JP2012144735A - Water-based coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating for protecting the surface of a specific flooring material.SOLUTION: A method includes protecting the surface of a flooring material on which protective layer of a specific water-based coating is formed on a face to which woody material and a backer layer made of a synthetic resin composed of a laminate comprising woody material, the backer layer composed of the specific synthetic resin, a decorative sheet and a protective layer; wherein (1) the water-based coating is a water containing composition comprising mixed acrylic urethane based resin comprising an acrylic resin containing keto groups and a urethane based resin containing hydrazide groups, (2) the backer layer made of the synthetic resin has a layered structure comprising a single, double or more layers and the topmost layer includes amorphous polyethylene terephthalate when the layer has two or more layers, (3) the flooring material is provided with grooves penetrating the backer layer made of synthetic resin from the decorative sheet side that reach the woody material, and chamfered part to which the synthetic resin and woody material are exposed; and (4) a coated layer on the groove parts and the chamfered part is formed on the surface exposed to the groove and the chamfered part by coating or wipe-treating the water-based resin.

Description

  The present invention relates to a water-based paint applied to impart water resistance and the like to floor materials such as houses.

  Conventionally, as a flooring material, a wood veneer veneer is laminated and coated on a plywood, or a wood veneer veneer is laminated on the MDF surface of a laminate of plywood and medium density fiberboard (MDF). Is known. In addition, there are also known ones that have been subjected to groove processing and chamfering processing of a depth reaching the plywood or MDF from the wood veneer side to provide a groove portion and a chamfered portion to improve the design.

  However, wood veneer veneer obtained by thinly slicing innocuous natural wood increases the price of wood and the quality of materials due to the depletion of wood resources or the rise of the global resource protection movement. Timber has become difficult to obtain.

  For this reason, a decorative sheet having a beautiful print such as a wood grain pattern is used instead of the wooden decorative veneer. As this typical thing, the thing which stuck the decorative sheet on the plywood, and the thing which stuck the decorative sheet on the said MDF surface of the laminated board which laminated | stacked the plywood and MDF are used.

  However, as with the case of using a wood veneer veneer for the former, there is a problem that caster resistance, impact resistance, etc. are inferior. There is a problem of catching wire. Further, the latter has a problem that, as in the case of using a wood veneer veneer, the MDF swells due to water intrusion due to the low water resistance of the MDF, thereby impairing the design.

  On the other hand, for example, Patent Literature 1 includes a plywood / synthetic resin layer (backer layer) / decorative sheet, and has a specific yield point load, tensile elastic modulus, and yield elongation as a backer layer. Has been proposed. According to this floor material, excellent caster resistance, impact resistance, water resistance, and the like can be obtained. Here, the backer layer has a role of buffering an impact applied to the flooring material, and can impart caster resistance, impact resistance and the like to the flooring material. As the backer layer, a synthetic resin layer having a thickness of 200 μm or more is generally used.

  However, when the flooring decorative material having the synthetic resin layer as described above is laminated on the wood to constitute the flooring, there is inevitably a difference in the thermal expansion coefficient between the synthetic resin layer and the laminated wood. When the thermal expansion or shrinkage of one of the synthetic resin layer and the wood increases and the other cannot follow, warping occurs in the flooring. In order to reduce the difference in thermal expansion, a measure to reduce the thickness of the synthetic resin layer can be considered. However, if the synthetic resin layer is made thinner, there arises a problem that caster resistance, scratch resistance and the like are lowered accordingly.

JP 2003-239517 A

  Regarding the above-mentioned problem, a floor material in which a synthetic resin layer (backer layer) and a decorative sheet are sequentially laminated on a wooden material, and by providing a groove reaching the wooden material from the decorative sheet side, the synthetic resin layer and the decorative material are provided. Development of a flooring in which the sheet is divided into two or more independent compartments is in progress. In this case, the groove needs to be coated to protect the wood material.

  However, in the case of the floor material, the synthetic resin layer is exposed together with the wood material, and therefore the synthetic resin layer is also coated at the same time. In this case, when the coating film is peeled off from the synthetic resin layer, the coating on the wooden material may be peeled off continuously.

  Therefore, the main object of the present invention is to provide a paint that is effective (high adhesion) for both the wood material and the synthetic resin.

  As a result of intensive studies in view of the problems of the prior art, the present inventor has found that a paint having a specific composition can achieve the above object, and finally completed the present invention.

That is, the present invention relates to a method for protecting the following flooring surface.
1. It consists of a woody material, a synthetic resin backer layer, a decorative sheet and a protective layer, and
Both the synthetic resin backer layer and the wooden material of the laminate formed by sequentially laminating 1) a synthetic resin backer layer containing amorphous polyethylene terephthalate having a thickness of 200 μm or more and 2) a decorative sheet on the wood material It is a method for protecting a floor surface in which a protective layer using an aqueous paint made of an aqueous composition containing an acrylic urethane resin is formed on the exposed surface,
(1) The aqueous paint comprises an aqueous composition containing an acrylic urethane-based resin obtained by mixing a keto group-containing acrylic resin and a hydrazide group-containing urethane resin,
(2) The synthetic resin backer layer has a single layer or a layer structure of two or more layers,
(3) a) in the case of a single layer or b) in the case of two or more layers, at least the uppermost layer of the synthetic resin layer contains amorphous polyethylene terephthalate,
(4) The floor material includes A) a groove reaching the wooden material from the decorative sheet side through the synthetic resin backer layer, and B) a chamfered portion where both the synthetic resin and the wooden material are exposed. At least one is formed,
(5) A method of forming a coating layer on the groove portion and the chamfered portion by applying the surface and the chamfered portion exposed in the groove to the whole surface with the water-based paint and wiping.
2. Item 2. The method according to Item 1, wherein the aqueous composition further comprises a curing agent.
3. Item 3. The method according to Item 1 or 2, wherein the aqueous composition further contains silicon.
4). Item 4. The method according to any one of Items 1 to 3, wherein the aqueous paint is in the form of an emulsion.
5. Item 5. The method according to any one of Items 1 to 4, wherein the surface on which both the synthetic resin backer layer and the wooden material are exposed is a region including a boundary line where the synthetic resin backer layer and the wooden material are in contact with each other.
6). The surface where both the synthetic resin backer layer and the wood material are exposed,
A) A groove reaching the wood material through the synthetic resin backer layer from the decorative sheet side, and
B) A chamfered portion where both the synthetic resin backer layer and the wood material are exposed,
Item 6. The method according to any one of Items 1 to 5, wherein in the floor material on which at least one of the above is formed, the surface and the chamfered portion exposed in the groove.

Hereinafter, the water-based paint of the present invention will be described in detail.
1. Water-based paint The water-based paint of the present invention contains an acrylic urethane resin as a resin component. It does not specifically limit as acrylic urethane type resin, A well-known thing or a commercial item can be used. For example, a reaction product of an acrylic polyol and an isocyanate compound, a compound obtained by crosslinking an acrylic resin having a functional group and a urethane resin having a functional group can be used.

  In the present invention, the acrylic urethane resin is a keto group-containing acrylic resin in that high adhesion to a synthetic resin layer (especially a polyester resin) is obtained together with excellent water resistance, chemical resistance, scratch resistance, and the like. It is preferably obtained by mixing with a hydrazide group-containing urethane resin. By such mixing, the acrylic resin and the urethane resin are cross-linked by a keto group and a hydrazide group, and the acrylic resin and the urethane resin are combined. In this composite resin aqueous emulsion (urethane / acrylic composite emulsion), the particles of the resin are dispersed as composite particles in which the acrylic resin component is present inside the particle and the urethane resin component is present outside the particle. A commercial item can also be used as such a composite emulsion. For example, the product name “Boncoat CG-5000” (manufactured by Dainippon Ink & Chemicals, Inc.) can be suitably used.

  The ratio of the acrylic resin component and the urethane resin component in the urethane / acrylic composite emulsion is not limited, but the urethane resin component is preferably 20 to 40% by weight in the total of 100% by weight of both. By setting to such a range, the adhesiveness with the synthetic resin can be further enhanced.

  The content of the acrylic urethane-based resin in the paint of the present invention can be appropriately set according to the type of resin and the like, but is generally about 5 to 60% by weight, particularly 20 to 40% by weight. desirable. For example, a product name “W-SF” (manufactured by Showa Ink Industries Co., Ltd.) is suitable as a commercially available paint having a resin content within the above range and containing silicon described later.

  In this invention, a crosslinking degree can also be raised by using a hardening | curing agent with respect to acrylic urethane resin. For example, an isocyanate curing agent, an epoxy curing agent, a melamine curing agent, an aziridine curing agent, and the like can be given. In the present invention, an isocyanate curing agent is particularly preferred from the standpoint that the low-temperature crosslinking performance, weather resistance, water resistance, pot life and the like can be further enhanced. The content of the curing agent is usually about 20 to 70 parts by weight with respect to 100 parts by weight of the acrylic urethane resin, although it depends on the type of the curing agent to be used.

  Moreover, it is desirable for the paint of the present invention to contain silicon. By adding silicon, a more excellent defoaming effect, water repellent effect, leveling property (swelling property with respect to plastic) and the like can be obtained. The amount of silicon added may be 0.5 to 5% by weight in the paint of the present invention.

  In the water-based paint of the present invention, additives contained in known water-based paints can be blended. For example, colorants (pigments, dyes), viscosity modifiers, gloss modifiers (extreme pigments), and the like can be used.

  Although water is mainly used as a solvent in the paint of the present invention, a water-soluble organic solvent can be used in combination as necessary. For example, in addition to alcohols such as isopropyl alcohol, glycols and glycol ethers can also be used.

  What is necessary is just to determine suitably solid content of this invention coating material in the range of 5 to 80 weight% normally according to the kind etc. of component to be used.

  The paint of the present invention may be in any form such as a solution or an emulsion, but it is particularly desirable to be in the form of an emulsion.

  The water-based paint of the present invention is an aqueous composition containing an acrylic urethane resin, and is excellent not only in woody materials but also in adhesiveness to synthetic resins. In particular, the synthetic resin can exhibit excellent adhesion to amorphous polyethylene terephthalate (so-called A-PET).

  Furthermore, the paint of the present invention can achieve even better adhesion, water resistance, and the like by using a curing agent together with an acrylic urethane resin.

2. Use of water-based paint The water-based paint of the present invention is preferably used as a paint for protecting at least the exposed surface of both the synthetic resin and the woody material in a laminate formed by laminating at least a synthetic resin and a woody material. it can. As the laminate, for example, (I) a laminate obtained by sequentially laminating a 1) synthetic resin backer layer having a thickness of 200 μm or more and 2) a decorative sheet on a wooden material,
(II) The laminated body etc. which laminate | stack the decorative sheet which has a synthetic resin layer on a wooden material are mentioned.

  The laminate (I) is exemplified in FIGS. 1 and 2, for example. In FIG. 1, a wood material is indicated by 1 in the figure, a synthetic resin backer layer is indicated by 2 in the figure, and a decorative sheet is indicated by 3 in the figure. FIG. 2 is a more specific example of the laminate shown in FIG. In FIG. 2, the wood material is indicated by 21 in the figure, the synthetic resin backer layer is indicated by 23, and the decorative sheet is indicated by 25-32 in the figure.

  The laminate of (II) corresponds to, for example, a laminate obtained by removing the synthetic resin backer layer from the laminate illustrated in FIGS. 1 and 2. In this case, the decorative sheet needs to include a synthetic resin layer. For example, in the decorative sheet in FIG. 2, the adhesive layer (29 in the figure) and the transparent resin layer (30 in the figure) are synthetic resin layers. .

  Such a laminated body is used for decorating the surfaces of furniture, home electric appliances, etc., in addition to the interior and exterior (floor materials, wall surfaces, etc.) of building structures. The paint of the present invention can be used for any laminate applied to them.

  In particular, the paint of the present invention is also suitably used for flooring. Specifically, it consists of a laminated body in which 1) a synthetic resin backer layer having a thickness of 200 μm or more and 2) a decorative sheet are laminated in order on a wooden material, and A) a synthetic resin backer from the decorative sheet side. In the floor material in which at least one of a groove that penetrates and reaches the wooden material, and B) a chamfered portion where both the synthetic resin and the wooden material are exposed, a surface and a chamfered portion that are exposed in the groove are formed. It is useful as a paint used for coating. When used in such applications, the surface or portion where both the synthetic resin and the wood material are exposed is a region including a boundary line where the synthetic resin and the wood material are in contact, and a coating film is formed over the region. Since the paint of the present invention can form a coating film with high adhesion to both woody materials and synthetic resins, the coating film can be formed without worrying about problems such as peeling due to the difference in the material of the coated surface. . Further, since the coating film has high water resistance (water permeability prevention), weather resistance, chemical resistance, and the like, these performances can be simultaneously imparted to both the surface of the woody material and the synthetic resin.

  In addition, in the said laminated body, depending on the formation conditions of a groove | channel and a chamfering part, a wooden base material may not be exposed to the surface and chamfering part exposed to the groove | channel, but only a synthetic resin may be exposed. In such a case, of course, the paint of the present invention can also be used for the purpose of forming a protective layer on the surface and the chamfered portion where only the synthetic resin is exposed. That is, it consists of a laminated body in which 1) a synthetic resin backer layer having a thickness of 200 μm or more and 2) a decorative sheet are sequentially laminated on a wooden material, and A) a groove reaching the synthetic resin backer from the decorative sheet side, In addition, in the floor material on which at least one kind of chamfered portion where the synthetic resin is exposed is formed, a protective layer made of an aqueous paint containing an acrylic urethane resin is formed on the surface exposed on the groove and the chamfered portion. can do.

  Further, the laminate is formed by laminating a decorative sheet having a synthetic resin layer on a wooden material, and A) a groove reaching the wooden material from the decorative sheet side, and B) both the synthetic resin and the wooden material are exposed. In the floor material in which at least one kind of the chamfered portion is formed, it is also useful as a paint used for coating the surface exposed to the groove and the chamfered portion. As described above, the paint of the present invention is useful as a paint for coating a surface or a portion where both the synthetic resin and the woody material are exposed on the flooring material. Also in this case, good water resistance, weather resistance, chemical resistance, and the like can be simultaneously imparted to both the synthetic resin layer and the wooden base material included in the decorative sheet.

  In FIG. 1, the cross section of the flooring which is one of the object of this invention coating is shown. This flooring has a configuration in which a synthetic resin backer layer 2 and a decorative sheet 3 are sequentially laminated on a wood material 1, and a groove portion 4 reaching the wood material is provided. As shown in FIG. 1, after the groove 4 is provided, at least both the wood material and the synthetic resin are exposed. The paint of the present invention is applied to the exposed portion, and the coating film 5 is formed. By this coating film, the exposed surface of the woody material and the synthetic resin is protected. A coating film is similarly formed on the exposed portion of the decorative sheet.

  The method for forming the coating film of the paint of the present invention is not limited, and may be performed by printing or the like in addition to application by brush, roller, spray or the like. In particular, for flooring or the like, it is preferable to apply the paint of the present invention on the entire surface of the decorative sheet by coating or the like, and then remove excess paint adhering to other than the groove using a scraping roller or the like.

  In FIG. 1, the groove portion has a V-shaped cross section, but may have any other shape such as a concave shape or a U shape. The method for forming the groove or the chamfered portion may follow a known method, and for example, it may be processed by a known device such as a tenoner.

  The synthetic resin backer layer in the flooring may be a single layer or may be composed of two or more layers. In the case of two or more layers, the lamination method may be a known method such as an extrusion method.

  The material of the synthetic resin backer layer in the flooring is not particularly limited. For example, polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene), vinyl chloride resin, polystyrene, polypropylene, methacrylic resin, acrylonitrile styrene resin, polyamide resin, acrylonitrile butadiene styrene resin, polyimide resin, polyamideimide resin, fluorine resin, Examples include urethane resin, polysulfone, polycarbonate, polyacetal, polyphenylene ether, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyarylate. Amorphous polyethylene terephthalate (so-called A-PET) [Mitsubishi Chemical Corporation: Nova Clear (trade name)], PETG and the like can also be suitably used. Among these, the paint of the present invention can be suitably used for a layer containing A-PET.

  In particular, the synthetic resin backer layer has a layer structure of one layer (single layer) or two or more layers, and the uppermost layer is a mixed layer containing at least one selected from A-PET, PEN and PETG. It is desirable. That is, in the case of a single layer, in the case of two or more layers, it is necessary that the layer closest to the decorative layer is the mixed layer. This uppermost layer is laminated on the decorative sheet via an adhesive layer and / or a primer layer. In this invention, it becomes possible to improve adhesiveness with a decorative sheet more by making the uppermost layer into the said mixed layer. In the case of a single layer, the single layer is a mixed layer.

  In the sheet of the present invention, when it has a layer structure of three or more layers, it is desirable that at least the uppermost layer and the lowermost layer are a mixed layer containing at least one selected from A-PET, PEN and PETG. Thereby, not only the adhesiveness with a decorative sheet but the adhesiveness with a synthetic resin backer layer and a flooring can also be improved. The uppermost layer is the layer closest to the decorative sheet as described above. The lowest layer refers to a layer closest to the laminated wood material (that is, a layer constituting the back surface of the sheet of the present invention).

  As a preferred embodiment of the present invention, for example, (1) the synthetic resin backer layer has a layer structure composed of three layers, and (2) the uppermost layer and the lowermost layer are selected from A-PET, PEN and PETG. There is a decorative sheet for flooring, which is a mixed layer containing at least one kind and the core layer is a layer made of A-PET.

  Although the said mixed layer contains at least 1 sort (s) selected from A-PET, PEN, and PETG, the other resin component may be contained. Examples thereof include polyester resins such as PBT and polyarylate. In the present invention, a two-component mixed layer composed of A-PET and PETG or PEN is particularly preferable. Even in the case of a two-component system, additives other than the polyester resin may be included.

  The content of A-PET and PETG or PEN in the mixed layer can be appropriately set according to the grade of each component, the use conditions of the sheet of the present invention, and the like. In the sheet of the present invention, in the above two-component system, it is desirable that PETG or PEN is about 20 to 80% by weight, particularly 40 to 60% by weight, in a total of 100% by weight of A-PET and PETG or PEN.

  The thickness of the synthetic resin backer layer (the total thickness in the case of two or more layers) is not limited. However, considering caster resistance, scratch resistance, etc., the thickness is generally about 200 to 500 μm. desirable. The thickness of each layer in the case of two or more layers can be appropriately determined according to the components of each layer.

  The method of laminating each layer in the flooring is not limited, and various methods such as adhesion using an adhesive or the like, lamination, and the like can be employed. In particular, the synthetic resin backer layer and the decorative sheet are desirably laminated via a urethane adhesive layer and / or a urethane primer layer.

  The wood material used for the flooring is not particularly limited, for example, veneer made from various materials such as cedar, firewood, firewood, pine, lauan, teak, melapy, wood veneer, wood plywood, particle board, MDF etc. are mentioned.

  The decorative sheet in the flooring can be configured in the same manner as a known decorative sheet. For example, a decorative sheet formed by sequentially laminating a base sheet, a pattern ink layer, a transparent resin layer, a surface protective layer, and the like can be used. In particular, a decorative sheet (for flooring) as shown in the following embodiment can be suitably used.

  FIG. 2 shows a layer structure showing a specific embodiment of the flooring. This flooring is composed of an adhesive layer 24, a primer layer 25, a base sheet 26, a solid ink layer 27, a pattern ink layer 28, an adhesive layer 29, a transparent resin layer 30, a primer layer (on a synthetic resin backer layer 23. (Not shown) and the surface protective layer 31 are sequentially laminated. Embossing is performed from the surface protective layer side, and a concave embossed portion 32 is provided. On the other hand, the wood material 21 is laminated on the back surface of the synthetic resin backer layer via the adhesive layer 22. And in this flooring, the wood material 21 is reached from the decorative sheet side, and the groove | channel 20 which has a front-end | tip in a wood material is provided, and, thereby, the synthetic resin backer layer is divided for every independent division piece. In this case, the decorative sheet is also divided in the same pattern as the synthetic resin layer. Hereinafter, each layer which comprises a decorative sheet is demonstrated.

  The adhesive layer can be appropriately selected from known or commercially available adhesives. Examples thereof include thermosetting resins such as polyester resins, polyurethane resins, and epoxy resins, in addition to polyolefin resins such as polyethylene and polypropylene.

  Among these, in this invention, a urethane type resin adhesive is preferable at the point that heat resistance etc. can be improved more. Examples of the urethane resin adhesive include a two-component curable urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).

  The polyol has two or more hydroxyl groups in the molecule. For example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol and the like are used.

  Moreover, as said isocyanate, the polyvalent isocyanate which has a 2 or more isocyanate group in a molecule | numerator is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, aliphatics such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate (or Alicyclic) isocyanates are used. Further, adducts or multimers of the above various isocyanates can also be used. Examples thereof include adducts of tolylene diisocyanate and trimers of tolylene diisocyanate.

  If necessary, the adhesion surface can be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment.

  What is necessary is just to implement according to a well-known method as an adhesion | attachment method according to the kind etc. of adhesive agent to be used. For example, by using a polyolefin resin such as polyethylene or polypropylene, a method of coating on a pattern layer by melt extrusion (extrusion coating method), a thermosetting resin such as a polyester resin, a polyurethane resin, or an epoxy resin is isocyanate. Apply an adhesive to which a crosslinking agent such as amine, a polymerization initiator such as methyl ethyl ketone peroxide, hydroperoxide, azabisisobutyronitrile, or a polymerization accelerator such as cobalt naphthenate or dimethylaniline is added if necessary. A dry laminating method can be adopted. In the present invention, an adhesive capable of thermocompression bonding may be used, and the pattern layer and the transparent resin layer may be laminated by thermocompression bonding.

  In the present invention, a known easy adhesion treatment such as a corona discharge treatment, a plasma treatment, a degreasing treatment, a surface roughening treatment or the like can be applied to the adhesion surface as necessary.

  The thickness of the adhesive layer varies depending on the transparency protective layer, the type of adhesive to be used, and the like, but is usually about 0.1 to 30 μm.

  A primer layer is for improving the adhesiveness of the surface of a base material sheet or a transparent resin layer. Examples of the resin used for this purpose include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and the like. These resins can be used alone or in combination. A coating composition or an ink composition can be formed using an appropriate application means such as a roll coating method or a gravure printing method.

  The base sheet is made of paper such as thin paper, fine paper, kraft paper, Japanese paper, titanium paper, resin-impregnated paper, paper-reinforced paper, wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, etc. One or two or more laminates such as woven fabrics and nonwoven fabrics, or synthetic resin sheets such as polyolefin, polyester, polyacryl, polyamide, polyurethane, and polystyrene can be used. Appropriately, 300 μm is suitable. In addition, the base sheet for the decorative sheet described above may be appropriately colored by adding a pigment or the like, or may be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment on a necessary surface. .

  The pattern layer is composed of a pattern ink layer and a solid ink layer. These can generally be formed using ink by a known printing method such as gravure printing, offset printing, silk screen printing or the like. Examples of the pattern ink layer include a wood grain pattern, a stone pattern, a texture pattern, a crest pattern, a geometric pattern, characters, symbols, line drawings, various abstract pattern patterns, and a solid ink layer includes a colored ink having a concealing property. This is a solid print. In this embodiment, both the pattern ink layer and the solid ink layer are provided, but either one of the configurations may be used.

  As the ink used for the pattern layer, as a vehicle, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, and vinyl chloride-vinyl acetate are used. A polymer, a cellulose-based resin, a polyamide-based resin, or the like may be used alone or in combination, and a pigment, a solvent, various auxiliary agents, and the like may be added thereto to make an ink. In the present invention, in consideration of environmental problems, adhesion to the printing surface, etc., one or a mixture of two or more of polyester, polyurethane comprising polyisocyanate and polyol, polyacryl, polyamide resin and the like is mixed. The wiping ink can also be formed with the same ink as that used for the pattern layer described above.

  The transparent resin layer is not limited as long as it is transparent. As a transparent resin layer, what was formed, for example with the thermoplastic resin can be used conveniently.

  Specifically, soft, semi-rigid or rigid polyvinyl chloride, PET, PBT, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, Examples include ionomers, acrylic acid esters, and methacrylic acid esters. Among these, polyolefin resin such as polypropylene is preferable in the present invention.

  The transparent resin layer may be colored as necessary. In this case, a coloring material (pigment or dye) can be added to the above thermoplastic resin for coloring. As the coloring material, the pigments or dyes mentioned in the colored translucent layer can be used. These can select 1 type, or 2 or more types. Further, the addition amount of the colorant may be appropriately set according to the desired color tone.

  For the transparent resin layer, a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component (as necessary) For example, various additives such as rubber) may be included.

  The surface protective layer is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, water resistance, and stain resistance required for the decorative sheet. The resin for forming the surface protective layer is suitably formed using a curable resin such as a thermosetting resin or an ionizing radiation curable resin. In particular, it is more preferable to use an ionizing radiation curable resin because it has a high surface hardness and excellent productivity.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea cocondensation resin, silicon resin, polysiloxane resin, etc. can be mentioned.

  A curing agent such as a cross-linking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin as necessary. For example, as curing agents, isocyanates, organic sulfonates, etc. are added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. are added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator is added to the unsaturated polyester resin.

  As a method of forming the surface protective layer with the thermosetting resin, for example, the thermosetting resin described above is used as a solution, and this solution is applied by a well-known application method such as a roll coating method or a gravure coating method and then dried. And a curing method. The coating amount of the above solution is suitably about 5 to 30 μm in solid content, and preferably 15 to 25 μm.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a cross-linking polymerization reaction by irradiation with ionizing radiation and changes to a three-dimensional polymer structure. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams. In particular, it is desirable to use ultraviolet rays, electron beams, and the like. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of about 190 to 380 nm can be used. As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. As an electron beam to be used, generally about 100 to 1000 keV, preferably 100 to 300 keV can be used. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  The ionizing radiation curable resin is a monomer, prepolymer or polymer having a radically polymerizable unsaturated group such as (meth) acryloyl group, (meth) acryloyloxy group, or a cationically polymerizable functional group such as epoxy group in the molecule. A polymer (hereinafter collectively referred to as a compound). These monomers, prepolymers, and polymers can be used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate.

  Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and polyvinylpyrrolidone. This prepolymer usually has a molecular weight of about 10,000 or less. When the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. Although the acrylate and methacrylate can be used in common, the acrylate is more advantageous for the purpose of curing efficiently at a high speed and in a short time because the acrylate is faster in terms of the crosslinking curing rate with ionizing radiation.

  Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, and ester vinyl ethers. And prepolymers such as vinyl ether resins, cyclic ether compounds, and spiro compounds.

  As a monomer having a radical polymerizable unsaturated group, for example, as a monofunctional monomer of a (meth) acrylate compound, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, Examples include 2- (meth) acryloyloxypropyl hydrogen terephthalate.

  Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth). Acrylate, dipropylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) a Relate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyl Examples thereof include oxyethyl phosphate. As the monomer having a cationic polymerizable functional group, a prepolymer monomer having the cationic polymerizable functional group can be used.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when cured by irradiation with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin system having a cationic polymerizable functional group, for example, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, a freeloxysulfoxonium diallyl iodosyl salt, etc., alone or as a mixture Can be used as

  Although the addition amount of a photoinitiator is not specifically limited, Generally it should just be about 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable resins.

  As a method for forming the protective layer with an ionizing radiation curable resin, for example, an ionizing radiation curable resin may be used as a solution, and this solution may be applied by a known coating method such as a gravure coating method or a roll coating method. In this case, the coating amount of the solution may be about 5 to 30 μm, more preferably 15 to 25 μm as the solid content.

  In addition, an inorganic filler can be blended as necessary when the surface protective layer 31 formed of an ionizing radiation curable resin is further given scratch resistance and wear resistance. For example, powdered aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, gold sand, glass fiber Etc.

  Although the usage-amount of an inorganic filler is not limited, Usually, what is necessary is just to be about 1-80 weight part with respect to 100 weight part of ionizing radiation curable resins.

  The lamination of each layer may be performed by a normal procedure. For example, the ink layers 27 and 28 are sequentially formed on one side of the colored base sheet 26 by printing, and further formed on the pattern layer 28 with a known dry lamination adhesive such as a two-component curable urethane resin. A transparent resin layer 30 is laminated by a known dry lamination method, T-die extrusion method or the like through an adhesive layer 29, a primer layer is provided on the entire surface of the transparent resin layer 30, and a surface protective layer 31 is formed thereon. do it.

  And the uneven | corrugated pattern 32 can be formed by embossing from the surface protective layer 31 side as needed. The concavo-convex pattern can be formed by heating press, hairline processing, or the like. Examples of the uneven pattern include a conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, and a multiline groove.

  By laminating the synthetic resin backer layer and the decorative sheet in order on the wood material, a flooring can be obtained. The lamination method to the wood material is not limited. For example, a method of sticking a synthetic resin backer layer to the wood material with an adhesive can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of a base material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like. The method of laminating the decorative sheet on the synthetic resin backer layer is not limited. For example, a method of adhering the synthetic resin backer layer and the decorative sheet with an adhesive can be employed. If a primer layer is formed in advance on the attachment surface of the decorative sheet, it can be attached easily. In the case of forming a flooring by laminating a decorative sheet having a synthetic resin layer on a wooden material, it can be formed in the step of removing the synthetic resin-made backer layer from the above forming method.

  The water-based paint of the present invention is an aqueous composition containing an acrylic urethane resin, and is excellent not only in woody materials but also in adhesiveness to synthetic resins. In particular, the synthetic resin can exhibit excellent adhesion to A-PET.

  Furthermore, the paint of the present invention can achieve even better adhesion, water resistance, and the like by using a curing agent together with an acrylic urethane resin.

It is a figure which shows the cross-section of the floor material made into the object of this invention coating material. It is sectional drawing which shows an example of embodiment of a flooring.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Production Example 1
Preparation of water-based paint Acrylic urethane resin (Product name “Boncoat CG-5000” Dainippon Ink and Chemicals, Urethane / acrylic composite emulsion) and (Product name “W-SF” Showa Ink Industry) About 30% by weight (resin content) ), About 9% by weight of the color pigment, about 6% by weight of the extender pigment (silica), 2% by weight of silicon, 4% by weight of isopropyl alcohol and 49% by weight of water. On the other hand, isocyanurate-based polyisocyanate as a curing agent was mixed with water at a ratio of 1: 1 (weight ratio), and 20 parts by weight was mixed with 100 parts by weight of the mixture. As a result, an aqueous colored paint comprising an aqueous emulsion was obtained.

Production Example 2
Production of flooring material First, a decorative sheet was produced.

(1) Production of decorative sheet Urethane cellulose resin (5 parts by weight of hexamethylene diisocyanate was added to 100 parts by weight of a mixture of urethane and nitrified cotton on one surface of a colored polypropylene film having a thickness of 60 μm subjected to double-sided corona discharge treatment. Were coated by a gravure coating method so as to have a solid content of 2 g / m ² to form a back primer layer. On the other side, an acrylic urethane-based resin (100 parts by weight of acrylic polyol added with 5 parts by weight of hexamethylene diisocyanate) is applied by a gravure coating method so as to have a solid content of 2 g / m ^2, and a primer layer for printing Formed.

  Next, a solid ink layer and a pattern ink layer are sequentially formed by gravure printing using a printing ink containing an acrylic urethane resin (100 parts by weight of acrylic polyol and 5 parts by weight of hexamethylene diisocyanate) as a binder. A patterned ink layer was formed.

  Next, after applying a urethane-based adhesive on the pattern layer, a transparent resin layer was formed by heating and extruding a propylene-based resin with a T-die extruder so as to have a thickness of 80 μm.

  The transparent resin layer is subjected to corona discharge treatment, and a surface protective layer is applied to the treated surface by an acrylic urethane-based resin (100 parts by weight of acrylic polyol added with 5 parts by weight of hexamethylene diisocyanate) by a gravure coating method. A primer layer was formed.

A urethane acrylate electron beam curable resin is applied on the primer layer for the surface protective layer by a roll coating method so as to have a solid content of 15 g / m ² , dried, and then oxygen is applied to the uncured electron radiation curable resin layer. A surface protective layer made of an electron radiation curable resin was formed by irradiating and curing an electron beam (acceleration voltage 175 KeV, irradiation amount 5 Mrad) in an environment having a concentration of 200 ppm or less.

  Subsequently, embossing was performed from the surface protective layer side with a wood grain conduit embossed plate or a wood texture / abstract embossed plate having a plate depth of 50 μm to obtain a decorative sheet having a wood grain conduit shape or a wood texture / abstract textured pattern.

(2) Production of synthetic resin backer layer A-PET is used as a core layer, and a mixed resin layer of A-PET 60% by weight and PEN 40% by weight is mixed resin layer / core layer / mixed resin layer = 1/14 / A synthetic resin sheet (synthetic resin backer layer) having a thickness of 0.4 mm was obtained by a co-extrusion method using a T-die extruder so that the thickness ratio was 1.

(3) Lamination of synthetic resin backer layer and decorative sheet A synthetic resin backer layer was laminated by a dry laminating method with a urethane adhesive layer interposed in the back primer layer of the decorative sheet.

(4) Production of flooring Lauan plywood (thickness 12 mm) is laminated with a water-soluble emulsion adhesive on the synthetic resin backer layer side of the laminate produced in (3) above, and a predetermined dimension (300 mm × 1800 mm). ), The tenoner is used to process the four sides (sap), and the V-shaped grooves (grooves) with a depth reaching the lauan plywood from the decorative sheet side as viewed from the floor surface and It was formed in the short direction. Moreover, the chamfered part was formed in the side part of the elongate direction seen from the flooring plane.

Example 1
Using the water-based paint obtained in Production Example 1, a coating layer was formed on the groove portion and the chamfered portion by applying the V-shaped groove and the chamfered portion of the floor material of Production Example 2 over the entire surface and wiping.

Comparative Example 1
A coating layer was formed in the same manner as in Example 1 except that a commercially available water-based urethane paint was used as the water-based paint.

Test example 1
About the coating layer formed in the Example and the comparative example, 1) Water resistance, 2) Moisture and heat resistance, 3) Thinner resistance, 4) Acid resistance, 5) Alkali resistance, 6) Adhesion test of cello tape (registered trademark) 7) Weather resistance and 8) Ammonia resistance test were examined respectively. As a result, Example 1 passed in all items, whereas Comparative Example 1 failed in all items.

  Each test method was performed as follows.

  1) Water resistance: A cup water permeability test was conducted. The test specimen was contacted with water droplets for 144 hours, and the presence or absence of changes in the appearance of the test specimen was confirmed after removing the water droplets. Those whose appearance change was not recognized were accepted.

  2) Moist heat resistance: JAS wet heat test was carried out. After fixing the test body horizontally, boiling water was dropped on the surface of the test body, and a 1 L capacity aluminum container containing 0.5 L of boiling water was left on it for 20 minutes, and then rubbed with a dry cloth. It was left as it was for 24 hours. The presence or absence of appearance changes after 24 hours was confirmed. Those whose appearance change was not recognized were accepted.

  3) Thinner resistance: The presence or absence of a change in appearance after leaving for 4 hours after dropping the thinner onto the groove surface of the test specimen was confirmed. Those whose appearance change was not recognized were accepted.

  4) Acid resistance: It was confirmed whether or not the appearance changed after dropping for 4 hours after dropping a 10% hydrochloric acid aqueous solution onto the groove surface of the test specimen. Those whose appearance change was not recognized were accepted.

  5) Alkali resistance: 10% sodium hydroxide aqueous solution was dropped on the surface of the groove of the test specimen, and the presence or absence of appearance change after standing for 4 hours was confirmed. Those whose appearance change was not recognized were accepted.

  6) Adhesion test of cellotape (registered trademark): Cellotape (registered trademark) (manufactured by Nichiban) was pressure-bonded to the coating film, peeled off in the vertical direction, and one that hardly peeled off was regarded as acceptable.

  7) Weather resistance: After irradiating the sunshine fade meter for 500 hours, the presence or absence of appearance change was observed. Those whose appearance change was not recognized were accepted.

  8) Ammonia resistance test: An 18% aqueous ammonia solution (pseudopet urine) was dropped on the surface of the groove of the test specimen, and the presence or absence of changes in appearance after standing for 24 hours was confirmed. Those whose appearance change was not recognized were accepted.

Claims (6)

It consists of a woody material, a synthetic resin backer layer, a decorative sheet and a protective layer, and
Both the synthetic resin backer layer and the wooden material of the laminate formed by sequentially laminating 1) a synthetic resin backer layer containing amorphous polyethylene terephthalate having a thickness of 200 μm or more and 2) a decorative sheet on the wood material It is a method for protecting a floor surface in which a protective layer using an aqueous paint made of an aqueous composition containing an acrylic urethane resin is formed on the exposed surface,
(1) The aqueous paint comprises an aqueous composition containing an acrylic urethane-based resin obtained by mixing a keto group-containing acrylic resin and a hydrazide group-containing urethane resin,
(2) The synthetic resin backer layer has a single layer or a layer structure of two or more layers,
(3) a) in the case of a single layer or b) in the case of two or more layers, at least the uppermost layer of the synthetic resin layer contains amorphous polyethylene terephthalate,
(4) The floor material includes A) a groove reaching the wooden material from the decorative sheet side through the synthetic resin backer layer, and B) a chamfered portion where both the synthetic resin and the wooden material are exposed. At least one is formed,
(5) A method of forming a coating layer on the groove portion and the chamfered portion by applying the surface and the chamfered portion exposed in the groove to the whole surface with the water-based paint and wiping. The method of claim 1, wherein the aqueous composition further comprises a curing agent. The method according to claim 1 or 2, wherein the aqueous composition further contains silicon. The method according to claim 1, wherein the aqueous paint is in the form of an emulsion. The method according to any one of claims 1 to 4, wherein the surface on which both the synthetic resin backer layer and the wood material are exposed is a region including a boundary line where the synthetic resin backer layer and the wood material are in contact with each other. The surface where both the synthetic resin backer layer and the wood material are exposed,
A) A groove reaching the wood material through the synthetic resin backer layer from the decorative sheet side, and
B) A chamfered portion where both the synthetic resin backer layer and the wood material are exposed,
The method according to any one of claims 1 to 5, wherein the floor material on which at least one of the above is formed is a surface exposed to the groove and a chamfered portion.

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