JP2006169426A - Composition for top coating curable by actinic energy ray and member using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for top-coating curable by an actinic energy ray and a member coated with the composition, wherein moving of goods contained in a drawer, etc., by impact upon their store and take-out can be suppressed, fouling attached can easily be removed and also low gloss coating required in bottom plates in a drawer of kitchen, etc., can be performed. <P>SOLUTION: The member 5 is manufactured by coating an adhesive 2 on a substrate 1, and adhering a decorative sheet of paper as a decorative layer 3 thereon, and then coating thereon a composition 4 for top-coating curable by an actinic energy ray, which comprises 40.0-60.0 mass% of an acrylate-based oligomer having a number average molecular weight of 2,000-15,000 and 0.5-2.0 mol/kg of a solid content of an unsaturated group curable by an actinic energy ray, 30.0-50.0 mass% of a monofunctional monomer as a reactive diluent, and 1.0-30.0 mass% of an amine-modified oligomer or monomer, followed by curing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composition for a top coat used for kitchen drawers and the like and a base material on which this cured film is formed. More specifically, even if dirt such as oil stains or seasonings adheres, the stains can be easily removed. The present invention relates to an active energy ray-curable composition for a top coat that can be wiped off, and can reduce sliding movement of the contents contained therein even when the drawer is opened and closed, and a member formed with this cured film.

  In general, a drawer used in a kitchen or the like contains cooking utensils such as pots and kettles, tableware, or seasonings such as soy sauce, oil, and sauce. Opening and closing the drawer when necessary will allow the contained items to be taken in and out, but at this time, the cooking utensils will move and become damaged due to the impact of the opening and closing, and the dishes will become messy. Often, the seasoning may fall or stain the inside of the drawer.

  For this reason, a commercially available anti-slip mat may be used, but since it is generally a rubber-based foam material, it is effective in preventing slipping, but seasonings and the like soak into it. Since the drawer itself is generally a wood-based board, the seasoning that has flowed out of the anti-slip mat to the drawer soaks directly into the exposed part of the drawer. There is a problem that dirt is difficult to remove. Furthermore, when the seasoning soaked in cannot be wiped off well, mold and the like may gradually be generated in the soiled part, resulting in hygiene problems.

  For this reason, there is a demand for a function that allows the drawer itself to be subjected to anti-slip processing and can be easily wiped even when dirt such as seasonings adheres. For this reason, for example, the inside of the drawer may be painted or coated with a resin, but it has been difficult to satisfy both the functions of reducing slipperiness and ease of wiping off dirt.

  Also, if the surface is glossy, such as a kitchen drawer bottom plate, it will become noticeable when you put in and out of a pot or kettle. In addition to reducing slipperiness and facilitating wiping of dirt, it has been difficult to satisfy the required characteristics of the matte at the same time.

  On the other hand, although it is different as a use, there exists what made the coating composition for wood materials containing the silicone-modified active energy ray-curable compound and the crosslinked polymer fine particles having rubber elasticity easily formed on the surface of the wood material to wipe off oil stains. (For example, refer to Patent Document 1).

  According to this Patent Document 1, by applying the wood material coating composition to a wood material such as a flooring material used for the interior of a building, the stain resistance against oil stains such as crayons and oil-based felt pens is increased. While maintaining for a period, the risk of falling is reduced.

  However, as described above, the wooden material according to Patent Document 1 is mainly for floors and the like, and if the surface friction coefficient is too large, there is a risk that a person will trip and fall, from the viewpoint of preventing the risk of falling. It was necessary to formulate a composition that would reduce the friction coefficient to some extent.

However, it is possible to increase the coefficient of friction by changing the composition of the above composition in order to prevent the contents from moving by applying it to the bottom plate for the kitchen drawer, There is a problem that dirt such as it becomes easy to adhere or the attached dirt cannot be easily wiped off.
Japanese Patent Laying-Open No. 2003-213211 (Claims, paragraphs [0005] to [0007])

  The problem to be solved by the present invention is that the coefficient of static friction is 0.15 to 0.40 so as to reduce the movement of the stored items due to the impact when the stored items in the drawer and the like are taken in and out. Range, preferably in the range of 0.20 to 0.40, and can be easily wiped even when dirt is attached, and can also be applied to the matte specification required for a kitchen bottom plate and the like. It is providing the base material which formed the composition and this cured film.

  As a result of intensive studies, the present inventors have determined that an active energy ray-curable composition for topcoats includes an acrylate oligomer, a monofunctional monomer, an amine-modified oligomer or a monomer having a low unsaturated group concentration and a relatively large number average molecular weight. It was found that the above-mentioned problems can be solved by combining the above-mentioned compounds with a predetermined content, and that the desired properties are further improved by using the extender pigments together, and the present invention has been completed.

  That is, the present invention provides an acrylate oligomer having a number average molecular weight of 2000 to 15000 and a solid content concentration of the active energy ray-curable unsaturated group of 0.5 to 2.0 mol / kg of 40.0 to 60. 1.0% by mass, 30.0-50.0% by mass of a monofunctional monomer as a reactive diluent, and 1.0-30.0% by mass of an amine-modified oligomer or monomer An energy ray-curable composition is provided.

  Further, the present invention is a member obtained by applying the above-described active energy ray-curable composition for topcoat to the outermost layer and curing the composition, and the thickness of the cured coating film of the active energy ray-curable composition for topcoat The present invention provides a member having a thickness of 10 to 150 μm.

  When the base material on which the active energy ray-curable composition for topcoat according to the present invention is applied to form a cured film is used for drawers such as kitchens, the coefficient of static friction is 0.15 even when the drawers are opened and closed. Since the cured film in the range of 0.40, preferably 0.20 to 0.40 is provided as the top coat, the contents in the drawer are difficult to move, and soy sauce, sauce, oil, etc. Even if seasonings adhere, they can be easily wiped off. Further, it can be provided as a base material sufficiently satisfying the required characteristics of the matte required for the kitchen bottom plate.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a case where an adhesive 2 is applied to a base material 1 and a decorative paper 3 is laminated thereon as a decorative layer 3, and then an active energy ray-curable composition 4 for top coat according to the present invention is applied. It is a schematic cross section of the member 5 which shows the state hardened by the line.

  Moreover, FIG. 2 is other embodiment, after apply | coating a urethane paint as the decorative layer 3 to the base material 1, and drying, after apply | coating the active energy ray curable composition 4 for topcoats by this invention, It is a schematic cross section of the member 5 which shows the state hardened with the active energy ray.

  For example, in the case of a base plate for a kitchen or storage drawer, the base material 1 can be made of materials used for various building materials such as wood-based particle board, solid wood, plywood, and non-combustible base material. . In addition, when applied to a separate type sheet material that can be easily placed in a place where slipperiness reduction and dirt wiping ease are required, the present invention is applied to the substrate 1 such as a plastic film, a plastic sheet, and a rubber sheet. It is also possible to obtain a member 5 which is coated with the active energy ray-curable composition 4 for topcoat and cured with active energy rays.

  Further, as the decorative layer 3, decorative paper, painting, printing, or the like can be appropriately selected according to the types of the various base materials 1 described above.

  Examples of the acrylate oligomer used in the present invention include urethane oligomers, epoxy oligomers, polyester oligomers, polyether oligomers and the like, but the number average molecular weight is 2000 to 15000, and the active energy ray-curable unsaturated group. The solid content concentration of the active energy ray-curable unsaturated group is more preferably 0.5 to 2.0 mol / kg, more preferably the number average molecular weight is 2500 to 5000. Is 0.7 to 1.5 mol / kg.

  When the number average molecular weight is less than 2000 or when the unsaturated group concentration exceeds 2.0 mol / kg, the anti-slip property tends to be insufficient, but the number average molecular weight tends to be insufficient. This is because, when the concentration exceeds 15000 or the unsaturated group concentration is less than 0.5 mol / kg, even if anti-slip properties are satisfied, the surface hardness tends to be low and the blocking resistance tends to decrease.

  Among the above oligomers, urethane acrylate oligomers are particularly preferable from the viewpoint of balance between curability and anti-slip properties. The urethane acrylate oligomer is a polymer having an acryloyl group (CH═CHCO—) and a urethane bond (—NH—COO—) by reacting isocyanates, polyols and hydroxyacrylates.

  Specific examples of the isocyanates include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHMDI), tolylene diisocyanate (TDI), 4,4-diphenyl diisocyanate ( MDI), xylene diisocyanate (XDI), and the like, and TDI and IPDI are preferable.

  Examples of the polyols include polyester resins, polyether polyols, polyester polyether polyols, polycarbonate polyols, polybutadiene polyols, polyol resins selected from the group consisting of polyolefin polyol resins, and other polyols.

  Specific examples of other polyols include a diol component or a compound having an equivalent effect, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, and dipropylene glycol. 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6 hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2 Examples thereof include ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, spiroglycols, monoglycidyl ethers, and monoepoxides.

  Furthermore, examples of the trivalent or higher polyol component include polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and compounds having the same effect. In addition, polybutadiene polyol, polypentadiene polyol, epoxy resin, or the like can be given as an alcohol component or a component having an equivalent effect.

  Examples of hydroxy acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, monohydroxy mono (meth) acrylate such as hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, biscoat 214HP ( Monohydroxy di (meth) acrylate such as Osaka Organic Co., Ltd., monohydroxy triacrylate such as pentaerythritol triacrylate, dihydroxy mono (meth) acrylate such as glycerin mono (meth) acrylate, and ethylene oxide, Examples thereof include compounds obtained by addition polymerization of propylene oxide and tetrahydrofuran, or compounds obtained by addition polymerization of ε-caprolactone or the like.

  The active energy ray-curable composition for topcoat of the present invention uses a reactive diluent and an amine-modified oligomer or monomer together with an acrylate oligomer in order to satisfy anti-slip properties, blocking resistance, dirt wiping properties, and the like. It becomes important.

  The content of the acrylate oligomer used in the active energy ray-curable composition for topcoat of the present invention needs to be 40.0% by mass or more, and the curability by the active energy ray and the toughness of the cured film. From this point, it is necessary that it is 60.0 mass% or less, and the range of 45.0-55.0 mass% is more preferable.

  Examples of reactive diluents include all monofunctional monomers, preferably acryloylmorpholine, triethylene glycol divinyl ether, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, N-vinylformamide, isobornyl acrylate, phenoxydiethylene glycol acrylate. Ethoxydiethylene glycol acrylate and the like.

  The content of the monofunctional monomer as the reactive diluent is required to be 30.0% by mass or more from the viewpoint of curability by active energy rays and toughness of the cured film, and has an appropriate viscosity. Thus, in order to improve surface properties and improve workability, it is necessary to be 50.0% by mass or less, and 35.0 to 45.0% by mass is more preferable.

  In addition to this monofunctional monomer, a bifunctional monomer can be used in combination in the range of 0 to 10.0% by mass as a reactive diluent to improve slip resistance. In this case, the slip resistance of the cured film is lowered.

  The amine-modified oligomer or monomer is an oligomer or monomer to which an amino group is added, and examples thereof include an amino acrylate monomer, an amino methacrylate monomer, and an amine-modified polyether acrylate.

  The content of the amine-modified oligomer or monomer is required to be 1.0% by mass or more from the viewpoint of wiping off dirt, and 30.3% from the viewpoint of slip resistance and matting properties (matte degree). It is necessary that it is 0 mass% or less, and 5.0-20.0 mass% is more preferable.

  Even if such an amine-modified oligomer or monomer is used in a relatively small amount, a remarkable effect is obtained with respect to the curability near the surface of the cured coating film and the ability to wipe off dirt.

  The composition ratio of each component is in the above-mentioned range. For example, the acrylate oligomer is 40.0% by mass, the monofunctional monomer as a reactive diluent is 30.0% by mass, and the amine-modified oligomer or monomer is 30. The acrylate oligomer may be 60.0% by mass, the monofunctional monomer as a reactive diluent may be 30.0% by mass, the amine-modified oligomer or monomer may be 5.0% by mass, Other components may be 5.0% by mass.

  In addition to the acrylate oligomer, the monofunctional monomer as the reactive diluent, and the essential component of the amine-modified oligomer or monomer for matting, 1.0 to 10.0% by mass of extender pigment is contained. It is preferable to do. Even when this extender pigment is contained, it is appropriately selected and used within the range of the composition ratio of each component as described above.

  The active energy ray-curable composition for topcoat of the present invention can be applied to a conventionally known roll coater, knife coater, flow coater, etc., and corresponds to the type of the coater, coating conditions, and the like. Additives such as antifoaming agents, leveling agents, waxes, antibacterial agents, antifungal agents, polymerization initiators, polymerization inhibitors and organic solvents can be used in combination as necessary.

  Since the above-described active energy ray-curable composition for topcoat of the present invention is applied on top so as to be 10 to 150 μm at the time of curing, the coefficient of static friction is in the range of 0.15 to 0.40. It is possible to obtain a substrate that can sufficiently reduce the slipperiness and that also satisfies the characteristics of good dirt wiping property.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Example 1
A beige, plain, 30 μm thick rewritable decorative paper (30 g reinforced paper) is bonded to one side of a particle board with a thickness of 1.5 mm, a length of 60 cm, and a width of 30 cm, with the vinyl acetate adhesive. Prepared by pasting ordinary decorative paper (30 g reinforced paper) together. The reason why the decorative paper is pasted on both sides is to prevent the substrate from warping.

The active energy ray curable composition for top coat was made into the following composition ratios.
Urethane acrylate (acrylate oligomer) having a number average molecular weight of 5000 and a solid content concentration of active energy ray-curable unsaturated groups of 1.0 mol / kg: 48.7% by mass, ethoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent) ): 27.5% by mass, phenoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent): 5.5% by mass, ethylene oxide-modified bisphenol A diacrylate (bifunctional monomer): 5.5% by mass, amine-modified poly Ether acrylate (amine-modified oligomer): 10.0% by mass, benzophenone (polymerization initiator): 1.4% by mass, 1-hydroxycyclohexyl phenyl ketone (polymerization initiator): 1.4% by mass

  In addition, this active energy ray-curable composition for topcoat has a viscosity at 40 ° C. of Iwata Cup 50 sec (200 MPa · s) and is transparent.

While transporting the base material at a line speed of 40 m / min, the UV curable resin heated to 40 ° C. is applied onto a recoupable decorative paper so as to be 22 g / m ² (about 25 μm) by a natural roll coater. Applied.

Thereafter, ultraviolet rays were immediately irradiated with a UV lamp (high pressure mercury lamp) having an irradiation intensity of 100 mW / cm ² so as to obtain an integrated light quantity of 200 mJ / cm ² , thereby curing the ultraviolet curable resin, and thus a test member 1 was obtained.

(Example 2)
A test member 2 was obtained in the same manner as in Example 1 except that the active energy ray-curable composition for top coat was changed to the following composition ratio.
Urethane acrylate (acrylate oligomer) having a number average molecular weight of 5000 and a solid content concentration of active energy ray-curable unsaturated groups of 1.0 mol / kg: 44.0% by mass, ethoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent) ): 27.5% by mass, phenoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent): 5.5% by mass, ethylene oxide-modified bisphenol A diacrylate (bifunctional monomer): 5.5% by mass, amine-modified poly Ether acrylate (amine-modified oligomer): 10.0% by mass, bentonite clay (extreme pigment): 4.7% by mass, benzophenone (polymerization initiator): 1.4% by mass, 1-hydroxycyclohexyl phenyl ketone (polymerization initiator) ): 1.4% by mass

(Comparative Example 1)
A test member 3 was obtained in the same manner as in Example 1 except that the active energy ray-curable composition for top coat was changed to the following composition ratio.
Urethane acrylate (acrylate oligomer) having a number average molecular weight of 5000 and a solid content concentration of active energy ray-curable unsaturated groups of 1.0 mol / kg: 54.0% by mass, ethoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent) ): 27.5% by mass, phenoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent): 5.5% by mass, ethylene oxide-modified bisphenol A diacrylate (bifunctional monomer): 5.5% by mass, bentonite clay ( Extender pigment): 4.7 mass%, benzophenone (polymerization initiator): 1.4 mass%, 1-hydroxycyclohexyl phenyl ketone (polymerization initiator): 1.4 mass%

(Comparative Example 2)
A test member 4 was obtained in the same manner as in Example 1 except that the active energy ray-curable composition for top coat was changed to the following composition ratio.
Urethane acrylate (acrylate oligomer) having a number average molecular weight of 5000 and a solid content concentration of active energy ray-curable unsaturated groups of 1.0 mol / kg: 20.0% by mass, ethoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent) ): 27.5% by mass, phenoxydiethylene glycol acrylate (monofunctional monomer of reactive diluent): 29.5% by mass, ethylene oxide-modified bisphenol A diacrylate (bifunctional monomer): 5.5% by mass, amine-modified poly Ether acrylate (amine-modified oligomer): 10.0% by mass, bentonite clay (extreme pigment): 4.7% by mass, benzophenone (polymerization initiator): 1.4% by mass, 1-hydroxycyclohexyl phenyl ketone (polymerization initiator) ): 1.4% by mass

(Comparative Example 3)
On the same base material as the base material of Example 1, a non-slip mat for mating (AGO FORM) made of an extruded product of a surface unevenness type made of polystyrene was laid to make a test member 5. This product is gray.

(Comparative Example 4)
A general low-pressure melamine decorative board for kitchen drawer (manufactured by EGGER) having a thickness of 1.5 mm was processed into a length of 60 cm and a width of 30 cm to obtain a test member 6.

(Evaluation of parts)
For the static friction coefficient, a tester of Tribogear type 10 (manufactured by HEIDON) was used. Specifically, a test member was placed on an inclined table, and a 35 mm × 75 mm, 200 g brass chrome plating weight was placed thereon to incline and calculated from the angle at which sliding started.

  The gloss of the surface of each plate was evaluated using a gloss checker IG-330 (manufactured by HORIBA). In addition, when the presence or absence of gloss is visually observed, the gloss value is approximately 80% or more glossy, 40 to 80% semi-gloss, and 40% or less glossless. It was.

  In the wiping test, various seasonings, detergents and the like were dropped or adhered, wiped with a dry cloth, then wiped with a cloth soaked with ethanol, and visually evaluated. These measurement results are summarized in Table 1. In general, coffee stains are the hardest to wipe off.

  From the above results, a member coated with the active energy ray-curable composition for topcoat according to the present invention has a sufficient coefficient of static friction in the range of 0.15 to 0.40. Even if the drawer is opened and closed, the cooking utensils and the like do not move, and the risk of the seasoning falling down can be reduced.

  Moreover, even if dirt, such as various seasonings, adheres, it can wipe off easily and it turns out that the spot after wiping off is also a range which is satisfactory practically. Furthermore, it is in a practically satisfactory range for the matte properties required for drawer bottom plates such as kitchens.

  On the other hand, the commercially available mat of the member 5 is sufficient in terms of slipperiness, but the stain after wiping off the seasoning is quite conspicuous despite being gray. Moreover, although the low-pressure melamine decorative board generally used for the member 6 is good with almost no stain after wiping off the seasoning, the cooking utensil easily moves when the drawer is opened and closed.

The schematic cross section which shows one Embodiment of the member by this invention. The schematic cross section which shows other embodiment of the member by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Adhesive 3 Cosmetic layer 4 Active energy ray-curable composition for topcoats 5 Member

Claims (3)

40.0-60.0% by mass of an acrylate oligomer having a number average molecular weight of 2000-15000 and a solid content concentration of the active energy ray-curable unsaturated group of 0.5-2.0 mol / kg, reaction Active energy ray-curable composition for topcoat, comprising 30.0 to 50.0% by mass of a monofunctional monomer and 1.0 to 30.0% by mass of an amine-modified oligomer or monomer as a reactive diluent . Furthermore, the active-energy-ray-curable composition for topcoats of Claim 1 containing 1.0-10.0 mass% of extender pigments. A member obtained by applying the active energy ray-curable composition for topcoat according to claim 1 or 2 to the outermost layer and curing the composition, and a thickness of the cured coating film of the active energy ray-curable composition for topcoat A member having a thickness of 10 to 150 μm.

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