JP4286949B2 - Decorative paper with abrasion resistance - Google Patents

Decorative paper with abrasion resistance Download PDF

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Publication number
JP4286949B2
JP4286949B2 JP03965999A JP3965999A JP4286949B2 JP 4286949 B2 JP4286949 B2 JP 4286949B2 JP 03965999 A JP03965999 A JP 03965999A JP 3965999 A JP3965999 A JP 3965999A JP 4286949 B2 JP4286949 B2 JP 4286949B2
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Prior art keywords
curable resin
ionizing radiation
layer
resin
radiation curable
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JP2000238196A (en
Inventor
和保 河野
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大日本印刷株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to interior paper such as floors, walls, ceilings, etc. of buildings, surface decoration materials such as furniture and various cabinets, surface decorative materials for joinery, decorative paper used as surface decorative paper used for vehicle interiors, etc. In particular, the present invention relates to a decorative paper used for applications requiring surface wear resistance and weather resistance.
[0002]
[Prior art]
Conventionally, as a decorative sheet used for decorative surfaces such as interiors of buildings, furniture, cabinets, etc., a printing ink layer such as a pattern layer or a solid printing layer is provided on one side of a base sheet, and this ink layer is protected. For this purpose, a thermosetting urethane resin or the like is applied as a top coat layer, and is thermally dried and thermally cured to form a thermosetting resin layer, or an ionizing radiation curable resin is applied and irradiated with ionizing radiation. Then, there is a method of curing the coating film and forming a cured ionizing radiation curable resin layer on the surface.
In particular, an ionizing radiation curable resin layer cured using an ionizing radiation curable resin having a high crosslink density has excellent physical properties such as surface hardness, chemical resistance, and contamination resistance.
[0003]
By using a hard resin as the binder resin as described above, the wear resistance is certainly improved.
Therefore, in the case of a decorative material using a hard base material such as a melamine decorative board, the flexibility of the surface resin layer is not a problem, so a hard resin is used on the surface as a method of improving the wear resistance. To do is an effective means.
However, when using a flexible base material such as thin paper or plastic sheet as the base material, increasing the crosslink density of the resin impairs the flexibility of the resin layer, and impacts the surface resin layer. This causes problems such as cracking and the tendency for cracks to occur.
Therefore, even if it is attempted to improve the wear resistance by increasing the cross-linking density of the surface resin, there is a limit when flexibility is required.
[0004]
Therefore, a method of adding an inorganic material to the resin layer has been conventionally performed as a method for improving the wear resistance without reducing the flexibility of the resin layer.
For example, JP-A-60-23642 discloses silica (SiO 2) having an average particle size of 1 to 50 μm, which is used as an abrasive for sandblasting or brush polishing.2 ) And alumina (Al2 OThree It is disclosed that a surface resin layer is formed using a paint in which a natural glass powder containing) as a main component is blended.
The surface protective layer formed by the coating material had higher hardness and flexibility than conventional products, and exhibited physical properties excellent in wear resistance and scratch resistance.
[0005]
In the case of a transfer sheet, the ionizing radiation curable resin for forming the surface protective layer has an average particle diameter of 1 to 5 μm for the purpose of improving the wear resistance and scratch resistance of the surface of the transferred material after transfer. It is disclosed that 10 to 30 parts by weight of alumina powder is added to 100 parts by weight of ionizing radiation curable resin, and a protective layer of a transfer sheet is formed using this alumina-containing ionizing radiation curable resin.
[0006]
[Problems to be solved by the invention]
However, when a decorative layer for a decorative sheet is formed using a paint to which an inorganic filler such as alumina or natural glass powder is added, the wear resistance of the decorative material is improved more than that without adding an inorganic material. When an impregnating base material such as paper is used as a sheet, there is a problem that a coating film required by impregnating paper with a coating solution cannot be obtained.
[0007]
That is, in order to obtain an ionizing radiation curable resin layer having high hardness without impairing flexibility, it is necessary to increase the crosslinking density of the ionizing radiation curable resin, and a polyfunctional ionizing radiation curable resin having a small molecular weight is used. There is a need.
However, since the ionizing radiation curable resin having a low molecular weight has a low viscosity, it was impregnated into the paper when coated on the paper, and a coating film having a required thickness on the surface of the paper could not be obtained.
In addition, when ionizing radiation curable resin added with spherical alumina is applied, the ionizing radiation curable resin impregnating the paper with ionizing radiation curable resin reduces the amount of ionizing radiation curable resin holding spherical alumina, and spherical alumina is ionizing radiation cured. The resin layer is not sufficiently retained, and sufficient wear resistance cannot be exhibited.
[0008]
Therefore, when an ionizing radiation curable resin layer is formed on the surface using an impregnating substrate such as paper, it is necessary to thicken the ionizing radiation curable resin layer in order to stably obtain predetermined physical properties.
However, increasing the application amount of the ionizing radiation curable resin also increases the amount of expensive spherical alumina used and increases the production cost.
Further, when the application amount of the ionizing radiation curable resin is increased, the curling of the decorative paper becomes intense due to the shrinkage that occurs when the ionizing radiation curable resin is cured.
Therefore, in the post-processing of the decorative paper, workability is deteriorated, leading to an increase in production cost, which becomes a big problem.
[0009]
Furthermore, when the substrate is coated by a gravure roll coating method using a coating liquid to which an inorganic filler is added, the inorganic filler alumina or natural glass powder has a polygonal shape with sharp corners. The blade was worn or damaged, which was a serious problem in processing.
Furthermore, the coating film formed using the coating liquid which added the hard and the sharp-pointed polygonal powder had a bad touch feeling, and could not be utilized for what attaches importance to a touch. Further, when used as a flooring material, there is a problem that the object is worn when directly contacting the decorative material such as footwear.
[0010]
[Means for Solving the Problems]
  In order to solve the above problems, the decorative paper was configured as follows. On the fibrous base material, a pattern layer, a sealer layer, and a cured ionizing radiation curable resin are laminated in this order, and the sealer layer is
With butyral resinTwo-component curing typeA decorative paper comprising a resin composition containing a blend resin of urethane resin as a binder and further containing an aliphatic isocyanateWas. Also, with the butyral resinTwo-component curing typeA decorative paper characterized in that the thickness of the sealer layer made of a blend resin of urethane resin is 2 to 5 μmWas. Further, the ionizing radiation curable resin layer contains 15 to 20% by weight of alumina, and the coating amount is 10 to 22 g / in as the resin composition amount after curing.m 2 A decorative paper characterized by The sealer layer suppresses the penetration of the ionizing radiation curable resin composition into the impregnating substrate when the ionizing radiation curable resin composition is applied to the impregnating substrate such as a fibrous substrate. It means a coating film formed for the purpose.
[0011]
  That is, when a decorative paper is produced by laminating a pattern layer, a sealer layer, and a cured ionizing radiation curable resin layer on the surface of an impregnable fibrous base material, butyral resin and urethane are used as binder resins for the sealer layer. By using a resin blend resin, the coating amount of the ionizing radiation curable resin containing alumina is 10 to 22 g / m. 2 The curling problem of the decorative paper can be solved. Moreover, the addition amount of the expensive spherical alumina to the ionizing radiation curable resin can be reduced to 15 to 20% by weight, and the manufacturing cost can be reduced. And the decorative paper which was excellent in abrasion resistance and a weather resistance was obtained by making decorative paper into the above-mentioned composition..
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of the decorative paper of the present invention.
FIG. 2 is another embodiment of the decorative paper of the present invention, and is a schematic cross-sectional view of the decorative paper when spherical ion is contained in the ionizing radiation curable resin layer.
FIG. 3 is an explanatory diagram when producing the decorative paper of the present invention.
FIG. 4 is an explanatory view when producing decorative paper containing spherical alumina in an ionizing radiation curable resin layer.
FIG. 5 is an explanatory diagram when producing decorative paper according to Example 1, and FIG. 6 is an explanatory diagram when producing decorative paper according to Example 5.
FIG. 7 is an explanatory diagram when a decorative paper is produced according to Comparative Example 1. FIG.
[0013]
As shown in FIG. 1, the decorative paper of the present invention basically comprises an impregnated fibrous base material 11, a picture layer 12, a sealer layer 13, and a cured ionizing radiation curable resin layer 14. .
Moreover, as shown in FIG. 2, the spherical ionized alumina 15 is contained in the cured ionizing radiation curable resin layer 14, and the wear resistance is further improved.
That is, the feature of the present invention is that a pattern layer 12 is formed on a permeable fibrous base material 11 such as paper by printing or the like, and then a sealer layer 13 is formed on the pattern layer 12. When a cured ionizing radiation curable resin is applied, the amount of the ionizing radiation curable resin applied is reduced by suppressing penetration into the fibrous base material 11, and the ionizing radiation curable resin is cured. This prevents the decorative paper from curling.
In particular, by forming a thin ionizing radiation curable resin layer containing spherical alumina, it is possible to prevent the decorative paper from curling and to produce a decorative paper excellent in abrasion resistance and weather resistance.
In addition, by thinning the ionizing radiation curable resin layer containing spherical alumina, the amount of expensive spherical alumina used can be reduced, and the production cost can be reduced.
[0014]
In order to increase the hardness of the ionizing radiation curable resin layer that forms the surface protective layer without impairing flexibility, when the ionizing radiation curable resin layer is cured by irradiation with ionizing radiation, the crosslinking density of the ionizing radiation curable resin is increased. It is necessary to use a polyfunctional ionizing radiation curable resin having a small molecular weight.
However, since the ionizing radiation curable resin having a low molecular weight has a low viscosity, when it is applied to a permeable base material such as paper, it penetrates the base material and has a necessary thickness on the surface of the base material. It was difficult to form a coating film.
Therefore, in order to form an ionizing radiation curable resin layer having wear resistance, it was necessary to increase the coating amount. However, if the ionizing radiation curable resin is increased, the ionizing radiation curable resin is cured. Due to the shrinkage that occurs, the curling of the decorative paper becomes intense, and this has been a serious problem in that workability is deteriorated in post-processing of the decorative paper.
[0015]
Therefore, in the present invention, an acrylic resin, for the purpose of suppressing penetration of uncured ionizing radiation curable resin into the fibrous base material after forming the pattern layer on the permeable fibrous base material, Alternatively, by forming a sealer layer using a blend resin of a butyral resin and a urethane resin, a necessary coating film can be formed even with an ionizing radiation curable resin having a low molecular weight and a low viscosity.
Furthermore, when forming the ionizing radiation curable resin layer containing spherical alumina, the content of spherical alumina is 15 to 20% by weight, and the coating amount is 10 to 22 g / m.2By forming in this range, the curling of the decorative paper is reduced, the productivity is improved, and the production cost can be reduced.
[0016]
In addition, by using scale-like particles such as scale-like alumina, titanium dioxide-coated mica, and fish scale foil instead of spherical alumina as a filler, the coating liquid can penetrate into a permeable substrate such as paper. Therefore, it is possible to form a coating film made of an ionizing radiation curable resin containing a scaly filler and to produce a decorative paper excellent in abrasion resistance.
[0017]
Below, the manufacturing method of the decorative paper of this invention is demonstrated.
First, as shown in FIG. 3 (a), as the fibrous base material 11, using impregnated paper or synthetic paper, a solid print layer 12a and a wood grain pattern are formed on the fibrous base material 11 by gravure printing or the like. The pattern layer 12 is formed.
Next, as shown in FIG. 3B, in order to reduce the amount of ionizing radiation curable resin penetrating into the fibrous base material 11, a two-component curable urethane is provided on the pattern layer 12 side of the fibrous base material 11. The sealer layer 13 is formed with a thickness of 2 to 5 μm using a coating liquid made of a blend resin of a resin and a butyral resin.
Further, the sealer layer 13 may be formed with a thickness of 30 to 150 μm by a coating solution using an acrylic resin.
[0018]
Next, as shown in FIG. 3C, a polyfunctional ionizing radiation curable resin having a small molecular weight is applied to form an uncured ionizing radiation curable resin layer 14a.
In the present invention, even the ionizing radiation curable resin having a low viscosity and penetrating properties can suppress the penetration into the fibrous base material by the sealer layer 13, so that the ionizing radiation curable resin is uncured with a relatively small coating amount. Layer 14a can be formed.
Next, as shown in FIG. 3 (d), the uncured ionizing radiation curable resin layer 14a is irradiated with ionizing radiation 16 such as an electron beam or ultraviolet rays to crosslink and cure the ionizing radiation curable resin, A decorative paper 1 having an ionizing radiation curable resin layer 14 cured on the surface is prepared.
The resulting decorative paper 1 has a high crosslink density and a high hardness ionizing radiation curable resin layer as a surface protective layer, and therefore has flexibility and excellent wear resistance.
[0019]
Further, by using a coating liquid obtained by adding spherical alumina to an ionizing radiation curable resin, an ionizing radiation curable resin layer containing spherical alumina is formed on the surface, thereby obtaining a decorative paper having better wear resistance. be able to.
Also in this case, as described above, as shown in FIGS. 4A and 4B, after the solid print layer 12a and the pattern layer 12 are printed on the fibrous base material 11, the sealer layer 13 is formed.
[0020]
Next, a coating liquid is prepared by adding 15 to 20% by weight of spherical alumina having an average particle diameter of 10 to 30 μm to the ionizing radiation curable resin, and using this coating liquid, as shown in FIG. The uncured ionizing radiation curable resin layer 14 a containing the spherical alumina 15 is applied to the sealer layer 13.
In this case, since the uncured ionizing radiation curable resin is prevented from penetrating into the fibrous base material by the sealer layer 13, the spherical alumina 15 is maintained in the uncured ionizing radiation curable resin layer 14a. To do.
[0021]
Next, as shown in FIG. 5 (d), an uncured ionizing radiation curable resin layer 14a containing spherical alumina 15 is irradiated with ionizing radiation 16 such as an electron beam or ultraviolet rays, so that the ionizing radiation curable resin is obtained. The decorative paper 1 is produced by crosslinking and curing to form a cured ionizing radiation curable resin layer 14 containing spherical alumina 15 on the surface.
The obtained decorative paper 1 has an ionizing radiation curable resin layer having a high crosslinking density formed as a surface protective layer, and the spherical alumina is firmly fixed to the ionizing radiation curable resin. Abrasion is fully exhibited, flexible, and extremely excellent in wear resistance.
[0022]
The cured ionizing radiation curable resin layer 14 containing the spherical alumina 15 contains 15 to 20% by weight of spherical alumina having an average particle size of 10 to 30 μm, and the coating amount is 10 to 22 g / m.2Therefore, conventionally, the content of spherical alumina and the amount of coating thereof are reduced.
That is, in the past, it was necessary to increase the coating amount in consideration of the amount of ionizing radiation curable resin impregnated into the paper, so the addition amount of spherical alumina was 21 to 25% by weight and the coating amount was 23 to 30 g. / M2However, in the present invention, it was possible to reduce expensive spherical alumina by about 20% and the coating amount by 22 to 25%.
As the spherical alumina used in the present invention, those having an average particle diameter of 5 to 50 μm can be used. In the present invention, the coating amount is 18 to 22 g / m.2Since the coating film is relatively thin, the average particle diameter of the spherical alumina is preferably 10 to 30 μm.
[0023]
In the present invention, when an ionizing radiation curable resin is coated on a permeable fibrous base material, a flaky filler may be used as a filler in order to suppress impregnation of the fibrous base material. .
The coating liquid in which the flaky filler is dispersed in the ionizing radiation curable resin is flat when the permeable fibrous base material is coated. Therefore, the flaky filler has a void in the fibrous base material. It closes and the penetration of the coating liquid into the fibrous base material is suppressed.
As the flaky filler, flaky alumina, titanium dioxide-coated mica, fish scale foil, natural pearl foil, metal foil piece or the like is used. The average particle size is preferably 0.1 to 5 μm.
[0024]
The ionizing radiation curable resin used in the present invention is one that is applied in an uncured state and then irradiated with ionizing radiation such as an electron beam or ultraviolet ray to cure the coating film. The physical properties of the film change.
That is, the higher the crosslinking density, the higher the hardness of the cured coating film and the higher the wear resistance, but the lower the flexibility. Therefore, in order to obtain a surface coating film that is flexible and excellent in wear resistance, it is necessary to add a filler such as spherical alumina to the ionizing radiation curable resin and improve the wear resistance by the filler.
[0025]
When a coating film is formed by adding a filler such as spherical alumina to an ionizing radiation curable resin, it is common to use an electron beam having a high permeability to the coating film as the ionizing radiation.
When the spherical alumina particles become large in the ultraviolet ray, the ultraviolet ray is prevented from being transmitted, so that a sufficient irradiation amount to the ultraviolet curable resin cannot be obtained, and the ultraviolet curable resin is not sufficiently cured.
Further, in order to sufficiently cure the ultraviolet curable resin, the ultraviolet irradiation time becomes too long, so that there are practical problems such as a reduction in production efficiency.
[0026]
In the present invention, when an ionizing radiation curable resin is coated on a permeable fibrous base material, a sealer layer is formed in order to suppress the penetration into the fibrous base material. A mixture of urethane resin and butyral resin or acrylic resin was selected.
A two-part curable urethane resin is used as the urethane resin, and a polyvinyl butyral resin is used as the butyral resin.
Even if an uncured ionizing radiation curable resin is applied on the coating film by forming a coating film made of a mixture of a two-component curable urethane resin and a polyvinyl butyral resin as the sealer layer, the coating film is not ionizing radiation. Since it is resistant to the constituent components (monomers and the like) of the curable resin and does not dissolve or break, the penetration of the ionizing radiation curable resin into the fibrous base material is suppressed.
[0027]
Therefore, even if the thickness of the coating film is relatively thin as 2 to 5 μm, the penetration of the ionizing radiation curable resin into the fibrous base material is suppressed.
In addition, polyvinyl butyral resin has strong adhesive strength to the resin of the pattern layer and the cured ionizing radiation curable resin, and since there is no delamination of the ink, etc., even in post-processing of decorative paper, Trouble is not caused by bending.
[0028]
As the two-component curable urethane resin used in the present invention, a urethane resin having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) is used.
As the polyol, one having 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.
As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used.
For example, aromatic or alicyclic aromatic isocyanates such as 2,4 tolylene diisocyanate, xylene diisocyanate, 4,4 diphenylmethane diisocyanate, or hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Group isocyanates are used.
Alternatively, these isocyanate adducts or multimers may be used. For example, there are adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like.
[0029]
Further, the sealer layer 13 may be formed by applying a coating liquid using an acrylic resin.
In this case, the coating film of the sealer layer is relatively thick and is formed with a thickness of 30 to 150 μm.
By thickening the sealer layer made of an acrylic resin, there is no penetration of the uncured ionizing radiation curable resin into the fibrous base material, so the application amount of the ionizing radiation curable resin is 10 to 15 g / m.2Even if it is reduced to a small extent, a surface protective layer having excellent wear resistance can be formed.
That is, by thickening the sealer layer and preventing the penetration of uncured ionizing radiation curable resin into the fibrous base material, the ionizing radiation curable resin layer containing expensive spherical alumina can be made thin. Thus, the production cost can be reduced.
[0030]
Examples of the acrylic resin used in the sealer layer include polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene (meth) acrylate. Acrylic resin such as copolymer (however, (meth) acrylate means acrylate or methacrylate) alone or a mixture of two or more, or methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylate alkyl esters such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutylethyl (meth) acrylate, 2- Dorokishi 3-phenoxypropyl (meth) having a hydroxyl group in the molecule acrylate (meth) may be used an acrylic polyol obtained by copolymerizing acrylic acid esters.
[0031]
The ionizing radiation curable resin used in the present invention is a composition in which prepolymers (including so-called oligomers) having a polymerized unsaturated bond or a cationically polymerizable functional group in the molecule and / or monomers are appropriately mixed and ionized. Those that can be cured by radiation are used.
Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually an electron beam or an ultraviolet ray is used.
[0032]
Specifically, as the ionizing radiation curable resin, a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, a cationically polymerizable functional group such as an epoxy group, or a thiol group is included in the molecule. It consists of a monomer having two or more or a prepolymer.
These monomers or prepolymers are used alone or in combination.
Here, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and hereinafter (meth) is used in the same meaning.
[0033]
Examples of prepolymers having radically polymerizable unsaturated groups include polyester (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, polyether acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth). Acrylate or the like can be used.
The molecular weight is usually about 250 to 100,000.
[0034]
Examples of polyfunctional monomers having radically polymerizable unsaturated groups include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
[0035]
Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, dipentaerythritol tetrathioglycolate, and the like.
[0036]
When the ionizing radiation curable resin is cured with ultraviolet rays or visible light, a photopolymerization initiator is added to the ionizing radiation curable resin. In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or in combination as a photopolymerization initiator.
In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
In addition, the addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
[0037]
Various additives may be added to the ionizing radiation curable resin as necessary. These additives include, for example, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, thermoplastic resin such as acrylic resin, cellulosic resin, etc., and constitution comprising fine powder such as calcium carbonate, barium sulfate, silica, alumina, etc. There are colorants such as pigments (fillers), dyes, and pigments.
[0038]
As a coating method of ionizing radiation curable resin, gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, dip coating, solid coating by silk screen coating, wire bar coating, comma coating, Spray coating, float coating, pouring coating, brush coating, spray coating and the like can be used. Of these, gravure coating is preferred.
[0039]
As the ionizing radiation irradiation apparatus for curing the ionizing radiation curable resin, an ultraviolet irradiation apparatus or an electron beam irradiation apparatus is used.
As the ultraviolet irradiation device, for example, a light source such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, or the like is used. As a wavelength of ultraviolet rays, a wavelength region of 190 to 380 nm is usually mainly used.
As the electron beam irradiation device, various electron beam accelerators such as a Cockloftwald type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used.
[0040]
And when irradiating an electron beam, it irradiates with acceleration voltage 100-1000 KeV, Preferably it is 100-300 KeV, and as an absorbed dose, it is about 1-300 kGy (kilo gray) normally. When the absorbed dose is less than 1 kGy, the coating film is insufficiently cured, and when the irradiation dose exceeds 300 kGy, the cured coating film and the fibrous base material are yellowed or damaged.
In the case of ultraviolet irradiation, the irradiation amount is 50 to 1000 mJ / cm.2The range of is preferable.
UV irradiation amount is 50mJ / cm2If it is less than 1, the curing of the coating film becomes insufficient, and the irradiation amount is 1000 mJ / cm.2If it exceeds 1, the cured coating will turn yellow.
In addition, as a method of irradiating with ionizing radiation, first, ultraviolet rays are irradiated to cure the ionizing radiation curable resin at least to the extent that the surface is dry to the touch, and then the electron beam is irradiated to completely cure the coating film. There is also a way to make it.
[0041]
As the permeable fibrous base material used in the present invention, sheet-like materials such as paper, synthetic paper, and nonwoven fabric are used.
The paper used as the fibrous base material is thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper original paper, high-quality paper, coat, and so on. Examples include paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, and Japanese paper.
In addition, paper-like sheets include glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, and other inorganic fiber sheets, and synthetic resin fibers such as polyester, vinylon, polyethylene, and polypropylene. A non-woven fabric or woven fabric made of is used.
[0042]
A pattern layer is formed on the fibrous base material by printing or the like. The pattern layer can be formed on one side or both sides of the substrate. Moreover, before providing a pattern layer, a solid printing layer may be provided in the base-material surface.
As the pattern layer, there are a printing pattern by printing, an embossing pattern by embossing, a concavo-convex pattern by hairline processing, etc., and further, a colored ink is filled into the concave part of the concavo-convex pattern by a known wiping method to form a pattern layer You can also.
Examples of the printed pattern layer include a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, characters, symbols, various abstract patterns, and a full-color printing.
The concealing layer for full surface solid printing may be omitted depending on the surface state of the adherend to which the decorative paper is to be attached.
[0043]
Ink for pattern printing varies depending on the material and form of the substrate, but in general, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, nitrified cotton, cellulose acetate, vinyl chloride, vinyl acetate, vinyl chloride, A vinyl acetate copolymer, polyvinyl butyral, urethane resin, acrylic resin, polyester resin, etc., or a mixture of two or more kinds of resins is used as a vehicle, and this is combined with colorants such as ordinary pigments and dyes, extender pigments, curing An ink composed of an agent, an additive, a solvent and the like is used.
[0044]
As coloring agents, inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, carbon black, and organic pigments such as isoindolinone, banzai yellow A, quinacridone, permanent red 4R, phthalocyanine blue, etc. Alternatively, metallic pigments made of foil powder such as dye, aluminum, brass, pearlescent pigment made of foil powder such as titanium dioxide-coated mica, basic zinc carbonate, etc. are used.
Moreover, you may add an inorganic filler as needed, and powders, such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide), etc. are mentioned. The addition amount is usually 5 to 60% by weight.
[0045]
As the printing of the pattern, ordinary printing methods such as gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, and inkjet printing can be used.
Alternatively, a separate pattern may be formed once on the releasable sheet to create a transfer sheet, and the pattern print may be transferred by a transfer printing method from the obtained transfer sheet.
[0046]
Instead of the printed pattern, a metal film such as aluminum, chromium, gold, silver, copper or the like may be formed on the base material by vacuum evaporation, sputtering, or the like to form a metal thin film on the entire surface or part of the substrate to form a picture layer.
Moreover, as embossing, it heats and softens a base material sheet | seat, pressurizes and shapes with an embossing plate, forms by cooling and solidifying, A well-known single wafer or a rotary embossing machine is used.
Examples of the uneven shape include a wood grain conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain texture, a hairline, and a striated groove.
[0047]
An easy adhesion layer may be provided on the pattern layer in order to improve the adhesion between the printing ink and the ionizing radiation curable resin layer.
Easy adhesion layer (also called primer layer or anchor layer) is made of acrylic resin, urethane resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, polyurethane resin, chlorinated polyethylene, chlorinated polypropylene, etc. A coating solution dissolved in a solvent is used, and those using a mixture of a two-component curable urethane resin and a butyral resin are particularly preferable.
A coating solution obtained by dissolving the resin in a solvent is applied and dried by a known method to form an easy-adhesion layer.
[0048]
The decorative paper of the present invention can be used for various applications by being laminated on various adherends and subjected to a predetermined molding process or the like.
For example, interior decorations of buildings such as walls, ceilings, floors, surface decorations of furniture such as window frames, doors, handrails, surface decorations of furniture or cabinets of light electric / OA equipment, interiors of vehicles such as automobiles and trains, aircraft It can be used for interior decoration and window glass makeup.
Therefore, when the decorative paper cannot be directly adhered to the material or the like, it is adhered to the adherend through an appropriate easy adhesion layer or adhesive layer.
However, when the decorative paper can be adhered to the adherend by heat fusion or the like, the easy adhesion layer or the adhesive layer may be omitted.
[0049]
As the adherend, plate materials such as flat plates and curved plates of various materials, sheets (or films), or various three-dimensional articles (molded products) are targeted.
For example, the decorative paper of the present invention can be bonded to a molded product having a curved surface such as an injection molded product.
[0050]
The material used for any three-dimensional object, plate or sheet (film) as the adherend is a wood material such as wood fiberboard such as wood veneer, wood plywood, particle board, medium density fiberboard (MDF), etc. , Metals such as iron and aluminum, acrylic resin, polycarbonate resin, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester resin, polystyrene, polyolefin resin, ABS, phenol resin, polyvinyl chloride, cellulose resin, rubber, etc. Resin.
[0051]
【Example】
Below, based on an Example, this invention is demonstrated in more detail.
Example 1
First, as the fibrous base material 11, a basis weight of 50 g / m impregnated with an acrylic resin latex2Using solid impregnated paper (manufactured by Kojin Co., Ltd.), printing solid print and wood grain pattern by gravure printing, as shown in FIG. 5 (a), solid printing with a thickness of 2 μm on the fibrous base material 11 Layer 12a and pattern layer 12 were formed.
Next, as shown in FIG. 5 (b), a two-component curable gravure ink (a gravure ink made of a blend resin of a two-component curable urethane resin and a butyral resin is applied to the fibrous base material 11 on the pattern layer 12 side. Coated with a polyisocyanate: manufactured by Showa Ink Industries Co., Ltd.) by gravure printing and dried to a film thickness of 4 g / m2The sealer layer 13 was formed.
[0052]
Next, using the following electron beam curable resin composition (A) (manufactured by Sanyo Chemical Industries, Ltd.), as shown in FIG. The sealer layer 13 surface is coated with a coating amount of 20 g / m.2 An uncured electron beam curable resin layer 14b containing spherical alumina 15 (as a dry matter) was formed.
[0053]
Composition of electron beam curable resin composition (A)
・ Bisphenol A ethylene oxide-modified diacrylate 50 parts by weight
・ 20 parts by weight of trimethylolpropane-modified triacrylate
・ Spherical alumina (average particle size 25μ) 17 parts by weight
・ Organic silica 12 parts by weight
・ Both-end methacrylate-modified silicone 1 part by weight
[0054]
Next, as shown in FIG. 5D, the absorbed dose becomes 50 kGy (kilo gray) at an acceleration voltage of 175 keV using the electron beam irradiation device on the uncured electron beam curable resin layer 14b. Thus, the electron beam 16a was irradiated, the electron beam curable resin was completely cured to form a cured electron beam curable resin layer 14c containing the spherical alumina 15, and the decorative paper 1 was produced.
[0055]
(Example 2)
Basis weight 60 g / m impregnated with acrylic resin latex as fibrous base material 112As shown in FIG. 5 (a), a solid printing layer 12a having a thickness of 2 μm is formed on the fibrous base material 11 by gravure printing in the same manner as in Example 1 using the impregnated paper (manufactured by Kojin Co., Ltd.). The pattern layer 12 was formed.
Next, gravure printing was performed with an acrylic ink (a two-part curable acrylic ink composed of a copolymer of ethyl methacrylate and hydroxyethyl ethyl methacrylate and an aliphatic isocyanate) using an oblique engraving plate with a plate depth of 150 μm. As shown in FIG. 5B, the coating amount is 70 g / m.2The sealer layer 13 was formed.
[0056]
Next, using the following electron beam curable resin composition (B) (manufactured by Sanyo Chemical Industries Co., Ltd.), as shown in FIG. 11 sealer layer 13 surface coated, application amount 10g / m2 An uncured electron beam curable resin layer 14b containing spherical alumina 15 (as a dry matter) was formed.
[0057]
Composition of electron beam curable resin composition (B)
・ 59 parts by weight of bisphenol A ethylene oxide-modified diacrylate
・ 20 parts by weight of trimethylolpropane-modified triacrylate
・ Spherical alumina (average particle size 25μ) 20 parts by weight
・ Both-end methacrylate-modified silicone 1 part by weight
[0058]
Next, as shown in FIG. 5D, the absorbed dose becomes 50 kGy (kilo gray) at an acceleration voltage of 175 keV using the electron beam irradiation device on the uncured electron beam curable resin layer 14b. Thus, the electron beam 16a was irradiated, the electron beam curable resin was completely cured to form a cured electron beam curable resin layer 14c containing the spherical alumina 15, and the decorative paper 1 was produced.
[0059]
(Example 3)
Basis weight 60 g / m impregnated with acrylic resin latex as fibrous base material 112In the same manner as in Example 1, as shown in FIG. 6 (a), a solid print layer 12a having a thickness of 2 μm is formed on the fibrous base material 11 by gravure printing. The pattern layer 12 was formed.
Next, using a raised plate engraved with a pattern synchronized with the printed pattern (a plate engraved plate with a raised plate depth of 100 μm and a bank width of 15 μm), an acrylic raised ink (ethyl methacrylate and hydroxyethyl ethyl methacrylate) The raised portion was gravure-printed in a pattern with a two-component curable acrylic ink comprising a polymer and an aliphatic isocyanate.
Thereafter, it is dried with hot air, and as shown in FIG. 6B, the coating amount is 100 g / m.2The raised sealer layer 13a was formed.
[0060]
Next, using the following resin composition (B) (manufactured by Sanyo Kasei Kogyo Co., Ltd.) as an electron beam curable resin, as shown in FIG. Coating on the surface of the raised sealer layer 13a of the substrate 11, the coating amount 15g / m2 An uncured electron beam curable resin layer 14b containing spherical alumina 15 (as a dry matter) was formed.
[0061]
Composition of electron beam curable resin composition (B)
・ 59 parts by weight of bisphenol A ethylene oxide-modified diacrylate
・ 20 parts by weight of trimethylolpropane-modified triacrylate
・ Spherical alumina (average particle size 25μ) 20 parts by weight
・ Both-end methacrylate-modified silicone 1 part by weight
[0062]
Next, as shown in FIG. 6 (d), the absorbed dose becomes 50 kGy (kilo gray) at an acceleration voltage of 175 keV on the uncured electron beam curable resin layer 14b using an electron beam irradiation apparatus. Thus, the electron beam 16a was irradiated, the electron beam curable resin was completely cured to form a cured electron beam curable resin layer 14c containing the spherical alumina 15, and the decorative paper 1 was produced.
[0063]
(Comparative Example 1)
As in Example 1, as shown in FIG. 7, the fibrous base material 11 (basis weight 50 g / m2A solid printed layer 12a and a pattern layer 12 having a thickness of 2 μm were formed.
Next, without providing the sealer layer 13, the electron beam curable resin composition (A) was applied onto the pattern layer 12 of the fibrous base material 11 in the same manner as in Example 1, and FIG. ), An uncured electron beam curable resin layer 14b containing spherical alumina 15 was formed.
Next, the uncured electron beam curable resin layer 14b is irradiated with an electron beam to cure the coating film, and as shown in FIG. 7C, a cured electron beam curable resin layer containing spherical alumina 15 is obtained. A decorative paper la having 14c was prepared.
[0064]
(Comparative Example 2)
Basis weight 60 g / m as the fibrous base material 112In the same manner as in Example 1, a solid print layer 12a and a pattern layer 12 having a thickness of 2 μm were formed using the impregnated paper.
Next, the following electron beam curable resin composition (C) is applied to the surface of the pattern layer 12 of the fibrous base material 11 by the gravure roll coating method in the same manner as in Example 1, and the coating film is electronically coated. As shown in FIG. 7C, a decorative paper having a cured electron beam curable resin layer 14c containing spherical alumina 15 was produced.
[0065]
Composition of electron beam curable resin composition (C)
・ Bisphenol A ethylene oxide-modified diacrylate 50 parts by weight
・ 20 parts by weight of trimethylolpropane-modified triacrylate
・ Spherical alumina (average particle size 25μ) 20 parts by weight
・ Organic silica 9 parts by weight
・ Both-end methacrylate-modified silicone 1 part by weight
[0066]
(Comparative Example 3)
Similar to Example 2, fibrous base material 11 (basis weight 60 g / m2A solid printed layer 12a and a pattern layer 12 having a thickness of 2 μm were formed.
Next, without providing the sealer layer 13, the electron beam curable resin composition (B) was applied onto the pattern layer 12 of the fibrous base material 11 in the same manner as in Example 2 and irradiated with an electron beam. As shown in FIG. 7C, a decorative paper 1a having a cured electron beam curable resin layer 14c containing spherical alumina 15 was produced.
[0067]
(Comparative Example 4)
Similar to Example 3, fibrous base material 11 (basis weight 60 g / m2A solid printed layer 12a and a pattern layer 12 having a thickness of 2 μm were formed.
Next, without providing the sealer layer 13, the electron beam curable resin composition (B) was applied onto the pattern layer 12 of the fibrous base material 11 in the same manner as in Example 3 and irradiated with an electron beam. As shown in FIG. 7C, a decorative paper 1a having a cured electron beam curable resin layer 14c containing spherical alumina 15 was produced.
[0068]
(Abrasion resistance and weather resistance test)
The decorative paper produced in Examples 1, 2, 3 and Comparative Examples 1, 2, 3, 4 were tested for abrasion resistance and weather resistance by the following methods.
(1) Abrasion resistance test
In accordance with the JAS abrasion A test, the initial point (the number of rotations at which the pattern layer starts to be removed) of each sample was measured using a Taber abrasion tester.
(2) Weather resistance test
Using a carbon arc FOM FM-002 model manufactured by Suga Test Instruments Co., Ltd., each sample was exposed for 500 hours under conditions of a black panel temperature of 63 ° C. and an environmental humidity of 40% RH, and the color fading state of the pattern layer was observed. .
[0069]
The test results of the abrasion resistance and weather resistance of the decorative paper produced in Examples 1, 2, 3 and Comparative Examples 1, 2, 3, 4 are shown in Table 1.
[0070]
[Table 1]
[0071]
As shown in Table 1, the decorative paper produced in Examples 1, 2, and 3 is superior in both wear resistance and weather resistance as compared with the decorative paper produced in the comparative example, and the effect of the sealer layer is remarkable. It appears in
That is, a fibrous base material such as paper is formed by providing a sealer layer using a blend of urethane resin and butyral resin, or acrylic resin, so that the electron beam curable resin applied thereon can penetrate into the paper. Is suppressed, and a predetermined cured electron beam curable resin layer is formed on the surface, so that the cured electron beam curable resin layer containing spherical alumina exhibits excellent wear resistance and weather resistance. It is considered a thing.
[0072]
【The invention's effect】
According to the present invention, since the ionizing radiation curable resin layer having high hardness is formed on the surface of a permeable fibrous base material such as paper without impairing flexibility, the wear resistance and weather resistance are improved. Excellent decorative paper can be obtained.
Conventionally, in order to form a resin layer having high hardness with an ionizing radiation curable resin, it has been necessary to use a polyfunctional ionizing radiation curable resin having a small molecular weight in order to increase the crosslinking density of the ionizing radiation curable resin. .
Low molecular weight ionizing radiation curable resin has a low viscosity, so when coated on paper, the paper cannot be impregnated to obtain the required coating thickness on the surface of the paper. Therefore, it was necessary to thicken the ionizing radiation curable resin layer.
However, increasing the amount of ionizing radiation curable resin applied increases the amount of expensive spherical alumina added to the ionizing radiation curable resin, which increases manufacturing costs and cures the ionizing radiation curable resin. Due to the shrinkage that occurs, the curling of the decorative paper becomes intense, and the workability deteriorates in post-processing, leading to an increase in production costs.
[0073]
  Therefore, in the present invention, after forming a pattern layer on a permeable fibrous base material, a sealer is formed using a resin composition containing a blend resin of butyral resin and urethane resin as a binder and further containing an aliphatic isocyanate. By forming the layer, penetration of the fibrous base material can be suppressed and a necessary coating film can be formed even with an ionizing radiation curable resin having a low molecular weight and a low viscosity. As a result, when a blend resin of butyral resin and urethane resin is used for the sealer layer, the content of expensive spherical alumina is reduced to 15 to 20% by weight, and the coating amount is also 18 to 22 g / m. 2 The production cost can be reduced. In addition, the obtained decorative paper is excellent in V-cut aptitude and folding process aptitude when pasted on an adherend and then processed..
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a decorative paper of the present invention.
FIG. 2 is a schematic cross-sectional view when spherical alumina is contained in a surface-cured ionizing radiation curable resin layer in another embodiment of the decorative paper of the present invention.
FIG. 3 is an explanatory diagram when producing the decorative paper of the present invention.
FIG. 4 is an explanatory view when producing a decorative paper in which spherical alumina is contained in an ionizing radiation curable resin layer in another embodiment of the decorative paper of the present invention.
FIG. 5 is an explanatory diagram when producing the decorative paper of the present invention according to Example 1.
6 is an explanatory diagram when producing decorative paper of the present invention according to Example 3. FIG.
7 is an explanatory diagram when producing decorative paper according to Comparative Example 1. FIG.
[Explanation of symbols]
1 decorative paper
1a Decorative paper (made in comparative example)
11 Fibrous substrate
12 Pattern layer
12a Solid printing layer
13 Sealer layer
13a Raised sealer layer
14 Cured ionizing radiation curable resin layer
14a Uncured ionizing radiation curable resin layer
14b Uncured electron beam curable resin layer
14c Cured electron beam curable resin layer
15 Spherical alumina
16 Ionizing radiation
16a electron beam

Claims (3)

  1. The fibrous base material, the pattern layer, a sealer layer and cured ionizing radiation-curable resin was laminated in this order, the sealer layer, a blend resin of a butyral resin and two-component curing type urethane resin as a binder, further aliphatic isocyanate A decorative paper comprising a resin composition containing
  2. The decorative paper according to claim 1, wherein a thickness of a sealer layer made of a blend resin of the butyral resin and a two-component curable urethane resin is 2 to 5 µm.
  3. The ionizing radiation curable resin layer contains 15 to 20% by weight of alumina, and the coating amount is 10 to 22 g / m 2 as a resin composition amount after curing . The decorative paper according to any one of the above.
JP03965999A 1999-02-18 1999-02-18 Decorative paper with abrasion resistance Expired - Fee Related JP4286949B2 (en)

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Application Number Priority Date Filing Date Title
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Publication number Priority date Publication date Assignee Title
US7279205B2 (en) 2001-02-07 2007-10-09 Sonoco Development, Inc. Packaging material
US8313824B2 (en) 2003-12-18 2012-11-20 Dai Nippon Printing Co., Ltd. Decorative multilayer material impregnated with resin
JP5879721B2 (en) * 2011-03-30 2016-03-08 大日本印刷株式会社 Decorative plate and method of manufacturing the decorative plate
JP5790371B2 (en) * 2011-09-22 2015-10-07 大日本印刷株式会社 Decorative plate and method of manufacturing the decorative plate

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