercial facility, a convenience store, etc., and can maintain the aesthetic appearance of the floor surface for a long time The present invention relates to a method for forming a surface protective coating on a floor surface.
　オフィスビルや商業施設、コンビニエンスストア等の床面は、擦り傷や汚れ等から床材を保護するとともに、艶を出し、美観を向上させる目的で水性フロアポリッシュが使用されている。しかしながら、樹脂エマルションを主成分とするこれらの水性フロアポリッシュは、人の歩行や台車の運搬により傷や汚れが蓄積しやすく艶（美観）が早期に低下するという問題があった。また、洗浄でのメンテナンスで改善がみられない場合は床面上の被膜を剥離する必要があり、その際に発生する廃水が産業廃棄物になるという問題も内在している。 In floor surfaces of office buildings, commercial facilities, convenience stores, etc., an aqueous floor polish is used for the purpose of protecting floor materials from scratches and dirt, etc., as well as providing gloss and improving the appearance. However, these aqueous floor polishes having a resin emulsion as a main component have a problem that scratches and dirt easily accumulate due to walking of a person or transportation of a carriage, and the gloss (aesthetic appearance) is reduced early. In addition, if no improvement is found in the maintenance for cleaning, it is necessary to peel off the coating on the floor surface, and there is an inherent problem that the wastewater generated at that time becomes an industrial waste.
　そこで、これらの問題を解決するために、例えば特許文献１には、水性ウレタン樹脂、水、１－（２－メトキシ－２－メチルエトキシ）－２－プロパノールからなるフロアーコーティング剤が開示されている。特許文献１に記載のフロアーコーティング剤は、水性ウレタン樹脂により被膜を形成することから、耐久性、密着性及び光沢等に優れるが、ラッカータイプ（溶剤を揮発させることにより成膜する揮発乾燥型塗料）であり架橋密度が低いため、擦り傷が早期に発生し、美観を長期にわたって維持できないという問題がある。 Therefore, in order to solve these problems, for example, Patent Document 1 discloses a floor coating agent comprising an aqueous urethane resin, water, and 1- (2-methoxy-2-methylethoxy) -2-propanol. . The floor coating agent described in Patent Document 1 is excellent in durability, adhesion, gloss and the like because a film is formed of an aqueous urethane resin, but a lacquer type (a volatilization-drying type coating formed by evaporating a solvent) Since the crosslink density is low, abrasions occur early and there is a problem that the appearance can not be maintained for a long time.
　また、特許文献２には、ケイ素原子１個あたり平均０．９～１．１個の炭化水素基がケイ素原子に結合し、及びケイ素原子に結合した水酸基を１分子あたり少なくとも２個有するポリオルガノシロキサン樹脂を含有し、０．１０ｋｇｆ以上の滑り抵抗性を有する室温硬化性のフロアーコーティング剤組成物が開示されている。特許文献２に記載のフロアーコーティング剤は、シラノール基を有するポリオルガノシロキサン樹脂により、乾燥性及び硬化性に優れる被膜が得られるが、樹脂の極性が低いため床材の種類によっては密着性が不十分となる場合があった。 Further, in Patent Document 2, a polyorgan having an average of 0.9 to 1.1 hydrocarbon groups bonded to a silicon atom per silicon atom, and at least two hydroxyl groups bonded to a silicon atom per molecule. A room temperature curable floor coating composition containing a siloxane resin and having a slip resistance of 0.10 kgf or greater is disclosed. The floor coating agent described in Patent Document 2 can obtain a film excellent in drying property and curability by a polyorganosiloxane resin having a silanol group, but since the polarity of the resin is low, adhesion may not be obtained depending on the type of floor material. It might have been enough.
　特許文献３には、床面に各種常温硬化乾燥型の塗料組成物を塗装しプライマー層を塗設せしめ、次いで紫外線硬化性の中塗り及び／又は上塗りを硬化せしめる床面の現場塗装硬化方法が記載されている。しかしながら、特許文献３に記載の発明は、上塗りを紫外線で硬化させるために装置が大掛かりとなる他、特許文献３に開示のプライマーでは乾燥性に問題があり、塗装作業性、得られる工程膜の耐水性、仕上がり性及び密着性を必ずしも満足するものではなかった。 In Patent Document 3, a floor surface on-site coating curing method is applied in which various cold setting drying type coating compositions are applied to a floor surface, a primer layer is applied, and then an ultraviolet curing middle coat and / or a top coat is cured. Have been described. However, the invention described in Patent Document 3 requires a large-scale apparatus for curing the top coat with ultraviolet light, and the primer disclosed in Patent Document 3 has a problem in drying property, and coating workability, the process film obtained The water resistance, finish and adhesion were not always satisfactory.
日本国特開２００４－３０７７５４公報Japanese Patent Application Laid-Open No. 2004-307754 日本国特開２０１２－１２４７７公報Japan JP 2012-12477 gazette 日本国特開昭６２－６８５７３号公報Japanese Patent Application Laid-Open No. 62-68573
　本発明は上記事情に鑑みてなされたものであり、簡便かつ短時間での施工ができ、得られる表面保護被膜の密着性、仕上がり性、耐ワレ性、耐擦り傷性及び艶感に優れる、床面の表面保護被膜形成方法を提供することである。 The present invention has been made in view of the above-mentioned circumstances, and the construction can be carried out simply and in a short time, and the adhesion, finish, tear resistance, scratch resistance and glossiness of the obtained surface protective film are excellent. A method of forming a surface protective film on a surface is provided.
　かかる状況の下、本発明者らは鋭意研究した結果、床面にハードコート層形成用コーティング剤によるハードコート層を形成する際に予め、特定の常温硬化型ウレタンプライマー組成物による硬化塗膜層を形成する工程を含むことにより、上記課題を解決できることを見出した。 Under these circumstances, the inventors of the present invention conducted intensive studies and found that when forming a hard coat layer by a coating agent for forming a hard coat layer on a floor surface, a cured coating layer by a specific room temperature curing urethane primer composition in advance. It has been found that the above problems can be solved by including the step of forming
　本発明は、下記の態様を包含する床面の表面保護被膜形成方法を提供する：
　（態様１）
　床面に、常温硬化型ウレタンプライマー組成物（Ａ）を塗装し、該組成物による硬化塗膜層（Ｉ）を形成する工程、次いでハードコート層形成用コーティング剤（Ｂ）を塗布し、少なくとも１層のハードコート層（ＩＩ）を形成する工程、を含む床面の表面保護被膜形成方法であって、前記常温硬化型ウレタンプライマー組成物（Ａ）が、
水酸基含有アクリル樹脂（ａ）を含む主剤と、ポリイソシアネート化合物（ｂ）を含む硬化剤とを含有し、前記硬化剤中に含まれるポリイソシアネート化合物（ｂ）のイソシアネート基と主剤中に含まれる水酸基含有アクリル樹脂（ａ）の水酸基との比率（ＮＣＯ／ＯＨ）が、０．７～２．０の範囲内であることを特徴とする床面の表面保護被膜形成方法。 The present invention provides a method of forming a surface protective coating on a floor surface, which includes the following aspects:
(Aspect 1)
A step of coating a room temperature curing type urethane primer composition (A) on a floor surface to form a cured coating layer (I) by the composition, and then applying a coating agent for forming a hard coat layer (B), A method of forming a surface protective film on a floor surface comprising the step of forming one hard coat layer (II), wherein the cold-curable urethane primer composition (A) is
The main component containing a hydroxyl group-containing acrylic resin (a) and a curing agent containing a polyisocyanate compound (b), and the isocyanate group of the polyisocyanate compound (b) contained in the curing agent and the hydroxyl group contained in the main component A method of forming a surface protective film on a floor surface, wherein the ratio (NCO / OH) of the contained acrylic resin (a) to the hydroxyl group is in the range of 0.7 to 2.0.
　（態様２）
　前記ハードコート層形成用コーティング剤（Ｂ）が、エポキシシランオリゴマー（ｃ）と、平均粒子径が１～１００ｎｍの範囲内のコロイダルシリカ（ｄ）と、硬化触媒（ｅ）と、を含む態様１に記載の床面の表面保護被膜形成方法。 (Aspect 2)
Aspect 1 in which the hard coat layer-forming coating agent (B) contains an epoxysilane oligomer (c), colloidal silica (d) having an average particle diameter in the range of 1 to 100 nm, and a curing catalyst (e) The surface protective film formation method of the floor surface as described in-.
　（態様３）
　前記水酸基含有アクリル樹脂（ａ）のガラス転移温度が、２０～９０℃の範囲である態様１又は２に記載の床面の表面保護被膜形成方法。 (Aspect 3)
The method for forming a surface protective film of floor surface according to aspect 1 or 2, wherein the glass transition temperature of the hydroxyl group-containing acrylic resin (a) is in the range of 20 to 90 ° C.
　（態様４）
　前記水酸基含有アクリル樹脂（ａ）の水酸基価が、１５～２００ｍｇＫＯＨ／ｇの範囲内である態様１～３のいずれか１の態様に記載の床面の表面保護被膜形成方法。 (Aspect 4)
The method for forming a surface protective film for floors according to any one of the embodiments 1 to 3, wherein the hydroxyl value of the hydroxyl group-containing acrylic resin (a) is in the range of 15 to 200 mg KOH / g.
　（態様５）
　前記常温硬化型ウレタンプライマー組成物（Ａ）が、充填剤及び／又はポリウレタン樹脂を含む態様１～４のいずれか１の態様に記載の床面の表面保護被膜形成方法。 (Aspect 5)
The method for forming a surface protective film on a floor according to any one of the modes 1 to 4, wherein the cold-curable urethane primer composition (A) contains a filler and / or a polyurethane resin.
　（態様６）
　前記常温硬化型ウレタンプライマー組成物（Ａ）の塗装時における固形分含有率が、１５～７０質量％である態様１～５のいずれか１の態様に記載の床面の表面保護被膜形成方法。 (Aspect 6)
The method for forming a surface protective film of a floor surface according to any one of the embodiments 1 to 5, wherein the solid content of the cold-curable urethane primer composition (A) at the time of coating is 15 to 70% by mass.
　（態様７）
　前記ハードコート層形成用コーティング剤（Ｂ）が、加水分解性シラン及び／又はその縮合物、並びにシリカを含む、態様１～６のいずれか１の態様に記載の床面の表面保護被膜形成方法。 (Aspect 7)
The method for forming a surface protection film on a floor according to any one of aspects 1 to 6, wherein the hard coat layer-forming coating agent (B) comprises a hydrolyzable silane and / or a condensate thereof, and silica. .
　（態様８）
　前記硬化塗膜層（Ｉ）のマルテンス硬度が３０Ｎ／ｍｍ２以上、ハードコート層のマルテンス硬度が１００～３００Ｎ／ｍｍ２にある態様１～７のいずれか１の態様に記載の床面の表面保護被膜形成方法。 (Aspect 8)
The floor surface according to any one of the embodiments 1 to 7, wherein the Martens hardness of the cured coating layer (I) is 30 N / mm 2 or more and the Martens hardness of the hard coat layer is 100 to 300 N / mm 2 Method of forming a protective film.
　（態様９）
　前記床面が、塩化ビニル樹脂系である態様１～７のいずれか１の態様に記載の床面の表面保護被膜形成方法。 (Aspect 9)
The method for forming a surface protective film on a floor according to any one of the modes 1 to 7, wherein the floor is a vinyl chloride resin system.
　本発明の床面の表面保護被膜形成方法（以下、「本方法」と略称する場合がある）によれば、常温硬化型ウレタンプライマー組成物が常温でも被膜を形成するため、床材に対して容易に施工でき、塗装過程における塗り重ね時間が短く、工期短縮化が図れる。また、本方法により形成された複層被膜（工程膜と略称する場合がある）は、床材との密着性に優れ、前記仕上がり性、耐ワレ性、耐擦り傷性及び艶感等の塗膜物性を長期間維持することのできるものである。 According to the method of forming a surface protective film of a floor surface of the present invention (hereinafter sometimes referred to as "the present method"), a room temperature curing type urethane primer composition forms a film even at normal temperature, so It can be easily constructed, the coating time in the painting process is short, and the construction period can be shortened. Moreover, the multilayer film (it may be abbreviated as a process film) formed by this method is excellent in adhesion with the floor material, and has a coating film such as finish, resistance to rubbing, scratch resistance and gloss. Physical properties can be maintained for a long time.
＜床面の表面保護被膜形成方法＞
　本方法は、床面に、特定の常温硬化型ウレタンプライマー組成物（Ａ）を塗装し、該組成物による硬化塗膜層（Ｉ）を形成する工程、次いで該硬化塗膜層上にハードコート層形成用コーティング剤（Ｂ）を塗布し、少なくとも１層のハードコート層（ＩＩ）を形成する工程、を含むことを特徴とする。以下順に説明する。 <Method of forming surface protective coating on floor surface>
In this method, a floor surface is coated with a specific cold-curable urethane primer composition (A) to form a cured coating layer (I) of the composition, and then a hard coat is formed on the cured coating layer. Applying a layer forming coating agent (B) to form at least one hard coat layer (II). These will be described in order.
　本方法を適用する被塗物は床面である。 The object to which this method is applied is a floor surface.
　この床面を構成するものとしては、一般的な床材であり、例えば、陶磁器、磁器タイルなどのセラミックス系床材；鉄、アルミニウム等の金属系床材；天然木、合板等の木質系床材；塩化ビニル樹脂等の合成樹脂系床材；御影石、大理石等の石材系床材；これらの素材を複合した床材等を挙げることができ、表面に保護シールや旧塗膜が設けられたものもであってもよい。床材の形状、大きさは特に制限されない。新設又は既設の床材どちらであってもよい。 The floor surface is constituted by a general floor material, for example, ceramic floor materials such as porcelain and porcelain tiles; metal floor materials such as iron and aluminum; and wood floors such as natural wood and plywood Materials: Synthetic resin flooring such as vinyl chloride resin; Stone flooring such as granite and marble; flooring made of composites of these materials, etc .; and protective seal and old paint film provided on the surface It may also be one. The shape and size of the floor material are not particularly limited. It may be either a new floor or an existing floor.
　また、本方法を適用する前に、被塗物に洗浄や研磨等の素地調整を行ってもよい。特に、本方法を適用する被塗物としては、塩化ビニル樹脂系床材が好ましい。 Moreover, before applying this method, you may perform base adjustment, such as washing | cleaning and grinding | polishing, to a to-be-coated-article. In particular, as a substrate to which the present method is applied, a vinyl chloride resin-based floor material is preferable.
　本方法は、特定の常温硬化型ウレタンプライマー組成物（Ａ）使用する。 This method uses a specific cold-curable urethane primer composition (A).
　該常温硬化型ウレタンプライマー組成物（Ａ）を塗装する際の塗装方法としては、例えば、モップ塗装、スプレー塗り、ローラー塗り、刷毛塗り、流し塗り等の公知の手段で塗装することができ、基材の適用される現場に応じて適宜選択して使用することができる。塗装回数は特に制限されることなく、１回又は複数回塗り重ねてもよい。乾燥膜厚としては、被塗物の状態や周囲環境によって異なるが、一般には１回あたり３～５０μｍ、好ましくは７～３０μｍの範囲内とすることができる。 As a coating method at the time of coating the said room temperature curing type urethane primer composition (A), it can be coated by publicly known means, such as mop coating, spray coating, roller coating, brush coating, flow coating, for example. It can be appropriately selected and used according to the site where the material is applied. The number of times of coating is not particularly limited, and may be applied one or more times. The dry film thickness varies depending on the condition of the object to be coated and the surrounding environment, but can generally be in the range of 3 to 50 μm, preferably 7 to 30 μm at one time.
　乾燥方法としては、常温乾燥が採用され、乾燥によって塗膜を得ることができるが、塗装環境等に応じて、加熱乾燥又は強制乾燥しても特に問題はない。必要に応じてブロアー等を用いて風乾燥を併用してもよい。常温乾燥では、例えば５～４５℃の環境下で乾燥することにより塗膜を得ることができる。塗装時における相対湿度（以下ＲＨと略すことがある）は、８０％以下、特に７０％以下が好ましい。 As a drying method, normal temperature drying is adopted, and a coating film can be obtained by drying, but there is no particular problem even if it is dried by heating or forced drying depending on the coating environment and the like. You may use wind drying together using a blower etc. as needed. In the case of normal temperature drying, for example, a coating can be obtained by drying under an environment of 5 to 45.degree. The relative humidity (hereinafter sometimes abbreviated as RH) at the time of coating is preferably 80% or less, particularly 70% or less.
　風乾燥を併用する場合は、例えば、常温環境下、サーキュレーター等を設置し、１０～６０分好ましくは１５～５５分換気をすることにより、乾燥を促進させ、かつ、硬化状態が均一な塗膜を得ることができる。 When wind drying is used in combination, for example, a circulator or the like is installed in a normal temperature environment, and ventilation is performed for 10 to 60 minutes, preferably 15 to 55 minutes, thereby promoting drying and a coating film having a uniform curing state. You can get
　本方法に用いる常温硬化型ウレタンプライマー組成物（Ａ）の塗装後の乾燥時間は、硬化状態が半硬化乾燥状態以上となるまで乾燥することが、得られる工程膜の仕上がり性及び後述するハードコート層を形成した際の耐ワレ性の点から好ましい。 The drying time after coating of the room temperature curing type urethane primer composition (A) used in the present method is to dry until the cured state becomes a semi cured dry state or more, the finish of the process film obtained and the hard coat described later It is preferable from the point of the crack resistance at the time of forming a layer.
　ここで、本明細書中において、半硬化乾燥状態とは、ＪＩＳ　Ｋ　５６００－１－１（２００４）に規定された半硬化乾燥状態、すなわち、塗面の中央を指先で静かに軽くこすって塗面にすり跡が付かない状態の塗膜である。一方、半硬化乾燥状態未満の硬化塗膜とは、塗膜が上記硬化乾燥状態に至っていない状態であって、ＪＩＳ　Ｋ　５６００－１－１（２００４）に規定された指触乾燥状態以下をいう。 Here, in the present specification, the semi-cured and dried state means the semi-cured and dried state defined in JIS K 5600-1-1 (2004), that is, the center of the coated surface is gently rubbed with a fingertip and coated. It is a coating film in a state where no marks are formed on the surface. On the other hand, a cured coating film less than the semi-cured and dried state is a state in which the coating film has not reached the cured and dried state, and refers to the non-touch-dried state specified in JIS K 5600-1-1 (2004). .
　本方法の常温硬化型ウレタンプライマー組成物（Ａ）は、前記半硬化乾燥状態以上であれば、後述するハードコート層形成用コーティング剤（Ｂ）を重ね塗りした際、仕上がり性及び密着性に優れる床面の表面保護被膜を形成することができる。 The room temperature curing type urethane primer composition (A) of the present method is excellent in finishability and adhesion when a coating agent (B) for forming a hard coat layer described later is applied repeatedly if it is at least the above-mentioned semicured and dried state. A surface protective coating can be formed on the floor surface.
　本明細書中において、初期乾燥性とは、塗膜状態が前記硬化乾燥状態になるまでの時間を示し、短い方がより乾燥性が良く速乾性である。 In the present specification, the initial drying property means the time until the coated film state reaches the cured and dried state, and the shorter the better, the better the drying property and the quick drying property.
　本方法に用いられる常温硬化型ウレタンプライマー組成物（Ａ）を前記半硬化乾燥状態とするまでには、乾燥膜厚と塗装環境のバランスによって異なるが、例えば、乾燥膜厚が５０μｍ以下の場合、３時間未満とすることができ、１～２時間であってもよい。 It depends on the balance between the dry film thickness and the coating environment until the room temperature curing type urethane primer composition (A) used in the present method is brought into the semi-cured dry state, but for example, when the dry film thickness is 50 μm or less It may be less than 3 hours, and may be 1 to 2 hours.
　常温硬化型ウレタンプライマー組成物（Ａ）を下塗り（プライマー）として用いる本方法は、比較的短時間で、後述するハードコート層形成用コーティング剤（Ｂ）を重ね塗りすることができ作業効率に優れる。本方法において、重ね塗りまでの時間が、３時間以上など長時間を要しても、特段問題はない。 This method using a room temperature curing type urethane primer composition (A) as a primer (primer) can coat a coating agent (B) for forming a hard coat layer described later in a relatively short time, and is excellent in working efficiency . In this method, there is no particular problem even if it takes a long time such as 3 hours or more until the time of overpainting.
　かくして、常温硬化型ウレタンプライマー組成物（Ａ）による硬化塗膜層（Ｉ）が形成される。 Thus, a cured coating layer (I) is formed by the cold-curable urethane primer composition (A).
　本発明において、硬化塗膜層（Ｉ）は、工程膜の耐ワレ性の点から下記条件でのマルテンス硬度が３０Ｎ／ｍｍ２以上であることが好ましく、特に好ましくは５０～３００Ｎ／ｍｍ２である。 In the present invention, the cured coating layer (I) preferably has a Martens hardness of 30 N / mm 2 or more, particularly preferably 50 to 300 N / mm 2 under the following conditions from the viewpoint of the warpage resistance of the step film. is there.
　本明細書においてマルテンス硬度は、ガラス板に試料を乾燥膜厚が２０μｍとなるようにアプリケーターを用いて塗布し、２３℃、５０％相対湿度の雰囲気下で２４時間乾燥させたものを試験板とし、超微小硬度計を用いて測定した値である。 In the present specification, Martens hardness is a test plate obtained by applying a sample to a glass plate using an applicator so that the dry film thickness is 20 μm and drying for 24 hours under an atmosphere of 23 ° C. and 50% relative humidity. It is a value measured using an ultra-microhardness tester.
　超微小硬度計としては、例えば、（株）フィッシャー・インストルメンツ社製、フィッシャースコープＨＭ－２０００（商品名）などが挙げられ、２３℃、５０％相対湿度の雰囲気下で、ビッカース圧子を用いて荷重＝２０ｍＮ／２５秒の条件で測定して求めるものとする。 Examples of the ultra-micro hardness tester include Fisher Scope HM-2000 (trade name) manufactured by Fisher Instruments Co., Ltd., etc., using a Vickers indenter under an atmosphere of 23 ° C. and 50% relative humidity. The load shall be measured under the condition of 20 mN / 25 seconds.
　次いで、前記常温硬化型ウレタンプライマー組成物（Ａ）による硬化塗膜層（Ｉ）上に、ハードコート層形成用コーティング剤（Ｂ）を塗布し、少なくとも１層のハードコート層（ＩＩ）を形成する。 Next, the hard coat layer-forming coating agent (B) is applied on the cured coating layer (I) of the room temperature curing type urethane primer composition (A) to form at least one hard coat layer (II). Do.
　前記ハードコート層形成用コーティング剤（Ｂ）を塗装する際の塗装方法としては、例えば、モップ塗装、スプレー塗り、ローラー塗り、刷毛塗り、流し塗り等の公知の手段で塗装することができ、基材の適用される現場に応じて適宜選択して使用することができる。さらに必要に応じて塗装後の余剰分を拭き取ることもできる。 As a coating method at the time of coating the coating agent (B) for hard-coat layer formation, it can be coated by publicly known means, such as mop coating, spray coating, roller coating, brush coating, flow coating, for example. It can be appropriately selected and used according to the site where the material is applied. Furthermore, it is also possible to wipe off the excess after painting if necessary.
　塗装回数は特に制限されることなく、１回又は複数回塗り重ねてもよい。 The number of times of coating is not particularly limited, and may be applied one or more times.
　１回あたりの乾燥膜厚は、仕上がり性、耐ワレ性の点から２～５０μｍ、好ましくは３～３０μｍの範囲内とすることができる。 The dry film thickness per one time can be in the range of 2 to 50 μm, preferably 3 to 30 μm, from the viewpoint of finishability and resistance to cracking.
　形成塗膜の乾燥は、常温乾燥で行うことができるが、塗装環境等に応じて、加熱乾燥又は強制乾燥してもよい。また、必要に応じてブロアー等を用いて風乾燥を併用してもよい。 Drying of the formed coating film can be carried out by normal temperature drying, but depending on the coating environment etc., heat drying or forced drying may be carried out. Moreover, you may use wind drying together using a blower etc. as needed.
　常温乾燥では、例えば５～４５℃の環境下で乾燥することにより塗膜を得ることができる。塗装時における相対湿度（以下ＲＨと略すことがある）は、８０％以下、特に７０％以下が好ましい。 In the case of normal temperature drying, for example, a coating can be obtained by drying under an environment of 5 to 45.degree. The relative humidity (hereinafter sometimes abbreviated as RH) at the time of coating is preferably 80% or less, particularly 70% or less.
　風乾燥を併用する場合は、例えば、常温環境下、サーキュレーター等を設置し、乾燥の間換気することにより乾燥を促進させることができる。 When wind drying is used in combination, for example, a circulator or the like may be installed in a normal temperature environment to promote drying by ventilating during drying.
　本発明は、床面に、特定の常温硬化型ウレタンプライマー組成物（Ａ）による硬化塗膜層（Ｉ）を形成し、該塗膜層（Ｉ）の上に、後述するハードコート層形成用コーティング剤（Ｂ）を塗装し、少なくとも１層のハードコート層（ＩＩ）を形成することにより、得られる工程膜の密着性に優れ、かつ、床面の耐擦り傷性と仕上がり性を向上させることができる。 In the present invention, a cured coating layer (I) is formed on a floor surface by a specific room temperature curing type urethane primer composition (A), and a hard coating layer to be described later is formed on the coating layer (I). By coating the coating agent (B) and forming at least one hard coat layer (II), the adhesion of the process film to be obtained is excellent, and the scratch resistance and finish of the floor surface are improved. Can.
　（Ａ）常温硬化型ウレタンプライマー組成物
　本方法に適用される、前記常温硬化型ウレタンプライマー組成物（Ａ）について説明する。 (A) Room Temperature Curing Urethane Primer Composition The room temperature curing urethane primer composition (A) applied to the present method will be described.
　本方法に適用される常温硬化型ウレタンプライマー組成物（Ａ）は、硬化後塗膜中にウレタン結合を有する塗膜を形成するもので、水酸基含有アクリル樹脂（ａ）を含む主剤と、ポリイソシアネート化合物（ｂ）を含む硬化剤とを含有し、前記硬化剤中に含まれるポリイソシアネート化合物（ｂ）のイソシアネート基と主剤中に含まれる水酸基含有アクリル樹脂（ａ）の水酸基との比率（ＮＣＯ／ＯＨ）が、０．７～２．０の範囲内であることを特徴とする。 The room temperature curing type urethane primer composition (A) applied to the present method is to form a coating film having a urethane bond in a coating film after curing, and a main agent containing a hydroxyl group-containing acrylic resin (a) and a polyisocyanate A ratio of the isocyanate group of the polyisocyanate compound (b) contained in the curing agent to the curing agent containing the compound (b) and the hydroxyl group of the hydroxyl group-containing acrylic resin (a) contained in the main agent (NCO / OH) is characterized in that it is in the range of 0.7 to 2.0.
　ＮＣＯ／ＯＨが上記範囲内であると、初期乾燥性に優れ、ハードコート層形成用コーティング剤（Ｂ）の塗り重ねが短時間で可能になると同時に、仕上がり性、耐ワレ性、耐擦り傷性に優れた表面保護被膜を形成することができる。 When the NCO / OH is in the above range, the initial drying property is excellent, and the coating agent (B) for forming a hard coat layer can be coated in a short time, and at the same time, the finishability, cracking resistance and scratch resistance are achieved. An excellent surface protective film can be formed.
　常温硬化型ウレタンプライマー組成物（Ａ）の仕上がり性及びポットライフの観点から、ＮＣＯ／ＯＨは、０．８～１．８の範囲内が好ましく、０．９～１．６の範囲内がより好ましく、１．０を超えて１．６未満の範囲内がさらに好ましい。 The NCO / OH is preferably in the range of 0.8 to 1.8, more preferably in the range of 0.9 to 1.6, from the viewpoint of the finish and the pot life of the room temperature curing type urethane primer composition (A). Preferably, a range of more than 1.0 and less than 1.6 is more preferable.
　本方法に適用される常温硬化型ウレタンプライマー組成物（Ａ）は、常温で硬化可能でありポリウレタン架橋塗膜を形成するのであれば、水性塗料及び有機溶剤型塗料のいずれの形態であってもよい。本方法に適用される組成物は、環境負荷を低減する観点及び臭気の点から、水性塗料組成物であることが好ましい。 The room temperature curing type urethane primer composition (A) applied to this method may be any form of water-based paint and organic solvent type paint, as long as it can be cured at normal temperature and forms a polyurethane cross-linked coating film. Good. The composition applied to the present method is preferably an aqueous coating composition from the viewpoint of reducing the environmental impact and the point of odor.
　　（ａ）水酸基含有アクリル樹脂
　主剤に含まれる水酸基含有アクリル樹脂（ａ）は、後述のポリイソシアネート化合物（ｂ）と共にポリウレタン架橋塗膜形成成分となる成分である。 (A) Hydroxyl Group-Containing Acrylic Resin The hydroxyl group-containing acrylic resin (a) contained in the main agent is a component to be a polyurethane cross-linked film-forming component together with the later-described polyisocyanate compound (b).
　特に、水酸基含有アクリル樹脂（ａ）のガラス転移温度（以下Ｔｇと略す場合がある）は、初期乾燥性及び表面保護被膜の耐ワレ性の点から、２０～９０℃の範囲内が好ましく、長期耐久性の点から、２５～８０℃の範囲内がより好ましく、３０～７０℃の範囲内がさらに好ましい。 In particular, the glass transition temperature (hereinafter sometimes abbreviated as Tg) of the hydroxyl group-containing acrylic resin (a) is preferably in the range of 20 to 90 ° C. from the viewpoint of the initial drying property and the warpage resistance of the surface protective film. From the viewpoint of durability, the range of 25 to 80 ° C. is more preferable, and the range of 30 to 70 ° C. is more preferable.
　特に、水酸基含有アクリル樹脂（ａ）の水酸基価は、初期乾燥性及びポットライフのバランスの点から、１５～２００ｍｇＫＯＨ／ｇの範囲内が好ましく、３０～１８０ｍｇＫＯＨ／ｇの範囲内がより好ましく、５０～１６０ｍｇＫＯＨ／ｇの範囲内がさらに好ましい。 In particular, the hydroxyl value of the hydroxyl group-containing acrylic resin (a) is preferably in the range of 15 to 200 mg KOH / g, more preferably in the range of 30 to 180 mg KOH / g, from the viewpoint of the balance between initial drying and pot life. More preferably, it is in the range of ̃160 mg KOH / g.
　なお、本明細書において、上記水酸基含有アクリル樹脂のガラス転移温度（Ｔｇ）は、下記式により算出される値である。 In the present specification, the glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin is a value calculated by the following equation.
　１／Ｔｇ（Ｋ）＝Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋・・・Ｗｎ／Ｔｎ
　Ｔｇ（℃）＝Ｔｇ（Ｋ）－２７３
　式中、Ｗ１、Ｗ２、・・・Ｗｎは各モノマーの質量分率であり、Ｔ１、Ｔ２・・・Ｔｎは各モノマーのホモポリマーのガラス転移温度Ｔｇ（Ｋ）である。なお、各モノマーのホモポリマーのガラス転移温度は、ＰＯＬＹＭＥＲ　ＨＡＮＤＢＯＯＫ　Ｆｏｕｒｔｈ　Ｅｄｉｔｉｏｎ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｅ．ｈ．Ｉｍｍｅｒｇｕｔ，Ｅ．Ａ．Ｇｒｕｌｋｅ編（１９９９年）による値であり、該文献に記載されていないモノマーのガラス転移温度は、該モノマーのホモポリマーを重量平均分子量が５０，０００程度になるようにして合成したときの静的ガラス転移温度とする。 1 / Tg (K) = W 1 / T 1 + W 2 / T 2 +... W n / T n
Tg (° C.) = Tg (K) -273
In the formula, W 1 , W 2 ,... W n are mass fractions of respective monomers, and T 1 , T 2 ... T n are glass transition temperatures Tg (K) of homopolymers of respective monomers . In addition, the glass transition temperature of the homopolymer of each monomer is described in POLYMER HANDBOOK Fourth Edition, J. Org. Brandrup, E. h. Immergut, E., et al. A. The glass transition temperature of a monomer which is a value according to Grulke (1999) and which is not described in the literature is static when a homopolymer of the monomer is synthesized to have a weight average molecular weight of about 50,000. Let it be the glass transition temperature.
　上記静的ガラス転移温度は、例えば、試料を測定カップにとり、真空吸引して完全に溶剤を除去した後、示差走査熱量計「ＤＳＣ－５０Ｑ型」（商品名、島津製作所製）を用いて、３℃／分の昇温速度で－１００℃～１５０℃の範囲で熱量変化を測定し、低温側における最初のベースラインの変化点を静的ガラス転移温度とすることによって、測定することができる。 The static glass transition temperature is obtained, for example, by taking a sample in a measuring cup and vacuum suction to completely remove the solvent, and then using a differential scanning calorimeter “DSC-50Q type” (trade name, manufactured by Shimadzu Corporation), It can be measured by measuring the heat change in the range of -100 ° C. to 150 ° C. at a heating rate of 3 ° C./min, and using the initial baseline change point on the low temperature side as the static glass transition temperature. .
　上記水酸基含有アクリル樹脂（ａ）としては、通常、水酸基含有重合性不飽和モノマー及び該水酸基含有重合性不飽和モノマーと共重合可能な他の重合性不飽和モノマーを、従来公知の方法、例えば、有機溶媒中での溶液重合法、水中での乳化重合法などの方法により、共重合せしめることによって製造することができる。 As the hydroxyl group-containing acrylic resin (a), usually, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer can be obtained by a conventionally known method, for example, It can be produced by copolymerization by a method such as a solution polymerization method in an organic solvent or an emulsion polymerization method in water.
　水酸基含有重合性不飽和モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物；該（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物のε－カプロラクトン変性体；アリルアルコール等を挙げることができる。 Examples of the hydroxyl group-containing polymerizable unsaturated monomer include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid and monoester of dihydric alcohol of 2 to 8 carbon atoms; ε-caprolactone modified product of monoester of (meth) acrylic acid and dihydric alcohol of 2 to 8 carbon atoms; allyl alcohol Etc. can be mentioned.
　また、水酸基含有重合性不飽和モノマーと共重合可能な他の重合性不飽和モノマーとしては、例えば、メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル又はシクロアルキル（メタ）アクリレート；イソボルニル基を有する重合性不飽和モノマー；アダマンチル基を有する重合性不飽和モノマー；ビニル芳香族化合物；アルコキシシリル基を有する重合性不飽和モノマー；パーフルオロアルキル（メタ）アクリレート；フッ素化アルキル基を有する重合性不飽和モノマー；マレイミド基等の光重合性官能基を有する重合性不飽和モノマー；ビニル化合物；（メタ）アクリル酸、マレイン酸、クロトン酸、フマル酸、イタコン酸等のカルボン酸、β－カルボキシエチル（メタ）アクリレート等やジカルボン酸モノエステル等のカルボキシル基含有重合性不飽和モノマー；含窒素重合性不飽和モノマー；重合性不飽和基を１分子中に２個以上有する重合性不飽和モノマー；グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、３，４－エポキシシクロヘキシルエチル（メタ）アクリレート、３，４－エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基含有重合性不飽和モノマー；分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート；スルホン酸基を有する重合性不飽和モノマー；リン酸基を有する重合性不飽和モノマー；紫外線吸収性官能基を有する重合性不飽和モノマー；紫外線安定性重合性不飽和モノマー；アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４～７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基を有する重合性不飽和モノマー化合物等が挙げられ、これらはそれぞれ単独でもしくは２種以上組み合わせて使用することができる。 Further, as other polymerizable unsaturated monomers copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert- Alkyl or cycloalkyl (meth) acrylates such as butyl (meth) acrylate and cyclohexyl (meth) acrylate; polymerizable unsaturated monomers having an isobornyl group; polymerizable unsaturated monomers having an adamantyl group; vinyl aromatic compounds; alkoxysilyl groups Perfluoroalkyl (meth) acrylate; polymerizable unsaturated monomer having a fluorinated alkyl group; polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group; vinyl compound; ) Acrylic acid, maleic acid, black Carboxylic acid such as fumaric acid and itaconic acid, carboxyl group-containing polymerizable unsaturated monomer such as β-carboxyethyl (meth) acrylate and dicarboxylic acid monoester; nitrogen-containing polymerizable unsaturated monomer; polymerizable unsaturated Polymerizable unsaturated monomer having two or more groups in one molecule; glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (Meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, epoxy group-containing polymerizable unsaturated monomer such as allyl glycidyl ether; (meth) acrylate having polyoxyethylene chain whose molecular terminal is an alkoxy group; sulfone Polymerizable unsaturated having an acid group Monomer; polymerizable unsaturated monomer having a phosphoric acid group; polymerizable unsaturated monomer having a UV-absorbing functional group; UV-stable polymerizable unsaturated monomer; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate And polymerizable unsaturated monomer compounds having a carbonyl group such as formyl styrene and vinyl alkyl ketones having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone). They can be used alone or in combination of two or more.
　さらに、上記水酸基含有アクリル樹脂（ａ）は変性されていてもよく、例えば、ウレタン変性、エポキシ変性、シリコーン変性などを挙げることができる。 Furthermore, the hydroxyl group-containing acrylic resin (a) may be modified, and examples thereof include urethane modification, epoxy modification, silicone modification and the like.
　水酸基含有アクリル樹脂（ａ）の形態としては、水分散型、水溶性、有機溶剤系のいずれであってもよいが、塗装環境の安全衛生面や臭気の点から、水分散型又は水溶性であることが好ましく、さらに耐水性の点から水分散型が好ましい。 The form of the hydroxyl group-containing acrylic resin (a) may be any of water dispersion type, water solubility, and organic solvent type, but from the viewpoint of safety and health of the coating environment and odor, water dispersion type or water solubility The water dispersion type is preferable from the viewpoint of water resistance.
　水酸基含有アクリル樹脂の水分散体の製造方法としては、従来公知の方法を使用することができる。例えば、乳化剤存在下、重合性不飽和モノマーを乳化重合する方法や、前記溶液重合法により製造された樹脂に含まれるカルボキシル基等のアニオン性基の一部又は全部をアミン等の塩基性化合物で中和してイオン化することによって水中に分散させる方法、前記溶液重合法により製造された樹脂を撹拌機等により強制分散させる方法を用いることが可能である。必要に応じて、乳化剤や界面活性剤を用いてもよく、中和剤の添加前もしくは水分散後に過剰な有機溶剤を除去してもよい。 A conventionally known method can be used as a method for producing a water dispersion of a hydroxyl group-containing acrylic resin. For example, a method of emulsion-polymerizing a polymerizable unsaturated monomer in the presence of an emulsifier, or a part or all of an anionic group such as a carboxyl group contained in a resin produced by the solution polymerization method is a basic compound such as an amine It is possible to use a method of dispersing in water by neutralization and ionization, and a method of forcibly dispersing the resin produced by the solution polymerization method using a stirrer or the like. If necessary, an emulsifying agent or surfactant may be used, and excess organic solvent may be removed before addition of the neutralizing agent or after water dispersion.
　さらに、上記水分散型水酸基含有アクリル樹脂が、相異なる組成の重合性不飽和モノマー成分を多段階に分けて共重合してもよく、単層だけでなく、コア・シェルタイプと言われる多層構造であってもよい。 Furthermore, the above-mentioned water-dispersed hydroxyl group-containing acrylic resin may be copolymerized by dividing the polymerizable unsaturated monomer components having different compositions into multiple steps, and it is not only a single layer but also a multilayer structure called core-shell type. It may be
　上記水酸基含有アクリル樹脂（ａ）を水分散する場合、水分散体の安定性の点からカルボキシル基含有重合性不飽和モノマーを含有することが好ましい。該カルボキシル基含有重合性不飽和モノマーとしては特に限定されないが、前記カルボキシル基含有重合性不飽和モノマーの例示で挙げたものを使用できる。中でもアクリル酸、メタクリル酸が好ましい。 When the hydroxyl group-containing acrylic resin (a) is dispersed in water, it is preferable to contain a carboxyl group-containing polymerizable unsaturated monomer from the viewpoint of the stability of the aqueous dispersion. The carboxyl group-containing polymerizable unsaturated monomer is not particularly limited, but those exemplified for the carboxyl group-containing polymerizable unsaturated monomer can be used. Among them, acrylic acid and methacrylic acid are preferable.
　さらに、貯蔵安定性の点から上記水酸基含有アクリル樹脂（ａ）に中和剤を加えて、カルボキシル基の少なくとも一部を中和してもよい。該中和剤としては特に限定されず、例えば、アンモニア；モノメチルアミン、ジメチルアミン、トリメチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン及びジメチルエタノールアミン等の有機アミン；水酸化ナトリウム、水酸化カリウム等の無機塩基類等が挙げられる。これらの中和剤は単独で使用してもよく、２種以上を併用してもよい。 Furthermore, from the viewpoint of storage stability, a neutralizing agent may be added to the hydroxyl group-containing acrylic resin (a) to neutralize at least a part of the carboxyl groups. The neutralizing agent is not particularly limited, and examples thereof include: ammonia; organic amines such as monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine and dimethylethanolamine; and inorganic bases such as sodium hydroxide and potassium hydroxide And the like. These neutralizing agents may be used alone or in combination of two or more.
　前記中和する前の水酸基含有アクリル樹脂（ａ）の酸価は、アクリル樹脂の水分散安定性、貯蔵安定性及び塗膜の耐水性の点から、５０ｍｇＫＯＨ／ｇ以下が好ましい。　
　以上に述べた水酸基含有アクリル樹脂（ａ）の重量平均分子量は、一般に３，０００～２，０００，０００の範囲内で適宜調整することができ、塗装作業性及び初期乾燥性の点から、５，０００～１，０００，０００の範囲内が好ましい。 The acid value of the hydroxyl group-containing acrylic resin (a) before neutralization is preferably 50 mg KOH / g or less from the viewpoint of the water dispersion stability of the acrylic resin, the storage stability and the water resistance of the coating film.
The weight average molecular weight of the hydroxyl group-containing acrylic resin (a) described above can be generally adjusted in the range of 3,000 to 2,000,000, and from the viewpoint of coating workability and initial drying property, 5 A range of from 1,000 to 1,000,000 is preferable.
　一方、水酸基含有アクリル樹脂（ａ）が溶液重合法により製造された樹脂である場合には、該樹脂（ａ）の重量平均分子量は、３，０００～１００，０００、さらに、５，０００～６０，０００の範囲内がより好ましい。 On the other hand, when the hydroxyl group-containing acrylic resin (a) is a resin produced by a solution polymerization method, the weight average molecular weight of the resin (a) is 3,000 to 100,000, and further 5,000 to 60. The range of 1,000 is more preferable.
　また、溶液重合法により製造された水酸基含有アクリル樹脂（ａ）の酸価は、製造安定性、貯蔵安定性、塗膜の耐水性の点から、０～５０ｍｇＫＯＨ／ｇの範囲内が好ましく、３～４８ｍｇＫＯＨ／ｇの範囲内がより好ましい。 The acid value of the hydroxyl group-containing acrylic resin (a) produced by the solution polymerization method is preferably in the range of 0 to 50 mg KOH / g, from the viewpoint of production stability, storage stability, and water resistance of the coating film. It is more preferably in the range of ̃48 mg KOH / g.
　本明細書において、樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）により、標準ポリスチレンを基準として測定した。下記製造例等における測定は、ＧＰＣ装置として、「ＨＬＣ８１２０ＧＰＣ」（商品名、東ソー（株）製）、カラムとして、「ＴＳＫｇｅｌ　Ｇ－４０００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ－３０００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ－２５００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ－２０００ＨＸＬ」（いずれも東ソー（株）製、商品名）の４本を用いて、移動相；テトラヒドロフラン、測定温度；４０℃、流速；１ｃｃ／分、検出器；ＲＩの条件で行った。 In the present specification, the weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) based on standard polystyrene. The measurement in the following production examples etc. is “HLC8120GPC” (trade name, manufactured by Tosoh Corp.) as a GPC apparatus, “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” as a column, Using four “TSKgel G-2000HXL” (all manufactured by Tosoh Corp., trade name): Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: performed under RI conditions The
　前記水酸基含有アクリル樹脂（ａ）が水分散体である場合には、分散樹脂の平均粒子径は０．０５～１．０μｍの範囲内が好ましく、０．０８～０．８μｍの範囲内がより好ましい。 When the hydroxyl group-containing acrylic resin (a) is a water dispersion, the average particle diameter of the dispersion resin is preferably in the range of 0.05 to 1.0 μm, and more preferably in the range of 0.08 to 0.8 μm. preferable.
　本明細書において平均粒子径としてはコールターカウンターＮ４（商品名、ベックマン・コールター株式会社製、粒度分布測定装置）にて、試料を脱イオン水にて測定に適した濃度に希釈して、常温（２０℃程度）にて測定した値とする。 In the present specification, as the average particle size, a sample is diluted with deionized water to a concentration suitable for measurement with Coulter Counter N4 (trade name, manufactured by Beckman Coulter, Inc., particle size distribution measuring apparatus), The value is measured at about 20 ° C.
　水酸基含有アクリル樹脂（ａ）の樹脂固形分は、水酸基含有アクリル樹脂（ａ）の分散安定性の点から、３５～６５質量％程度であることが好ましい。 The resin solid content of the hydroxyl group-containing acrylic resin (a) is preferably about 35 to 65% by mass from the viewpoint of the dispersion stability of the hydroxyl group-containing acrylic resin (a).
　ここで、本明細書において樹脂固形分とは、試料約２．０ｇを直径約５ｃｍのアルミニウム箔カップに採取し、１１０℃で１時間加熱後の残分（ｇ）を測定して算出した値である。 Here, in the present specification, resin solid content is a value calculated by collecting about 2.0 g of a sample in an aluminum foil cup having a diameter of about 5 cm and measuring the residual content (g) after heating at 110 ° C. for 1 hour It is.
　　（ｂ）ポリイソシアネート化合物
　本発明で用いる硬化剤中に含まれるポリイソシアネート化合物（ｂ）は、１分子中に遊離のイソシアネート基を２個以上有する化合物であり、従来からポリウレタンの製造に使用されているものを使用することができる。 (B) Polyisocyanate Compound The polyisocyanate compound (b) contained in the curing agent used in the present invention is a compound having two or more free isocyanate groups in one molecule, and has conventionally been used for the production of polyurethane Can be used.
　例えば、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネートなどの脂肪族ジイソシアネ－ト；４,４’－メチレンビス（シクロヘキシルイソシアネート）、イソホロンジイソシアネートなどの脂環族ジイソシアネート；キシリレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリフェニルメタンジイソシアネート（以下ポリメリックＭＤＩ）などの芳香族ジイソシアネート；及びこれらのイソシアヌレート体やビュウレット体等の誘導体化合物が挙げられる。これらのうち、特に、少なくともその成分の一部に、脂肪族ジイソシアネート、脂環族ジイソシアネート及びこれらの誘導体化合物が用いられていることが好ましく、具体的には、ヘキサメチレンジイソシアネート（ＨＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＭＤＩ）の誘導体化合物、イソホロンジイソシアネート（ＩＰＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）の誘導化合物体などが用いられていることが好適である。 For example, aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like; alicyclic diisocyanates such as 4,4'-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate; Aromatic diisocyanates such as diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane diisocyanate (hereinafter referred to as polymeric MDI); and derivative compounds such as these isocyanurates and burettes. Among these, in particular, aliphatic diisocyanates, alicyclic diisocyanates and derivative compounds thereof are preferably used for at least a part of the components, and specifically, hexamethylene diisocyanate (HMDI), hexamethylene Derivative compounds of diisocyanate (HMDI), isophorone diisocyanate (IPDI), derivatives of isophorone diisocyanate (IPDI), and the like are preferably used.
　また、ポリエーテル基やカルボキシル基、スルホン酸基、リン酸基又はべタイン構造含有基等の親水性基を前記ポリイソシアネート化合物に導入した親水化ポリイソシアネート化合物や、界面活性剤を用いてポリイソシアネート化合物を水中で分散状態とすることができる水分散性ポリイソシアネート化合物などの水性塗料用ポリイソシアネート化合物も挙げることがきる。以上のポリイソシアネート化合物は１種又は２種以上混合して使用できる。 In addition, a hydrophilicized polyisocyanate compound in which a hydrophilic group such as a polyether group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or a betaine structure-containing group is introduced into the polyisocyanate compound, or a polyisocyanate using a surfactant. Mention may also be made of polyisocyanate compounds for aqueous coatings, such as water-dispersible polyisocyanate compounds, which allow the compounds to be dispersed in water. The above polyisocyanate compounds can be used alone or in combination of two or more.
　常温硬化型ウレタンプライマー組成物（Ａ）が水性塗料である場合には、ポリイソシアネート化合物（ｂ）としては、塗装直前に水と混合できる水性塗料用に変性されたポリイソシアネート化合物を用いることが好ましいが、中でも、得られる塗膜の平滑性などの観点から、アニオン性基含有ポリイソシアネート化合物が好ましい。アニオン性基含有ポリイソシアネートとしては、スルホン酸基及び／又はリン酸基を有するポリイソシアネート化合物が特に好ましい。 When the room temperature curing type urethane primer composition (A) is an aqueous paint, it is preferable to use, as the polyisocyanate compound (b), a polyisocyanate compound modified for an aqueous paint which can be mixed with water immediately before coating. Among them, anionic group-containing polyisocyanate compounds are preferable from the viewpoint of the smoothness of the obtained coating film and the like. As the anionic group-containing polyisocyanate, polyisocyanate compounds having a sulfonic acid group and / or a phosphoric acid group are particularly preferred.
　前記ポリイソシアネート化合物（ｂ）のイソシアネート基含有率は、層間密着性及び耐ワレ性の点から、６～２５質量％の範囲内のものが好ましい。 The isocyanate group content of the polyisocyanate compound (b) is preferably in the range of 6 to 25% by mass from the viewpoint of interlayer adhesion and cracking resistance.
　ここで、本明細書において、イソシアネート基含有率は、化合物中に含まれるイソシアネート基の量を質量分率で表したものである。該イソシアネート基の量の測定は、ＪＩＳ　Ｋ　１６０３－１（２００７）に準拠して行うことができる。具体的には、試料に過剰のジブチルアミンを加え充分に反応させた後、未反応のジブチルアミンを塩酸標準溶液で逆滴定することによって求めた値である。 Here, in the present specification, the isocyanate group content refers to the mass fraction of the amount of isocyanate groups contained in the compound. The measurement of the amount of the isocyanate group can be performed in accordance with JIS K 1603-1 (2007). Specifically, it is a value determined by back titration of unreacted dibutylamine with a hydrochloric acid standard solution after adding an excess of dibutylamine to the sample to cause a reaction sufficiently.
　硬化剤中に含まれるポリイソシアネート化合物（ｂ）の含有量は、硬化剤の合計質量を基準として、１０～９９．９質量％、３０～８０質量％の範囲内に調整することがより好ましい。 The content of the polyisocyanate compound (b) contained in the curing agent is more preferably adjusted in the range of 10 to 99.9% by mass and 30 to 80% by mass based on the total mass of the curing agent.
　硬化剤を希釈する有機溶剤としては、従来から公知のものを使用することができるが、前述したポリイソシアネート化合物（ｂ）と反応することがあるため、水酸基を有さない水溶性溶剤の中から適宜選択することが好ましい。例えば、アセテート系、ケトン系、エステル系、エーテル系、グリコールエーテル系が挙げられ、特に安全衛生面や仕上がり性の点から水酸基を有さないアセテート系水溶性溶剤、水酸基を有さないグリコールエーテル系水溶性溶剤から選ばれる少なくとも１種が好ましい。 As the organic solvent for diluting the curing agent, conventionally known ones can be used, but since they may react with the above-mentioned polyisocyanate compound (b), among the water-soluble solvents having no hydroxyl group It is preferable to select suitably. For example, an acetate type, a ketone type, an ester type, an ether type, a glycol ether type may be mentioned, and an acetate type water soluble solvent having no hydroxyl group, a glycol ether type having no hydroxyl group, from the viewpoint of safety and health and finishability. At least one selected from water-soluble solvents is preferred.
　アセテート系としては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート（別名；酢酸ｎ－ブチルセロソルブ）、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、３－メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート（別名：メトキシプロピルアセテート）、１－メトキシプロピル－２－アセテート等が挙げられる。 Examples of acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate (alias: n-butyl cellosolve acetate), diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate And 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (alias: methoxypropyl acetate), 1-methoxypropyl-2-acetate and the like.
　ケトン系としては、例えば、アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソブチルケトン等が挙げられる。 As a ketone system, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone etc. are mentioned, for example.
　エステル系としては、例えば、酢酸エチル（別名：エチルアセテート）、酢酸ブチル（別名：ブチルアセテート）、酢酸イソブチル（別名：イソブチルアセテート）、安息香酸メチル（別名：メチルベンゾエート）、エトキシプロピオン酸エチル、プロピオン酸エチル、プロピオン酸メチル等が挙げられる。 Examples of esters include ethyl acetate (alias: ethyl acetate), butyl acetate (alias: butyl acetate), isobutyl acetate (alias: isobutyl acetate), methyl benzoate (alias: methyl benzoate), ethyl ethoxypropionate, propion Ethyl acid, methyl propionate and the like can be mentioned.
　エーテル系としては、例えば、テトラヒドロフラン、ジオキサン、ジメトキシエタン、芳香族炭化水素類、脂肪族炭化水素類等が挙げられる。 Examples of the ether group include tetrahydrofuran, dioxane, dimethoxyethane, aromatic hydrocarbons, aliphatic hydrocarbons and the like.
　グリコールエーテル系としては、例えば、エチレングリコールジメチルエーテル及びエチレングリコールジエチルエーテル等のエチレングリコールジエーテル；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジビニルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジエチレングリコールブチルメチルエーテル等のジエチレングリコールジエーテル；トリエチレングリコールジメチルエーテル、トリエチレングリコールジビニルエーテル等のトリエチレングリコールジエーテル；テトラエチレングリコールジエチルエーテル等のテトラエチレングリコールジエーテル等；プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジ－ｎ－プロピルエーテル、プロピレングリコールジイソプロピルエーテル、プロピレングリコールジ－ｎ－ブチルエーテル、プロピレングリコールジイソブチルエーテル、プロピレングリコールジアリルエーテル、プロピレングリコールジフェニルエーテル等のプロピレングリコールジエーテル；ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、及びジプロピレングリコールジ－ｎ－ブチルエーテル、ジプロピレングリコールジイソブチルエーテル、ジプロピレングリコールアリルエーテル等のジプロピレングリコールジエーテル；トリプロピレングリコールジメチルエーテル、トリプロピレングリコールジエチルエーテル、及びトリプロピレングリコールジ－ｎ－ブチルエーテル、トリプロピレングリコールジイソブチルエーテル、トリプロピレングリコールジアリルエーテル等のトリプロピレングリコールジエーテル等；ブチレングリコールジメチルエーテル、ブチレングリコールジエチルエーテル、及びブチレングリコールジ－ｎ－ブチルエーテル等のブチレングリコールジエーテル等、２－ブトキシエチルジエトキシエチルエーテル、２－ブトキシエチルトリエトキシエーテル、２－ブトキシエチルテトラエトキシエチルエーテル等が挙げられる。 Examples of glycol ethers include ethylene glycol diethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol divinyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether and the like Diethylene glycol diether; triethylene glycol diether such as triethylene glycol dimethyl ether, triethylene glycol divinyl ether; tetraethylene glycol diether such as tetraethylene glycol diethyl ether; propylene glycol dimethyl ether, pro Propylene glycol diethers such as propylene glycol diether, propylene glycol di-n-propyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether, propylene glycol diaryl ether, propylene glycol diphenyl ether; dipropylene glycol Dipropylene glycol diethers such as dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol di-n-butyl ether, dipropylene glycol diisobutyl ether, dipropylene glycol allyl ether; tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripro Tripropylene glycol diethers such as glycol di-n-butyl ether, tripropylene glycol diisobutyl ether, tripropylene glycol diaryl ether, etc .; butylene glycol di ether such as butylene glycol dimethyl ether, butylene glycol diethyl ether, and butylene glycol di-n-butyl ether Ether and the like, 2-butoxyethyl diethoxyethyl ether, 2-butoxyethyl triethoxy ether, 2-butoxyethyl tetraethoxyethyl ether and the like can be mentioned.
　上記有機溶剤を含有する場合の含有量は、硬化剤の合計質量を基準として、ポリイソシアネート化合物（ｂ）との混和性、すなわち仕上がり性の観点から、１０質量％以上、特に２０～７０質量％の範囲内に調整することが好ましい。 The content in the case of containing the organic solvent is 10% by mass or more, particularly 20 to 70% by mass from the viewpoint of the miscibility with the polyisocyanate compound (b), that is, the finish based on the total mass of the curing agent. It is preferable to adjust in the range of
　ウレタン硬化触媒は、従来から公知のものを使用することができ、例えば、オクチル酸錫、ジブチル錫ジアセテート、ジブチル錫ジ（２－エチルヘキサノエート）、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、ジオクチル錫ジアセテート、ジオクチル錫ジ（２－エチルヘキサノエート）、ジブチル錫オキサイド、ジブチル錫サルファイト、ジオクチル錫オキサイド、ジブチル錫脂肪酸塩、２－エチルヘキサン酸鉛、オクチル酸亜鉛、ナフテン酸亜鉛、脂肪酸亜鉛類、オクタン酸ビスマス、２－エチルヘキサン酸ビスマス、オレイン酸ビスマス、ネオデカン酸ビスマス、バーサチック酸ビスマス、ナフテン酸ビスマス、ナフテン酸コバルト、オクチル酸カルシウム、ナフテン酸銅、テトラ（２－エチルヘキシル）チタネート等の有機金属化合物；第三級アミン；イミダゾール化合物等が挙げられ、これらはそれぞれ単独でもしくは２種以上組み合せて使用することができる。 As the urethane curing catalyst, conventionally known ones can be used. For example, tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin Diacetate, dioctyltin di (2-ethylhexanoate), dibutyltin oxide, dibutyltin sulfite, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zinc Such as bismuth octanoate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate, etc. Yes Metal compounds; tertiary amines; imidazole compound, and the like. These may be used either alone or two or more kinds in combination.
　また、上記硬化触媒を使用する場合、乾燥性とポットライフ（可使時間）のバランス及び、得られる塗膜の耐水性及び工程膜での仕上がり性の点から、その含有量としては、常温硬化型ウレタンプライマー組成物（Ａ）中の固形分総量に対して、０．０００１～１．０質量％の範囲内が好ましく、０．０００５～０．５質量％の範囲内であることがより好ましい。 In the case of using the above-mentioned curing catalyst, the content of the curing catalyst is room temperature curing, from the viewpoint of the balance between the drying property and the pot life (working life) and the water resistance of the coating film obtained and the finish of the step film. It is preferably in the range of 0.0001 to 1.0% by mass, more preferably in the range of 0.0005 to 0.5% by mass, relative to the total amount of solids in the urethane primer composition (A) .
　常温硬化型ウレタンプライマー組成物（Ａ）の固形分総量とは、前記水酸基含有アクリル樹脂（ａ）の樹脂固形分、ポリイソシアネート化合物（ｂ）の樹脂固形分及び配合されるその他の添加剤等の有効成分の合計質量を指す。ここで、本明細書中において、有効成分とは、試料から、水、有機溶剤などの溶媒を除いた残渣の合計質量を意味する。 The total solid content of the room temperature curing type urethane primer composition (A) refers to the resin solid content of the hydroxyl group-containing acrylic resin (a), the resin solid content of the polyisocyanate compound (b) and other additives to be blended It refers to the total mass of the active ingredient. Here, in the present specification, the active ingredient means the total mass of the residue obtained by removing the solvent such as water and organic solvent from the sample.
　本発明に用いられる常温硬化型ウレタンプライマー組成物（Ａ）は、上記水酸基含有アクリル樹脂（ａ）を含む主剤と、硬化剤と、を含む２液型のプライマー組成物であり、これらを使用直前に混合することによって容易に調製することができる。 The room temperature curing type urethane primer composition (A) used in the present invention is a two-component type primer composition comprising a main agent containing the above-mentioned hydroxyl group-containing acrylic resin (a) and a curing agent, It can be easily prepared by mixing it with
　常温硬化型ウレタンプライマー組成物（Ａ）は、前記各成分以外にも必要に応じて、水酸基含有アクリル樹脂（ａ）以外の樹脂（例えば、ポリウレタン樹脂）、表面調整剤、体質顔料、着色顔料、充填剤（例えば、タルク、ガラスビーズ、マイカ等）、染料、分散安定剤、粘度調整剤、紫外線吸収剤、光安定剤、ポリマー微粒子、造膜助剤、防腐剤、消泡剤、中和剤、レベリング剤、シランカップリング剤、可塑剤、凍結防止剤、香料、ｐＨ調整剤、難燃化剤等の添加剤や希釈溶媒を含有してもよい。これらは、水酸基含有アクリル樹脂（ａ）を含む主剤とポリイソシアネート化合物（ｂ）を含む硬化剤の双方に含有することができ、また、いずれか一方に含有してもよい。 The room temperature curing type urethane primer composition (A) is a resin other than the hydroxyl group-containing acrylic resin (a) (for example, polyurethane resin), a surface control agent, an extender pigment, a color pigment, if necessary, in addition to the above components. Fillers (eg, talc, glass beads, mica etc.), dyes, dispersion stabilizers, viscosity modifiers, UV absorbers, light stabilizers, polymer particles, film forming aids, preservatives, antifoaming agents, neutralizing agents You may contain additives, such as a leveling agent, a silane coupling agent, a plasticizer, an antifreeze agent, a fragrance, a pH adjuster, a flame retardant, and a dilution solvent. These can be contained in both of the main agent containing the hydroxyl group-containing acrylic resin (a) and the curing agent containing the polyisocyanate compound (b), or may be contained in either one.
　中でも、充填剤やその他の樹脂としてポリウレタン樹脂を添加すると、高温高湿度（梅雨や夏場）もしくは低温低湿度（冬場）を含む幅広い環境下においても工程膜と床材との密着性、仕上がり性、耐ワレ性、耐擦り傷性及び艶感等の塗膜物性に優れるため好ましい。なお、タルクの添加量は、常温硬化型ウレタンプライマー組成物（Ａ）中の固形分総量に対して、０．３～１５質量％が好ましい。ポリウレタン樹脂の添加量は、常温硬化型ウレタンプライマー組成物（Ａ）中の固形分総量に対して、ポリウレタン樹脂の固形分として０．３～１５質量％が好ましく、より好ましくは１．０～１０質量％である。 Above all, when a polyurethane resin is added as a filler or other resin, the adhesion between the process film and the floor material, finish, even under a wide range of environments including high temperature and high humidity (rainy season and summer season) or low temperature and low humidity (winter season) It is preferable because it is excellent in coating film properties such as cracking resistance, abrasion resistance and gloss. The addition amount of talc is preferably 0.3 to 15% by mass with respect to the total solid content in the room temperature curing type urethane primer composition (A). The amount of the polyurethane resin added is preferably 0.3 to 15% by mass, more preferably 1.0 to 10%, as the solid content of the polyurethane resin, based on the total solid content in the room temperature curing type urethane primer composition (A). It is mass%.
　これらのうち前記表面調整剤としては、例えば、ジアルキルスルホコハク酸塩類、アルキルナフタレンスルホン酸塩類及び脂肪酸塩類等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリルエーテル類、アセチレングリコール類及びポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類等のノニオン性界面活性剤；アルキルアミン塩類及第四級アンモニウム塩類等のカチオン性界面活性剤；シリコーン系界面活性剤；フッ素系界面活性剤などが挙げられる。 Among them, as the surface modifier, for example, anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycol Surfactants and nonionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; silicone surfactants; fluorosurfactants and the like It can be mentioned.
　中でも常温硬化型ウレタンプライマー組成物（Ａ）の床素材への濡れ広がり性の点から、シリコーン系界面活性剤またはフッ素系界面活性剤が好ましい。 Among them, silicone surfactants or fluorosurfactants are preferable from the viewpoint of the wettability to the floor material of the room temperature curing type urethane primer composition (A).
　さらに、本方法で形成された複層膜の耐ワレ性の点からコロイダルシリカを含有してもよく、コロイダルシリカとしては、後述するハードコート層形成用のコーティング剤（Ｂ）で挙げるものを特に好適に使用できる。 Furthermore, colloidal silica may be contained from the viewpoint of the warpage resistance of the multilayer film formed by the present method, and as the colloidal silica, those mentioned in the coating agent (B) for forming a hard coat layer described later are particularly mentioned It can be used suitably.
　本発明に用いる常温硬化型ウレタンプライマー組成物（Ａ）は、塗装時において、仕上り性、床面への塗れ広がりやすさ及び均一な架橋塗膜形成の点から、固形分含有率を通常１５～７０質量％、特に２０～６０質量％の範囲内とすることが好ましい。 The room temperature curing type urethane primer composition (A) used in the present invention has a solid content of usually 15 to 15 in view of finish, ease of spreading on a floor surface and formation of a uniform crosslinked coating during coating. The content is preferably 70% by mass, and more preferably 20 to 60% by mass.
　常温硬化型ウレタンプライマー組成物（Ａ）の粘度は、塗装作業性の点から２５Ｐａ・ｓ以下であることが好ましい。前記粘度は、２３℃、５０％ＲＨ条件下で主剤と硬化剤を１分間混合した後、１分間静置してＢ型粘度計６０ｒｐｍで測定した値である。 The viscosity of the room temperature curing type urethane primer composition (A) is preferably 25 Pa · s or less from the viewpoint of coating workability. The viscosity is a value measured by mixing a main agent and a curing agent under conditions of 23 ° C. and 50% RH for 1 minute, leaving it to stand for 1 minute, and using a B-type viscometer at 60 rpm.
　（Ｂ）ハードコート層形成用コーティング剤
　本方法に適用されるハードコート層形成用のコーティング剤（Ｂ）は、硬化後、塗膜中にシロキサン結合を有する塗膜を形成するものを好適に使用することができる。具体的にはコーティング剤組成物中の加水分解性基及びシラノール基が反応してシロキサン結合を形成し、３次元のガラス質の硬化膜を形成しうるものであることができる。該硬化膜を形成しうる成分としては、例えば、シリカ、加水分解性シラン及び／又はその縮合物が挙げられ、さらに、シランカップリング剤などが挙げられ、これらは単独で又は適宜組み合わせて用いることができる。 (B) Coating Agent for Forming Hard Coat Layer The coating agent (B) for forming a hard coat layer applied to the present method is suitably used one that forms a coating having a siloxane bond in the coating after curing. can do. Specifically, the hydrolyzable group and the silanol group in the coating agent composition may be reacted to form a siloxane bond to form a three-dimensional glassy cured film. As a component which can form the said cured film, a silica, a hydrolysable silane, and / or its condensate are mentioned, for example, Furthermore, a silane coupling agent etc. are mentioned, These are used individually or in combination suitably Can.
　特に、ハードコート層形成用のコーティング剤（Ｂ）が、加水分解性シランとしてエポキシシランオリゴマー（ｃ）と、平均粒子径が１～１００ｎｍの範囲内のコロイダルシリカ（ｄ）と、硬化触媒（ｅ）と、を含むものであることが、乾燥性、耐ワレ性及び耐擦り傷性の点から特に好ましい。 In particular, the coating agent (B) for forming the hard coat layer comprises an epoxysilane oligomer (c) as a hydrolyzable silane, colloidal silica (d) having an average particle diameter in the range of 1 to 100 nm, and a curing catalyst (e It is particularly preferable from the viewpoint of drying property, cracking resistance and scratch resistance that the ink composition contains
　　（ｃ）エポキシシランオリゴマー
　エポキシシランオリゴマー（ｃ）は、分子内にエポキシ基とシロキサン結合を有する化合物であり、例えば、下記一般式（Ｉ）で表されるエポキシ基含有加水分解性シランの加水分解縮合物（ｃ１）、及び／又は、該エポキシ基含有加水分解性シランとエポキシ基を有さない下記一般式（ＩＩ）で表される加水分解性シランとの混合物の加水分解縮合物（ｃ２）であることができる。 (C) Epoxysilane Oligomer The epoxysilane oligomer (c) is a compound having an epoxy group and a siloxane bond in the molecule, and, for example, hydrolysis of an epoxy group-containing hydrolyzable silane represented by the following general formula (I) Hydrolyzed condensate (c2) of a condensate (c1) and / or a mixture of the epoxy group-containing hydrolyzable silane and a hydrolyzable silane represented by the following general formula (II) having no epoxy group Can be.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
[式（Ｉ）中、Ｒ１はエポキシ基を含有する有機基であり、Ｘは、加水分解性基であり、ａは１～３の整数である。]
　前記Ｘは加水分解性基であり、例えば、アルコキシ基、アセトキシ基、オキシム基、アミノキシ基、ハロゲン原子などが挙げられるが、入手しやすい炭素数１～６のアルコキシ基が好ましく、加水分解縮合の反応速度の点から、メトキシ基が好ましい。 [In the formula (I), R 1 is an epoxy-containing organic group, X is a hydrolyzable group, and a is an integer of 1 to 3. ]
The above-mentioned X is a hydrolyzable group, and examples thereof include an alkoxy group, an acetoxy group, an oxime group, an aminoxy group, a halogen atom and the like, and an alkoxy group having 1 to 6 carbon atoms which is easily available is preferable. From the viewpoint of reaction rate, a methoxy group is preferred.
　前記Ｒ１のエポキシ基を含有する有機基としては、具体的には、グリシドキシプロピル基等のグリシドキシ基、（３，４－エポキシシクロヘキシル）メチル基、（３，４－エポキシシクロヘキシル）エチル基等の３，４－エポキシシクロヘキシル基等を挙げることができる。 Specific examples of the organic group containing an epoxy group of R 1 include glycidoxy groups such as glycidoxypropyl group, (3,4-epoxycyclohexyl) methyl group, (3,4-epoxycyclohexyl) ethyl group And 3,4-epoxycyclohexyl groups.
　前記一般式（Ｉ）で表される加水分解性シランとしては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルジメトキシシランなどが挙げられる。 Examples of the hydrolyzable silane represented by the above general formula (I) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane and the like can be mentioned.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
[式（ＩＩ）中、Ｒ２はエポキシ基を有さない有機基であり、Ｘは同一又は異なってもよい加水分解性基、ａは０～３の整数を示す]。 [In the formula (II), R 2 is an organic group having no epoxy group, X is a hydrolyzable group which may be the same or different, and a represents an integer of 0 to 3].
　エポキシ基を有さない有機基としては、耐擦り傷性の点から、炭素数１～１８の１価の有機基が好ましく、直鎖でも分岐していてもよく、ウレタン結合、エステル結合、エーテル結合等を有していてもよく、フッ素などのハロゲン等により置換されていてもよい。 The organic group having no epoxy group is preferably a monovalent organic group having 1 to 18 carbon atoms in view of scratch resistance, and may be linear or branched, and urethane bond, ester bond, ether bond And may be substituted by halogen such as fluorine.
　前記一般式（ＩＩ）で表される加水分解性シランとして具体的には、例えば、前記ａが０～３の整数であり、単官能性、２官能性、３官能性又は４官能性の加水分解性シランが挙げられる。 Specifically, as the hydrolyzable silane represented by the above general formula (II), for example, a monofunctional, bifunctional, trifunctional or tetrafunctional hydrolysis wherein the a is an integer of 0 to 3 Degradable silanes can be mentioned.
　ａ＝１である３官能性の加水分解性シランとしては、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、メチルトリメトキシシランの部分加水分解縮合物（商品名「ＫＣ－８９Ｓ」、信越化学工業製）、ｐ－スチリルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、γ－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン；メトキシＰＥＧ－１０プロピルトリメトキシシラン等のポリアルキレングリコール変性トリメトキシシランなどを挙げることができる。 As trifunctional hydrolyzable silanes where a = 1, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, partially hydrolyzed condensate of methyltrimethoxysilane (trade name “KC-89S”, Shin-Etsu Chemical Co., Ltd.), p-styryltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Triethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriol Tokishishiran, vinyltrimethoxysilane, vinyltriethoxysilane, polyalkylene glycol-modified silane, such as methoxy PEG-10 propyl trimethoxy silane can be cited.
　ａ＝２である２官能性の加水分解性シランとしては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、メチルエチルジメトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、メチルプロピルジメトキシシラン、メチルプロピルジエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－アクリロキシプロピルジメトキシシラン、３－アミノプロピルメチルジメトキシシラン、３－アミノプロピルメチルジエトキシシラン；ジメチルジクロロシラン、トリメチルクロロシラン等のオルガノハロシランなどを挙げることができる。 As difunctional hydrolyzable silanes where a = 2, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyl Dimethoxysilane, methylpropyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldisilane Ethoxysilanes and organohalosilanes such as dimethyldichlorosilane and trimethylchlorosilane can be mentioned.
　ａ＝３である単官能性の加水分解性シランとしては、トリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルイソプロピルプロポキシシラン、ジメチルイソブチルメトキシシランなどを挙げることができる。 Examples of monofunctional hydrolyzable silanes where a = 3 include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropylpropoxysilane, dimethylisobutylmethoxysilane and the like.
　ａ＝０である４官能性の加水分解性シランとしては、具体的には、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラフェノキシシランなどのテトラアルコキシシラン；テトラクロロシランなどのテトラハロシランを挙げることができる。 Specifically, tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraphenoxysilane, and the like; tetrahalosilanes such as tetrachlorosilane; It can be mentioned.
　単官能性、２官能性、３官能性又は４官能性の加水分解性シランは、必要に応じて２種以上を組み合わせて使用してもよい。 The monofunctional, bifunctional, trifunctional or tetrafunctional hydrolyzable silanes may be used in combination of two or more, if necessary.
　前記エポキシシランオリゴマー（ｃ）の重量平均分子量は、乾燥性向上と耐ワレ性の点から、５００～２０，０００の範囲内となるよう調整されることが好ましく、さらに８００～１０，０００の範囲内となるよう調整されることが好ましい。 The weight average molecular weight of the epoxysilane oligomer (c) is preferably adjusted to be in the range of 500 to 20,000, and more preferably in the range of 800 to 10,000, from the viewpoint of improving the drying property and the cracking resistance. It is preferable to be adjusted to be inside.
　前記エポキシシランオリゴマー（ｃ）のエポキシ当量は、水希釈安定性と硬化性の点から、１５０～１，０００（ｇ／ｅｑ）の範囲内が好ましく、２００～８００（ｇ／ｅｑ）の範囲内がより好ましい。 The epoxy equivalent of the epoxysilane oligomer (c) is preferably in the range of 150 to 1,000 (g / eq), and in the range of 200 to 800 (g / eq), from the viewpoint of water dilution stability and curability. Is more preferred.
　ここで、本明細書中においてエポキシ当量とは、ＪＩＳ　Ｋ７２３６に準拠した方法により測定した１グラム当量のエポキシ基を含む樹脂のグラム数である。 Here, in the present specification, the epoxy equivalent is the number of grams of a resin containing one gram equivalent of an epoxy group measured by the method according to JIS K7236.
　また、本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用いて測定した保持時間（保持容量）を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間（保持容量）によりポリスチレンの分子量に換算して求めた値である。具体的には、ゲルパーミエーションクロマトグラフ装置として、「ＨＬＣ－８１２０ＧＰＣ」（商品名、東ソー社製）を使用し、カラムとして、「ＴＳＫｇｅｌ　Ｇ４０００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ３０００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ２５００ＨＸＬ」及び「ＴＳＫｇｅｌ　Ｇ２０００ＨＸＬ」（商品名、いずれも東ソー社製）の計４本を使用し、検出器として、示差屈折率計を使用し、移動相：テトラヒドロフラン、測定温度：４０℃、流速：１ｍＬ／ｍｉｎの条件下で測定することができる。 Further, in the present specification, the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene of known molecular weight, which is measured under the same conditions as the retention time (retention capacity) measured using gel permeation chromatography (GPC) It is the value calculated by converting it into the molecular weight of polystyrene. Specifically, "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph apparatus, and "TSKgel G4000HXL", "TSKgel G3000HXL", "TSKgel G2500HXL" and "TSKgel" are used as columns. A total of four G2000HXL (trade names, all manufactured by Tosoh Corporation) are used, a differential refractometer is used as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 mL / min. It can be measured below.
　エポキシシランオリゴマー（ｃ）の製造方法
　前記エポキシシランオリゴマー（ｃ）は、一般的なオルガノシランオリゴマーの製造に用いられている製造方法と従来公知の化学反応とを組み合わせることにより得ることができる。例えば、以下の製造方法を用いて製造することができる。 Method for Producing Epoxy Silane Oligomer (c) The epoxy silane oligomer (c) can be obtained by combining a production method used for producing a general organosilane oligomer with a conventionally known chemical reaction. For example, it can manufacture using the following manufacturing methods.
　具体的には例えば、出発物質に前記式（Ｉ）で表されるエポキシ基含有加水分解性シランと、必要に応じて前記式（ＩＩ）で表されるエポキシ基を有さない加水分解性シランとを、水及び触媒の存在下で加水分解縮合反応を行いエポキシシランオリゴマー（ｃ）を製造する方法が挙げられる。 Specifically, for example, a hydrolyzable silane having no epoxy group-containing hydrolyzable silane represented by the formula (I) and optionally an epoxy group represented by the formula (II) as a starting material And hydrolytic condensation reaction in the presence of water and a catalyst to produce an epoxysilane oligomer (c).
　エポキシシランオリゴマー（ｃ）は、特に耐擦り傷性の点から、エポキシシランオリゴマー（ｃ）が、前記一般式（Ｉ）で表されるエポキシ基含有加水分解性シランの加水分解縮合物（ａ１）、及び／又は、該エポキシ基含有加水分解性シランと前記一般式（ＩＩ）で表されるエポキシ基を有さない加水分解性シランとの混合物の加水分解縮合物（ａ２）が好ましく、特に前記一般式（Ｉ）で表されるエポキシ基含有加水分解性シランと前記一般式（ＩＩ）で表されるエポキシ基を有さない加水分解性シランとの混合物の加水分解縮合物（ａ２）が好ましい。 The epoxysilane oligomer (c) is a hydrolysis condensate (a1) of an epoxy group-containing hydrolyzable silane represented by the above general formula (I), particularly from the viewpoint of scratch resistance, the epoxysilane oligomer (c) And / or a hydrolytic condensate (a2) of a mixture of the epoxy group-containing hydrolyzable silane and the epoxy group-free hydrolyzable silane represented by the general formula (II) is preferred, and in particular The hydrolytic condensate (a2) of a mixture of the epoxy group-containing hydrolyzable silane represented by the formula (I) and the hydrolyzable silane having no epoxy group represented by the general formula (II) is preferred.
　上記のうち、エポキシシランオリゴマー（ｃ）が、前記加水分解化合物（ａ２）である場合には、前記式（Ｉ）で表されるエポキシ基含有加水分解性シランと前記式（ＩＩ）で表されるエポキシ基を有さない加水分解性シランとの割合が、前者／後者（モル比）として９９／１～５５／４５の範囲内であることが好ましく、８５／１５～６０／４０の範囲内で調整されることがさらに好ましい。 Among the above, when the epoxysilane oligomer (c) is the hydrolysis compound (a2), it is represented by the epoxy group-containing hydrolyzable silane represented by the formula (I) and the formula (II) The ratio to the hydrolyzable silane having no epoxy group is preferably in the range of 99/1 to 55/45 as the former / the latter (molar ratio), and is in the range of 85/15 to 60/40. It is further preferred that the
　前記エポキシシランオリゴマー（ｃ）は、前記加水分解縮合物（ａ１）と前記加水分解縮合物（ａ２）を併用してもよい。 The epoxysilane oligomer (c) may be used in combination with the hydrolysis condensate (a1) and the hydrolysis condensate (a2).
　本発明に使用するエポキシシランオリゴマー（ｃ）の製造方法における加水分解縮合反応は、前記触媒の存在下で、例えばｐＨ１～７．５、好ましくはｐＨ２～７の範囲の条件を採用するのがよい。上記ｐＨ領域で反応させることで合成中にゲル化や、凝集物が発生したりすることを抑制できる。 The hydrolysis condensation reaction in the method for producing the epoxysilane oligomer (c) used in the present invention may employ, for example, conditions of pH 1 to 7.5, preferably pH 2 to 7 in the presence of the catalyst. . By reacting in the above-mentioned pH range, it is possible to suppress gelation and generation of aggregates during synthesis.
　触媒としては、前記ｐＨ領域に調整できるものであれば、その種類は特に制限はなく、例えば、ギ酸、酢酸、プロピオン酸、シュウ酸、クエン酸、マレイン酸、安息香酸、マロン酸、グルタール酸、トルエンスルホン酸などの有機酸類もしくはフッ化水素、塩酸、硝酸、リン酸、硫酸等の無機酸類、又は表面にカルボン酸基やスルホン酸基を有する陽イオン交換樹脂等の固体酸触媒等が挙げられる。 The catalyst is not particularly limited as long as it can be adjusted to the above-mentioned pH range, and for example, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, Organic acids such as toluene sulfonic acid or inorganic acids such as hydrogen fluoride, hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, or solid acid catalysts such as cation exchange resin having carboxylic acid group and sulfonic acid group on the surface .
　前記触媒の使用量は、特に限定されるものではないが、多すぎるとコスト高になる、合成中や貯蔵中にゲル化する等の問題があり、少ないと反応が遅くなる場合がある。 The amount of the catalyst used is not particularly limited. However, if the amount is too large, there are problems such as cost increase, gelation during synthesis or storage, etc., and if less, reaction may be delayed.
　そのため、前記触媒の使用量は、出発物質として配合される加水分解性シラン１００質量部に対して０．１～２０質量部、好ましくは０．５～１５質量部の範囲が適当である。 Therefore, the amount of the catalyst used is suitably in the range of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compounded as the starting material.
　前記加水分解縮合反応において、有機溶媒を使用してもよい。有機溶媒を用いることは、ゲル化を防止する点及び製造時の粘度を調節できる点から好ましい。 An organic solvent may be used in the hydrolysis and condensation reaction. It is preferable to use an organic solvent from the viewpoint of preventing gelation and in that the viscosity at the time of production can be adjusted.
　有機溶媒としては、例えば、メタノール、エタノール、イソプロパノールなどのアルコール類、トルエン、キシレンなどの芳香族化合物類、アセトンなどのケトン類、酢酸エチルなどのエステル類が挙げられる。 Examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol, aromatic compounds such as toluene and xylene, ketones such as acetone, and esters such as ethyl acetate.
　加水分解縮合時の反応温度としては、通常０～２００℃、好ましくは１０～１９０℃、さらに好ましくは１０～１２０℃である。また、この反応は圧力によらず実施できるが、０．０２～０．２ＭＰａの圧力範囲が好ましく、特に０．０８～０．１５ＭＰａの圧力範囲が好ましい。当該反応は、通常、１～１５時間程度で終了する。 The reaction temperature at the time of hydrolysis and condensation is generally 0 to 200 ° C., preferably 10 to 190 ° C., and more preferably 10 to 120 ° C. The reaction can be carried out regardless of the pressure, but a pressure range of 0.02 to 0.2 MPa is preferable, and a pressure range of 0.08 to 0.15 MPa is particularly preferable. The reaction usually completes in about 1 to 15 hours.
　加水分解縮合後の混合液からは、反応で生成したアルコール、溶媒及び触媒を公知の手法で除去してもよい。尚、得られた生成物は、その目的に応じて、洗浄、カラム分離、固体吸着剤による吸着等の各種の精製法によって触媒を除去し、さらに精製してもよい。効率の点から水洗により反応で生成したアルコール及び触媒を除去することが好ましい。 From the mixture after hydrolysis and condensation, the alcohol, the solvent and the catalyst produced in the reaction may be removed by a known method. The product obtained may be further purified according to the purpose by removing the catalyst by various purification methods such as washing, column separation, adsorption by a solid adsorbent, and the like. From the point of efficiency, it is preferable to remove the alcohol and catalyst generated in the reaction by washing with water.
　ここで、前記加水分解縮合反応において前記加水分解性シランの加水分解性基の縮合割合によりエポキシシランオリゴマーの構造が変化するが、本製造方法により得られる生成物には、Ｓｉ－ＯＨ基が１００％縮合した、完全籠型構造、Ｓｉ－ＯＨ基が残存した直鎖状、分岐状、ラダー構造、不完全籠型構造及び／又はランダム縮合体のエポキシシランオリゴマーが含まれる場合がある。本製造方法により得られる（ｃ）成分であるエポキシシランオリゴマーは、それら完全籠型構造、直鎖状、分岐状、ラダー構造、不完全籠型構造及び／又はランダム縮合体のいずれであってもよい。 Here, the structure of the epoxysilane oligomer changes depending on the condensation ratio of the hydrolyzable group of the hydrolyzable silane in the hydrolytic condensation reaction, but the product obtained by the present production method has a Si-OH group of 100 In some cases, it may include an epoxysilane oligomer of a fully caged structure, a linear, branched, ladder structure, an incomplete caged structure and / or a random condensation product in which a fully caged structure, a Si-OH group remains. The epoxysilane oligomer which is the component (c) obtained by the present production method may be any one of the complete cage structure, linear, branched, ladder structure, incomplete cage structure and / or random condensation product. Good.
　ハードコート層形成用のコーティング剤（Ｂ）中のエポキシシランオリゴマーの含有量は、得られる被膜の硬度と耐擦り傷性の点から、ハードコート層形成用のコーティング剤（Ｂ）の有効成分の総量に対して、２０～８０質量％の範囲内が好ましく、３５～７５質量％の範囲内がより好ましい。 The content of the epoxysilane oligomer in the coating agent (B) for forming a hard coat layer is the total amount of the active ingredients of the coating agent (B) for forming a hard coat layer from the viewpoint of the hardness and abrasion resistance of the obtained film On the other hand, the range of 20 to 80% by mass is preferable, and the range of 35 to 75% by mass is more preferable.
　　（ｄ）コロイダルシリカ
　コロイダルシリカの、市販品としては、コロイダルシリカ微粒子が挙げられる。 (D) Colloidal Silica A commercially available product of colloidal silica includes colloidal silica fine particles.
　コロイダルシリカは、シリカの超微粒子を分散媒に分散させたものである。 Colloidal silica is obtained by dispersing ultrafine particles of silica in a dispersion medium.
　分散媒としては、例えば、水；メタノール、エタノール、イソプロパノール、ｎ－プロパノール、イソブタノール、ｎ－ブタノール等のアルコール系溶剤；エチレングリコール等の多価アルコール系溶剤；エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等の多価アルコール誘導体；メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール等のケトン系溶剤；２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、テトラヒドロフルフリルアクリレート等のモノマーが挙げられる。コーティング剤が水性である場合には、水、メタノール、エタノール等の水溶性溶剤、特に水を分散媒としたものであることが、コーティング剤に適用した際の安定性の点から好ましい。 As the dispersion medium, for example, water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol and n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol mono Examples thereof include polyhydric alcohol derivatives such as butyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; and monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and tetrahydrofurfuryl acrylate. When the coating agent is aqueous, it is preferable to use a water-soluble solvent such as water, methanol, ethanol or the like, particularly water as a dispersion medium, from the viewpoint of stability when applied to the coating agent.
　水を分散媒とするコロイダルシリカとしては、例えば、酸性コロイダルシリカ、塩基性コロイダルシリカ等が挙げられる。 As colloidal silica which makes water a dispersion medium, acidic colloidal silica, basic colloidal silica, etc. are mentioned, for example.
　酸性コロイダルシリカとしては、特に限定されないが、例えば、市販品としてスノーテックスＡＫ、スノーテックスＯ、スノーテックスＯ－４０、スノーテックスＯＬ、スノーテックスＯＵＰ、スノーテックスＯＸＳ、スノーテックスＯＹＬ（以上、商品名、日産化学工業社製、スノーテックスは登録商標）、アデライトＡＴ－２０Ｑ（商品名、ＡＤＥＫＡ社製、アデライトは登録商標）等が挙げられる。 The acidic colloidal silica is not particularly limited. For example, as commercial products, Snowtex AK, Snowtex O, Snowtex O-40, Snowtex OL, Snowtex OUP, Snowtex OXS, Snowtex OYL (all trade names) Manufactured by Nissan Chemical Industries, Ltd., Snowtex is a registered trademark, Adelite AT-20Q (trade name, manufactured by ADEKA, Adelite is a registered trademark), and the like.
　塩基性コロイダルシリカとしては、特に限定されないが、例えば、市販品としてスノーテックスＣ、スノーテックスＮ、スノーテックスＮＸＳ（以上、商品名、日産化学工業社製、スノーテックスは登録商標）、アデライトＡＴ－２０、アデライトＡＴ－２０Ｎ（以上、商品名、ＡＤＥＫＡ社製、アデライトは登録商標）等が挙げられる。 The basic colloidal silica is not particularly limited. For example, as commercially available products, Snowtex C, Snowtex N, Snowtex NXS (trade names, manufactured by Nissan Chemical Industries, Ltd., Snowtex is a registered trademark), Adelite AT- 20, Adelite AT-20N (trade names, manufactured by ADEKA, Adelite is a registered trademark), and the like.
　水溶性溶剤を分散媒とするコロイダルシリカとしては、特に限定されないが、例えば、市販品としてＭＡ－ＳＴ－Ｍ、ＩＰＡ－ＳＴ、ＥＧ－ＳＴ、ＰＧＭ－ＳＴ（以上、商品名、日産化学工業社製）等が挙げられる。 The colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited. For example, commercially available products such as MA-ST-M, IPA-ST, EG-ST, PGM-ST (all trade names, Nissan Chemical Industries, Ltd.) And the like.
　これらコロイダルシリカは単独で用いても、２種以上を併用してもよい。２種以上のコロイダルシリカを併用する方法としては、具体的には例えば、平均一次粒子径が１０～１５ｎｍの酸性コロイダルシリカと平均一次粒子径が２０～２５ｎｍの酸性コロイダルシリカとを、質量比（前者／後者）が、好ましくは１０／９０～７０／３０の範囲内となるように併用する方法、平均一次粒子径が２０～２５ｎｍの酸性コロイダルシリカと平均一次粒子径が５０～８０ｎｍの酸性コロイダルシリカとを、質量比（前者／後者）が、好ましくは１０／９０～６０／４０となるように併用する方法が挙げられる。 These colloidal silicas may be used alone or in combination of two or more. As a method of using two or more types of colloidal silica in combination, specifically, for example, the mass ratio of acidic colloidal silica having an average primary particle size of 10 to 15 nm and acidic colloidal silica having an average primary particle size of 20 to 25 nm Acidic colloidal silica having an average primary particle size of 20 to 25 nm and an acid colloidal having an average primary particle size of 50 to 80 nm, preferably used in combination such that the former / latter) is preferably in the range of 10/90 to 70/30. A method of using silica and a mass ratio (the former / the latter) preferably in the range of 10/90 to 60/40 can be mentioned.
　さらに、コロイダルシリカには、アルミナゾル、チタニアゾル、セリアゾル等のシリカ微粒子以外の無機質微粒子を含有させることもできる。 Furthermore, inorganic fine particles other than silica fine particles such as alumina sol, titania sol, ceria sol can also be contained in the colloidal silica.
　コロイダルシリカ（ｄ）の平均粒子径は、硬化塗膜の透明性及び硬度の点から１～１００ｎｍの範囲内が好ましく、８～５０ｎｍの範囲内がさらに好ましい。 The average particle diameter of the colloidal silica (d) is preferably in the range of 1 to 100 nm, and more preferably in the range of 8 to 50 nm, from the viewpoint of the transparency and hardness of the cured coating.
　中でも、前記コロイダルシリカは、ハードコート層形成用コーティング剤（Ｂ）の安定性、塗膜外観から酸性コロイダルシリカが好適に使用できる。 Among them, acidic colloidal silica can be suitably used as the colloidal silica from the viewpoint of the stability of the hard coat layer-forming coating agent (B) and the appearance of the coating film.
　本明細書において、平均粒子径は、コロイダルシリカ粒子の一次粒子の平均粒子径である。本明細書において、コロイダルシリカの平均粒子径は、特に断りのない限り窒素吸着法（ＢＥＴ法）によって算出される平均粒子径をいう。 In the present specification, the average particle size is an average particle size of primary particles of colloidal silica particles. In the present specification, the average particle size of colloidal silica refers to the average particle size calculated by the nitrogen adsorption method (BET method) unless otherwise specified.
　前記コロイダルシリカ（ｄ）の含有量は、得られる被膜の硬度と耐擦り傷性の点から、ハードコート層形成用コーティング剤（Ｂ）の有効成分の総量に対して、２０～８０質量％の範囲内が好ましく、３５～７５質量％の範囲内がより好ましい。 The content of the colloidal silica (d) is in the range of 20 to 80% by mass based on the total amount of the active ingredients of the coating agent (B) for forming a hard coat layer from the viewpoint of the hardness and abrasion resistance of the obtained film. The content is preferably in the range of 35 to 75% by mass.
　　（ｅ）硬化触媒
　硬化触媒としては、加水分解性基を有する化合物を加水分解縮合させて硬化性を促進させうるものであれば、特に限定されず、前記エポキシシランオリゴマー（ｃ）の製造方法の項に例示した触媒の他、例えば、ジアセチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジオクチル錫ジラウレート、ジアセチル錫ジオクトエート、オクチル酸錫、ジブチル錫ジアセテート、ジブチル錫ジオクチレートなどの有機錫化合物；アルミニウムトリメトキシド、トリス（アセチルアセトネート）アルミニウム、アルミニウムトリ－ｎ－ブトキシド、アルミニウムトリス（アセチルアセトン）、アルミニウムトリス（アセトアセテートエチル）、アルミニウムジイソプロポキシ（アセトアセテートエチル）、アルミニウムアセチルアセトネート等の有機アルミニウム化合物；チタニウムテトラキス（エチレングリコールモノメチルエーテル）、チタニウムテトラキス（エチレングリコールモノエチルエーテル）、チタニウムテトラキス（エチレングリコールモノブチルエーテル）、テトラノルマルブチルチタネート等の有機チタン化合物；ジルコニウムテトラキス（エチレングリコールモノメチルエーテル）、ジルコニウムテトラキス（エチレングリコールモノエチルエーテル）、ジルコニウムテトラキス（エチレングリコールモノブチルエーテル）、ジルコニウムノルマルプロピレート、ジルコニウムノルマルブチレート、ジルコニウムテトラキス（アセチルアセトネート）等の有機ジルコニウム化合物；ナフテン酸亜鉛等の有機亜鉛化合物；オクチル酸コバルト、ナフテン酸コバルト等の有機コバルト化合物；ホウ酸、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル、ホウ酸トリフェニル、ホウ酸トリ（４－クロロフェニル）、ホウ酸トリヘキサフルオロイソプロピル等のホウ酸エステル等のホウ酸化合物等；水酸化カリウム、水酸化ナトリウム、水酸化セシウム等のアルカリ金属水酸化物；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド等の水酸化アンモニウム塩；テトラブチルアンモニウムフルオリド等のフッ化アンモニウム塩；ジエチルアミン、トリエチルアミン等のアミン類；モノエタノールアミン、トリエタノールアミン、Ｎ－メチルジエタノールアミン等のエタノールアミン類、ＤＢＵ等の強塩基３級アミン化合物等が挙げられる。上記硬化触媒は、単独で使用してもよいし、２種以上を併用してもよい。 (E) Curing Catalyst The curing catalyst is not particularly limited as long as it can accelerate the curing by hydrolytic condensation of a compound having a hydrolyzable group, and the method for producing the epoxysilane oligomer (c) is not particularly limited. In addition to the catalysts exemplified in the section, for example, organotin compounds such as diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octoate, dibutyltin diacetate, dibutyltin dioctyrate; Aluminum trimethoxide, tris (acetylacetonate) aluminum, aluminum tri-n-butoxide, aluminum tris (acetylacetone), aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), al Organoaluminum compounds such as titanium acetylacetonate; titanium tetrakis (ethylene glycol monomethyl ether), titanium tetrakis (ethylene glycol monoethyl ether), titanium tetrakis (ethylene glycol monobutyl ether), organic titanium compounds such as tetranormal butyl titanate, etc .; zirconium tetrakis Organic zirconium compounds such as (ethylene glycol monomethyl ether), zirconium tetrakis (ethylene glycol monoethyl ether), zirconium tetrakis (ethylene glycol monobutyl ether), zirconium normal propylate, zirconium normal butyrate, and zirconium tetrakis (acetylacetonate); Organozinc compounds such as zinc acid acid; Organic cobalt compounds such as cobalt acid and cobalt naphthenate; boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, triphenyl borate, tri (4-chlorophenyl) borate, trihexaborate Boric acid compounds such as boric acid esters such as fluoroisopropyl; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide; tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, Ammonium hydroxide salts such as benzyltrimethylammonium hydroxide; ammonium fluoride salts such as tetrabutylammonium fluoride; amines such as diethylamine and triethylamine; monoethanolamine, triethanolamine Emissions, ethanol amines such as N- methyldiethanolamine, strong tertiary amine compound DBU and the like, and the like. The curing catalysts may be used alone or in combination of two or more.
　上記硬化触媒の中でも、乾燥性や耐擦り傷性、水希釈安定性の点からリン酸化合物、有機錫化合物が好ましい。上記リン酸化合物としては、例えば、オルトリン酸、メタリン酸、ピロリン酸、亜リン酸、ポリリン酸、ホスホン酸、メタンホスホン酸、ベンゼンホスホン酸、１－ヒドロキシエタン－１，１－ジホスホン酸、ホスフィン酸；これらのリン酸化合物のアルカリ金属塩又はアンモニウム塩などが挙げられる。 Among the above-mentioned curing catalysts, phosphoric acid compounds and organic tin compounds are preferable in view of drying property, scuff resistance, and water dilution stability. Examples of the above phosphoric acid compounds include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphinic acid And alkali metal salts or ammonium salts of these phosphoric acid compounds.
　硬化触媒（ｅ）の含有量としては、ハードコート層形成用のコーティング剤（Ｂ）の有効成分の総量に対して、０．１～３０質量部の範囲内が好ましく、さらに０．５～２０質量部となる範囲内で調整されることが望ましい。 The content of the curing catalyst (e) is preferably in the range of 0.1 to 30 parts by mass with respect to the total amount of the active ingredients of the coating agent (B) for forming the hard coat layer, and more preferably 0.5 to 20 It is desirable to adjust in the range which becomes a mass part.
　本発明に用いるハードコート層形成用コーティング剤（Ｂ）はさらにシランカップリング剤を配合することができ、シランカップリング剤としては、前記コーティング剤（Ｂ）に凝集が発生せず、常温で反応し得る官能基であれば特に制限されないが、具体的には、エポキシ基、水酸基、アミノ基、ウレイド基、メルカプト基、ビニル基、（メタ）アクリロイル基又はイソシアネート基等を挙げることができる。 The coating agent (B) for hard-coat layer formation used for this invention can mix | blend a silane coupling agent further, An aggregation does not generate | occur | produce in the said coating agent (B) as a silane coupling agent, It reacts at normal temperature The functional group is not particularly limited as long as it is functional, and specific examples thereof include epoxy group, hydroxyl group, amino group, ureido group, mercapto group, vinyl group, (meth) acryloyl group and isocyanate group.
　例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、等のグリシドキシ基含有シランカップリング剤、（３，４－エポキシシクロヘキシル）メチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルジメトキシシラン等の（３，４－エポキシシクロヘキシル）基含有シランカップリング剤等のエポキシ基含有シランカップリング剤；３－（２－アミノエチル）アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルトリメトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルメチルジメトキシシラン等のアミノ基含有シランカップリング剤；３－ウレイドプロピルトリアルコキシシラン等のウレイド基含有シランカップリング剤；３－メルカプトプロピルトリメトキシシラン等のメルカプト基含有シランカップリング剤；ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（メトキシエトキシ）シラン等のビニル基含有シランカップリング剤；３－（メタ）アクリロイルオキシプロピルトリメトキシシラン、３－（メタ）アクリロイルオキシプロピルトリエトキシシラン、３－（メタ）アクリロイルオキシプロピルジメトキシメチルシラン等の（メタ）アクリロイル基含有シランカップリング剤；３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤等が挙げられる。前記コーティング剤（Ｂ）の安定性、耐擦り傷性の点からウレイド基含有シランカップリング剤、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）メチルジメトキシシラン等のエポキシ基含有シランカップリング剤が好ましい。 For example, glycidoxy group-containing silane cups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc. Ring agent, (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 Epoxy group-containing silane coupling agents such as (3,4-epoxycyclohexyl) group-containing silane coupling agents such as 2,4-epoxycyclohexyl) methyldimethoxysilane; 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3 -Aminopropyl Amino group-containing silane coupling agents such as liethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane; 3-ureidopropyltrialkoxysilane Ureido group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane; vinyl group-containing silane cups such as vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (methoxyethoxy) silane Ring agent; (meth) acrylo such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyldimethoxymethylsilane, etc. Le group-containing silane coupling agent; 3- isocyanatopropyltriethoxysilane isocyanate group-containing silane coupling agents such as and the like. Ureido group-containing silane coupling agent, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl from the viewpoint of the stability and scratch resistance of the coating agent (B) Methyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3, Epoxy group-containing silane coupling agents such as 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) methyldimethoxysilane are preferred.
　シランカップリング剤をハードコート層形成用コーティング剤（Ｂ）に含有させる場合、その含有率としては、塗膜外観、耐擦り傷性の点から、ハードコート層形成用コーティング剤（Ｂ）の有効成分の総量を基準として、１～７０質量％の範囲内が好ましく、５～５０質量％の範囲内がより好ましい。 When the silane coupling agent is contained in the hard coat layer-forming coating agent (B), the content thereof is the active ingredient of the hard coat layer-forming coating agent (B) from the viewpoint of the coating film appearance and the scratch resistance. It is preferably in the range of 1 to 70% by mass, more preferably in the range of 5 to 50% by mass, based on the total amount of
　本発明に用いるハードコート層形成用コーティング剤（Ｂ）は、その他、希釈溶媒、ＲＴＶゴム、着色顔料、体質顔料、染料、艶消し剤、骨材、樹脂粒子、表面調整剤、粘度調整剤、消泡剤、抗菌剤、防カビ剤、難燃剤、防曇剤、可塑剤、スリップ剤、脱水剤、紫外線吸収剤、光安定化剤、金属酸化物微粒子、金属粉、酸化防止剤、界面活性剤、造膜助剤、増粘剤、帯電防止剤、撥水性付与剤、繊維類等の添加剤；イソシアネート化合物やメラミン樹脂等の架橋剤；樹脂エマルション、ワックスエマルション等の樹脂成分；アクリル樹脂、フッ素樹脂、各種有機変性シリコーンオイル等の改質剤などを適宜配合することができる。 The coating agent (B) for forming a hard coat layer used in the present invention is, in addition, a dilution solvent, RTV rubber, color pigment, extender pigment, dye, matting agent, aggregate, resin particles, surface conditioner, viscosity modifier, Antifoaming agent, antibacterial agent, antifungal agent, flame retardant, antifogging agent, plasticizer, slip agent, dehydrating agent, ultraviolet absorber, light stabilizer, metal oxide fine particles, metal powder, antioxidant, surfactant Agents, film forming aids, thickeners, antistatic agents, water repellent agents, additives such as fibers; crosslinking agents such as isocyanate compounds and melamine resins; resin components such as resin emulsions and wax emulsions; acrylic resins, Modifiers such as fluorocarbon resins and various organically modified silicone oils can be appropriately blended.
　本発明に用いるハードコート層形成用コーティング剤（Ｂ）は、無溶剤でもよく、または有機溶剤を含有してもよい。有機溶剤を含有することにより、前記加水分解性シランとシリカとの相溶性を向上させることができ特に好ましい。有機溶剤としては、上記加水分解性シラン化合物を溶解し、その加水分解縮合反応が進行した後も溶解し得る限り、任意の適切なものを用いることができる。 The coating agent (B) for hard-coat layer formation used for this invention may be a non-solvent, or may contain the organic solvent. By containing an organic solvent, the compatibility between the hydrolyzable silane and the silica can be improved, which is particularly preferable. Any appropriate organic solvent may be used as long as it dissolves the hydrolyzable silane compound and can be dissolved even after the hydrolysis condensation reaction proceeds.
　有機溶剤としては、例えば、メタノール、エタノール、ブタノール、メチルイソブチルカルビノール、２－エチルヘキサノール、ベンジルアルコール等のアルコール系溶剤；アセトン、メチルイソブチルケトン等のケトン系溶剤；酢酸エチル、酢酸ブチル、安息香酸メチル、プロピオン酸メチル等のエステル系溶剤；シクロヘキサノン、テトラヒドロフラン、ジオキサン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノターシャリーブチルエーテル、プロピレングリコールモノメチルエーテル、イソプロピルグリコール等のエーテル系溶剤；ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、３－メトキシ－３－メチル－１－ブタノール等のグリコールエーテル系溶剤、芳香族炭化水素系溶剤、脂肪族炭化水素類系溶剤が挙げられる。これらは、粘度の調整、塗布性の調整等の目的に応じて適宜組み合わせて使用することができる。 Examples of the organic solvent include alcohol solvents such as methanol, ethanol, butanol, methyl isobutyl carbinol, 2-ethylhexanol and benzyl alcohol; ketone solvents such as acetone and methyl isobutyl ketone; ethyl acetate, butyl acetate and benzoic acid Ester solvents such as methyl and methyl propionate; Ether solvents such as cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether and isopropyl glycol; diethylene glycol monomethyl Ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3 Glycol ether solvents such as methoxy-3-methyl-1-butanol, aromatic hydrocarbon solvents include aliphatic hydrocarbons solvents. These can be used in combination as appropriate depending on the purpose such as adjustment of viscosity and adjustment of coating property.
　上記有機溶剤の水への溶解度（２０℃）としては、５ｇ／水１００ｇ以上が好ましく、仕上がり性と前記加水分解性シランとシリカの相溶性向上の点から、好ましくは２０ｇ／水１００ｇ以上、より好ましくは５０ｇ／水１００ｇ以上である。 The solubility (20 ° C.) of the organic solvent in water is preferably 5 g / 100 g or more, and from the viewpoint of the finish and the improvement of the compatibility between the hydrolyzable silane and the silica, 20 g / water 100 g or more is preferable. Preferably it is 50 g / 100 g or more of water.
　仕上がり性と硬化性の点から、上記有機溶剤の中でも、塗装作業性と相溶性の点から、ブタノール、３－メトキシ－３－メチル－１－ブタノール、エチレングリコールモノターシャリーブチルエーテルの中から選ばれる少なくとも１種を用いることが好ましい。 From the viewpoint of finishability and curability, among the above organic solvents, it is selected from among butanol, 3-methoxy-3-methyl-1-butanol and ethylene glycol monotertiary butyl ether from the viewpoint of coating workability and compatibility. Preferably, at least one is used.
　有機溶剤をハードコート層形成用コーティング剤（Ｂ）に含有させる場合、その含有率としては、塗膜外観、塗装作業性の点から、前記ハードコート形成用コーティング剤（Ｂ）の有効成分の総量１００質量部を基準として、例えば５～２００質量部、好ましくは１０～５０質量部である。 When the organic solvent is contained in the coating agent for hard coat layer formation (B), the content thereof is the total amount of the active ingredients of the coating agent for forming hard coat (B) from the viewpoint of coating appearance and coating workability. The amount is, for example, 5 to 200 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass.
　（ｆ）１～４官能性の加水分解性シランから選ばれる少なくとも１種の加水分解性シラン及び／又はその加水分解縮合物
　ハードコート層形成用コーティング剤（Ｂ）は、加水分解性シランとして、１～４官能性の加水分解性シランから選ばれる少なくとも１種の加水分解性シラン及び／又はその加水分解縮合物（ｆ）を含有してもよい。前記（ｆ）成分としては、前記一般式（ＩＩ）で表される加水分解性シランの加水分解縮合物を好適に使用することができる。 (F) At least one hydrolyzable silane selected from hydrofunctional silanes having 1 to 4 functional groups and / or its hydrolytic condensates The coating agent for forming a hard coat layer (B) is a hydrolyzable silane, It may contain at least one hydrolyzable silane selected from hydrofunctional silanes having 1 to 4 functions and / or its hydrolytic condensate (f). As the component (f), a hydrolysis condensate of the hydrolyzable silane represented by the general formula (II) can be suitably used.
　前記一般式（ＩＩ）で表される１～４官能性のエポキシ基を有さない加水分解性シランが具体的に挙げられるが、中でも、特に乾燥性の点から、メチルトリメトキシシランが好ましい。 Specific examples of the hydrolyzable silane having no 1 to 4 functional epoxy group represented by the above general formula (II) are mentioned, and among them, methyltrimethoxysilane is preferable in particular from the viewpoint of drying property.
　前記１～４官能性のエポキシ基を有さない加水分解性シランから選ばれる少なくとも１種の加水分解性シラン及び／又はその加水分解縮合物（ｆ）をハードコート層形成用コーティング剤（Ｂ）に含有させる場合、その含有率としては、耐擦り傷性と耐クラック性などのバランスの点から適宜調整することができるが、ハードコート層形成用コーティング剤（Ｂ）の有効成分の総量に対して、１～４０質量％、好ましくは３５～３０質量％である。 The coating agent (B) for hard-coat layer formation of at least 1 sort (s) of hydrolysable silane chosen from the hydrolysable silane which does not have the said 1-4 functional epoxy group and / or its hydrolysis condensation product (f) When it is contained in the coating composition, the content thereof can be appropriately adjusted from the viewpoint of the balance between the abrasion resistance and the crack resistance etc., but the content is based on the total amount of the active ingredients of the hard coat layer forming coating agent (B). And 1 to 40% by mass, preferably 35 to 30% by mass.
　（ｇ）４官能性の加水分解性シラン及び／又はその加水分解縮合物
　ハードコート層形成用コーティング剤（Ｂ）は、前記（ｆ）成分のうち、少なくともその成分の一部に４官能性の加水分解性シラン及び／又はその加水分解縮合物（ｇ）を含有してもよい。 (G) A tetrafunctional hydrolyzable silane and / or a hydrolytic condensate thereof A coating agent (B) for forming a hard coat layer is tetrafunctional in at least a part of the components (f) among the components (f). It may contain a hydrolyzable silane and / or its hydrolytic condensate (g).
　（ｇ）成分としては、下記一般式（ＩＩＩ）で表される加水分解性シラン及び／又はその加水分解縮合物が挙げられる。 Examples of the component (g) include hydrolyzable silanes represented by the following general formula (III) and / or hydrolytic condensates thereof.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
 [前記式（ＩＩＩ）中、Ｘは前記と同じ意味である。]
　上記一般式（ＩＩＩ）は、４官能性の加水分解性シランであり、具体的には、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラフェノキシシランなどのテトラアルコキシシラン；テトラクロロシランなどのテトラハロシラン等を挙げることができる。 [In said Formula (III), X is the same meaning as the above. ]
The general formula (III) is a tetrafunctional hydrolyzable silane, and specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraphenoxysilane, etc .; Halosilane etc. can be mentioned.
　前記４官能性の加水分解性シランの加水分解縮合物としては、平均縮合度が２～１５のものが好適であり、該オルガノシリケート化合物を９００℃で焼成した際にシリカとなって残る該シリカの重量分率で２０～６０質量％の範囲内となるまで縮合せしめた縮合物が好適である。また該加水分解縮合物には、直鎖状の縮合物以外に、分岐状或いは環状構造の縮合物を含んでいてもよい。 As the hydrolytic condensate of the above-mentioned tetrafunctional hydrolyzable silane, one having an average degree of condensation of 2 to 15 is preferable, and the silica remaining as silica when the organosilicate compound is calcined at 900 ° C. Condensates condensed to a weight fraction of 20 to 60% by mass are preferred. In addition to the linear condensate, the hydrolytic condensate may contain a condensate of a branched or cyclic structure.
　なお、前記平均縮合度は、４官能性の加水分解性シランの縮合化合物におけるゲルパーミエーションクロマトグラフィ（ＧＰＣ）から得られる分子量を用いて求めることができる。 The average degree of condensation can be determined using the molecular weight obtained from gel permeation chromatography (GPC) of a condensation compound of a tetrafunctional hydrolyzable silane.
　前記一般式（ＩＩＩ）で表される４官能性の加水分解性シラン及び／又はその加水分解縮合物（Ｇ）を含有させる場合のその含有率は、耐擦り傷性と乾燥性、耐クラック性のバランスの観点から、ハードコート層形成用コーティング剤（Ｂ）の有効成分の総量に対して１～２０質量％、好ましくは１．５～１５質量％の範囲内が好ましい。 The content of the tetrafunctional hydrolyzable silane represented by the general formula (III) and / or its content in the case of containing the hydrolytic condensate (G) is the scratch resistance, the drying property, and the crack resistance. From the viewpoint of balance, the content is preferably in the range of 1 to 20% by mass, and more preferably 1.5 to 15% by mass, with respect to the total amount of the active ingredients of the hard coat layer forming coating agent (B).
　ここで、本明細書において、有効成分とは、試料から、水、有機溶剤などの溶媒を除いた残渣を意味する。有効成分の量は、例えば水、有機溶剤等が含まれる混合物・組成物等を１０５℃の熱風乾燥機中で３時間乾燥して溶剤等を揮散させたときの加熱残分により求めることができる。尚、本明細書において、加水分解性シラン及びシランカップリング剤などのケイ素化合物に関しては有効成分に含むものとする。 Here, in the present specification, the active ingredient means a residue obtained by removing a solvent such as water and an organic solvent from a sample. The amount of the active ingredient can be determined, for example, from the heating residue when the solvent, etc. is volatilized by drying the mixture, composition, etc. containing water, organic solvent etc. in a hot air drier at 105 ° C. for 3 hours . In the present specification, silicon compounds such as hydrolyzable silanes and silane coupling agents are included in the active ingredients.
　（ｈ）水
　ハードコート層形成用コーティング剤（Ｂ）は、水（ｈ）を含有してもよい。水を含有することにより、塗膜形成時に乾燥を促進することができる。また、塗装時に水で後から希釈することによりハードコート層形成用コーティング剤（Ｂ）の粘度を適宜調整し、塗装作業性を調製することができる。ハードコート層形成用コーティング剤（Ｂ）は水を含むことが可能であると共に、塗装段階の希釈作業において、有機溶剤ではなく水を用いることができるため、屋内作業においても、作業者の健康や周辺の衛生環境を損なう恐れが少なく安全性が高い。 (H) Water The coating agent (B) for hard coat layer formation may contain water (h). By containing water, drying can be promoted at the time of film formation. Moreover, the viscosity of the coating agent (B) for hard-coat layer formation can be suitably adjusted by diluting with water at the time of coating later, and coating workability can be prepared. The coating agent (B) for hard coat layer formation can contain water, and water can be used instead of the organic solvent in the dilution operation of the coating step. There is little risk of damaging the surrounding sanitation environment and safety is high.
　水（ｈ）としては、任意のものを用いることができ、例えば、水道水、イオン交換水、および純水が好ましく用いられる。 As water (h), arbitrary things can be used, for example, tap water, ion exchange water, and a pure water are used preferably.
　上記水（ｈ）の含有量は、ハードコート層形成用コーティング剤（Ｂ）の仕上がり性や塗装時のハジキ性を配慮した範囲内で適宜調節することができる。 The content of the water (h) can be appropriately adjusted within the range in which the finishing properties of the hard coat layer forming coating agent (B) and the repelling properties at the time of coating are considered.
　後から添加する場合、その添加量としては、例えば希釈前のハードコート層形成用コーティング剤（Ｂ）の有効成分の総量に対して、１～３０質量％の範囲内とすることができる。 When added later, the addition amount thereof can be, for example, in the range of 1 to 30% by mass with respect to the total amount of the active ingredients of the coating agent (B) for hard coat layer formation before dilution.
　ハードコート層形成用コーティング剤（Ｂ）は、その他、性能を損なわない範囲で、前記硬化触媒以外の硬化触媒、ＲＴＶゴム、着色顔料、体質顔料、光輝性顔料等の顔料、染料、艶消し剤、骨材、樹脂粒子、表面調整剤、粘度調整剤、消泡剤、抗菌剤、防カビ剤、難燃剤、防曇剤、可塑剤、スリップ剤、脱水剤、紫外線吸収剤、光安定化剤、金属酸化物微粒子、金属粉、酸化防止剤、界面活性剤、造膜助剤、増粘剤、帯電防止剤、撥水性付与剤、繊維類等の添加剤；イソシアネート化合物やメラミン樹脂等の架橋剤；樹脂エマルション、ワックスエマルション等の樹脂成分；アクリル樹脂、フッ素樹脂、各種有機変性シリコーンオイル等の改質剤などを適宜配合することができる。 In addition, the coating agent (B) for forming a hard coat layer is a curing catalyst other than the curing catalyst, a RTV rubber, a coloring pigment, an extender pigment, a pigment such as a luster pigment, a dye, and a matting agent as long as the performance is not impaired. Aggregates, resin particles, surface conditioners, viscosity modifiers, antifoaming agents, antibacterial agents, antifungal agents, flame retardants, flame retardants, antifogging agents, plasticizers, slip agents, dehydrating agents, ultraviolet light absorbers, light stabilizers , Metal oxide fine particles, metal powder, antioxidant, surfactant, film-forming aid, thickener, antistatic agent, water repellent agent, additives such as fibers; crosslinking of isocyanate compound, melamine resin, etc. Agents; resin components such as resin emulsions and wax emulsions; modifiers such as acrylic resins, fluorine resins, and various organically modified silicone oils, etc. may be suitably blended.
　ハードコート層形成用コーティング剤（Ｂ）の形態及び調製方法
　本方法に適用するハードコート層形成用コーティング剤（Ｂ）は、一液型組成物であってもよいし、二液以上の多液型組成物であってもよい。 The form and preparation method of the coating agent (B) for hard-coat layer formation The coating agent (B) for hard-coat layer formation applied to this method may be a one-pack type composition, and two or more multi-packs It may be a mold composition.
　多液型とする場合は、例えば、加水分解性シランを第１成分に、硬化触媒（ｅ）を第２成分にし、それ以外のその他成分をいずれかもしくは第３成分に振り分ける方法を挙げることができる。 In the case of a multi-liquid type, for example, a method of using a hydrolyzable silane as the first component, a curing catalyst (e) as the second component, and distributing the other components to any or third components may be mentioned. it can.
　ハードコート層形成用コーティング剤（Ｂ）において、貯蔵安定性及び塗装作業性の観点から、例えば、エポキシシランオリゴマー（ｃ）を含む第一液、硬化触媒（ｅ）を含む第二液及び、コロイダルシリカ（ｄ）を含む第三液を個別に作成し、使用直前に全液を混合して使用することができる。前記シランカップリング剤、有機溶剤、（ｆ）～（ｈ）成分やその他、顔料分散剤、沈降防止剤、消泡剤、酸化防止剤、紫外線吸収剤等の各種添加剤等を第一～三液のいずれかに適宜含ませることができる。 In the coating agent (B) for hard coat layer formation, from the viewpoint of storage stability and coating workability, for example, a first liquid containing an epoxysilane oligomer (c), a second liquid containing a curing catalyst (e), and a colloidal The third solution containing silica (d) can be individually prepared, and the entire solution can be mixed and used immediately before use. The above-mentioned silane coupling agent, organic solvent, components (f) to (h) and other various additives such as pigment dispersant, anti-settling agent, anti-foaming agent, anti-oxidant, ultraviolet absorber etc. It can be suitably contained in any of the solutions.
　上記の例の場合、混合中に凝集物が発生するのを抑制する観点から、前記第一液および前記第三液を先に混合した後、前記第二液を最後に混合することが好ましい。 In the case of the above example, it is preferable to mix the first liquid and the third liquid first, and then to mix the second liquid last, from the viewpoint of suppressing the generation of aggregates during mixing.
　シランカップリング剤を含有する場合には、コロイダルシリカ（ｄ）と予め分散せしめてから硬化触媒（ｅ）を混合することで相溶性が向上する場合があり好ましい。 When a silane coupling agent is contained, the compatibility may be improved by mixing the colloidal silica (d) with the curing catalyst (e) in advance, which is preferable in some cases.
　上述のように、本方法に適用するハードコート層形成用コーティング剤（Ｂ）は、無溶剤でもよく、さらに希釈溶媒を含有してもよい。希釈溶媒としては、水及び有機溶剤が挙げられ、臭気及び相溶性の点から、先の硬化剤を希釈する有機溶剤の項で例示に挙げたものを好適に使用することができる。 As mentioned above, the coating agent (B) for hard-coat layer formation applied to this method may be a non-solvent, and may contain a dilution solvent. As the dilution solvent, water and an organic solvent may be mentioned, and from the viewpoint of odor and compatibility, those exemplified in the section of the organic solvent for diluting the above-mentioned curing agent can be suitably used.
　本発明に用いるハードコート層形成用コーティング剤（Ｂ）は、塗装時において、作業性と仕上り性の点から、有効成分の含有率は通常１５質量％以上、特に２０～６０質量％の範囲内とすることが好ましい。 The coating agent (B) for hard coat layer formation used in the present invention has a content of the active ingredient of usually 15% by mass or more, particularly in the range of 20 to 60% by mass from the viewpoint of workability and finish during coating. It is preferable to
　本発明においてハードコート層（ＩＩ）は、工程膜の耐スリキズ性、耐ワレ性の点から、マルテンス硬度が１００～３００Ｎ／ｍｍ２、特に１２０～３００Ｎ／ｍｍ２の範囲内にあることが適している。 In the present invention, it is suitable that the hard coat layer (II) has a Martens hardness in the range of 100 to 300 N / mm 2 , particularly 120 to 300 N / mm 2 from the viewpoint of scratch resistance and cracking resistance of the process film. ing.
　以下、実施例を挙げて本発明をさらに詳細に説明する。尚、「部」及び「％」は、特記しない限り「質量部」及び「質量％」を示す。 Hereinafter, the present invention will be described in more detail by way of examples. In addition, "part" and "%" show "mass part" and "mass%", unless it mentions specially.
　（製造例１）水酸基含有アクリル樹脂（ａ－１）
　温度計、撹拌機、還流冷却管、窒素導入口を備えた２リットルのガラス製４ツ口フラスコに、脱イオン水４００部、ドデシルベンゼンスルホン酸ソーダ１部を仕込み、内部の空気を窒素置換した後、撹拌しながら８２℃まで昇温させた。別容器に、脱イオン水４４０部、ドデシルベンゼンスルホン酸ソーダ４０部、過硫酸アンモニウム２部を添加し、よく撹拌後、その中に表１の水酸基含有アクリル樹脂名（ａ－１）の欄に記載のモノマー配合からなる混合物を加え乳化物とし、該乳化物を８２℃に保ったガラス製４ツ口フラスコに４時間かけて一定速度で滴下した。滴下終了後、さらに８２℃で２時間撹拌した後、４０℃まで冷却し、アンモニアでｐＨを７．５に調整することにより、平均粒子径１５０ｎｍ、樹脂固形分５０％の水酸基含有アクリル樹脂（ａ－１）の水分散体を得た。該水酸基含有アクリル樹脂（ａ－１）の水酸基価は１０３ｍｇＫＯＨ／ｇ、ガラス転移温度は４１℃であった。 Production Example 1 Hydroxyl Group-Containing Acrylic Resin (a-1)
400 parts of deionized water and 1 part of sodium dodecylbenzenesulfonate were charged into a 2-liter glass four-necked flask equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet, and the internal air was replaced with nitrogen After that, the temperature was raised to 82 ° C. while stirring. In a separate container, 440 parts of deionized water, 40 parts of sodium dodecylbenzene sulfonate, and 2 parts of ammonium persulfate are added, and after thorough stirring, the mixture is described in the column of hydroxyl group-containing acrylic resin name (a-1) in Table 1 therein. A mixture consisting of the following monomer blend was added to form an emulsion, and the emulsion was dropped at a constant speed over 4 hours into a glass four-necked flask kept at 82 ° C. After completion of the dropwise addition, the mixture is further stirred at 82 ° C. for 2 hours, cooled to 40 ° C., and adjusted to pH 7.5 with ammonia to obtain a hydroxyl group-containing acrylic resin having an average particle diameter of 150 nm and a resin solid content of 50% (a An aqueous dispersion of -1) was obtained. The hydroxyl value of the hydroxyl group-containing acrylic resin (a-1) was 103 mg KOH / g, and the glass transition temperature was 41 ° C.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　（製造例２）水酸基含有アクリル樹脂（ａ－２）
　温度計、撹拌機、還流冷却管、窒素導入口を備えた２リットルのガラス製４ツ口フラスコに、脱イオン水３００部、ドデシルベンゼンスルホン酸ソーダ１部を仕込み、内部の空気を窒素置換した後、撹拌しながら８２℃まで昇温させた。別容器に、脱イオン水３４０部、ドデシルベンゼンスルホン酸ソーダ２０部、過硫酸アンモニウム１部を添加し、よく撹拌後、その中に表１の水酸基含有アクリル樹脂（ａ－２）のコア部の欄に記載のモノマー配合からなる混合物を加え乳化物とし、該乳化物を８２℃に保ったガラス製４ツ口フラスコに２時間かけて一定速度で滴下した。 Production Example 2 Hydroxyl Group-Containing Acrylic Resin (a-2)
300 parts of deionized water and 1 part of sodium dodecylbenzene sulfonate were charged into a 2-liter glass four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet, and the internal air was replaced with nitrogen After that, the temperature was raised to 82 ° C. while stirring. In a separate container, 340 parts of deionized water, 20 parts of sodium dodecylbenzene sulfonate, and 1 part of ammonium persulfate are added, and after thorough stirring, the column of the core part of the hydroxyl group-containing acrylic resin (a-2) in Table 1 A mixture consisting of the monomer blend described in the above was added to form an emulsion, and the emulsion was added dropwise at a constant speed over 2 hours to a glass four-necked flask kept at 82 ° C.
　滴下終了後、８２℃で３０分間撹拌した後、別容器にて脱イオン水２００部、ドデシルベンゼンスルホン酸ソーダ２０部、過硫酸アンモニウム１部を添加し、よく撹拌後、その中に表１の水酸基含有アクリル樹脂（ａ－２）のシェル部の欄に記載のモノマー配合からなる混合物を加え乳化物としたものを８２℃に保ったガラス製４ツ口フラスコに２時間かけて一定速度で滴下した。滴下終了後、さらに８２℃で２時間撹拌した後、４０℃まで冷却し、アンモニアでｐＨを７．５に調整することにより、平均粒子径１５０ｎｍ、樹脂固形分５０％の水酸基含有アクリル樹脂（ａ－２）のコア・シェル型水分散体を得た。該水酸基含有アクリル樹脂の水酸基価は１０３ｍｇＫＯＨ／ｇ、ガラス転移温度は４０℃であった。 After completion of the dropwise addition, the mixture is stirred at 82 ° C. for 30 minutes, then 200 parts of deionized water, 20 parts of sodium dodecylbenzenesulfonate and 1 part of ammonium persulfate are added in separate containers, and after sufficient stirring, hydroxyl groups in Table 1 A mixture consisting of the monomer combination described in the column of the shell part of the contained acrylic resin (a-2) was added to make an emulsion and dropped at a constant speed over 2 hours into a glass four-necked flask kept at 82 ° C. . After completion of the dropwise addition, the mixture is further stirred at 82 ° C. for 2 hours, cooled to 40 ° C., and adjusted to pH 7.5 with ammonia to obtain a hydroxyl group-containing acrylic resin having an average particle diameter of 150 nm and a resin solid content of 50% (a A core-shell type aqueous dispersion of -2) was obtained. The hydroxyl value of the hydroxyl group-containing acrylic resin was 103 mg KOH / g, and the glass transition temperature was 40 ° C.
　（製造例３）水酸基含有アクリル樹脂（ａ－３）
　製造例２において、モノマー混合物の配合を表１の水酸基含有アクリル樹脂（ａ－３）の欄に示す通りとする以外は製造例２と同様にして水酸基含有アクリル樹脂（ａ－３）のコア・シェル型水分散体を得た。 Production Example 3 Hydroxyl Group-Containing Acrylic Resin (a-3)
A core of a hydroxyl group-containing acrylic resin (a-3) was prepared in the same manner as in Production Example 2 except that the composition of the monomer mixture in Preparation Example 2 was as shown in the column of hydroxyl group-containing acrylic resin (a-3) in Table 1. A shell-type water dispersion was obtained.
　（製造例４）水酸基含有アクリル樹脂（ａ－４）
　温度計、撹拌機、還流冷却管、窒素導入口を備えた２リットルのガラス製４ツ口フラスコに「スワゾール１０００」（コスモ石油（株）製、炭化水素系有機溶剤）６４０部、ｎ－ブタノール８０部を仕込み、内部の空気を窒素置換した後、撹拌しながら９０℃まで昇温した。９０℃に達したところで、表１の水酸基含有アクリル樹脂（ａ－４）の欄に記載のモノマー配合及びアゾビスイソブチロニトリル３２部からなる混合溶液を４時間かけて滴下し、滴下終了後さらに９０℃で１時間撹拌を続けた。　 Production Example 4 Hydroxyl Group-Containing Acrylic Resin (a-4)
A 2-liter glass four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet; 640 parts of "Swazol 1000" (manufactured by Cosmo Oil Co., Ltd., hydrocarbon-based organic solvent), n-butanol After 80 parts were charged and the internal air was replaced with nitrogen, the temperature was raised to 90 ° C. while stirring. After reaching 90 ° C., a mixed solution consisting of the monomer combination described in the column of hydroxyl group-containing acrylic resin (a-4) in Table 1 and 32 parts of azobisisobutyro nitrile is added dropwise over 4 hours, and after the end of the dropwise addition Stirring was further continued at 90 ° C. for 1 hour.
　その後、アゾビスイソブチロニトリル４部を「スワゾール１０００」８０部に溶解させたものを１時間かけて滴下し、さらに９０℃で１時間撹拌を続けた後、４０℃まで冷却し、樹脂固形分５０％の水酸基含有アクリル樹脂（ａ－４）の溶液を得た。該アクリル樹脂の水酸基価は１０３ｍｇＫＯＨ／ｇ、ガラス転移温度は３９℃、重量平均分子量は１５，０００であった。 Thereafter, a solution of 4 parts of azobisisobutyronitrile dissolved in 80 parts of "Swazol 1000" is added dropwise over 1 hour, and stirring is further continued at 90 ° C for 1 hour, and then cooled to 40 ° C. A 50% solution of hydroxyl group-containing acrylic resin (a-4) was obtained. The acrylic resin had a hydroxyl value of 103 mg KOH / g, a glass transition temperature of 39 ° C., and a weight average molecular weight of 15,000.
　（製造例５）水酸基含有アクリル樹脂（ａ－５）
　温度計、撹拌機、還流冷却管、窒素導入口を備えた２リットルのガラス製４ツ口フラスコに有機溶剤としてプロピレングリコールモノプロピルエーテルを４００部入れ、撹拌しながら１２０℃まで昇温した。１２０℃に達したところで表１の水酸基含有アクリル樹脂（ａ－５）の一段階目の欄に記載のモノマー配合及びｔ－ブチルパーオキシ－２－エチルヘキサノエート１２部からなる混合溶液１を４時間かけて滴下し、滴下終了後さらに同温度で１時間撹拌を続けた。　　 Production Example 5 Hydroxyl Group-Containing Acrylic Resin (a-5)
400 parts of propylene glycol monopropyl ether as an organic solvent was charged into a 2-liter glass four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet, and the temperature was raised to 120 ° C. while stirring. When the temperature reached 120 ° C., mixed solution 1 consisting of the monomer combination described in the first column of the hydroxyl group-containing acrylic resin (a-5) in Table 1 and 12 parts of t-butylperoxy-2-ethylhexanoate The solution was added dropwise over 4 hours, and after completion of the dropwise addition, stirring was continued at the same temperature for 1 hour.
　次に、１２０℃の温度を保持したまま、上記フラスコ中に、表１の水酸基含有アクリル樹脂（ａ－５）二段階目の欄に記載のモノマー配合及びｔ－ブチルパーオキシ－２－エチルヘキサノエート２．４部からなる混合溶液２を１時間かけて滴下し、さらに滴下終了後同温度で１．５時間撹拌を続け、水酸基含有アクリル樹脂（ａ－５）溶液を得た。　　
　得られた水酸基含有アクリル樹脂溶液（ａ－５）の樹脂固形分は７７．５％であった。続いて、得られた水酸基含有アクリル樹脂溶液から固形分が８５％になるまでプロピレングリコールモノプロピルエーテルを減圧下で留去した。 Next, while maintaining the temperature of 120 ° C., in the above flask, the monomer combination described in the column of the second step of the hydroxyl group-containing acrylic resin (a-5) of Table 1 and t-butylperoxy-2-ethylhexa The mixed solution 2 consisting of 2.4 parts of noate was added dropwise over 1 hour, and after completion of the dropwise addition, stirring was continued at the same temperature for 1.5 hours to obtain a hydroxyl group-containing acrylic resin (a-5) solution.
The resin solid content of the obtained hydroxyl group-containing acrylic resin solution (a-5) was 77.5%. Subsequently, propylene glycol monopropyl ether was distilled off under reduced pressure from the obtained hydroxyl group-containing acrylic resin solution until the solid content became 85%.
　これを９５℃まで冷却し、ジメチルエタノールアミン２．８部を添加して３０分間撹拌した。さらに、撹拌しながら樹脂固形分が５０％となるように脱イオン水を２時間かけて滴下して、水酸基含有アクリル樹脂（ａ－５）の分散体を得た。該水酸基含有アクリル樹脂の分散体の水酸基価は１０３ｍｇＫＯＨ／ｇ、ガラス転移温度は４３℃、重量平均分子量は３０，０００であった。 It was cooled to 95 ° C., 2.8 parts of dimethylethanolamine was added and stirred for 30 minutes. Furthermore, while stirring, deionized water was added dropwise over 2 hours so that the resin solid content was 50%, to obtain a dispersion of a hydroxyl group-containing acrylic resin (a-5). The dispersion of the hydroxyl group-containing acrylic resin had a hydroxyl value of 103 mg KOH / g, a glass transition temperature of 43 ° C., and a weight average molecular weight of 30,000.
　（製造例６）比較用樹脂（ａ’－１）
　製造例１において、モノマー混合物の配合を表１のアクリル樹脂（ａ’－１）の欄に示す通りとする以外は製造例１と同様にして水酸基非含有であり、架橋官能基モノマーとしてダイアセトンアクリルアミドを共重合したアクリル樹脂（ａ’－１）の水分散体を得た。 Production Example 6 Comparative Resin (a'-1)
In Production Example 1, except that the composition of the monomer mixture is as shown in the column of acrylic resin (a'-1) in Table 1, it is hydroxyl-free in the same manner as in Production Example 1 and diacetone as a crosslinking functional group monomer. An aqueous dispersion of an acrylic resin (a'-1) obtained by copolymerizing acrylamide was obtained.
　製造例１～６で得られた水酸基含有アクリル樹脂又はアクリル樹脂の樹脂固形分、平均粒子径、水酸基価、酸価及びガラス転移温度を表２に示す。 The resin solid content, average particle diameter, hydroxyl value, acid value and glass transition temperature of the hydroxyl group-containing acrylic resin or acrylic resin obtained in Production Examples 1 to 6 are shown in Table 2.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　（製造例７）ポリイソシアネート化合物（ｂ－１）
　ポリイソシアネート化合物ｂ〔市販品、ヘキサメチレンジイソシアネートのヌレート体、２１．７％のＮＣＯ含有率、平均ＮＣＯ基数＝３．５（ＧＰＣによる）、モノマーＨＤＩ含有量０．１％、粘度（２３℃）３０００ｍＰａ・ｓ〕９７０ｇ（５．００ｍｏｌ）、３－（シクロヘキシルアミノ）プロパンスルホン酸３０ｇ（０．１４ｍｏｌ）、ジメチルシクロヘキシルアミン１７．４ｇ（０．１４ｍｏｌ）及び１－メトキシプロピル－２－アセテート（水酸基を有さないアセテート系水溶性溶剤）２５４ｇを、窒素雰囲気下、８０℃で５時間撹拌することにより、固形分８０％、イソシアネート基含有率１６．０％のスルホン酸変性イソシアネート化合物（ｂ－１）を得た。 Production Example 7 Polyisocyanate Compound (b-1)
Polyisocyanate compound b [Commercial product, nurate of hexamethylene diisocyanate, NCO content of 21.7%, average number of NCO groups = 3.5 (by GPC), monomer HDI content 0.1%, viscosity (23 ° C) 970 g (5.00 mol), 30 g (0.14 mol) of 3- (cyclohexylamino) propanesulfonic acid, 17.4 g (0.14 mol) of dimethylcyclohexylamine and 1-methoxypropyl-2-acetate (hydroxyl group A sulfonic acid-modified isocyanate compound (b-1) having a solid content of 80% and an isocyanate group content of 16.0% by stirring 254 g of an acetate water-soluble solvent (not having water) at 80 ° C. for 5 hours under a nitrogen atmosphere I got
　（製造例８）常温硬化型ウレタンプライマー組成物（Ａ－１）
　上記製造例１で得られた水酸基含有アクリル樹脂（ａ－１）２００部（固形分１００部）、脱イオン水１００部、ジプロピレングリコールジメチルエーテル（水酸基を有さないグリコールエーテル系水溶性溶剤）３０部、「サーフロン　Ｓ－２１１」（注１）１．４部（固形分０．７部）を混合し、ディスパーで１５分間撹拌することにより、主剤を製造した。次に、硬化剤として、前記製造例７で得られたポリイソシアネート化合物（ｂ－１）７５部（固形分６０部）とジオクチルスズジラウレート０．３部を加え、ディスパーを用いて混合して常温硬化型ウレタンプライマー組成物（Ａ－１）を作製した。 Production Example 8 Room Temperature Curing Urethane Primer Composition (A-1)
200 parts (solid content 100 parts) of the hydroxyl group-containing acrylic resin (a-1) obtained in the above Preparation Example 1, 100 parts of deionized water, dipropylene glycol dimethyl ether (glycol ether water-soluble solvent having no hydroxyl group) 30 Part and 1.4 parts (solid part 0.7 part) of "Surflon S-211" (note 1) were mixed, and the main agent was manufactured by stirring for 15 minutes with a disper. Next, as a curing agent, 75 parts (solid content 60 parts) of the polyisocyanate compound (b-1) obtained in the above-mentioned Preparation Example 7 and 0.3 parts of dioctyltin dilaurate are added, mixed using a disper, and room temperature A curable urethane primer composition (A-1) was produced.
　常温硬化型ウレタンプライマー組成物（Ａ－１）の固形分含有率及びＮＣＯ／ＯＨ比を表３に示す。なお、常温硬化型ウレタンプライマー組成物（Ａ－１）の初期乾燥性評価の結果及びマルテンス硬度の値も合わせて表３に示す。 The solid content and NCO / OH ratio of the room temperature curing type urethane primer composition (A-1) are shown in Table 3. The results of the initial drying evaluation of the room temperature curing type urethane primer composition (A-1) and the value of Martens hardness are also shown in Table 3.
　（製造例９～２２）
　製造例８において、主剤と硬化剤の配合量を表３の通りに変更する以外は、製造例８と同様にして、常温硬化型ウレタンプライマー組成物（Ａ－２）～（Ａ－１２）、比較例用常温硬化型ウレタンプライマー組成物（Ａ’－１）～（Ａ’－３）を得た。 (Manufacturing Examples 9 to 22)
In the same manner as in Production Example 8 except that the blending amounts of the main agent and the curing agent in Production Example 8 are changed, the room temperature curing type urethane primer composition (A-2) to (A-12), Room temperature curing type urethane primer compositions (A'-1) to (A'-3) for comparative examples were obtained.
Figure JPOXMLDOC01-appb-T000006
 
Figure JPOXMLDOC01-appb-T000006
 
　表中の「－」は算出できないことを示し、注は下記を示す。 “-” In the table indicates that it can not be calculated, and notes indicate the following.
　（注１）サーフロンＳ－２１１：商品名、ＡＧＣセイミケミカル社製、パーフルオロアルキルカルボン酸系界面活性剤、有効成分５０％。 (Note 1) Surfron S-211: trade name, manufactured by AGC Seimi Chemical Co., Ltd., perfluoroalkylcarboxylic acid surfactant, active ingredient 50%.
　（注２）ポリイソシアネート化合物（ｂ－２）：デュラネート　ＴＳＡ－１００、商品名、旭化成株式会社製、ヘキサメチレンジイソシアネートのヌレート体、固形分１００質量％、イソシアネート基含有率２０．６質量％。
　（注３）ポリウレタン樹脂エマルション（第一工業製薬株式会社製スーパーフレックス１５０、固形分＝３０質量％）平均粒子径０．０３μｍ
　（注４）タルク（日本タルク株式会社製Ｐ－３、粒子径Ｄ５０＝５μｍ） (Note 2) Polyisocyanate compound (b-2): Duranate TSA-100, trade name, manufactured by Asahi Kasei Corporation, a nurate body of hexamethylene diisocyanate, solid content 100% by mass, isocyanate group content 20.6% by mass.
(Note 3) Polyurethane resin emulsion (Superflex 150, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content = 30% by mass) Average particle size 0.03 μm
(Note 4) Talc (Nippon Talc Co., Ltd. P-3, particle diameter D50 = 5 μm)
　表中の試験項目の試験方法及び評価基準は下記の通りである。 The test methods and evaluation criteria of the test items in the table are as follows.
　（試験項目１．）初期乾燥性：
　気温２３℃、湿度５０％ＲＨの条件下、各常温硬化型ウレタンプライマー組成物（Ａ）を厚さ２ｍｍのガラス板（１５０×７０ｍｍ）に乾燥膜厚が１０μｍになるようにアプリケーターを用いて塗装した。その後、同条件下、指で軽くこすっても跡が付かなくなる、半硬化乾燥状態になるまでの時間（以下半硬化時間という）を測定し、以下の基準で評価した。　　
　◎：半硬化時間が１時間未満、
　○：半硬化時間が１時間以上かつ２時間未満
　△：半硬化時間が２時間以上かつ４時間未満
　×：半硬化時間が４時間以上。 (Test item 1.) Initial dryness:
Paint each room temperature curing type urethane primer composition (A) on a glass plate (150 x 70 mm) with a thickness of 2 mm using an applicator so that the dry film thickness will be 10 μm under conditions of temperature 23 ° C and humidity 50% RH. did. Thereafter, under the same conditions, the time until it was in a semi-cured dry state (hereinafter referred to as a semi-cured time) was measured and evaluated according to the following criteria.
:: The half curing time is less than 1 hour,
○: half curing time is 1 hour or more and less than 2 hours Δ: half curing time is 2 hours or more and less than 4 hours ×: half curing time is 4 hours or more.
　（試験項目２．）ポットライフ（可使時間）：
　主剤に硬化剤を均一に混合した各常温硬化型プライマー組成物を、気温２３℃、湿度５０％ＲＨの条件下、２時間放置した後の塗料状態を目視にて観察し、以下の基準で評価した。　　
　◎：粘度上昇やブツの発生などなく、問題なく使用できる
　○：わずかに粘度上昇が認められるが、ブツはなく実用上問題なく使用できる
　△：粘度上昇やブツが認められる
　×：ゲル化する。 (Test item 2.) Pot life (use time):
Each cold-setting primer composition in which the main agent was uniformly mixed with the curing agent was visually observed for paint conditions after being left for 2 hours under the conditions of air temperature 23 ° C., humidity 50% RH, and evaluated according to the following criteria did.
A: Can be used without any problems such as viscosity rise and lumps. ○: A slight rise in viscosity is observed, but there is no lump and can be used practically without any problem. Δ: Viscosity rise and lumps are observed. X: Gelation occurs.
　（試験項目３．）マルテンス硬度：
　明細書記載の方法に準じて測定した。 (Test item 3.) Martens hardness:
It measured according to the method of a statement statement.
　（製造例２３）ハードコート層形成用コーティング剤（Ｂ－１）
　エポキシシランオリゴマー（注５）（ｃ－１）６２．５部（有効成分として５０部）、スノーテックスＯ－４０（注６）１２５部（有効成分として５０部）、ＫＢＭ－４０３（注７）１５部（有効成分として１５部）、硬化触媒としてリン酸２部及び希釈溶剤として３－メトキシ－３－メチル－１－ブタノール４０部をディスパーで均一になるまで撹拌することによりハードコート層形成用コーティング剤（Ｂ－１）を得た。コーティング剤（Ｂ－１）による塗膜のマルテンス硬度は明細書記載の方法で求めたところ１７０Ｎ／ｍｍ２であった。 Production Example 23 Coating Agent for Forming Hard Coat Layer (B-1)
Epoxysilane oligomer (Note 5) (c-1) 62.5 parts (50 parts as an active ingredient), 125 parts of Snowtex O-40 (Note 6) (50 parts as an active ingredient), KBM-403 (Note 7) 15 parts (15 parts as an active ingredient), 2 parts of phosphoric acid as a curing catalyst, and 40 parts of 3-methoxy-3-methyl-1-butanol as a dilution solvent are uniformly stirred with a disper to form a hard coat layer A coating agent (B-1) was obtained. The Martens hardness of the coating film by the coating agent (B-1) was 170 N / mm 2 as determined by the method described in the specification.
　（製造例２４）ハードコート層形成用コーティング剤（Ｂ－２）
　エポキシシランオリゴマー（注５）（ｃ－１）６２．５部（有効成分として５０部）、スノーテックスＯ－４０（注６）１２５部（有効成分として５０部）、ＫＢＭ－４０３（注７）１５部（有効成分として１５部）、ＫＢＭ－１３（注８）１０部（有効成分として１０部）、硬化触媒としてリン酸２部、希釈溶剤として３－メトキシ－３－メチル－１－ブタノール４０部を混合し、ディスパーで均一になるまで撹拌することによりハードコート層形成用コーティング剤（Ｂ－２）を得た。
　コーティング剤（Ｂ－２）による塗膜のマルテンス硬度は明細書記載の方法で求めたところ１８０Ｎ／ｍｍ２であった。 Production Example 24 Coating Agent for Forming Hard Coat Layer (B-2)
Epoxysilane oligomer (Note 5) (c-1) 62.5 parts (50 parts as an active ingredient), 125 parts of Snowtex O-40 (Note 6) (50 parts as an active ingredient), KBM-403 (Note 7) 15 parts (15 parts as an active ingredient), 10 parts of KBM-13 (Note 8) (10 parts as an active ingredient), 2 parts of phosphoric acid as a curing catalyst, 3-methoxy-3-methyl-1-butanol 40 as a dilution solvent Parts were mixed and stirred with a disper until uniform to obtain a hard coat layer-forming coating agent (B-2).
The Martens hardness of the coating film by the coating agent (B-2) was 180 N / mm 2 as determined by the method described in the specification.
　（製造例２５）ハードコート層形成用コーティング剤（Ｂ－３）
　エポキシシランオリゴマー（注９）（ｃ－２）６２．５部(有効成分として５０部)、スノーテックスＯ－４０（注６）６２．５部（有効成分として２５部）、スノーテックスＯ（注１０）１２５部（有効成分として２５部）、ＫＢＭ－４０３（注７）１５部（有効成分として１５部）、硬化触媒としてリン酸２部、希釈溶剤として３－メトキシ－３－メチル－１－ブタノール４０部を混合し、ディスパーで均一になるまで撹拌することによりハードコート層形成用コーティング剤（Ｂ－３）を得た。
コーティング剤（Ｂ－３）による塗膜のマルテンス硬度は明細書記載の方法で求めたところ１８５Ｎ／ｍｍ２であった。 Production Example 25 Coating Agent for Forming Hard Coat Layer (B-3)
Epoxysilane oligomer (Note 9) (c-2) 62.5 parts (50 parts as active ingredient), 62.5 parts of Snowtex O-40 (Note 6) (25 parts as active ingredient), Snowtex O (Note 10) 125 parts (25 parts as an active ingredient), 15 parts of KBM-403 (Note 7) (15 parts as an active ingredient), 2 parts of phosphoric acid as a curing catalyst, 3-methoxy-3-methyl-1- as a dilution solvent 40 parts of butanol were mixed and stirred with a disper until uniform to obtain a coating agent for forming a hard coat layer (B-3).
The Martens hardness of the coating film by the coating agent (B-3) was 185 N / mm 2 as determined by the method described in the specification.
　前記製造例２３～２５において、注は下記を示す。 In the above Preparation Examples 23 to 25, notes indicate the following.
　（注５）エポキシシランオリゴマー（ｃ－１）：温度計、撹拌機、還流冷却器及び窒素導入管を取り付けたセパラブルフラスコに、ＫＢＭ－４０３（注７）２３６部（１．０ｍｏｌ）とメタノール３２部（１．０ｍｏｌ）を入れ、室温下混合撹拌した。次に撹拌しながら０．０５Ｎ塩酸水１０部を３０分かけて滴下し、さらに３０分間撹拌した。その後、マントルヒーターを用いて７５℃まで昇温させ、副生したメタノールも同時に除去しながら２時間還流させた。室温まで冷却後、ろ過を行い、エポキシシランオリゴマー（ｃ－１）を得た。　　
　生成物（ｃ－１）について１２０℃で１時間加熱した結果、加熱残分（有効成分）は８０％であった。また、重量平均分子量は１，１００、エポキシ当量は２２０ｇ／ｅｑであった。 (Note 5) Epoxysilane oligomer (c-1): 236 parts (1.0 mol) of KBM-403 (Note 7) and methanol in a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube 32 parts (1.0 mol) were added and mixed and stirred at room temperature. Next, 10 parts of 0.05 N hydrochloric acid water was added dropwise over 30 minutes while stirring, and the mixture was further stirred for 30 minutes. Thereafter, the temperature was raised to 75 ° C. using a mantle heater, and reflux was performed for 2 hours while simultaneously removing by-produced methanol. After cooling to room temperature, filtration was performed to obtain an epoxysilane oligomer (c-1).
As a result of heating the product (c-1) at 120 ° C. for 1 hour, the heating residue (active ingredient) was 80%. Moreover, the weight average molecular weight was 1,100 and the epoxy equivalent was 220 g / eq.
　（注６）スノーテックスＯ－４０：商品名、日産化学工業株式会社、平均粒子径２３ｎｍの水分散型酸性コロイダルシリカ、ｐＨ＝３、有効成分４０質量％。 (Note 6) Snowtex O-40: trade name, Nissan Chemical Industries, Ltd., water-dispersed acidic colloidal silica having an average particle diameter of 23 nm, pH = 3, 40% by weight of an active ingredient.
　（注７）ＫＢＭ－４０３：商品名、信越化学工業社製、３－グリシドキシプロピルトリメトキシシラン、分子量２３６．３４。
　（注８）ＫＢＭ－１３：商品名、信越化学工業製、メチルトリメトキシシラン。
　（注９）エポキシシランオリゴマー（ｃ－２）：温度計、撹拌機、還流冷却器及び窒素導入管を取り付けたセパラブルフラスコに、ＫＢＭ－４０３（注７）２３６部（１．０ｍｏｌ）とメタノール３２部（１．０ｍｏｌ）入れ、室温下混合撹拌した。次に撹拌しながら０．０５Ｎ塩酸水３部を３０分かけて滴下し、さらに３０分間撹拌した。その後、マントルヒーターを用いて７５℃まで昇温させ、副生したメタノールも同時に除去しながら２時間還流させた。室温まで冷却後、ろ過を行い、エポキシシランオリゴマー（ｃ－２）を得た。
　生成物（ｃ－２）について１２０℃で１時間加熱した結果、加熱残分（有効成分）は８０％であった。また、重量平均分子量は５００、エポキシ当量は１６７ｇ／ｅｑであった。
　（注１０）スノーテックスＯ：商品名、日産化学工業株式会社、スノーテックスは登録商標、平均一次粒子径１２．５ｎｍの水分散型酸性コロイダルシリカ、有効成分２０質量％。 (Note 7) KBM-403: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, molecular weight 236.34.
(Note 8) KBM-13: trade name, manufactured by Shin-Etsu Chemical, methyltrimethoxysilane.
(Note 9) Epoxysilane oligomer (c-2): 236 parts (1.0 mol) of KBM-403 (Note 7) and methanol in a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube 32 parts (1.0 mol) were added and mixed and stirred at room temperature. Next, 3 parts of 0.05 N hydrochloric acid water was added dropwise over 30 minutes while stirring, and the mixture was further stirred for 30 minutes. Thereafter, the temperature was raised to 75 ° C. using a mantle heater, and reflux was performed for 2 hours while simultaneously removing by-produced methanol. After cooling to room temperature, filtration was performed to obtain an epoxysilane oligomer (c-2).
As a result of heating the product (c-2) at 120 ° C. for 1 hour, the heating residue (active ingredient) was 80%. Moreover, the weight average molecular weight was 500, and the epoxy equivalent was 167 g / eq.
(Note 10) Snowtex O: Brand name, Nissan Chemical Industries, Ltd., Snowtex is a registered trademark, water-dispersed acidic colloidal silica having an average primary particle diameter of 12.5 nm, and 20% by weight of an active ingredient.
　（実施例１～９、１５～１９）
　３０５×３０５×２ｍｍのコンポジションビニル床タイル（商品名「ＰタイルＰ－６０」、タジマ製、塩化ビニル樹脂系床材）上に、表４に記載の各常温硬化型ウレタンプライマー組成物を、床用モップを用いて塗装し、気温２３℃、湿度５０％ＲＨの条件下で、２時間乾燥させ各プライマー硬化塗膜層（Ｉ）を形成した。乾燥膜厚は表４に示すとおりとした。このときの次工程の重ね塗りまでの間隔は乾燥時間の２時間とした。　　
　この上にハードコート層形成用コーティング剤（Ｂ－１）または（Ｂ－３）を、床用モップを用いて乾燥膜厚１５μｍになるように１回塗装し、気温２３℃、湿度５０％ＲＨの条件下で４日間乾燥させハードコート層（ＩＩ）を形成して各塗装タイルを得た。 (Examples 1 to 9, 15 to 19)
On a 305 × 305 × 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), each room temperature curing type urethane primer composition described in Table 4 The paint was applied using a floor mop and dried for 2 hours under conditions of a temperature of 23 ° C. and a humidity of 50% RH to form each primer cured coating layer (I). The dry film thickness was as shown in Table 4. The interval until the over-coating of the next process at this time was 2 hours of drying time.
A coating agent (B-1) or (B-3) for hard coat layer formation is applied once on this to a dry film thickness of 15 μm using a floor mop, air temperature 23 ° C., humidity 50% RH The coated film was dried for 4 days under the following conditions to form a hard coat layer (II) to obtain each painted tile.
　（実施例１０）
　３０５×３０５×２ｍｍのコンポジションビニル床タイル（商品名「ＰタイルＰ－６０」、タジマ製、塩化ビニル樹脂系床材）上に、表４に記載の各常温硬化型ウレタンプライマー組成物（Ａ－１）を、床用モップを用いて塗装し、気温２３℃、湿度５０％ＲＨの条件下で、２４時間乾燥させプライマー硬化塗膜層（Ｉ）を形成した。乾燥膜厚は表４に示すとおりとした。このときの次工程の重ね塗りまでの間隔は乾燥時間の２４時間とした。　　　 (Example 10)
Each room temperature curing type urethane primer composition (A shown in Table 4) on a 305 × 305 × 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material) -1) was painted using a floor mop and dried for 24 hours under conditions of an air temperature of 23 ° C. and a humidity of 50% RH to form a primer cured coating layer (I). The dry film thickness was as shown in Table 4. The interval until the over-coating of the next process at this time was 24 hours of the drying time.
　この上にハードコート層形成用コーティング剤（Ｂ－１）を、床用モップを用いて乾燥膜厚２５μｍになるように１回塗装し、気温２３℃、湿度５０％ＲＨの条件下で４日間乾燥させハードコート層（ＩＩ）を形成して塗装タイルを得た。 The coating agent (B-1) for hard-coat layer formation is once coated so that it may become dry film thickness 25micrometer using a floor mop on this, and it is 4 days on condition of temperature 23 ° C, humidity 50% RH. After drying, a hard coat layer (II) was formed to obtain a painted tile.
　（実施例１１）
　３０５×３０５×２ｍｍのコンポジションビニル床タイル（商品名「ＰタイルＰ－６０」、タジマ製、塩化ビニル樹脂系床材）上に、表４に記載の各常温硬化型ウレタンプライマー組成物を、床用モップを用いて塗装し、気温２３℃、湿度５０％ＲＨの条件下で、２時間乾燥させ各プライマー硬化塗膜層（Ｉ）を形成した。乾燥膜厚は表４に示すとおりとした。このときの次工程の重ね塗りまでの間隔は乾燥時間の２時間とした。　　 (Example 11)
On a 305 × 305 × 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), each room temperature curing type urethane primer composition described in Table 4 The paint was applied using a floor mop and dried for 2 hours under conditions of a temperature of 23 ° C. and a humidity of 50% RH to form each primer cured coating layer (I). The dry film thickness was as shown in Table 4. The interval until the over-coating of the next process at this time was 2 hours of drying time.
　この上に表４のハードコート層形成用コーティング剤１回目の欄に記載のものを、床用モップを用いて乾燥膜厚１５μｍになるように１回塗装し、気温２３℃、湿度５０％ＲＨの条件下で１８時間静置、その後さらにその上にハードコート層形成用コーティング剤２回目の欄に記載のものを、床用モップを用いて乾燥膜厚１５μｍになるように１回塗装し、同条件下で４日間乾燥させ、プライマー硬化塗膜層（Ｉ）上に２層のハードコート層（ＩＩ）が形成された塗装タイルを得た。２層目のハードコート剤を塗布するまでの、重ね塗りまでの間隔は乾燥時間の１８時間である。 The coating described in the first column of the hard coat layer forming coating in Table 4 is applied once on this to a dry film thickness of 15 μm using a floor mop, air temperature 23 ° C., humidity 50% RH Let stand for 18 hours under the following conditions, and then further coat the coating agent described in the second column of the hard coat layer forming coating once with a floor mop to a dry film thickness of 15 μm, It dried under the same conditions for 4 days, and obtained the coated tile in which two-layer hard-coat layer (II) was formed on primer cured coating layer (I). The interval to over-coating before applying the second layer hard coating agent is 18 hours of drying time.
　（実施例１２～１４）
　実施例１１において、常温硬化型プライマー組成物、ハードコート層形成用コーティング剤及び重ね塗間隔（時間：ｈ）を表４に示すものとする以外は実施例１と同様の工程で行い、各プライマー層（Ｉ）上に、２層のハードコート層（ＩＩ）が形成された塗装タイルを得た。 (Examples 12 to 14)
The same steps as in Example 1 are carried out except that the room temperature curing type primer composition, the coating agent for forming a hard coat layer, and the coating interval (time: h) are as shown in Table 4 in Example 11, and each primer On the layer (I), a painted tile in which two hard coat layers (II) were formed was obtained.
　（比較例１～３）
　実施例１において、常温硬化型プライマー組成物、ハードコート層形成用コーティング剤及び重ね塗間隔（時間：ｈ）を表４に示すものとする以外は実施例１と同様の工程で行い、プライマー層（Ｉ）上に、１層のハードコート層（ＩＩ）が形成された塗装タイルを得た。 (Comparative Examples 1 to 3)
The same steps as in Example 1 are carried out in Example 1 except that the room temperature curing type primer composition, the coating agent for forming a hard coat layer, and the overlapping coating interval (time: h) are as shown in Table 4; A painted tile having a hard coat layer (II) formed thereon was obtained on (I).
　（比較例４）
　３０５×３０５×２ｍｍのコンポジションビニル床タイル（商品名「ＰタイルＰ－６０」、タジマ製、塩化ビニル樹脂系床材）上に、常温硬化型ウレタンプライマー組成物を、塗装せず、ハードコート層形成用コーティング剤（Ｂ－１）を、床用モップを用いて乾燥膜厚１５μｍになるように１回塗装し、気温２３℃、湿度５０％ＲＨの条件下で４日間乾燥させハードコート層を形成しプライマー硬化塗膜層（Ｉ）を有さない塗装タイルを得た。 (Comparative example 4)
A hard coat is not coated on a 305 × 305 × 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), and the room temperature curing type urethane primer composition is not coated. The layer forming coating agent (B-1) was coated once using a floor mop to a dry film thickness of 15 μm, dried at a temperature of 23 ° C. and a humidity of 50% RH for 4 days, and a hard coat layer To obtain a coated tile having no primer cured coating layer (I).
　（比較例５）
　３０５×３０５×２ｍｍのコンポジションビニル床タイル（商品名「ＰタイルＰ－６０」、タジマ製、塩化ビニル樹脂系床材）上に、常温硬化型ウレタンプライマー組成物（Ａ－２）を、床用モップを用いて塗装して、気温２３℃、湿度５０％ＲＨの条件下で、２４時間乾燥させ各プライマー硬化塗膜層（Ｉ）を形成し、ハードコート層（ＩＩ）を有さない塗装タイルを得た。 (Comparative example 5)
A room temperature curing type urethane primer composition (A-2) on a 305 × 305 × 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), Paint using mop and dry for 24 hours under conditions of temperature 23 ° C and humidity 50% RH to form each primer cured coating layer (I) and coating without hard coat layer (II) I got a tile.
　（比較例６）
　３０５×３０５×２ｍｍのコンポジションビニル床タイル（商品名「ＰタイルＰ－６０」、タジマ製、塩化ビニル樹脂系床材）上に、常温硬化型ウレタンプライマー組成物を、塗装せず、ハードコート層形成用コーティング剤（Ｂ－２）を、床用モップを用いて乾燥膜厚１５μｍになるように１回塗装し、気温２３℃、湿度５０％ＲＨの条件下で１８時間静置、その後さらにその上にハードコート層形成用コーティング剤（Ｂ－２）を、床用モップを用いて乾燥膜厚１５μｍになるように１回塗装し、同条件下で４日間乾燥させ、プライマー硬化塗膜層（Ｉ）上に２層のハードコート層（ＩＩ）が形成された塗装タイルを得た。２層目のハードコート剤を塗布するまでの、重ね塗りまでの間隔は乾燥時間の１８時間である。 (Comparative example 6)
A hard coat is not coated on a 305 × 305 × 2 mm composition vinyl floor tile (trade name “P tile P-60”, made by Tajima, vinyl chloride resin floor material), and the room temperature curing type urethane primer composition is not coated. The layer forming coating agent (B-2) was coated once using a floor mop to a dry film thickness of 15 μm, allowed to stand for 18 hours under conditions of temperature 23 ° C., humidity 50% RH, and then further The coating agent (B-2) for hard-coat layer formation is once coated so that it may become a dry film thickness of 15 micrometers using a floor mop, and it is made to dry under the same conditions for 4 days. (I) There was obtained a painted tile in which two hard coat layers (II) were formed. The interval to over-coating before applying the second layer hard coating agent is 18 hours of drying time.
　上記のようにして得られた各塗装タイルを試験板とし、各種試験に供した。 Each painted tile obtained as described above was used as a test plate and subjected to various tests.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　＜性能評価＞
　各試験項目の試験方法及び評価基準は下記の通りである。
（試験項目４．）仕上がり性〔塗膜外観（目視）〕：　　
　各試験板について、塗膜外観を目視にて確認し、下記基準にて評価した。
　◎：平滑であり、均一な光沢感が認められる
　○：平滑であるが、ごくわずかな艶ムラが認められる
　△：ユズ肌や艶ムラが少し認められる
　×：顕著なユズ肌や艶ムラが認められる。 <Performance evaluation>
The test method and evaluation criteria of each test item are as follows.
(Test item 4.) Finishing property [coating film appearance (visual)]:
The coating film appearance of each test plate was visually confirmed and evaluated according to the following criteria.
:: Smooth and uniform gloss feeling is observed ○: Smooth but very slight gloss unevenness is observed Δ: Yuzu skin and gloss unevenness are slightly observed ×: Remarkable Yuz skin and gloss unevenness are recognized Be
　（試験項目５．）密着性：
　各試験板上の塗膜を素地に達するようにクロスカットし、その塗面に粘着セロハンテープを貼り付け強く剥離した後の塗膜面を目視にて確認し、タイルからの剥離に関して下記基準にて評価した。なお、塗膜が剥離した際の界面は、すべて、塩化ビニル樹脂素材／プライマー層間であった。　　
　◎：剥離が認められない
　○：クロスカットの線上に、ごくわずかに剥離が認められる
　△：クロスカットの周辺もあわせて部分的に剥離が認められる
　×：クロスカットの周辺もあわせて全面に剥離が認められる。 (Test item 5.) Adhesion:
The coated film on each test plate is cross-cut to reach the substrate, and the coated cell surface after sticking adhesive cellophane tape on the coated surface and peeling strongly is checked visually, and the following criteria for peeling from the tile It evaluated. In addition, all interfaces when the coating film was peeled were the vinyl chloride resin material / primer interlayer.
:: Peeling not observed 剥離: Peeling slightly observed on the crosscut line Δ: Peeling partially observed along the crosscut area ×: Peeling all over the crosscut area Is recognized.
　（試験項目６．）耐ワレ性：
　各試験板の塗膜外観を、下記基準にて評価した。　　
　◎：塗膜全体にワレの発生が全く認められない
　○：塗膜の一部分に微細なワレの発生が認められる
　△：塗膜全体に微細なワレの発生が認められる
　×：塗膜全体に著しいワレの発生が認められる。 (Test item 6.) Crack resistance:
The coating film appearance of each test plate was evaluated according to the following criteria.
:: No occurrence of cracking was observed at all in the entire coating film ○: Occurrence of fine cracking was observed at a part of the coating film :: Occurrence of fine cracking was observed in the entire coating film The occurrence of cracking is observed.
　（試験項目７．）耐擦り傷性：
　得られた各試験板を気温２３℃、湿度５０％ＲＨの条件下、４日放置してスチールウール＃００００を用い、塗膜表面を３００ｇ／ｃｍ２荷重で１００ｍｍの移動距離で１０往復させ、擦り傷を付けたときの塗膜外観を目視で評価した。　　
　◎：傷が認められない
　○：傷がわずかに認められるが、傷の本数は１０本未満である
　△：傷が認められ、傷の本数が１０本以上ある
　×：著しい傷がはっきりと認められる。 (Test item 7.) Scratch resistance:
The obtained test plates were left for 4 days under conditions of a temperature of 23 ° C. and a humidity of 50% RH for 4 days using steel wool # 0000, and the coating surface was reciprocated 10 times with a load of 300 g / cm 2 with a movement distance of 100 mm. The coating film appearance when scratched was visually evaluated.
:: no scratches are observed ○: some scratches are observed but the number of scratches is less than 10 Δ: some scratches are recognized, and more than 10 scratches are observed x: significant scratches are clearly recognized .
　（試験項目８．）耐水性：
　得られた各試験板を気温２３℃、湿度５０％ＲＨの条件下、４日放置した後、２０℃の水に２４時間浸漬した後、水洗いした試験板の外観を下記基準にて評価した。　　
　◎：試験前の塗膜に対して、全く外観の変化のないもの
　○：試験前の塗膜に対して、白化が見られるが、製品とした時に問題ないレベル
　△：試験前の塗膜に対して、若干白化が見られる
　×：試験前の塗膜に対して、著しく白化が見られる。 (Test item 8.) Water resistance:
The test boards obtained were left for 4 days under conditions of a temperature of 23 ° C. and a humidity of 50% RH for 4 days, and then immersed in water at 20 ° C. for 24 hours, and then the appearance of the test boards washed in water was evaluated according to the following criteria.
A: No change in appearance at all with respect to the coating before the test O: Whitening is observed with respect to the coating before the test, but no problem when made into a product. On the other hand, slight whitening is observed. X: Significant whitening is observed for the coating before the test.
　本出願を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１７年１０月１０日出願の日本特許出願（特願２０１７－１９６５９６）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present application has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.
This application is based on Japanese Patent Application (Application No. 2017-196596) filed on Oct. 10, 2017, the contents of which are incorporated herein by reference.

Claims (9)

  1. 　床面に、常温硬化型ウレタンプライマー組成物（Ａ）を塗装し、該組成物による硬化塗膜層（Ｉ）を形成する工程、次いでハードコート層形成用コーティング剤（Ｂ）を塗布し、少なくとも１層のハードコート層（ＩＩ）を形成する工程、を含む床面の表面保護被膜形成方法であって、
    前記常温硬化型ウレタンプライマー組成物（Ａ）が、
    水酸基含有アクリル樹脂（ａ）を含む主剤と、ポリイソシアネート化合物（ｂ）を含む硬化剤とを含有し、
    前記硬化剤中に含まれるポリイソシアネート化合物（ｂ）のイソシアネート基と主剤中に含まれる水酸基含有アクリル樹脂（ａ）の水酸基との比率（ＮＣＯ／ＯＨ）が、０．７～２．０の範囲内であることを特徴とする床面の表面保護被膜形成方法。     A step of coating a room temperature curing type urethane primer composition (A) on a floor surface to form a cured coating layer (I) by the composition, and then applying a coating agent for forming a hard coat layer (B), A method of forming a surface protective film on a floor surface comprising the step of forming one hard coat layer (II),
    The room temperature curing type urethane primer composition (A) is
    A main agent containing a hydroxyl group-containing acrylic resin (a) and a curing agent containing a polyisocyanate compound (b),
    The ratio (NCO / OH) of the isocyanate group of the polyisocyanate compound (b) contained in the curing agent to the hydroxyl group of the hydroxyl group-containing acrylic resin (a) contained in the main agent is in the range of 0.7 to 2.0 A method of forming a surface protective film on a floor, characterized in that
  2. 　前記ハードコート層形成用コーティング剤（Ｂ）が、エポキシシランオリゴマー（ｃ）と、平均粒子径が１～１００ｎｍの範囲内のコロイダルシリカ（ｄ）と、硬化触媒（ｅ）と、を含む請求項１に記載の床面の表面保護被膜形成方法。 The hard coat layer-forming coating agent (B) contains an epoxysilane oligomer (c), colloidal silica (d) having an average particle diameter in the range of 1 to 100 nm, and a curing catalyst (e). The surface protective film formation method of the floor surface as described in 1.
  3. 　前記水酸基含有アクリル樹脂（ａ）のガラス転移温度が、２０～９０℃の範囲である請求項１又は２に記載の床面の表面保護被膜形成方法。 The method for forming a surface protective film on a floor according to claim 1 or 2, wherein the glass transition temperature of the hydroxyl group-containing acrylic resin (a) is in the range of 20 to 90 ° C.
  4. 　前記水酸基含有アクリル樹脂（ａ）の水酸基価が、１５～２００ｍｇＫＯＨ／ｇの範囲内である請求項１～３のいずれか１項に記載の床面の表面保護被膜形成方法。 The method for forming a surface protective film on a floor according to any one of claims 1 to 3, wherein the hydroxyl value of the hydroxyl group-containing acrylic resin (a) is in the range of 15 to 200 mg KOH / g.
  5. 　前記常温硬化型ウレタンプライマー組成物（Ａ）が、充填剤及び／又はポリウレタン樹脂を含む請求項１～４のいずれか１項に記載の床面の表面保護被膜形成方法。 The method for forming a surface protective film on a floor according to any one of claims 1 to 4, wherein the cold-curable urethane primer composition (A) contains a filler and / or a polyurethane resin.
  6. 　前記常温硬化型ウレタンプライマー組成物（Ａ）の塗装時における固形分含有率が、１５～７０質量％である請求項１～５のいずれか１項に記載の床面の表面保護被膜形成方法。 The method for forming a surface protective film on a floor according to any one of claims 1 to 5, wherein the solid content of the room temperature curing type urethane primer composition (A) is 15 to 70% by mass.
  7. 　前記ハードコート層形成用コーティング剤（Ｂ）が、加水分解性シラン及び／又はその縮合物、並びにシリカを含む、請求項１～６のいずれか１項に記載の床面の表面保護被膜形成方法。 The method according to any one of claims 1 to 6, wherein the hard coat layer-forming coating agent (B) contains a hydrolyzable silane and / or a condensate thereof, and silica. .
  8. 　前記硬化塗膜層（Ｉ）のマルテンス硬度が３０Ｎ／ｍｍ２以上、ハードコート層のマルテンス硬度が１００～３００Ｎ／ｍｍ２にある請求項１～７のいずれか１項に記載の床面の表面保護被膜形成方法。 The Martens hardness of the cured coating layer (I) is 30 N / mm 2 or more, the surface of the floor according to any one of claims 1 to 7, Martens hardness of the hard coat layer is in the 100 ~ 300N / mm 2 Method of forming a protective film.
  9. 　前記床面が、塩化ビニル樹脂系である請求項１～８いずれか１項に記載の床面の表面保護被膜形成方法。 The method for forming a surface protective film on a floor according to any one of claims 1 to 8, wherein the floor is a vinyl chloride resin system.
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CN113930148A (en) * 2021-11-23 2022-01-14 广东科鼎功能材料有限公司 Woodware sealing primer and preparation method and application thereof
KR102583913B1 (en) * 2022-09-27 2023-09-27 김소중 Epoxy reconstruction method for under ground parking floor capable of shortening the construction period

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