JP2003062524A - Method for forming coating film using active energy ray- curable composition to substrate surface by on-site coating, substrate coated with the coating film, and method for preventing contamination of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a coating film which is excellent in the stain resistance of the coating film from after coating to before hardening by on-site coating. SOLUTION: In the method, an active energy ray-curable composition 20 is applied to the surface of a substrate 10 by the on-site coating. In the state that a composition containing a component (A) and a component (B) is laid between the surface of the substrate and the film 30, the active energy ray is irradiated from the film side, the composition is hardened, and the film is fallen off. The component (A) is a polymerizable compound having at least one kind of active energy ray polymerizable (meth)acryloyloxy group selected from the group consisting of urethane (meth)acrylate, epoxy(meth)acrylate and polyester(meth)acrylate. The component (B) is a compound having a radical polymerizable group which is copolymerizable with the component (A) and existing one or more in the molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming a coating film on the surface of a substrate by in-situ coating, a substrate coated with the coating film, and a method for preventing contamination of the substrate surface. A method for forming a coating film by in-situ coating on the surface of a base material, such that dust is not attached to the surface of the coating film before completion of curing and excellent stain resistance and the like, and a smooth cured coating film can be formed. The present invention relates to a coated substrate and a method for preventing contamination of the substrate surface.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a radical polymerization type active energy ray-curable composition is rapidly cured by irradiation with an active energy ray, and has scratch resistance, chemical resistance, abrasion resistance, heat resistance, It is widely used in various surface finishing fields, such as painting indoor interior parts and repairing buildings, because it gives a film with excellent water resistance.

The curing method using this active energy ray is
Compared to the room temperature / heat curing method, it can be cured in a short time,
It has the advantage that a film with excellent performance can be formed. Because of these advantages, the composition is widely used for surface protection of plastics, wood, inorganic materials, metals, plastic laminated metals, etc., for improving aesthetics, and the like.

However, it has been attempted to provide a coating film made of a radical polymerization type active energy ray-curable composition by a conventionally known method on the surface of a building interior material or an interior interior product at a work site. Then, dirt such as dust and dirt around will be applied during painting, after painting, and before curing is complete.
There is a problem in that it adheres to the uncured coating film, lacks specularity (surface smoothness), and the finish appearance of the obtained coating film is not sufficient and its appearance is not good.

For example, Japanese Examined Patent Publication No. 6-78691 discloses a building floor surface, wall surface, or ceiling in which the surface of the building floor surface, wall surface, or ceiling surface is removed and then UV curable resin coating is applied to the surface. A surface repair method has been proposed.If the stain oil part adhering to the base material oozes out on the surface, it is treated with a special primer to prevent it from oozing out on the surface. It is described that painting is applied.

Further, in Japanese Unexamined Patent Publication No. 8-126686, an old coating film on a portion to be repaired is peeled off and stains are removed to adjust the portion, and a UV-curable coating is newly added to the adjusted base. A coating repairing method of coating and irradiating the coating portion of the ultraviolet-curable coating material with ultraviolet rays by an ultraviolet irradiation device to dry and cure is proposed. According to this method,
It is stated that it is possible to easily perform painting and repair of interior materials such as counters of restaurants and the like, and buildings.

However, the repair methods described in these publications are not sufficient in terms of the surface smoothness of the obtained coating film, the prevention of contamination during coating, and the like. Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a specific active energy ray-curable composition is interposed between the substrate surface and the active energy ray-permeable film. Then, after curing the active energy ray-curable composition by irradiating the active energy ray-curable composition from the outside of the active energy ray-permeable film side to the active energy ray-curable composition, the film is peeled off, According to the method of forming a coating film on the surface of the substrate by in-situ coating, it is possible to secure the anti-staining property of the coating film at the time of on-site construction and before the completion of curing, and to obtain a coating film with excellent surface smoothness. As a result, the present invention has been completed and the present invention has been completed.

[0008] Note that: in the JP 61-258870 and JP-formula _{"(I): CH 2 = CR} 1 -COO-C m H 2m -C n F 2n -
_{X, (II): CH 2} = CR 1 -COO-C m H 2m -N (R 2) -SO
_{2 -C n F 2n -X (R} : H or CH _3, R ^2: H, alkyl group of C ₁ ~ _8, m, n specific integer, X: H, F) fluoroalkyl group-containing represented by "( An active energy ray-curable coating composition containing a (meth) acrylic monomer has been proposed, and as the functional group-containing base resin that can be blended with the composition, acrylic resin, epoxy acrylic resin, etc. are mentioned. . Further, it is described that the composition is applied to an object to be coated by a usual method and is cured by irradiation with an active energy ray, and a coating film made of the composition has good adhesion to a plastic material, It is described that the curability, abrasion resistance and stain resistance are good.

However, even if coating is carried out by the method described in the above publication, it is not possible to secure the anti-staining property of the coating film at the time of coating, and a coating film having sufficiently excellent surface smoothness cannot be obtained.

[0010]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and it is excellent in surface smoothness while ensuring the stain resistance of the coating film surface during on-site construction. Method for forming a stain-resistant cured coating film on a substrate surface such that a cured coating film can be formed on the substrate surface by on-site construction, a substrate coated with the coating film, and a method for preventing contamination of the substrate surface Is intended to provide.

[0011]

SUMMARY OF THE INVENTION A method of forming a coating film on a substrate surface by in-situ coating according to the present invention is a method of forming a coating film by coating an active energy ray-curable composition on the substrate surface in-situ. Therefore, the active energy ray-curable composition containing the following component (A) and component (B) is interposed between the surface of the substrate and the active energy ray-permeable film, and the active energy is The film is peeled off after the active energy ray-curable composition is cured by irradiating the active energy ray-curable composition from the outside of the side of the ray permeable film to cure the active energy ray-curable composition.

(A): Urethane (meth) acrylate,
At least one selected from the group consisting of epoxy (meth) acrylate and polyester (meth) acrylate
A polymerizable compound having a species of active energy ray-polymerizable (meth) acryloyloxy group. (B): A compound having one or more radically polymerizable groups in the molecule, which is copolymerizable with the component (A).

In the present invention, it is preferable that the surface of the base material is preliminarily preliminarily adjusted. In the present invention, the active energy ray-curable composition preferably further contains a photopolymerization initiator (C). In the present invention, the active energy ray-curable composition contains the photopolymerization initiator (C) in a total amount of the above components (A) and (B) of 1
It is preferably contained in an amount of 0.05 to 10 parts by weight with respect to 00 parts by weight.

In the present invention, the active energy ray transparent film is preferably made of at least one resin selected from the group consisting of polyolefin, polystyrene, polyester, polycarbonate, acrylic resin and polyfluoroolefin. In the method for forming a coating film on the surface of a base material according to the present invention by coating in situ, an aging / deteriorated coating film to be repaired / repaired is formed on the base material surface, and the deterioration / deteriorated coating film is peeled off. After removal, repair coating is performed by any of the methods described above.

The molded article (coated substrate, coated substrate) according to the present invention is characterized in that the substrate surface is coated with the cured coating film obtained by any one of the above-mentioned methods.
The method for preventing contamination of a substrate surface according to the present invention is characterized by coating the substrate surface with the cured coating film obtained by any one of the methods described above. According to the present invention as described above, a cured coating film which is excellent in stain resistance and smooth (that is, excellent in mirror surface property) is obtained on the spot while ensuring stain resistance during coating. A method of forming a coating film by in-situ coating on the surface of the base material, which can be formed on the surface of the base material by construction,
A substrate coated with the coating film and a method for preventing contamination of the substrate surface are provided.

[0016]

DETAILED DESCRIPTION OF THE INVENTION A method for forming a coating film on the surface of a substrate according to the present invention by in-situ coating, a substrate coated with the coating film, and a method for preventing contamination of the substrate surface are specifically described below. To do. In the method for forming a (cured) coating film on the surface of a base material according to the present invention by in-situ coating, a surface of the base material and an active energy ray transparent film (also simply referred to as “film” or the like).
And an active energy ray-curable composition containing the following component (A) and component (B) interposed between the active energy ray-permeable film side (outside) and the active energy ray-curable composition. After irradiating the curable composition with active energy rays to cure the active energy ray-curable composition, the film is peeled off.

(A): Urethane (meth) acrylate,
At least one selected from the group consisting of epoxy (meth) acrylate and polyester (meth) acrylate
A kind of polymerizable compound having active energy ray-polymerizable (meth) acryloyloxy group (also referred to as (meth) acryloyl group-containing polymerizable compound (A), component (A), etc.). (B): A compound having at least one radical-polymerizable group in the molecule, which is copolymerizable with the component (A) (also referred to as a radical-polymerizable compound (B), component (B), etc.).

First, the base material, the active energy ray permeable film and the active energy ray curable composition used in the method for forming a coating film on the surface of the base material by in-situ coating will be sequentially described. <Substrate> The substrate is not particularly limited in its material, wall thickness, size, use, and the like. For example, inorganic noncombustible material; plastic plate such as vinyl chloride, FRP; wood; metal plate; plastic laminated metal Etc. A primer layer, an undercoat layer, etc. are provided on the surface of these base materials,
Further, it may be printed or the like. In the present invention, a base material for interior building materials is particularly preferable.

<Active energy ray transparent film (Film
Rum)> The active energy ray permeable film (also referred to as a film) is an active energy ray which will be described later and is capable of efficiently transmitting active energy rays and is coated or cast under the film. A curable composition that can be reactively cured by irradiation with the active energy ray is used.

The film preferably has an ultraviolet transmittance (wavelength: 250 nm or more) of 10 to 100%,
Further, the thickness is preferably 30 to 100%, and the thickness thereof is not particularly limited as long as the ultraviolet transmittance is within the range, and may be a film, a sheet or the like. As the resin for producing such a film, polyolefin, polystyrene,
Examples thereof include polyesters, polycarbonates, acrylic resins and polyfluoroolefins, and these resins can be used alone or in combination of two or more kinds.

Among these, more specifically, the polyolefin resin is, for example, only one carbon-carbon double bond in the molecule of polyethylene, polypropylene, polybutene, poly-4-methyl-1-pentene or the like. In addition to homopolymers obtained by polymerizing one kind of olefin, ethylene-based copolymers, propylene-based copolymers, butene-based copolymers of olefin-based copolymers obtained by copolymerizing two or more kinds of olefins Examples thereof include polymer, 4-methyl-1-pentene-based copolymer, polyvinyl alcohol, and the like. Among these, polyethylene (PE), polypropylene (PP), and polyvinyl alcohol are low-cost, active energy ray-curable composition layers. It is particularly preferable from the standpoints of ease of peeling from the surface and ultraviolet transmittance. "Ethylene-based" in each of the above copolymers
The meanings such as "" and the like indicate that the copolymer contains a maximum amount of ethylene-derived ones as a main component unit.

In the present invention, one or two of these resins are used.
A combination of two or more species can be used. In such a film, in addition to the above resins, components that are usually contained in the film, for example, an ultraviolet absorber, a heat stabilizer, a weather stabilizer, an antioxidant, a plasticizer, a pigment, a dye, etc. May be included. In the present invention, the surface of such a film which comes into contact with the active energy ray-curable composition may be coated with a silicone oil, a release agent or the like so as not to be adhered to the composition and to be easily peeled off. Good.

[0023] As such a film, one that is commercially available is, for example, "Product Name: Gunze Co., Ltd."
Silfan, model number: ML-2 ”film and the like are preferable because they are inexpensive and have excellent workability. In the present invention, since the above-mentioned materials are used as the film material, a cheaper (lower cost) material having various materials and functions is appropriately selected according to its application, function, shape and the like. Can be used. As a result, it is possible to efficiently form a coating film excellent in the above-mentioned various properties (eg, specularity) on the surface of the substrate at low cost.

<Active energy ray curable composition> In the present invention, the active energy ray curable composition contains the above-mentioned (meth) acryloyl group-containing polymerizable compound (A) and radical polymerizable compound (B). What is done is used. <(Meth) acryloyl group-containing polymerizable compound (A)>
Examples of the (meth) acryloyl group-containing polymerizable compound (A) include urethane (meth) acrylate and epoxy (meth).
A polymerizable compound having at least one active energy ray-polymerizable (meth) acryloyloxy group selected from the group consisting of acrylate and polyester (meth) acrylate is used.

Urethane (meth) acrylate Specific examples of the urethane (meth) acrylate include 1,6-hexamethylene diisocyanate of 3
Urethane tri (meth) acrylate obtained by reacting a monomer with 2-hydroxyethyl (meth) acrylate, urethane di (meth) acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth) acrylate, isophorone diisocyanate with pentaerythritol triacrylate Urethane hexa (meth) acrylate reacted with (meth) acrylate, urethane di (meth) acrylate reacted with dicyclomethane diisocyanate and 2-hydroxyethyl (meth) acrylate, dicyclomethane diisocyanate with polytetramethylene glycol ( Repeating unit of tetramethylene glycol n = 6-1
Urethane poly (meth) acrylates such as urethane di (meth) acrylate obtained by reacting a urethanization reaction product with 5) with 2-hydroxyethyl (meth) acrylate can be mentioned.

Among these urethane (meth) acrylates, urethane di (meth) acrylate obtained by reacting isophorone diisocyanate or dicyclomethane diisocyanate with 2-hydroxyethyl (meth) acrylate and alkyl diol is preferable. Epoxy (meth) acrylate As the epoxy (meth) acrylate, specifically,
Examples thereof include epoxy poly (meth) acrylates such as epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid.

Among these epoxy poly (meth) acrylates, epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid is preferable. As the polyester (meth) acrylate polyester (meth) acrylate, specifically, for example, trimethylolethane and succinic acid, polyester (meth) acrylate obtained by reacting (meth) acrylic acid, trimethylolpropane and succinic acid, Examples thereof include polyester poly (meth) acrylates such as polyester (meth) acrylates reacted with ethylene glycol and (meth) acrylic acid.

<Radical polymerizable compound (B)> Radical polymerizable compound (B), that is, a compound (B) copolymerizable with the component (A) and having at least one radical polymerizable group in the molecule (B ) (Component (B)) is preferably a compound having a (meth) acrylate group, a vinyl ether group, an allyl group or the like in the molecule, and an aliphatic, alicyclic or aromatic mono- or poly ( (Meth) acrylate can be used. Such a radically polymerizable compound (B) is present in a coating film containing a copolymer cured product obtained by using the radically polymerizable compound (B), and has a stain resistance and abrasion resistance of the coating film. It also contributes to the improvement of durability, adhesion to the base material, and the like.

Specific examples of such a radically polymerizable compound (B) include the following. That is, aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene and divinylbenzene; vinyl acetate, vinyl butyrate,
Vinyl ester monomers such as N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; diallyl phthalate, trimethylolpropane diallyl Allyl compounds such as ether and allyl glycidyl ether; acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, Acryloylmorpholine, acrylamides such as methylenebisacrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate,
Phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, Mono (meth) acrylates such as phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Di (meta)
Polyethylene glycol acrylate (repeating unit of ethylene glycol n = 5 to 14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, di (meth) Tetrapropylene glycol acrylate, polypropylene glycol di (meth) acrylate (Propylene glycol repeating unit n = 5-1
4), 1,3-butylene glycol di (meth) acrylate,
Di (meth) acrylic acid 1,4-butanediol, di (meth) acrylic acid
Acrylic polybutylene glycol (butylene glycol repeating unit n = 3 to 16), di (meth) acrylic acid poly (1-methylbutylene glycol) (1-methylbutylene glycol repeating unit n = 5 to 20), di ( Meta)
Acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid neopentyl glycol, hydroxypivalic acid neopentyl glycol di (meth) acrylic acid ester, dicyclopentanediol 2 to 5 at both ends of di (meth) acrylate and neopentyl glycol hydroxypivalate
Di (meta) of the adduct with ε-caprolactone
Acrylic ester, a di (meth) acrylic ester of an adduct of bisphenol A with a total of 2 to 5 caprolactone added to both ends thereof, a bisphenol A ethylene oxide adduct (a repeating unit of ethylene oxide n =
1 to 7) di (meth) acrylic acid ester, bisphenol A propylene oxide adduct (propylene oxide repeating unit n = 1 to 7) di (meth) acrylic acid ester, trimethylolpropane tri (meth) acrylic acid ester , Glycerin tri (meth) acrylic acid ester, ditrimethylolpropane tetra (meth) acrylic acid ester, pentaerythritol tri (meth) acrylic acid ester, trimethylolpropane ethylene oxide adduct (ethylene oxide repeating unit n = 1
To 5) tri (meth) acrylic acid ester, trimethylolpropane propylene oxide adduct (repeating unit of propylene oxide n = 1 to 5) tri (meth) acrylic acid ester, glycerine ethylene oxide adduct (repeating ethylene oxide) Tri (meth) acrylic acid ester of unit n = 1 to 5), tetra (meth) acrylic acid ester of ditrimethylolpropane ethylene oxide adduct (repeating unit of ethylene oxide n = 1 to 5), pentaerythritol ethylene oxide adduct (Ethylene oxide repeating unit n = 1 to 5) tri (meth) acrylic acid ester, pentaerythritol ethylene oxide adduct (ethylene oxide repeating unit n = 1 to 15) tetra (meth) acrylic acid ester, pentaerythritol Tri (meth) acrylic acid ester of liter propylene oxide adduct (repeating unit of propylene oxide n = 1 to 5), tetra (meth) of pentaerythritol propylene oxide adduct (repeating unit of propylene oxide n = 1 to 15) Acrylic ester, pentaerythritol tetra (meth) acrylic acid ester, dipenerythritol penta (meth)
Acrylic ester, dipentaerythritol hexa (meth) acrylic acid ester, N, N ', N "-tris ((meth) acryloxyethyl) isocyanurate, dipentaerythritol ethylene oxide adduct (ethylene oxide repeating unit n = 1 to 5) penta (meth) acrylic acid ester, dipentaerythritol ethylene oxide adduct (ethylene oxide repeating unit n =
1 to 15) hexa (meth) acrylic acid ester, N,
Examples include poly (meth) acrylates such as N ′, N ″ -tris ((meth) acryloxypoly (ethoxy repeating unit n = 1 to 4) (ethoxy) ethyl) isocyanurate.

Among these radically polymerizable compounds (B), tetrahydrofurfuryl (meth) acrylate,
Morphoryl (meth) acrylate, (meth) acrylic acid
2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
Phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di (meth) acrylic Acid polyethylene glycol (repeating unit of ethylene glycol n = 5 to 14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, di (meth) acrylic Acid 1,6-
Hexanediol, 1,9-nonanediol di (meth) acrylic acid, neopentyl glycol di (meth) acrylic acid, trimethylolpropane tri (meth) acrylic acid ester, glycerin tri (meth) acrylic acid ester,
Ditrimethylolpropane tetra (meth) acrylic acid ester, pentaerythritol tri (meth) acrylic acid ester, pentaerythritol tetra (meth) acrylic acid ester, dipentaerythritol (meth) acrylic acid ester, dipentaerythritol hexa (meth)
Acrylic ester, N, N ', N "-tris ((meth) acryloxyethyl) isocyanurate is preferred.

These radically polymerizable compounds (B) are
They can be used alone or in combination of two or more.
In the active energy ray-curable composition used in the present invention, the total of the (meth) acryloyl group-containing polymerizable compound (A) and the radical polymerizable compound (B) ((A) +
5 to 95 parts by weight of the (meth) acryloyl group-containing polymerizable compound (A) is usually added to 100 parts by weight of (B).
It is preferably contained in an amount of 40 to 85 parts by weight, and the radically polymerizable compound (B) is preferably contained in the balance.
(The same applies to parts by mass. The same applies to the following.) When the components (A) and (B) are contained in the active energy ray-curable composition in the above amounts, respectively, a cured coating film of the composition is obtained. Has excellent wear resistance and stain resistance,
Paint costs also tend to be cheaper.

<Other Components> In the present invention, the active energy ray-curable composition further contains a photopolymerization initiator (C) and, if necessary, a photosensitizer, a release agent, a lubricant,
Plasticizers, antioxidants, antistatic agents, light stabilizers, UV absorbers, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents, solvents, pigments, dyes, and other additives May be included.

In the present invention, as such an active energy ray-curable composition, a solventless type composition is desirable because it does not suffer from offensive odors or bad odors caused by a solvent during or after coating and is environmentally friendly. Photopolymerization Initiator (C) Specific examples of the photopolymerization initiator (C) include penzophenone, 4,4-bis (diethylamino) pentophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone,
t-butyl anthraquinone, 2-ethyl anthraquinone,
Thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl -Phenyl ketone,
Acetophenones such as 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;
Benzoin ethers such as benzoin methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Examples thereof include acylphosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoyl formate, 1,7-bisacridinyl heptane, and 9-phenylacridine.

Among these photopolymerization initiators (C), acetophenones are preferable, and 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone are particularly preferable. These photopolymerization initiators (C) can be used alone or in combination of two or more. In the present invention, when such a photopolymerization initiator (C) is used, such a photopolymerization initiator (C) is added in a total amount of 100 parts of the above-mentioned components (A) and (B).
Usually, 0.05 to 10 parts by weight (parts by mass), preferably 0.5 to 6 parts by weight (parts by mass) with respect to parts by weight (parts by mass).
Used in an amount of. In such an amount, the photopolymerization initiator (C)
When used, the active energy ray curability is excellent, the productivity is excellent, and the low odor after curing is also excellent, and the cured film formed from the composition tends to have excellent stain resistance, weather resistance, and heat resistance. is there.

As the photosensitizer, conventionally known ones can be widely used. Examples thereof include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, and 4-methylaminobenzoate.
Examples include ethyl dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone and the like.

The viscosity of such an active energy ray-curable composition can be adjusted as appropriate, for example, 10 to 10 when measured at room temperature (25 ° C.) with a rotary B-type viscometer.
When it is about 30,000 (100,000) mPa · s, it is often convenient for handling or coating, and especially 30
When it is from 0 to 2000 mPa · s, the coatability tends to be excellent.

<Activation energy between the substrate and the film
Preparation of interposition of wire-curable composition
)> In order to intervene (exist) such an active energy ray-curable composition between the substrate surface and the active energy ray permeable film at the construction site, for example, the following (a) to ( The method shown in (c) can be used.

Of these, the following method (a) is preferable in that the active energy ray-curable composition does not entrap air and the working efficiency is good. (A): An active energy ray-curable composition is applied or placed on the surface of a substrate, and a film is placed on the active energy ray-curable composition thus applied or placed, By pressing the active energy ray-curable composition from above the placed film, air (air bubbles) (not shown) in the active energy ray-curable composition is extruded, so that the composition has a uniform thickness. And spread the film over the surface of the substrate to spread the film over the composition.
y, cover) how to do.

(B): The film is placed or stretched on the surface of the base material which is inclined, and the active energy ray-curable composition is injected from the upper end of the base material between the base material and the film. Method of casting (not shown). (C): A method in which a film to which the active energy ray-curable composition has been applied in advance is arranged so that the active energy ray-curable composition adheres to the substrate, and the film is attached to the substrate. (Not shown).

In any of the above (a) to (c), air (air bubbles) is contained in the active energy ray-curable composition.
It is preferable to form an active energy ray-curable composition layer having a uniform thickness so as to prevent the core material from being involved. When carrying out these methods (a) to (c), The film is laminated and wound around the rod-shaped long object in a spiral shape in cross section, and the film is placed on the composition placed on the substrate to press the long bar-shaped object to spread the composition thinly. While
The film may be unwound (not shown). Further, air in the composition is pushed out from above the film with a bar (rolling pin) that is a long bar, a spatula that is a long plate, and the like to give a uniform thickness of the composition. You may push it apart.

The thickness S of the uncured active energy ray-curable composition layer is not particularly limited as long as it can be cured with active energy rays, but is usually 5 to 200 μm.
(Thickness), preferably about 10 to 100 μm (thickness). In order to interpose (exist) the active energy ray-curable composition between the surface of the base material and the active energy ray transparent film, more specifically, for example, the following is desirable.

That is, as shown in FIG. 1, the active energy ray-curable composition 20 is dropped onto the base material 10 in a required amount with respect to the area of the base material 10, and the active energy ray composition 20 is applied from above. After placing the film 30 so as to cover,
A total of four rollers 42, 42, 44, 44 arranged in the vertical direction and two in the horizontal direction so as to be parallel to the surface of the base material 10 and orthogonal to each other on the film 30, or 2 arranged in the vertical direction. It is desirable that the composition 20 is spread while being pushed by the rollers 42, 42 of the book or the rollers 44, 44 of which two rollers are arranged in the lateral direction to extrude bubbles. Here, the vertical direction refers to the feeding direction (traveling direction) of the base material 10, and the direction orthogonal thereto is referred to as the horizontal direction.

<Irradiation with Active Energy Ray> In the present invention,
The active energy ray-curable composition (also simply referred to as “composition”) is provided between the surface of the base material and the active energy ray-permeable film (film) by various methods as described above.
In the state of interposing, the active energy ray-curable composition is cured by irradiating the active energy ray-curable composition from the side (outer side) toward the active energy ray-curable composition with an active energy ray.

The irradiation dose of the active energy ray at this time is not generally determined depending on the thickness of the composition layer, the component composition, etc., but for example, the resin is formed by penetrating the film from outside the film side. 30-300 W / cm in the composition,
Preferably, a high pressure mercury lamp of 30 to 120 W / cm or an ultraviolet discharge lamp such as a metal highland lamp is used,
Usually 100 to 450 mJ / cm ² , preferably 150
It may be cured by irradiating with an active energy ray of about 350 mJ / cm ² .

For example, from the point of view of workability on site, Japanese Unexamined Patent Publication (Kokai) No. Hei 8 (1998)
As described in Japanese Patent No. 126861, when the high-pressure mercury lamp in the above range, which is in the range of 100 to 2000 W / cm, is used, without using a temporary power source in a general home or a construction site, It can be used with a household power source and is easy to handle. When the active energy ray-curable composition is thus irradiated with active energy rays, the composition is
The carbon-carbon double bond (C = C) in the (meth) acryloyl group-containing polymerizable compound (A) and the radical polymerizable compound (B) contained in the composition is cleaved to form (A). It is considered that the (B) and the (B) are randomly bonded or block-bonded with each other to form a copolymer, so that the copolymer is cured in a short time.

As the active energy rays, electron rays, ultraviolet rays, visible rays and the like can be used, and ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity. The light source is not particularly limited, and is a low-pressure, medium-pressure, high-pressure or ultra-high-pressure mercury lamp, metal halide mercury lamp, argon laser,
A helium-cadmium laser, a solid-state laser, a xenon lamp, a high frequency induction mercury lamp, sunlight, etc. are mentioned.

<Peeling of Film> Next, in the present invention,
The active energy ray permeable film adhered to the surface of the composition layer cured with active energy rays (cured composition layer) is removed by peeling. This film can be easily peeled and removed from the above-mentioned cured composition layer (stain-resistant cured coating).

The cured composition layer thus formed on the surface of the substrate is obtained by curing in the state of being covered with the active energy ray-permeable film, and therefore, when the composition is cured, There is no polymerization inhibition due to oxygen in the air,
The cured composition layer after peeling and removing the film is smooth, does not contain air bubbles or adheres dust, and has an excellent finished appearance.

In the present invention, a part of the above series of operations may be carried out in advance in a factory or the like by using a machine or the like, and all of the series of operations described above may be carried out in the construction of houses, buildings and other structures. Workers may sequentially perform each process (operation) at a repair site, etc., but especially when applied to the latter on-site construction, it is possible to prevent dust from adhering to the coating film surface during coating work, and to improve surface smoothness. Is obtained and a cured coating film having an excellent finished appearance can be obtained regardless of the skill of the operator, and a coating film having such surface smoothness can be obtained speedily, which is preferable for improving work efficiency.

<Molded Product> The molded product according to the present invention is characterized in that the surface of the substrate is coated with the stain resistant cured coating film obtained by any of the methods described above. Examples of such molded articles include building interior materials (ceiling materials, inner wall materials, floor materials), furniture, indoor water supply members (eg, kitchen, washroom interior materials), and the like. Among these, when applied to building interior materials for site construction, interior furniture, and other furnishings, there is no dust adhesion to the coating surface before coating and after drying and curing, and the obtained curing The coating film is preferable because it has excellent surface smoothness and the cost reduction efficiency at the time of manufacturing a molded body becomes large.

In the present invention, since the above-mentioned various molded products are manufactured by the method as described above, a cured coating film excellent in stain resistance, surface smoothness and the like is formed on the surface of the substrate to obtain these characteristics. The provided molded body can be efficiently manufactured at low cost. The substrate surface contamination prevention method according to the present invention is characterized in that the substrate surface is coated with the stain resistant cured coating film obtained by any one of the methods described above.

According to such a method for preventing contamination of the surface of a substrate, a cured coating excellent in stain resistance, surface smoothness, etc. does not adhere to the coating surface during coating work and after coating is completed but before curing is completed. The film can be efficiently formed on the surface of the base material.

[0053]

According to the present invention as described above, a wide variety of active energy ray-permeable films can be freely used to secure the stain resistance during coating, and also the stain resistance after completion of coating. Excellent and excellent in curability (that is, the required time from coating to completion of curing is "short time", and the resulting coating film is "hard"), and it is smooth and has excellent specularity. Provided are a method for forming a coating film on a substrate surface by in-situ coating, a substrate coated with the coating film, and a method for preventing contamination of the substrate surface so that the coating film can be efficiently formed on the substrate surface. .

[0054]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples and the like. The evaluation criteria are
As follows. <Evaluation Criteria> [Appearance Evaluation] The surface of the coating film was visually observed. [Evaluation of stain resistance] Various stain materials are dropped on the test piece,
The surface was covered and left for 24 hours. After that, remove the cover, wash the contaminated test piece with a neutral detergent, further wash with ethanol, and visually observe the surface change of the test piece before and after the contamination to check the stain resistance. The evaluation was made according to the following criteria.

The judgment criteria are as follows. 3: No change in hue and coating film on the surface of the test piece is observed. 2: A slight change in hue and coating film on the surface of the test piece is recognized. 1: Significant changes in hue and coating film on the surface of the test piece are recognized. The pollutant materials are as follows.

Black / red magic, black / red crayon, lacquer thinner, sauce, 5% NaOH, 5% HCl. [Adhesiveness] With a sharp blade on the surface of the test piece, 6 scoring lines are formed at intervals of 4 mm until reaching the surface of the base material (base material), and 25 grids are formed. Then, a cellophane tape (R) having a width of 12 mm was pressure-bonded to the surface of the test piece, and was rapidly peeled off in a direction immediately above (a direction perpendicular to the surface of the base material) to check whether or not the coating film having a cross-cut was peeled off. It was

[0057]

Example 1 A flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube was placed in an environment in which ultraviolet rays were shielded, and 10 parts by mass of dipentaerythritol hexane acrylate was added as the component (B). 30 parts by mass of 1,9-nonanediol diacrylate, 55 parts by mass of urethane (meth) acrylate as the component (A), (C)
As a radical photopolymerization initiator of the component, 2-hydroxy-
2-Methyl-1-phenyl-propan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals) was added in an amount of 5 parts by mass to a temperature of 25.
The mixture was stirred and mixed at 0 ° C. (mixing and stirring time of about 1 hour) to obtain an active energy ray-curable composition (viscosity of about 500 mPa · s at room temperature) as a colorless transparent viscous liquid.

Using this active energy ray-curable composition, a coated article was produced and the performance was evaluated as follows. <Production and Evaluation of Article Coated with Cured Coating> The above active energy ray-curable composition was dropped on a flexible board substrate undercoated with a urethane resin, and the surface thereof was made of a polyethylene film (film thickness 50 μm, Product name: Rix, manufactured by Toyobo Co., Ltd. (hereinafter also referred to as polyethylene (PE) film), and a roller is rolled on the PE film to form the active energy ray-curable composition on the surface of the substrate and the PE film. Then, the active energy ray curable composition was applied so that the uncured film thickness was about 30 μm (thickness).

Then, with the active energy ray-curable composition sandwiched between the substrate and the PE film, 80 W / cm was applied from the PE film side (outer side) toward the active energy ray-curable composition. About 30 using a high pressure mercury lamp
A coated article was produced by irradiating with ultraviolet rays of 0 mJ / cm ² to cure the composition, and after the composition was cured, the PE film was peeled off.

The cured coating-coated article thus obtained was evaluated for its appearance and stain resistance. As a result, the adhesiveness was good (no cross-cut peeling), the appearance was good in mirror surface property and finish, and the stain resistance was good (evaluation 3). The results are also shown in Table 1.

[0061]

Example 2 In Example 1, polyethylene (PE)
Example 1 was repeated except that a polypropylene (PP) film (film thickness: 50 μm, trade name Silfan ML2, manufactured by Gunze Co., Ltd., hereinafter also referred to as polypropylene (PP) film) was used instead of the film. .

The evaluation results are shown in Table 1.

[0063]

Third Embodiment In the first embodiment, the above (A), (B),
10 parts by mass of dipentaerythritol hexane acrylate as component (B) instead of component (C),
5 parts by mass of ethylhexyl acrylate, 80 parts by mass of urethane (meth) acrylate as the component (A),
As the photoradical polymerization initiator of the component (C), 5 parts by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals) is used. Active energy ray curable composition (viscosity at room temperature: about 1000 mP
Same as Example 1 except that a.s) was used.

The evaluation results are shown in Table 1.

[0065]

Comparative Example 1 The procedure of Example 1 was repeated, except that the surface of the substrate was coated with the active energy ray-curable composition film without using the film to produce a coated article.
The evaluation results are shown in Table 1.

[0066]

COMPARATIVE EXAMPLE 2 A coated article was prepared in the same manner as in Example 1 except that the active energy ray-curable composition was produced only from the components (B) and (C) without blending the component (A). Was manufactured. The evaluation results are shown in Table 1.

[0067]

COMPARATIVE EXAMPLE 3 A coated article was prepared in the same manner as in Example 1 except that the active energy ray-curable composition was produced only from the components (A) and (C) without blending the component (B). Was manufactured. The evaluation results are shown in Table 1.

[0068]

[Table 1]

[Brief description of drawings]

FIG. 1 shows an active energy ray-curable composition dropped on a substrate, and a film is placed on the substrate so as to cover the active energy ray composition. An explanation showing a state in which the composition is pushed and spread while pushing out air bubbles by pushing with a total of four rollers arranged two in each of the vertical direction (moving direction of the substrate) and the horizontal direction so as to be parallel and orthogonal to each other. It is a figure.

[Explanation of symbols]

10 ... Base material 20 ... Active energy ray curable composition, 30 ... ・ Film, 42, 44 ... Rollers, 50 ... ・ UV irradiation device.

Continued front page    (72) Inventor Akira Masuda             7 No. 2306 Mikami, Yasu-cho, Yasu-gun, Shiga Prefecture             Inside China Paint Co., Ltd. F-term (reference) 4D075 DA27 EA21 EB22 EB33 EB35                       EB38 EC37

Claims (8)

[Claims] 1. A method for forming a coating film by coating an active energy ray-curable composition on a surface of a base material in-situ, comprising: a surface of the base material and an active energy ray transparent film; With an active energy ray-curable composition containing the following component (A) and component (B) interposed, from the outside of the active energy ray-permeable film side toward the active energy ray-curable composition. A method for forming a coating film by in-situ coating on the surface of a base material, which comprises irradiating an active energy ray to cure the active energy ray-curable composition and then peeling off the film. (A): A polymerizable compound having at least one active energy ray-polymerizable (meth) acryloyloxy group selected from the group consisting of urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate. (B): A compound having one or more radically polymerizable groups in the molecule, which is copolymerizable with the component (A). 2. The method for forming a coating film on the surface of a base material by in-situ coating according to claim 1, wherein the surface of the base material has been preliminarily adjusted. 3. The formation of a coating film by in-situ coating on the surface of a base material according to claim 1, wherein the active energy ray-curable composition further contains a photopolymerization initiator (C). Method. 4. The active energy ray-curable composition comprises the photopolymerization initiator (C) in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). The method for forming a coating film by in-situ coating on the surface of a base material according to claim 2, wherein the coating film is contained in an amount of. 5. The active energy ray transparent film,
Coating by in-situ coating on the surface of a substrate according to any one of claims 1 to 4, which is made of at least one resin selected from the group consisting of polyolefin, polystyrene, polyester, polycarbonate, acrylic resin and polyfluoroolefin. Method of forming a film. 6. An aged / deteriorated coating film to be repaired / repaired is formed on the surface of the base material, and after the aged / deteriorated coating film is removed by peeling, A method for forming a coating film by in-situ coating on the surface of a base material according to any one of claims 1 to 5, wherein repair coating is performed by the method described above. 7. A molded product obtained by coating the surface of a base material with the cured coating film obtained by the method according to claim 1. 8. A method for preventing contamination of a surface of a base material, which comprises coating the surface of the base material with the cured coating film obtained by the method according to any one of claims 1 to 6.