CN100528558C - Decorating material - Google Patents
Decorating material Download PDFInfo
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- CN100528558C CN100528558C CNB2004800284101A CN200480028410A CN100528558C CN 100528558 C CN100528558 C CN 100528558C CN B2004800284101 A CNB2004800284101 A CN B2004800284101A CN 200480028410 A CN200480028410 A CN 200480028410A CN 100528558 C CN100528558 C CN 100528558C
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Abstract
A decorating material which comprises a substrate, a low glossy designated layer provided on at least a part thereof, and a surface-protecting layer which is present on and contacts with the designated layer and covers over the whole surface including the region having the designated layer and that having no designated layer, wherein said surface-protecting layer is formed by crosslinking and curing an ionization-curable resin composition, and wherein, in said surface-protecting layer, a low lustrous region being visually recognized as a concave portion is formed in the portion directly on said low glossy designated layer and in the vicinity of the portion. The decorating material has a design being formed on the surface thereof and exhibiting a difference in gloss according to the design, which difference is visually recognized as a concave portion, to provide a concave-convex feeling to the surface.
Description
Technical field
Thereby the present invention relates to form decorative pattern, by having the ornament materials that has visual concave-convex sense with the corresponding gloss difference of decorative pattern and contain the surface durability excellence of decorative pattern on the surface.
Background technology
As the incrustation plate of the kitchen cabinet of furniture and kitchen goods etc., the general use: adopt adhesive on metal species materials such as wooden class material, mineral-type materials, synthetic resin material, steel plate etc., to attach to be printed with the cosmetic sheet of wood grain tone decorative pattern for example etc. to form the decorative panel of structure.
The employed cosmetic sheet of this incrustation plate, the flexibility, machinability, resistance to fracture etc. that require to be used for the appropriateness of secondary operations such as lamination process, roll bending processing, V cutting processing are processed various characteristicses such as against weather under adaptability, the user mode, light resistance, hear resistance, resistance to water, solvent resistance, case hardness, abrasion performance, marresistance.
In order to satisfy such requirement, carrying out using the ground fully satisfy above-mentioned processing adaptability, and this surface of bottom material is being applied the work of sealer, as sealer, preferably use the ionizing radiation hardening resin composition.The ionizing radiation hardening resin composition is to utilize ionizing radiations such as ultraviolet ray or electron ray to come cured compositions; when using said composition; as sealer; can with an organic solvent not apply formation with solvent-free form; therefore good to environment; and can reach high crosslink density, therefore can obtain to realize easily the various advantages such as surface strength of abrasion performance etc.
Because consumer's quality goods points in recent years, also pursue feeling of high class for cabinet of floor tile and shingle nail or furniture and kitchen goods etc., for them employed decorative panel or cosmetic sheet, also wish it is decorative panel or cosmetic sheet with the outward appearance that gives feeling of high class.Therefore, carry out various printings on the surface of each ground sheet, or the film with patterned layer is set, in addition, giving of texture also becomes important, proposed consistent delustring or the concavo-convex method of giving of all specific parts with decorative pattern.
For example, following method has been proposed: promptly pass through the application face that decorative pattern shape ground is provided with on ground, after formation is different from the zone of surface of bottom material for the easy degree of wetting of electron ray curing type coating or Photocurable coating material, coating electron ray curing type coating or Photocurable coating material on ground, for this coating, in easily wetting zone coating surface is subside, make coating surface protuberance (for example referring to patent documentation 1 claims) in the wetting zone of difficulty., this method is in recess, i.e. easily wetting regional trickle occasion, and concavo-convex problem can not appear in existence gallantly.In addition, in the occasion that thick to a certain degree recess is arranged, though surface of bottom material can obtain ridge design, in the frontier district of portion of subsideing and protrusion, owing to the reasons such as surface tension of coating, the end that moves to recess from protuberance has circular arc, lack concavo-convex distinctiveness (acutance), produce the above protuberance of height of protrusion simultaneously, for example in the occasion of wood grain decorative pattern, do not have the sense of reality, have the bad problem of outward appearance and feel.
In addition, following method has been proposed: promptly, with added in utilizing the resin solidification that postpones no-solvent type coating cure retarder printing ink and do not contain the film of the ink printing multi color effect of this cure retarder, be coated in advance on the resin coating film of the no-solvent type coating that applies on the substrate, make resin solidification in curing environment after, stripping film carries out transfer printing (referring to claims of patent documentation 2).Adopt this method, can only make color patterned depression of the ink printing that has added cure retarder in the employing carry out transfer printing., this method needs special printing ink, has the curing reaction problem of unstable of the resin coating film of no-solvent type coating simultaneously.
Have again, following ornament materials has been proposed, this ornament materials is to set gradually flower-pattern layer that is made of common ink and these the 2 kinds of flower-pattern layers of convex flower-pattern layer that are made of the electron ray curing composition on ground, transparent resin layer more in the above is covered, after the lining, by above-mentioned transparent resin layer irradiation electron ray, the convex decorative pattern is solidified obtain (referring to claims of patent documentation 3)., such ornament materials has bigger concavo-convex physically, thus protuberance easy damaged, the particularly occasion that the protuberance area is big its become significantly, become problem.In addition, the occasion that gloss powers such as wood grain tone for example occur in hope, that is, major part is protuberance, and has the occasion of the concavity portion of extremely narrow width as wood grain conduit ditch, because flowing of the coating of formation transparent resin layer, landfill this concavity portion, and the degree of its landfill occurs uneven, therefore this gimmick is improper, and, owing to there is physical property concavo-convex, therefore there is the bad problem of feel.
In addition, a kind of facing paper with wood grain decorative pattern has been proposed, this facing paper is with the ultra-violet solidified printing-ink all print wood background color that contains the polishing material that disappears on thin paper, behind its irradiation active ray, with the high ultra-violet solidified printing-ink of gloss simulated grain decorative pattern in the above, again to its irradiation active ray and obtain (referring to claims of patent documentation 4).Adopt this facing paper,, appear as protuberance on apparent,, appear as recess on apparent, can obtain woodiness touch for the part of the printing ink that contains the polishing material that disappears for the part of having used the high printing ink of gloss.; here the facing paper of Ti Chuing is not owing to implement the facing transparent coating of filming as protection, therefore for the part of the so-called conduit printing ink that is used for the simulated grain decorative pattern; against weather, resistance to water, abrasion performance, marresistance etc. have to reduce the durability variation.
And then, a kind of method has been proposed, wherein, adopt covering property of ionizing radiation material, the ionizing radiation that has fissility on the surface sees through in the table of peeling off ground and on the arbitrary face decorative pattern is set, overlapping this peeled off ground, form with the ridge design of the layer of the uncured thing that has the ionizing radiation cured resin on the surface and to use ground, from peeling off ground side irradiation ionizing radiation, after only making the ionizing radiation cured resin curing suitable with the part that is not the decorative pattern that forms with covering property of ionization radioactive ray material, come along resin with peeling off ground, form ridge design (referring to the claim 8 of patent documentation 5) except that the uncured portion of ionizing radiation curing resin layer.According to this invention, part with the decorative pattern that forms with covering property of ionization radioactive ray material, the ionizing radiation cured resin is uncured but attached to peeling off on the ground, be removed with peeling off ground, on the other hand, in the part that is not the decorative pattern that forms with covering property of ionization radioactive ray material, residual thereby the ionizing radiation cured resin solidifies, therefore can form ridge design with the pattern same hue., there is the shortcoming that needs materials such as release liner and covering property of ionizing radiation material in this method, and in addition, thereby in uncured resin being attached to the method for peeling off removal on the ground, existence can not form the shortcoming of the high-definition recess of the degree of depth.And, use the occasion of electron ray curing resin as the ionizing radiation cured resin, have to be difficult to selected shortcoming of covering the material of electron ray.
In addition, proposed to have the manufacture method of the decorative panel of ridge design, wherein, print or on the substrate that has pasted facing paper, apply and carry out after the synthetic resin of radioactive ray polymerization, the irradiation radioactive ray during synthetic resin semi-cured state, are ended irradiation, after the cold press bodies such as roll squeezer that ridge design has been implemented in employing pressurize, synthetic resin is solidified fully (for example referring to patent documentation 6 claims)., have following problems, that is, specific condition when making stable resin ground become to a certain degree semi-cured state is not easy, in addition, the synthetic resin instability of semi-cured state, it is miscellaneous that curing is divided into 2 stages.
So, the concavo-convex method of following continuous formation has been proposed: use applying device on ground, to apply the electron ray curing resin, in the electron ray irradiating machine, make it to contact with the mould roller, on one side figuration mould roller is concavo-convex, shines electron ray on one side and makes it curing (for example referring to patent documentation 7 claims, Fig. 1)., have the special mould roller arrangement of this method needs, common printing equipment can not the concavo-convex rough sledding of figuration, and in addition, the speed of utilizing the mould roller to carry out figuration has the limit, has the low shortcoming of productivity ratio.
Have again; the ornament materials of following formation has been proposed; it has at surface of bottom material and is coated with the sealer that rete, flower-pattern layer, ionizing radiation hardening resin composition crosslinking curing obtain; flower-pattern layer be coated with rete relatively, the permeability height of ionizing radiation hardening resin composition (for example referring to patent documentation 8 claims, Fig. 1 and Fig. 2).Adopt this ornament materials, the ionizing radiation hardening resin composition is easier to be penetrated into the part that has decorative pattern, therefore forms recess in this part, obtains the surface and has concavo-convex ornament materials., this ornament materials needs to add a large amount of filler pigment or porous material for flower-pattern layer being given enough absorption permeability, at this moment, and flower-pattern layer porousization and fragilityization, so the durability of recess, stain resistance reduction.On the other hand, when for the durability that improves recess, stain resistance and when suppressing the porous of flower-pattern layer, existence can not form the problem of the recess with enough degree of depth and distinctiveness.In addition, because this ornament materials has physical property concavo-convex, so feel is bad, also has the further leeway of improvement in this.
Patent documentation 1: special public clear 51-26937 communique
Patent documentation 2: special public clear 51-33454 communique
Patent documentation 3: special fair 1-41505 communique
Patent documentation 4: the spy opens clear 51-84910 communique
Patent documentation 5: the spy opens flat 1-253449 communique
Patent documentation 6: special public clear 49-28264 communique
Patent documentation 7: special public clear 63-50066 communique
Patent documentation 8: the spy opens the 2001-199028 communique
Summary of the invention
The objective of the invention is, a kind of ornament materials is provided under such situation, it is to form decorative pattern on the surface, have and the corresponding gloss difference of decorative pattern, this gloss difference is visually become recess by understanding, the ornament materials that concave-convex sense is arranged on the surface, and, solvent resistance, abrasion performance or interlaminar strength height.
The inventor is lucubrate in order to achieve the above object and repeatedly; found that: a kind of ornament materials; it has low gloss pattern ink lay and sealer that part is provided with at least on ground; this sealer exists on this low gloss pattern ink lay; when contacting with it; be covered comprising the zone that has formed this low gloss pattern ink lay and do not form in whole the scope in zone of this low gloss pattern ink lay; wherein; this sealer is the layer that ionizing radiation hardening resin composition crosslinking curing obtains; and in this sealer; the positive top of low gloss pattern ink lay and near have visually that understanding is the low gloss zone of recess, can solve above-mentioned problem thus.The present invention is based on such opinion and finish.
That is, the invention provides:
(1) a kind of ornament materials; it has low gloss pattern ink lay and sealer that part is provided with at least on ground; this sealer is present on this low gloss pattern ink lay; when contacting with it; be covered comprising the zone that has formed this low gloss pattern ink lay and do not form in whole the scope in zone of this low gloss pattern ink lay; wherein; this sealer is the layer that ionizing radiation hardening resin composition crosslinking curing obtains; and in this sealer, the positive top of this low gloss pattern ink lay and near formation visually be familiar with low gloss zone for recess.
(2) a kind of ornament materials; it has low gloss pattern ink lay and sealer that part is provided with at least on ground; this sealer is present on this low gloss pattern ink lay; when contacting with it; be covered comprising the zone that has formed this low gloss pattern ink lay and do not form in whole the scope in zone of this low gloss pattern ink lay; it is characterized in that; this sealer is the layer that ionizing radiation hardening resin composition crosslinking curing obtains; the low gloss pattern printing ink that constitutes low gloss pattern ink lay contains the non-crosslinked urethane resin as adhesive, and the ionizing radiation hardening resin composition comprises (methyl) acrylate monomer.
(3) according to above-mentioned (2) described ornament materials, the low gloss pattern printing ink that constitutes low gloss pattern ink lay contains non-crosslinked urethane resin and unsaturated polyester resin as adhesive.
(4) according to above-mentioned (2) or (3) described ornament materials, the ionizing radiation hardening resin composition only is made up of (methyl) acrylate monomer.
(5) according to wantonly 1 described ornament materials of above-mentioned (1)-(4), it is characterized in that, constitute printing ink in uneven thickness of low gloss pattern ink lay.
(6) according to above-mentioned (5) described ornament materials, above-mentioned low gloss pattern ink lay comprises the thick film areas that thickness is thick relatively and the film zone of thickness relative thin, simultaneously, form the positive top of this thick film areas and neighbouringly be relative lower gloss, the positive top in this film zone and neighbouring be the low gloss zone of relative higher gloss.
(7) according to wantonly 1 described ornament materials of above-mentioned (1)-(6); it is characterized in that; contain particulate in the above-mentioned sealer, and the average grain diameter of this particulate is the positive side neighbor of maximum ga(u)ge of sealer that is positioned at the positive top of above-mentioned low gloss pattern ink lay.
(8) according to above-mentioned (7) described ornament materials, the coefficient of variation CV value of the size distribution of particulate [(standard deviation/average grain diameter of particle diameter) * 100] is below 30%.
(9), the average grain diameter of particulate is designated as d according to above-mentioned (7) or (8) described ornament materials
A, the maximum ga(u)ge that will be positioned at the sealer on the positive top of low gloss pattern ink lay is designated as t
M, will not exist the surface protection layer thickness in the zone of low gloss pattern ink lay to be designated as t
GThe time, satisfy formula (I)
1.05×t
M≤d
A≤t
G …(I)
Relation.
(10) according to wantonly 1 described ornament materials of above-mentioned (7)-(9), the content of the particulate in the sealer is 2-20 quality %.
(11) according to wantonly 1 described ornament materials of above-mentioned (1)-(10); above-mentioned sealer is that the ionizing radiation hardening resin composition crosslinking curing that contains oxirane modified poly compound obtains, and this sealer contains the calcined kaolin particle.
According to wantonly 1 described ornament materials of above-mentioned (1)-(11), it is characterized in that (12) the low gloss pattern printing ink that constitutes low gloss pattern ink lay contains filler pigment.
(13) according to wantonly 1 described ornament materials of above-mentioned (1)-(12), the ionizing radiation hardening resin composition is the electron ray curing resin combination.
(14) according to wantonly 1 described ornament materials of above-mentioned (1) and (5)-(13), the surface that is positioned at the sealer on top, low gloss zone has convex form.
(15) according to wantonly 1 described ornament materials of above-mentioned (1)-(14), between ground and low gloss pattern ink lay, also further has impermeable layer.
(16) according to above-mentioned (15) described ornament materials, ground is the permeability ground.
(17) according to wantonly 1 described ornament materials of above-mentioned (1)-(16); stacked dyed layer, patterned layer, impermeable layer on ground; have low gloss pattern ink lay and sealer in the above; this sealer is present on this low gloss pattern ink lay; in contact with it, be covered comprising the zone that has formed this low gloss pattern ink lay and do not form in whole the scope in zone of this low gloss pattern ink lay.
(18) according to above-mentioned (17) described ornament materials, patterned layer forms the wood grain decorative pattern, and low gloss pattern ink lay forms the low gloss part of conduit part.
(19) a kind of decorative panel, its wantonly 1 described ornament materials with above-mentioned (1)-(18) stick on the substrate and obtain.
Description of drawings
Fig. 1 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 2 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 3 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 4 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 5 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 6 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 7 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 8 is the schematic diagram in expression ornament materials of the present invention cross section.
Fig. 9 is the schematic diagram in expression ornament materials of the present invention cross section.
Figure 10 is the schematic diagram in expression decorative panel of the present invention cross section.
Symbol description
1. ornament materials
2. ground
3. low gloss pattern ink lay
3-a. low gloss pattern printing ink
3-b. low gloss pattern printing ink
3-c. low gloss pattern printing ink
4. low gloss zone
4-a. low gloss zone
4-b. low gloss zone
4-c. low gloss zone
5. sealer
6. dyed layer
7. patterned layer
8. impermeable layer
9. convex form
10-a. particulate
10-b. particulate
11. adhesive phase
12. substrate
The specific embodiment
Ornament materials of the present invention; on ground, have low gloss pattern ink lay and sealer that part is provided with at least; this sealer is present on this low gloss pattern ink lay; when contacting with it; be covered comprising the zone that has formed this low gloss pattern ink lay and do not form in whole the scope in zone of this low gloss pattern ink lay; it is characterized in that; this sealer is the layer that ionizing radiation hardening resin composition crosslinking curing obtains; and in this sealer, the positive top of this low gloss pattern ink lay and near formation visually be familiar with low gloss zone for recess.
Structure about ornament materials of the present invention describes with Fig. 1-Fig. 3.Fig. 1-Fig. 3 is the schematic diagram in the cross section of expression ornament materials 1 of the present invention.In the example shown in Figure 1, on ground 2, stacked gradually the sealer 5 that whole equally uniform dyed layer 6, patterned layer 7, equally uniform impermeable layer 8, low gloss pattern ink lay 3, the ionizing radiation hardening resin composition crosslinking curing of being covered obtains.Low gloss pattern ink lay 3 partly exists, its positive top and near sealer form low gloss zone 4.Observe ornament materials of the present invention from sealer 5 sides, low gloss zone 4 visually is familiar with is recess, and other zones visually are protuberance by understanding, therefore as a whole, visually are ridge design by understanding owing to this low gloss zone 4.In addition, low gloss zone 4 is showed by the set of point in the drawings.
In addition, the top in the low gloss zone 4 that sealer 5 is the most surperficial also can be accompanied by the formation of low gloss pattern ink lay 3 and swells, and has convex form 9.Surface by sealer 5 has convex form in this wise, and in this part light scattering, so surface area increases and the angle of visual field that can be familiar with low gloss is also expanded, and therefore coordinates with the effect in above-mentioned low gloss zone 4, has further strengthened the concave-convex sense of vision.In addition, for the height of this convex form, in the scope that obtains effect of the present invention, be not particularly limited, normally the scope of 2-3 μ m.
Secondly, in example shown in Figure 2, stacked low gloss pattern ink lay 3 on ground 2, the sealer 5 that stacked thereon again ionizing radiation hardening resin composition crosslinking curing obtains.Same with example shown in Figure 1, the positive top of low gloss pattern ink lay 3 and near sealer thereof form low gloss zone 4.Observe ornament materials of the present invention from sealer 5 sides, partly the low gloss zone 4 of Cun Zaiing is a recess by understanding visually, is familiar with into ridge design as a whole.
Degree of expansion for the low gloss zone 4 that in sealer 5, forms; as long as in the scope that obtains effect of the present invention; be not particularly limited; as depicted in figs. 1 and 2; can begin from the surface of low gloss pattern ink lay 3 to the Halfway Stopping of the thickness direction of sealer 5; in addition, as shown in Figure 3, also can arrive the most surperficial of sealer 5.And as shown in Figure 3, also can be at the most surperficial formation convex form of sealer 5.
Below describe the formation of ground, each layer in detail with Fig. 1-9.
As the ground 2 that uses among the present invention, so long as usually as getting final product that ornament materials uses, being not particularly limited, can be base material etc. according to plate, the ceramic industry of wooden classes such as the various stationeries of the suitable selection of purposes, plastic sheeting, plastic sheet, metal forming, sheet metal, metallic plate, timber.These materials can be distinguished separately and to use, and also can be the laminated body that the complex between the paper or the complex of paper and plastic sheeting etc. make up arbitrarily.
In the occasion that these grounds, particularly plastic sheeting or plastic sheet are used as ground, in order to improve and the adaptation of establishing layer thereon, can be as requested the physics or the chemical surface treatment of oxidizing process or concavo-convexization method etc. be implemented in single face or two sides.
As above-mentioned oxidizing process, for example enumerate Corona discharge Treatment, chromic acid oxidation processes, flame treatment, hot blast processing, ozone ultraviolet treatment etc., as concavo-convexization method, for example enumerate sand-blast, solvent treatment method etc.These surface treatments are selected according to the ground kind is suitable, but consider general preferred use Corona discharge Treatment method from aspects such as effect and operability.
In addition, this ground both can implement to form the processing of prime coat etc. for interlayer adaptation of strengthening ground and each layer or the like, also can be pre-formed the decorative pattern under the viewpoint of the application that is used to adjust color or design.
Various stationeries as ground can use thin paper, brown paper, titanium paper (チ Application Paper) etc.These paper grounds, for between the fiber of strengthening the paper ground or the interlaminar strength of other layers and paper ground, or prevent fuzzing, also can in these paper grounds, further add resins such as acrylic resin, styrene butadiene ribber, melamine resin, urethane resin (contain resin pickup after copying slurry, or fill out resin in copying when starching).For example be to strengthen paper, impregnation melaminated paper etc. between paper.
In addition, can also enumerate cotton linter paper, Cardboard Paper, plasterboard with silkworm seed paper or be provided with the various paper that the ethene wallpaper roll web etc. of vinyl chloride resin layer much uses in building materials field on the paper surface.And, can also use coated paper, art paper, template, cellophane cover, parchment, waxed paper or the Japan paper etc. that in office field and common printing, packing etc., use.In addition, though have any different with these paper, the fabric or the nonwoven that have with the various fibers of paper similar in appearance and proterties also can use as ground.As various fibers, can enumerate inorfil or synthetic resin fibers such as polyester fiber, acrylic fiber or vinylon fiber such as glass fibre, asbestos fibre, potassium titanate fibre, alumina fibre, silicon dioxide fibre or carbon fiber.
As plastic sheeting or plastic sheet, can enumerate the film or the sheet that form by various synthetic resin.As synthetic resin, can enumerate: vistanexes such as polyvinyl resin, acrylic resin, polymethylpentene resin, olefin-based thermoplastic elastomer (TPE); Vinyl resins such as Corvic, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymerization resin, ethane-acetic acid ethyenyl ester copolymer resins, ethylene-vinyl alcohol copolymer resin; Mylar such as pet resin, polybutylene terephthalate (PBT) resin, PEN-ethylene isophthalate copolymer resins, polyester based thermoplastic elastomer; Acrylic resins such as poly-(methyl) methyl acrylate resin, poly-(methyl) ethyl acrylate resin, poly-(methyl) butyl acrylate resin; The polyamide of representatives such as nylon 6 or nylon 66; Cellulose-based resins such as cellulose triacetate resin, cellophane; Polystyrene resin; Polycarbonate resin; Poly-arylide resin; Perhaps polyimide resin etc.
As metal forming, sheet metal or metallic plate, for example can use the ground that forms by aluminium, iron, stainless steel or copper etc., in addition, can also use these metals have been implemented the ground that plating etc. obtains.As the plate of various wooden classes, can enumerate veneer, glued board, clamping plate, particle board or the MDF wood fibre boards such as (medium density fibre board (MDF)s) of timber.As ceramic industry is the base material, and can exemplify out ceramic industrys such as plasterboard, calcium silicate board, wood chip cement plate is building materials, pottery, glass, enamel, calcining ceramic tile etc.In addition, fiber-reinforced plastic (FRP) plate, paste base material that iron plate obtains on the two sides of honeycomb paper, the complex of the various base materials such as base material that obtain with 2 aluminium sheet clamping polyvinyl resins also can use as ground.
The thickness of ground 2 is not particularly limited, and when using with plastics to the sheet of base material, thickness is normally about 20-150 μ m, the scope of 30-100 μ m preferably, and in the occasion of using the paper ground, weight per unit area is 20-150g/m normally
2About, 30-100g/m preferably
2Scope.
At the equally uniform dyed layer 6 of whole lining shown in Figure 1, be purpose layer that be provided with as requested, that be also referred to as hidden layer or comprehensive layer for the design that improves ornament materials of the present invention.Dyed layer 6 is by adjusting the surface color on the ground 2, makes ground 2 self painted, or intentional color is given on the surface to ground 2 that forms when uneven color is arranged.Usually form with body color mostly, but also form the decorative pattern that effectively utilizes substrate to have sometimes with painted Transparent color.effectively utilize ground 2 for the occasion of white or ground 2 self by the occasion of adequate colouration, there is no need to form dyed layer 6.
As the printing ink that is used to form dyed layer, use the material that colouring agent, filler pigment, solvent, stabilizing agent, plasticizer, catalyst, curing agent etc. such as suitable hybrid pigment, dyestuff obtain in adhesive.Being not particularly limited as this adhesive, is that resin, vinyl chloride/vinyl acetate acrylic copolymer resin, vinyl chloride/vinyl acetate/acrylic acid series copolymer resin, chlorinated polypropylene are that resin, acrylic resin, polyester based resin, polyamide-based resin, butyral are that the material arbitrarily selected among resin, polystyrene resin, nitrocellulose prime system resin, the acetate fiber prime system resin etc. can use a kind or mix more than 2 kinds and use separately from polyurethane for example.
As colouring agent, pearly luster (pearly-lustre) pigment that can use inorganic pigments such as carbon black (China ink), iron oxide black, titanium white, stibium trioxide, chrome yellow, titan yellow, iron oxide red, cadmium red, ultramarine, cobalt blue, the flakey paillon foil of the mica of organic pigment such as quinacridone is red, isoindolinone is yellow, phthalocyanine blue or dyestuff, the metallic pigments that formed by the flakey paillon foil of aluminium, brass etc., lining titanium dioxide, basic lead carbonate etc. forms etc.
So-called all print layer about this dyed layer 6 preferred used thickness 1-20 μ m.
7 pairs of grounds 2 of patterned layer shown in Figure 1 are given ornamental, form various decorative patterns by using printing ink and printing machine printing.As decorative pattern, cloth ground decorative pattern, the decorative pattern that ceramic tile is put up of the decorative pattern of the bag decorative pattern, woven design of wood grain decorative pattern, marbling imitation rock surfaces such as (for example calcareous tufa marblings) or imitation cloth shape, the decorative pattern that obtains of laying bricks etc. are arranged, also had the decorative pattern of the veneer of these decorative patterns, patchwork etc. compound.These decorative patterns form by the trichromatic polychrome printing of common yellow, redness, blueness and black, and the polychrome printing of the characteristic that the version of each color that in addition can be by prepare constituting decorative pattern is carried out waits and forms.
As the pattern printing ink that is used for patterned layer 7, can use the printing ink identical with the printing ink that is used for dyed layer 6.In addition, in ornament materials of the present invention, can utilize low gloss pattern ink lay 3 and the low gloss zone 4 described in detail later to implement to decorate, so patterned layer 7 optional inscapes.
Low gloss pattern ink lay 3 in the ornament materials of the present invention as shown in Figure 4, directly is layered on the ground 2, perhaps as shown in Figure 5, is layered in as required on the dyed layer 6 that is provided with, patterned layer 7, the impermeable layer 8 etc., and be the layer that produces the gloss difference of decorative pattern.
Fully do not separate bright about the mechanism that gloss difference takes place among the present invention; but results presumption: when the surface applied of low gloss pattern ink lay 3 is used to form the uncured thing of ionizing radiation curable resin of sealer 5 from various experiments and observation, mensuration; by the combination of each material, the suitable selection of coating condition, the resinous principle of low gloss pattern ink lay 3 and sealer embody due to the interactions such as part stripping, dispersion, mixing.Think at this moment, each resinous principle in the printing ink of low gloss pattern ink lay 3 and the uncured thing of ionizing radiation curable resin, in the short time, do not reach and mix state fully and become outstanding turbid state, be present in low gloss pattern ink lay 3 positive top and near, become the part scattered light of this outstanding turbid state, form the low gloss zone.Supposition under former state state with this outstanding turbid state by making the sealer crosslinking curing, when fixing this state, as shown in Figure 1-Figure 3, formation low gloss zone 4 partly in sealer, owing to the illusion of eyes, this part is familiar with is recess.
The low gloss pattern printing ink that forms low gloss pattern ink lay 3 have with the ionizing radiation hardening resin composition that forms sealer 5 between can embody stripping, dispersion, interactional character such as mix, according to suitable selecting with the related of this ionizing radiation hardening resin composition (uncured thing).Particularly; preferably has the printing ink of non-crosslinked resin as adhesive resin; for example thermoplasticity (non-crosslinked type) urethane resin etc. is suitable; at this; from making it and to form the interaction of ionizing radiation hardening resin composition of sealer 5 stronger; the viewpoint that obtains further decorative pattern gloss difference considers that the content of further preferred urethane resin is more than the 50 quality %.
As above-mentioned urethane resin, preferably select the non-crosslinked type, that is, be not that 3 dimension is crosslinked has mesh-shape stereo molecule structure, but become the material of thermoplastic resin with filiform molecular structure.As the urethane resin of such non-crosslinked type, can enumerate: make polyalcohols such as acrylic polyalcohol as polyol component, PEPA, PPG and the urethane resin that forms as isocyanate reactions such as aliphatic such as aromatic isocyanate, IPDI, two isocyanic acid hexa-methylene esters, hydrogenation two isocyanic acid tolylene esters such as two isocyanic acid tolylene esters of isocyanate prepolymer composition, xylene diisocyanate, methyl diphenylene diisocyanate or ester ring type isocyanates.Hydroxyl value in common polyalcohol 1 molecule and the NCO in isocyanates 1 molecule be average out to 2 respectively.In addition, because the mean molecule quantity of urethane resin is 10,000-50, about 000, glass transformation temperature (Tg) is that the material about-70 to-40 ℃ manifests the low gloss zone, and is therefore preferred.
In addition, in order to adjust the contrast that manifests degree, low gloss zone and the gloss difference around it in low gloss zone, can mix saturated or unsaturated polyester resin, acrylic resin or vinyl chloride vinyl acetate copolymer etc. as required.Among these materials, preferred polyester resin, preferred especially unsaturated polyester resin.The addition of unsaturated polyester resin is with respect to the adhesive total amount of low gloss pattern printing ink, the preferably scope of 10-50 quality %.When in this scope, can obtain manifesting the sufficient enhancing effect in low gloss zone.As unsaturated polyester resin, so long as the reactant of unsaturated dicarboxylic and glycol just is not particularly limited,, for example enumerate maleic acid, fumaric acid, itaconic acid etc. as unsaturated dicarboxylic, as glycol, can enumerate ethylene glycol, diethylene glycol, propane diols, butanediol etc.
Form the low gloss pattern printing ink of low gloss pattern ink lay 3, same with the ink composite that in dyed layer 6 or patterned layer 7, uses, has dyed layer, even himself also can provide pattern, in occasion with dyed layer shown in Figure 16 or patterned layer 7, owing to given color or decorative pattern to ground 2, it is painted therefore may not to add colouring agent in being used to form the low gloss pattern ink composite of low gloss pattern ink lay 3.That is,,, eliminate gloss, wish that visually the part and the low gloss pattern ink lay 3 of performance recess is synchronous, just can obtain having decorative pattern by the sense of vision recess due to the gloss difference by making among the decorative pattern that patterned layer 7 will show in occasion with patterned layer 7.For example, in the occasion that will utilize patterned layer 7 performance wood grain decorative patterns, the printing ink part by making low gloss pattern ink lay 3 and the duct portion of wood grain are synchronous, just can obtain duct portion visually becomes recess owing to gloss difference decorative pattern.Perhaps in the occasion of the decorative pattern that will utilize patterned layer 7 performance ceramic tiles to put up, the printing ink part by making low gloss pattern ink lay 3 and the seam ditch part of tiling just can obtain seam ditch part synchronously because gloss difference and visually become the decorative pattern of recess.
In addition, preferably in being used to form the low gloss pattern ink composite of low gloss pattern ink lay 3, contain filler pigment.By containing filler pigment, can give thixotropy (チ キ ソ) to low gloss pattern ink composite, when using version printing low gloss pattern ink lay 3, keep the shape of low gloss pattern ink composite.Thus, can strengthen from protuberance being transferred to concavo-convex distinctiveness (definition) on the end of recess, have the design performance of height to become possibility.
Be not particularly limited as the filler pigment that uses in the present invention, for example can from silica, talcum, clay, barium sulfate, brium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate etc., suitably select.Among these materials, the free degree height of materials such as preferred oil suction degree, particle diameter, pore volume design, design, whiteness, as the material silica of the coating excellent in stability of printing ink, the silica of preferred especially micropowder.As the particle diameter of silica, the scope of preferred 0.1-5 μ m.When being 0.1 μ m when above, in the time of in being added into printing ink, the thixotropy of printing ink can extremely not uprise, and in addition, the viscosity of printing ink can too not rise, the control of easily printing.In addition, show the occasion of the delustring of conduit decorative pattern part, the applied thickness of the printing ink of conduit decorative pattern part is normally below the 5 μ m, if the silica particle diameter is less than applied thickness, thereby it is unshowy then comparatively to have suppressed appearing of particle, therefore is difficult to cause the sense of discomfort of sense of vision.
The content of these filler pigments in low gloss pattern ink composite, the preferably scope of 5-15 quality %.When being 5 quality % when above, can give enough thixotropy to low gloss pattern ink composite, when being 15 quality % when following, can't see the effect of giving low gloss fully and reduce, so preferably.
About the coating amount of the low gloss pattern printing ink that forms low gloss pattern ink lay 3, preferably 1-30g/m
2Scope.When being 1g/m
2When above, the interaction of above-mentioned low gloss pattern printing ink and ionizing radiation hardening resin composition taking place, can fully obtain the low gloss zone, therefore obtains enough gloss differences on ornament materials surface.On the other hand, when being 30g/m
2When following, when low gloss pattern ink printing, there is not the mechanicalness restriction, also favourable economically in addition.From above viewpoint, the coating amount of low gloss pattern printing ink, further 2-20g/m preferably
2Scope, 5-10g/m especially preferably
2Scope.
In addition, change by the coating amount that makes low gloss pattern ink composite, can make the in uneven thickness of the printing ink that constitutes low gloss pattern ink lay 3, the degree ladder ground of the recess of visually being familiar with or variation thus continuously, as a result, can make the decorative pattern of ornament materials is the ladder decorative pattern of gloss difference ladder ground variation or all over design that gloss difference changes continuously.
Think this be because, along with the coating amount of low gloss pattern ink lay 3 relatively becomes more, the interaction between low gloss pattern ink lay 3 and the sealer 5 increases relatively, the degree of outstanding turbid state is higher, the gloss in low gloss zone 4 becomes lower.
Below use Fig. 6-9 at length to describe.In Fig. 6, make the thickness of the printing ink 3-a, the 3-b that constitute low gloss patterned layer 3 and 3-c different.That is, thickness is relatively pressed the sequential steps ground attenuation of 3-a, 3-b, 3-c.Thus, can make utilize sense of vision ridge design that low gloss zone 4 obtains visually be recessed part 4-a, 4-b, the variation of 4-c ladder ground, look recess by the sequential steps of 4-c, 4-b, 4-a deepen.Think that this is inhomogeneous because constitute the ink thickness of low gloss pattern ink lay 3, the thickness of this printing ink is pressed the order minimizing of 3-a, 3-b and 3-c when coating, therefore the big part of ink thickness looks that gloss is lower, the part that ink thickness is little looks that gloss is relatively high, looks that therefore gloss changes by the ground, sequential steps of 3-a, 3-b and 3-c.Change by the thickness that makes such printing ink thinlyyer, can see that also gloss changes continuously.
Utilization has the ornament materials of this spline structure can give more colorful texture.Make the method for the varied in thickness of the printing ink that constitutes low gloss patterned layer 3, can easily carry out by the coating amount that changes printing ink usually, change continuously by the coating amount that makes printing ink, the variation that yet can make above-mentioned ladder is not there to be the variation of ladder continuously.
Secondly; in example shown in Figure 7; on ground 2; low gloss pattern ink lay 3 is in the face inner stacks parallel with surface of bottom material; make thickness change continuously that (central portion is thick; more towards sidepiece attenuation more), the sealer 5 that stacked thereon again ionizing radiation hardening resin composition crosslinking curing obtains.Same with shown in Fig. 6, the positive top of low gloss pattern ink lay and near sealer thereof form the low gloss zone.In the example of Fig. 7, the thickness of low gloss pattern ink lay is pressed the order thickening of 3-c, 3-b, 3-a, and is corresponding with it, and gloss reduces continuously by the order of low gloss zone 4-c, 4-b, 4-a.As a result, on this order, look that the concave depth of sense of vision deepens continuously.See ornament materials of the present invention from sealer 5 sides, the low gloss zone is visually become recess by understanding, and in addition, other zones visually are protuberance by understanding, and as a whole, being familiar with is ridge design.
Degree of expansion for the low gloss zone 4 that in sealer 5, forms; as long as in the scope that obtains effect of the present invention; be not particularly limited; as shown in Figure 6; can begin Halfway Stopping from the surface of low gloss pattern ink lay 3 at the thickness direction of sealer 5; in addition, as shown in Figure 7 and Figure 8, also can arrive the most surperficial of sealer 5.And as shown in Figure 8, also can be at the most surperficial formation convex form of sealer 5.
Secondly, sealer 5 constitutes by the solidfied material of ionizing radiation hardening resin composition crosslinking curing as mentioned above.At this, the ionizing radiation hardening resin composition is meant: by being radiated at the radioactive ray that have the quanta of energy that can make molecule crosslinked, polymerization among electromagnetic wave or the charged particle ray, i.e. and irradiation ultraviolet radiation or electron ray etc. and resin combination crosslinked, that solidify.Specifically, can use from suitable selection the among the polymerizable monomer that was commonly used for the ionizing radiation hardening resin composition and polyreactive oligomers or the prepolymer in the past.
Typically, as polymerizable monomer, preferably in molecule, has (methyl) acrylate monomer of free-radical polymerised unsaturated group, by containing (methyl) acrylate monomer, produce the interaction with above-mentioned low gloss pattern printing ink, suitably form the gloss difference of decorative pattern.Consider from the viewpoint that makes it stronger, obtains further decorative pattern gloss difference with the interaction of low gloss pattern printing ink, the content of (methyl) acrylate monomer further preferably more than the 50 quality %, only be made up of (methyl) acrylate monomer by preferred especially ionizing radiation hardening resin composition.
As (methyl) acrylate monomer, preferably multi-functional (methyl) acrylate.At this, so-called " (methyl) acrylate " means " acrylate or methacrylate ".As multi-functional (methyl) acrylate, so long as (methyl) acrylate that in molecule, has 2 above ethene unsaturated bonds just can, be not particularly limited.Particularly, can exemplify out ethylene glycol bisthioglycolate (methyl) acrylate, propane diols two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, two cyclopenta two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, oxirane modified phosphate two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, chlorinated isocyanurates two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid modification dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (propenyloxy group ethyl) chlorinated isocyanurates, propionic acid modification dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, oxirane modification dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.These multi-functional (methyl) acrylate both can use a kind separately, also can make up more than 2 kinds and use.
In the present invention, in the scope of not damaging the object of the invention, for purposes such as its viscosity of reduction, can be with above-mentioned multi-functional (methyl) acrylate suitably also with simple function (methyl) acrylate.As simple function (methyl) acrylate, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate acyl ester, (methyl) isobornyl acrylate etc.These simple functions (methyl) acrylate both can use a kind separately, also can make up more than 2 kinds and use.
Secondly, as polyreactive oligomers, can enumerate the oligomer that in molecule, has free-radical polymerised unsaturated group, for example oligomer of epoxy radicals (methyl) acrylic ester, urethanes (methyl) acrylic ester, polyester (methyl) acrylic ester, polyethers (methyl) acrylic ester etc.At this, epoxy radicals (methyl) acrylic ester oligomer, the bisphenol-type epoxy resin that for example can be by making (methyl) acrylic acid and lower molecular weight or the oxirane environment-development of phenolic resin varnish type epoxy resin are given birth to reaction and are carried out esterification and obtain.In addition, also can use and adopt the duality carboxylic acid anhydrides this epoxy radicals (methyl) acrylic ester oligomer epoxy radicals (methyl) acrylate oligomer of the carboxy-modified type that obtains of modification partly.Urethanes (methyl) acrylic ester oligomer for example, carries out esterification by the polyurethane oligomer that will be obtained by the reaction of PPG or PEPA and PIC with (methyl) acrylic acid, thereby can access.As polyester (methyl) acrylic ester oligomer, for example, the hydroxyl that has a polyester oligomer of hydroxyl at two ends that will obtain by the condensation of polybasic carboxylic acid and polyalcohol carries out esterification with (methyl) acrylic acid, perhaps, the hydroxyl of the end of the oligomer that will obtain polybasic carboxylic acid addition alkylene oxide carries out esterification with (methyl) acrylic acid, thereby can access.Polyethers (methyl) acrylic ester oligomer can carry out esterification with (methyl) acrylic acid by the hydroxyl with PPG and obtain.
Have again, as polyreactive oligomers, also have in addition: the side chain at the polybutadiene oligomer has high polybutadiene (methyl) the acrylic ester oligomer of (methyl) acrylate-based hydrophobicity, siloxanes (methyl) the acrylic ester oligomer that on main chain, has the polysiloxanes key, to in little molecule, have amino resin (methyl) the acrylic ester oligomer that a plurality of reactive basic amino resin modifications obtain, perhaps at phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, aliphatic ethylene base ether, has the oligomer of cationically polymerizable functional group etc. in the molecule of aromatic ethenyl ether etc.
In the present invention; as mentioned above; it is important constituting the low gloss pattern printing ink of low gloss pattern ink lay 3 and the interaction of the ionizing radiation hardening resin composition that constitutes sealer 5; from this viewpoint; selected suitable printing ink and ionizing radiation hardening resin composition; but, preferably contain multi-functional (methyl) acrylate monomer as the ionizing radiation hardening resin composition.
In addition, the ionizing radiation curable resin that is preferred for sealer 5 contains oxirane modified poly compound, and sealer contains the calcined kaolin particle.By using the resin that contains oxirane modified poly compound in the ionizing radiation curable resin of this sealer, oil resistivity improves, and contains the calcined kaolin particle in the sealer, anti-マ-リ Application ゲ raising by making.That is, for oil resistivity, the ionizing radiation curable resin that contains oxirane modified poly compound by employing is as sealer, because the ethylene oxide moiety of this compound is a hydrophily, therefore can reduce the affinity of sealer and oil.As a result, can make: suppressed to be attached to the ornament materials that edible wet goods oil infiltrates in the sealer, oil resistivity is improved by sealer self on the sealer.
Oxirane modified poly compound is the compound that can carry out polymerisation under ionizing radiation, and be compound with oxirane modification part, as such oxirane modified poly compound, can suit to use and the purposes respective substance.As the concrete example of oxirane modified poly compound, for example can enumerate trimethylolpropane oxirane modification three (methyl) acrylate, bisphenol-A epoxy ethane modification two (methyl) acrylate etc.
In addition, the chain of the oxirane repetitive on the oxirane modification part is counted n (quantity of per 1 molecule) to be increased more, and oil resistivity increases more, on the other hand, because hydrophily increases, thereby the anti-pollution rerum natura that resistance to water reaches at aqueous stain such as water color inks reduces.Therefore, can suit to adjust the n number.For example, n is 2-20, more preferably 4-15.As oxirane modified poly compound, also can be 2 officials energy, 3 officials energy or other functional number, for example 4 officials can above compound.These compounds are can be with due regard to desired by film hardness etc. and determine as sealer.
As the ionizing radiation curable resin that is used for sealer 5; can constitute the resinous principle that can carry out polymerisation under ionizing radiation with oxirane modified poly compound all measures; but for oil resistivity beyond other rerum naturas, for example the surface is taken into account the stain resistance of water color ink etc., also can suit and with other can be at the polymerizable compound of polymerization under the ionizing radiation.Specifically, when only adopting oxirane modified poly compound, the hydrophily of sealer increases, though therefore oil resistivity raises, but then, to the affinity increase of aqueous substance, the stain resistance to aqueous stain matter such as water color inks reduces sometimes.In this case, can cooperate non-hydrophilic polymerizable compound, for example non-modification acrylate monomer of oxirane and/or prepolymer (common acrylate monomer and/or prepolymer).Make it to have simultaneously oil resistivity and to the occasion of the stain resistance of aqueous stain matter, the scope of preferred (oxirane modified poly compound)/(the non-modified poly compound of the oxirane)=3/7-5/5 (mass ratio) of this match ratio.In addition, expoxy propane also is the olefinated oxygen compound similar with oxirane, but when replacing the oxirane modified compound to use the epoxy pronane modification compound, the relative ratios of ehter bond diminishes, and hydrophilic increase tendency is little, can not get good oil resistivity.
As the occasion of ionizing radiation hardening resin composition use ultra-violet solidified resin composition,, preferably add the photopolymerization initator about the 0-1-5 mass parts with respect to resin combination 100 mass parts.As the photopolymerization initator, can from habitual in the past initator, suit to select, be not particularly limited, for example for polymerizable monomer that in molecule, has free-radical polymerised unsaturated group or polyreactive oligomers, can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, the benzoin isobutyl ether, acetophenone, the dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2 (hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, the 2-EAQ, 2-tertiary butyl anthraquinone, the 2-amino anthraquinones, 2-methyl thioxanthones, 2-ethyl thioxanthones, the 2-chloro thioxanthone, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal etc.
In addition, for polyreactive oligomers that in molecule, has cationically polymerizable functional group etc., can enumerate aromatic series sulfonium salt, aromatic series two diazo salts, aromatic series salt compounded of iodine, Metallocenic compound, benzoin sulphonic acid ester etc.
In addition, as photosensitizing agent, for example can use mesitylenic acid ester, tertiary amines, mercaptan is sensitizer etc.
In the present invention, as the ionizing radiation hardening resin composition, preferably use the electron ray curing resin combination.This is because the electron ray curing resin combination can solvent free, considers more preferably from environment and healthy viewpoint, in addition, does not need photopolymerization just can obtain stable curing characteristics with initator.
Ornament materials of the present invention preferably further cooperates particulate in the ionizing radiation hardening resin composition.As this particulate, using average grain diameter is the particulate of positive side neighbor of maximum ga(u)ge of sealer 5 that is positioned at the positive top of above-mentioned low gloss pattern ink lay 3.For the ornament materials of the present invention that has cooperated particulate, use Fig. 9 to describe in detail.Ornament materials shown in Figure 9 has cooperated particulate in the ionizing radiation hardening resin composition.
Be coupled to the particulate 10 (10-a, 10-b) in the sealer, its average grain diameter d
ABe the maximum ga(u)ge t of sealer 5 that is positioned at the positive top of low gloss pattern ink lay 3
MPositive side neighbor, i.e. d
ACompare t
MBig a little, appearing of this particulate 10-a taken place from the surface of the sealer 5 on the positive top that is positioned at low gloss pattern ink lay 3.This part that has taken place to appear forms convex form, and therefore scattering of light takes place.Meanwhile; inside at sealer 5; because the low gloss pattern printing ink in the low gloss pattern ink lay 3 and constitute the interaction of the ionizing radiation hardening resin composition of sealer 5, on the positive top of low gloss pattern ink lay 3 and adjacent portion form visually and be the low gloss zone 4 of recess by understanding.
On the other hand, be positioned at the particulate 10-b of the part on the positive top that is not low gloss pattern ink lay 3, can not appear, do not demonstrate the light scattering effect that resembles the particulate 10-a.
Therefore; by the low gloss zone 4 in this sealer 5, with the synergy of the light scattering that causes of appearing of these sealer 5 lip-deep particulates; and then the effect of the convex form that forms by the formation of following above-mentioned low gloss pattern ink lay 3, the concave-convex sense of sense of vision is further strengthened.
In addition, be positioned at the maximum ga(u)ge t of sealer 5 on the positive top of low gloss pattern ink lay 3
M, in the occasion that does not form the convex form that accompanies with the formation of above-mentioned low gloss pattern ink lay 3, be the thickness of sealer 5, in the occasion that forms this convex form, be the thickness that comprises this part.
For above-mentioned particulate, the approaching more single dispersion of size distribution, the setting of its consumption is easy more, simultaneously, just can bring into play above-mentioned effect well under few consumption, so preferred.
In the present invention, preferably the coefficient of variation CV value of the size distribution of this particulate [(standard deviation/average grain diameter of particle diameter) * 100] is below 30%.If above-mentioned CV value is below 30%, then this particulate has practical size distribution, and the consumption of the enough appropriateness of energy is given full play to above-mentioned effect.This CV value is more preferably below 20%, further preferably below 15%.
Further, be designated as d in average grain diameter with this particulate
A, the maximum ga(u)ge that will be positioned at the sealer on the positive top of low gloss pattern ink lay is designated as t
M, will not exist the surface protection layer thickness in the zone of low gloss pattern ink lay to be designated as t
GThe time, preferably satisfy the relation of formula (I).
1.05×t
M≤d
A≤t
G …(I)
If the average grain diameter d of this particulate
ABe 1.05 * t
MMore than, even then produce sinking to of this particulate in low gloss pattern ink lay, also can appearing of this particulate be taken place on the surface of the sealer that is positioned at this positive top of low gloss pattern ink lay, above-mentioned effect is given full play to.In addition, if this d
ABe t
GBelow, then in the sealer in the zone that does not have low gloss pattern ink lay, appearing of this particulate is suppressed.
Shape about this particulate is not particularly limited, and can use the particulate of spherical, ellipsoid shaped, polyhedral etc., preferred spheroidal particle.In addition, in the present invention, the spherical particle diameter of shape of microparticles in addition is the value of representing with the diameter of circumsphere.
This fraction of particle in the sealer also depends on the average grain diameter of this particulate and the coefficient of variation CV value of size distribution etc., and is selected in the scope of 2-20 quality % usually.If this content is more than the 2 quality %, the effect that then contains this particulate is brought into play, and in addition, if be below the 20 quality %, then the visibility of the decorative pattern that forms on the ornament materials surface is good.The preferred content of this particulate is 4-16 quality %, further 4-13 quality % preferably.
This particulate can be any one of inorganic particles and organic fine particles, aspect the visibility of the decorative pattern that forms on ornament materials surface, preferably has the transparency.Example as this particulate, as inorganic particles, can enumerate particles such as silica, aluminium oxide, alumino-silicate, kaolinite, calcium carbonate, barium sulfate, glass, as organic fine particles, can enumerate acrylic resin, polycarbonate resin, urethanes is that resin, urea are the particle of resin, benzoguanamine resin, benzoguanamine-melamine-formaldehyde condensation products etc.
These particulates can use a kind separately, and can also make up more than 2 kinds and use, from the aspect of the transparency and effect of the present invention, preferred silicon dioxide granule.
In addition, in ionizing radiation hardening resin composition of the present invention, can cooperate various additives according to the desired rerum natura of resulting curing resin layer.As this additive, for example can enumerate against weather improver, abrasion performance improving agent, polymerization inhibitor, crosslinking agent, infrared absorbent, antistatic additive, cohesive improving agent, levelling agent, thixotropy imparting agent, coupling agent, plasticizer, defoamer, filler, solvent, colouring agent etc.
At this,, can use ultra-violet absorber or light stabilizer as the against weather improver.For ultra-violet absorber, inorganic system, organic system can, as inorganic be ultra-violet absorber, can preferably use titanium dioxide about average grain diameter 5-120nm, cerium oxide, zinc oxide etc.In addition, as the organic system ultra-violet absorber, for example can enumerate BTA system, specifically can enumerate 3-[3-(BTA-2-the yl)-5-tert-butyl-hydroxy phenyl of 2-(2-hydroxy-5-methyl base phenyl) BTA, 2-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) BTA, polyethylene glycol] propionic ester etc.On the other hand,, for example can enumerate hindered amine system, specifically can enumerate 2-(3 as light stabilizer, the 5-di-tert-butyl-4-hydroxyl benzyl)-2 '-n-butylmalonic acid two (1,2,2,6,6-pentamethyl-4-piperidyl) ester, two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, four (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters etc.In addition, as ultra-violet absorber or light stabilizer, can also use in molecule reactive ultra-violet absorber or light stabilizer with polymerism bases such as (methyl) acryloyl groups.
As the abrasion performance improving agent, for example in inorganic matter, can enumerate the spherical particle of Alpha-alumina, silica, kaolinite, iron oxide, diamond, carborundum etc.Shape of particle can be enumerated ball, ellipsoid, polyhedron, scale shape etc., is not particularly limited, but preferably spherical.In organic matter, can enumerate synthetic resin pearls such as crosslinked acrylic resin, polycarbonate resin.Particle diameter is generally about the 30-200% of thickness.Among these materials, spherical Alpha-alumina hardness height, the effect that improves abrasion performance is big, in addition, and the spherical particle that relatively is easy to get, therefore preferred especially.
As polymerization inhibitor, for example can use quinhydrones, 1,4-benzoquinone, Hydroquinone monomethylether, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol etc., as crosslinking agent, for example can use polyisocyanate compounds, epoxide, metal-chelating compounds, aziridine cpd, oxazoline compound etc.
As filler, for example can use barium sulfate, talcum, clay, calcium carbonate, aluminium hydroxide etc.
As colouring agent, for example can use that quinacridone is red, isoindolinone is yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black etc. be known painted with pigment etc.
As infrared absorbent, for example can use two mercaptan is metal complex, phthalocyanine based compound, ジ イ Application モ ニ ウ Si compound etc.
In the present invention, mix above-mentioned polymerizable monomer or polyreactive oligomers and various additive in heterogeneity with given ratio respectively, the coating liquid that preparation ionizing radiation hardening resin composition forms as the ionizing radiation cure component.The viscosity of this coating liquid, so long as adopt viscosity that application pattern described later can form uncured resin layer at surface of bottom material just can, be not particularly limited.
In the present invention, adopt known modes such as heliogravure coating, rod are coated with, roller coat, contrary roller coat, comma coating, preferably adopt the heliogravure coating, apply the coating liquid of preparation like this at surface of bottom material, make the thickness after the curing reach 1-20 μ m, form uncured resin layer.Thickness when cured is 1 μ m when above, the curing resin layer that just can obtain having the function that requires.The thickness of the sealer after the curing is preferably about 2-20 μ m.
In the present invention, to ionizing radiations such as the uncured resin layer of such formation irradiation electron ray, ultraviolet rays, this uncured resin layer is solidified.At this, as the occasion of ionizing radiation use electron ray, about its accelerating potential, can be suitable selected according to the thickness of resin that uses or layer, preferably under about accelerating potential 70-300kV, make uncured resin layer curing usually.
In addition, in the irradiation of electron ray, accelerating potential is high more, the ability of seeing through increases more, therefore as the occasion of ground use because of the ground of electron ray deterioration, selected accelerating potential makes the thickness that sees through the degree of depth and resin bed of electron ray equal in fact, can suppress remaining electron ray irradiation ground thus, and the ground deterioration that the excess electron ray can be caused is limited in Min..
In addition, the useful to irradiation of rays amount, the amount that the crosslink density of preferred resin layer is saturated, selected in the scope of 5-300kGy (0.5-30Mrad) usually, preferably selected in the scope of 10-50kGy (1-5Mrad).
Have again, be not particularly limited as electronic radial source, for example can use various electron ray accelerators such as Cockcroft ワ Le ト Application type, model Dege loudspeaker husband type, resonance transformer type, insulation core transformers type or linear pattern, ダ イ Na ミ ト ロ Application type, high-frequency type.
Use ultraviolet occasion as ionizing radiation, radiation contains the ultraviolet radioactive ray of wavelength 190-380nm.Be not particularly limited as ultraviolet source, for example can use high-pressure sodium lamp, low pressure mercury lamp, metal halide lamp, carbon arc lamp etc.
Like this, in formed curing resin layer, add various additives, also can give various functions, for example high rigidity, the so-called hard conating function that marresistance is arranged, antifogging coating function, nonpolluting coating function, the anti-dazzle layer function, anti-reflection coating function, UV-preventing of being coated with are coated with layer function, infrared ray maskant function etc.
Ornament materials of the present invention can stick on the various substrates and use as decorative panel.Particularly, as shown in figure 10, on substrate 12, paste ornament materials 1 by adhesive phase 11.
The substrate that becomes the lining body is not particularly limited, and can suitably select plate, the ceramic industry of wooden systems such as plastic sheet, metallic plate, timber according to purposes is base material etc.The occasion that these substrates, particularly plastic sheet are used as substrate in order to improve the adaptation with ornament materials, can be implemented physics or chemical surface treatment such as oxidizing process or concavo-convexization method to single face or two sides as requested.
As above-mentioned oxidizing process, for example can enumerate Corona discharge Treatment, chromic acid oxidation processes, flame treatment, hot blast processing, ozone ultraviolet treatment etc., as concavo-convexization method, for example can enumerate sand-blast, solvent treatment method etc.These surface treatments are suitably selected according to the substrate kind, consider general preferred use Corona discharge Treatment method from aspects such as effect and operability.
As plastic sheet, can enumerate the plastic sheet that constitutes by various synthetic resin.As synthetic resin, can enumerate: polyvinyl resin, acrylic resin, the polymethylpentene resin, Corvic, the polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymerization resin, the ethane-acetic acid ethyenyl ester copolymer resins, ethylene-vinyl alcohol copolymer resin, pet resin, the polybutylene terephthalate (PBT) resin, PEN-ethylene isophthalate copolymer resins, plexiglass, the polyethyl methacrylate resin, the butyl polyacrylate resin, the polyamide of representatives such as nylon 6 or nylon 66, the cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, poly-arylide resin, perhaps polyimide resin etc.
As metallic plate, for example can use the metallic plate that constitutes by aluminium, iron, stainless steel or copper etc., in addition, can also use the metallic plate of these metals being implemented plating etc.
As the plate of wooden class, can enumerate China fir, Japanese cypress, beech, pine, lauan, teak, メ ラ ピ-etc. the sliced veneer, wood single-plate, wood gluing plate, chipboard, medium density fibre board (MDF) wood materials such as (MDF) etc. of various base materials.These plates can independent or stacked use.In addition, the plate of wooden system is not limited to wood based panel, also comprises the plastic plate that is added with the paper powder, is enhanced and stationery with intensity.
As ceramic industry is the base material, can exemplify out ceramic industrys such as plasterboard, calcium silicate board, wood chip cement plate and is building materials, pottery, glass, enamel, calcining ceramic tile, be plate of main material etc. with the volcanic ash.
In addition, fiber-reinforced plastic (FRP) plate, pasted on the two sides of honeycomb paper iron plate the base material, also can use with the complex of the various base materials such as base material of 2 aluminium sheet clamping polyvinyl resins as substrate.
In addition, this substrate both can implement to form the processing of prime coat etc., also can be pre-formed the decorative pattern under the viewpoint of the application that is used to adjust color or design.As the substrate that becomes the lining body, sheet material such as the flat board of various base materials, curved slab or above-mentioned base material are single or to carry out the compound three-dimensional shape article that obtain (moulding product) be object.
Also can paste lining materials such as Japan paper, external paper, synthetic paper, nonwoven, fabric, plumety, impregnated paper, synthetic resin sheet on ornament materials uses.By pasting lining material, produce following effects: ornament materials self strengthens, and prevents ornament materials cracking or destruction, prevents that adhesive is exuded to ornament materials surface etc., and when preventing defective products, operation becomes easily, can improve productive rate.
To on every, place ornament materials by adhesive like this or place the substrate of ornament materials continuously, compress with stickers such as cold press, hot press, roll squeezer, laminating machine, overlap joint, welt fitting machine, vacuum press, thereby ornament materials is bonded in substrate surface, makes decorative panel.
Adhesive uses sprayer, glue spreader, rod to be coated with applying device coatings such as machine.For this adhesive, can use adhesives such as vinyl acetate resin system, urea resin system, melamine resin system, phenolic resin system, isocyanate-based separately, perhaps, use these materials as being mixed the mixed type adhesive that obtains arbitrarily.Can in adhesive, add uses such as inorganic powder, wheat flour, wood powder, molding powder, colouring agent, insect-proof agent, mould inhibitor such as mixing talcum, calcium carbonate, clay, titanium white as required.Usually, the adhesive solids composition is 35-80 quality %, at coating amount 50-300g/m
2Scope in be coated in substrate surface.
Following method is usually adopted in the stickup of ornament materials on substrate: form adhesive phase at the ornament materials of the present invention back side, adhesive substrate, or on substrate applying adhesive, paste methods such as ornament materials.
The decorative panel of Zhi Zaoing can also cut off this decorative panel arbitrarily as described above, on the surface or timber crosscut oral area use cutting processing machines such as ditch slot milling machine, cutting machine to implement modifications arbitrarily such as ditch processing, groove processing.In addition, can be used in various uses, for example the incrustation plate of the casing of incrustation plate, kitchen, furniture or the light current of finishing facilities such as the interior decoration of buildings such as wall, ceiling, floor or external facing material, window frame, door leaf, handrail, skirting board, veranda, moulding, OA equipment etc., the interior trim of vehicle, outer decoration etc.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not subjected to any qualification of this embodiment.
(evaluation method)
For the ornament materials that in each embodiment, obtains, estimate in order to following method.
(1) evaluation of gloss
Use gloss analyzer (color technical research institute system " GMX-203 " in the village), under the condition of incidence angle 75 degree, measure the gloss number in high glaze zone and low gloss zone.Numeral is high more, and expression gloss is high more, and the low more expression gloss of numeral is low more.
(2) resistance to water
The cup that water is housed is being fallen to be fixed on the surface of ornament materials, placing and take away cup after 24 hours.Then, at room temperature placed 24 hours, whether the perusal surface variation such as expands.Estimate according to following determinating reference.
Zero does not change fully.
But though △ changes is slight, and it is no problem that actual use is gone up.
* expanding to wait changes obviously.
(3) fissility of process in time
Paste cellophane adhesive tape (the cellophane adhesive tape of ニ チ バ Application (strain) system, " セ ロ テ-プ (registration mark) " 2.5mm is wide) on ornament materials surface, placed 24 hours room temperature (25 ℃) and 50 ℃, pressure is peeled off then.The release surface of this ornament materials of perusal is estimated with following determinating reference.
Zero does not all have peeling off of pattern fully under any temperature.
Peeling off though △ is figuratum, is slight, and it is no problem that actual use is gone up.
Peeling off significantly of * pattern.
(4) stain resistance
According to JIS K-6902, in ornament materials surface applied pollutant, the residual condition of the pollutant after the perusal wiping.Estimate with following determinating reference.
Zero does not have the residual of pollutant fully.
Though △ has the residual of pollutant, be slight, it is no problem that actual use is gone up.
* pollutant residual significantly.
(5) マ-リ Application グ performance
Be adjusted to 29.4kPa (300g/cm
2) the weight of load on steel wool (#0000) is installed, the surface of friction ornament materials 50 times, the variation of this lustrous surface of perusal.Estimate with following determinating reference.
Zero does not change fully.
Though △ changes, be slight, it is no problem that actual use is gone up.
* be changed significantly.
As ground 2, use weight per unit area 30g/m made in U.S.A
2Building materials with strengthening paper between paper, on its one side, uses with acrylic resin and nitrocotton as adhesive, with titanium white, iron oxide red, chrome yellow printing ink, by photogravure enforcement coating amount 5g/m as colouring agent
2(comprehensively) layer, form dyed layer 6.Again in the above, use with nitrocotton as adhesive, contain with the printing ink of iron oxide red as the colouring agent of principal component, form the patterned layer 7 of wood grain decorative pattern by photogravure.
Then, use coating composition with coating amount 7g/m
2On whole, carry out photogravure, form impermeable layer 8 (prime coat), used coating composition is that resin and the PIC that is made of two isocyanic acid tolylene esters are as adhesive with the polyester urethanes of number-average molecular weight 20,000, glass transformation temperature (Tg)-59.8 ℃.
Secondly, use ink composite, form low gloss pattern ink lay 3 by photogravure, make it to be positioned at the duct portion of wood grain decorative pattern, tone is identical, and the used oil ink composition is with respect to number-average molecular weight 30,000, the polyester urethanes of glass transformation temperature (Tg)-62.8 ℃ is transparent ink 100 mass parts of resin as adhesive, cooperates the silicon dioxide granule of the average grain diameter 1.5 μ m of 10 mass parts to form.
On these ink laies, adopt heliogravure offset printing coating process with coating amount 5g/m
2Coating electron ray curing resin combination, this hardening resin composition comprises: as oxirane modification trimethylolpropane oxirane triacrylate 60 mass parts of 3 functional acrylate's monomers, as dipentaerythritol acrylate 40 mass parts of 6 functional acrylate's monomers, silicon dioxide granule 2 mass parts and siloxanes acrylic ester prepolymer 1 mass parts of average grain diameter 5 μ m.After the coating, the electron ray of irradiation accelerating potential 175kV, useful to irradiation of rays amount 50kGy (5Mrad) solidifies the electron ray curing resin combination, forms sealer 5.Then, 70 ℃ of maintenances of carrying out 24 hours, obtain ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 1 illustrates its result.
In the low gloss pattern printing ink of embodiment 1 record, with having mixed the polyester urethanes is that the mixture of resin 90 quality % and unsaturated polyester resin 10 quality % is as adhesive resin, and, as colouring agent, use and add carbon black and iron oxide red, be coloured to the colouring agent of pitchy, carry out similarly to Example 1 in addition, obtain ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 1 illustrates its result.
For the ornament materials that obtains among embodiment 1 and the embodiment 2; amplify its cross section with microscope and observe, observe: the positive top of the low gloss pattern ink lay in the sealer and near the low gloss state of one-tenth scattered light thereof, in addition; other superficial layers are scattered light not, becomes high pellucidity.In addition, from this ornament materials of sealer side perusal, low gloss pattern ink lay part is recess by understanding.
Making the silicon dioxide granule of the average grain diameter 5 μ m in the electron ray curing resin combination is 8 mass parts, carries out similarly to Example 1 in addition, obtains ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 1 illustrates its result.
The adhesive that is used in the printing ink that forms low gloss pattern ink lay is the mixture of resin 80 quality % and unsaturated polyester resin 20 quality % for the polyester urethanes that embodiment 1 puts down in writing, making the silicon dioxide granule of the average grain diameter 5 μ m in the electron ray curing resin combination is 8 mass parts, carry out similarly to Example 1 in addition, obtain ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 1 illustrates its result.
For the ornament materials that obtains among embodiment 3 and the embodiment 4; amplify its cross section with microscope and observe, observe: the positive top of the low gloss pattern ink lay in the sealer and near the low gloss state of one-tenth scattered light thereof, in addition; other superficial layers are scattered light not, becomes high pellucidity.In addition, from this ornament materials of sealer side perusal, low gloss pattern ink lay part is recess by understanding.
In addition, the outward appearance of the duct portion in the wood grain decorative pattern of the ornament materials that obtains in embodiment 4 is compared with embodiment 1, and the sense of vision recess of duct portion looks distincter.
Table 1
Make low gloss pattern ink lay 3 as described in Figure 6, the level for 3 ladders represented as 3-a, 3-b and 3-c in addition, carries out similarly to Example 1, obtains ornament materials.The coating amount of the printing ink that 3-a, 3-b and 3-c use is as shown in table 2.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application ゲ performance is estimated in time.Table 2 illustrates its result.
The coating amount of low gloss pattern printing ink is changed continuously, form low gloss pattern ink lay 3, make it as shown in Figure 7, the thickness of layer changes continuously, in addition, carries out similarly to Example 5, obtains ornament materials.In addition, the formation of ground, dyed layer, patterned layer and impermeable layer is identical with embodiment 5.
The coating amount of low gloss pattern printing ink is 8g/m in the thickest part of the thickness of layer
2, be the center with the thickest part of thickness, during by circular coating printing ink, reduce coating amount continuously, make the circumferential section of 1cm radius reach 0g/m
2
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 2 illustrates its result.
For the ornament materials that obtains among embodiment 5 and the embodiment 6; amplify its cross section with microscope and observe, observe: the positive top of the low gloss pattern ink lay in the sealer and near the low gloss state of one-tenth scattered light thereof, in addition; other superficial layers are scattered light not, becomes high pellucidity.In addition, from the ornament materials of sealer side perusal embodiment 5, low gloss pattern ink lay part is recess by understanding, and this recess is become the so-called level decorative pattern that ladder ground changes by understanding.In addition, from the ornament materials of sealer side perusal embodiment 6, low gloss pattern ink lay part is recess by understanding, and this recess is become the continually varying decorative pattern by understanding.
Table 2
As ground 2, use weight per unit area 30g/m made in U.S.A
2Building materials with strengthening paper between paper, on its one side, uses with acrylic resin and nitrocotton as adhesive, with titanium white, iron oxide red, chrome yellow printing ink, by photogravure enforcement coating amount 5g/m as colouring agent
2(comprehensively) layer, form dyed layer 6.Again in the above, use with nitrocotton as adhesive, contain with the printing ink of iron oxide red as the colouring agent of principal component, form the patterned layer 7 of wood grain decorative pattern by photogravure.
Then, use coating composition with coating amount 7g/m
2On whole, carry out photogravure, form impermeable layer 8, used coating composition is that resin and the PIC that is made of two isocyanic acid tolylene esters are as adhesive with the polyester urethanes of number-average molecular weight 20,000, glass transformation temperature (Tg)-59.8 ℃.
Secondly, use ink composite, form low gloss pattern ink lay 3 by photogravure, make it to be positioned at the duct portion of wood grain decorative pattern, tone is identical, and the used oil ink composition is with respect to number-average molecular weight 30,000, the polyester urethanes of glass transformation temperature (Tg)-62.8 ℃ is that resin is transparent ink 100 mass parts of adhesive, cooperates the silicon dioxide granule of the average grain diameter 1.5 μ m of 10 mass parts to form.The coating amount of this moment is 3g/m
2, the thickness of the low gloss pattern ink lay 3 behind the sealer of formation next procedure is 2 μ m.
On these ink laies, adopt heliogravure offset printing coating process with coating amount 6g/m
2Coating electron ray curing resin combination, this hardening resin composition comprises: as oxirane modification trimethylolpropane oxirane triacrylate 60 mass parts of 3 functional acrylate's monomers, dipentaerythritol acrylate 40 mass parts, the average grain diameter 2.5 μ m as 6 functional acrylate's monomers, silicon dioxide granule 8 mass parts and siloxanes acrylic ester prepolymer 1 mass parts of CV value 10%.After the coating, the electron ray of irradiation accelerating potential 175kV, useful to irradiation of rays amount 50kGy (5Mrad) solidifies the electron ray curing resin combination, forms sealer 5.Not having the thickness of sealer 5 in the zone of low gloss pattern ink lay 3 is 4 μ m.Then, 70 ℃ of maintenances of carrying out 24 hours, obtain ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application ゲ performance is estimated in time.Table 3 illustrates its result.
Reference example 1
In embodiment 7, as the silicon dioxide granule in the electron ray curing resin combination, use the silicon dioxide granule of average grain diameter 1.0 μ m, CV value 10%, in addition, carry out operation similarly to Example 1, make ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 3 illustrates its result.
Reference example 2
In embodiment 7, as the silicon dioxide granule in the electron ray curing resin combination, use the silicon dioxide granule of average grain diameter 6.0 μ m, CV value 10%, in addition, carry out operation similarly to Example 7, make ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 3 illustrates its result.
Reference example 3
In embodiment 7, do not contain silicon dioxide granule in the electron ray curing resin combination, in addition, carry out operation similarly to Example 7, make ornament materials.
For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application グ performance is estimated in time.Table 3 illustrates its result.
Ornament materials for embodiment 7 and reference example 1-3; amplify its cross section with microscope and observe, observe: the positive top of the low gloss pattern ink lay in the sealer and near the low gloss state of one-tenth scattered light thereof, in addition; other superficial layers are scattered light not, becomes high pellucidity.In addition; in embodiment 7; found that at the surface protection laminar surface on the positive top that is positioned at low gloss pattern ink lay silicon dioxide granule appears, simultaneously, do not found that at the surface protection laminar surface in the zone that does not have low gloss pattern ink lay silicon dioxide granule appears.
Relative with it, in reference example 1, at the sealer that is present in the positive top of low gloss pattern ink lay and there is not any surface of sealer in the zone of low gloss pattern ink lay, all do not find appearing of silicon dioxide granule.In addition, in reference example 2, at the sealer that is present in the positive top of low gloss pattern ink lay and there is not any surface of sealer in the zone of low gloss pattern ink lay, all found appearing of silicon dioxide granule.
In addition; from the above-mentioned ornament materials of sealer side perusal; the low gloss pattern ink lay part of all examples is all become recess by understanding; the outward appearance of the duct portion in the wood grain decorative pattern of the ornament materials that obtains among the embodiment 7; with comparing of comparative example, the sense of vision recess of duct portion looks distincter.
The useful to irradiation of rays amount that makes electron ray is 30kGy (3Mrad), carries out similarly to Example 1 in addition, obtains ornament materials.The conduit part that is observed visually this ornament materials is sharp keen shape.
Reference example 4
In conduit printing ink, do not add silica, carry out similarly to Example 8 in addition, obtain ornament materials.Be observed visually: the conduit part of this ornament materials is compared with the ornament materials that embodiment 8 makes, for lacking the shape of acutance.
Making the dioxide-containing silica in the conduit printing ink is 20 quality %, carries out similarly to Example 8 in addition, obtains ornament materials.Be observed visually: the gloss of the conduit part of this ornament materials is not too low, may not be enough as the design sense, but conduit part is sharp keen shape.
It is dark and make a plate that the version of using in the conduit printing ink is changed version, makes the transfer amount difference of printing ink, carries out similarly to Example 8 in addition, obtains ornament materials.Version the darkest dark part is 70 μ m, and it is dark that the stepless terrace land is adjusted version, makes the level version of the part of groove (cell) never to the part of the degree of depth 70 μ m.With the gloss of the corresponding part of part that does not have groove be gloss number 60, with the gloss of the corresponding part of version dark 30-40 μ m, be gloss number 30, with the gloss of the corresponding part of version dark 60-70 μ m, be gloss number 10, gloss stepless terrace land variation continuously between it.By using this version, and use conduit printing ink of the present invention, can obtain more ornament materials near the wood grain tone of natural goods.
In the electron ray curing resin combination, further add calcined kaolin 10 mass parts (average grain diameter 1.5 μ m), carry out similarly to Example 1 in addition, obtain ornament materials.For this ornament materials, to gloss, resistance to water, fissility, stain resistance and the マ of process-リ Application ゲ performance is estimated in time.Table 3 illustrates its result.By adding calcined kaolin, compare with the ornament materials that embodiment 1 obtains, マ-リ Application グ further improves.
Table 3
The back side of the ornament materials that embodiment 1 is made and bonding by adhesive phase as the lauan glued board 10 of the thickness 2.5mm of substrate, make the wooden decorative plate thus, it is that adhesive " BA-820 " is at coating amount 60g/m that the adhesive therefor layer is to use the aqueous emulsion ethylene vinyl acetate of central physics and chemistry (strain) system
2(wet) be coated under the condition and form on the wood gluing plate.
Industrial applicibility
According to the present invention, can access a kind of ornament materials, this ornament materials forms decorative pattern on the surface, have and the corresponding gloss difference of decorative pattern, this gloss difference is visually become recess by understanding, and the surface has concave-convex sense, and solvent resistance, abrasion performance or interlaminar strength height. Particularly in the occasion that is used for the wood grain decorative pattern, gloss difference and the concave-convex sense of duct portion can be showed truly, the texture same with the material that has used actual timber can be accessed.
Claims (19)
1. ornament materials; it has low gloss pattern ink lay and sealer that part is provided with at least on ground; this sealer is present on the described low gloss pattern ink lay and contact with it; and be covered comprising the zone that forms described low gloss pattern ink lay and do not form in the gamut in zone of described low gloss pattern ink lay; wherein; described sealer is the layer that ionizing radiation hardening resin composition crosslinking curing obtains; and in this sealer; the positive top of this low gloss pattern ink lay and near be formed with visually that understanding is the low gloss zone of recess, contain the non-crosslinked polyurethane resin as adhesive and constitute in the low gloss pattern printing ink of described low gloss pattern ink lay.
2. ornament materials; it has low gloss pattern ink lay and sealer that part is provided with at least on ground; this sealer is present on this low gloss pattern ink lay and contact with it; and be covered comprising the zone that forms this low gloss pattern ink lay and do not form in the gamut in zone of this low gloss pattern ink lay; it is characterized in that; this sealer is the layer that ionizing radiation hardening resin composition crosslinking curing obtains; the low gloss pattern printing ink that constitutes low gloss pattern ink lay contains the non-crosslinked polyurethane resin as adhesive, and the ionizing radiation hardening resin composition comprises (methyl) acrylate monomer.
3. ornament materials according to claim 2, the low gloss pattern printing ink that constitutes low gloss pattern ink lay contain non-crosslinked polyurethane resin and unsaturated polyester resin as adhesive.
4. according to claim 2 or 3 described ornament materials, the ionizing radiation hardening resin composition only is made up of (methyl) acrylate monomer.
5. according to wantonly 1 described ornament materials of claim 1-3, constitute printing ink in uneven thickness of low gloss pattern ink lay.
6. ornament materials according to claim 5, above-mentioned low gloss pattern ink lay comprises the thick film areas that thickness is thick relatively and the film zone of thickness relative thin, simultaneously, form positive top and the neighbouring positive top and near the low gloss zone thereof of this thick film areas for higher relatively gloss for lower relatively gloss, this film zone.
7. according to wantonly 1 described ornament materials of claim 1-3; it is characterized in that; contain particulate in the above-mentioned sealer, and the average grain diameter of this particulate is the positive side neighbor of maximum ga(u)ge that is positioned at the sealer on the positive top of above-mentioned low gloss pattern ink lay.
8. ornament materials according to claim 7, the coefficient of variation CV value of the size distribution of particulate i.e. (standard deviation/average grain diameter of particle diameter) * 100 are below 30%.
9. ornament materials according to claim 7 is designated as d with the average grain diameter of particulate
A, the maximum ga(u)ge that will be positioned at the sealer on the positive top of low gloss pattern ink lay is designated as t
M, will not exist the surface protection layer thickness in the zone of low gloss pattern ink lay to be designated as t
GThe time, satisfy the relation of formula (I):
1.05×t
M≤d
A≤t
G …(I)。
10. ornament materials according to claim 7, the content of the particulate in the sealer are 2-20 quality %.
11. wantonly 1 described ornament materials according to claim 1-3; above-mentioned sealer is to contain the layer that the ionizing radiation hardening resin composition crosslinking curing of oxirane modified poly compound obtains, and this sealer contains the calcined kaolin particle.
12. wantonly 1 the described ornament materials according to claim 1-3 is characterized in that, the low gloss pattern printing ink that constitutes low gloss pattern ink lay comprises filler pigment.
13. according to wantonly 1 described ornament materials of claim 1-3, the ionizing radiation hardening resin composition is the electron ray curing resin combination.
14. ornament materials according to claim 1, the surface that is positioned at the sealer on top, low gloss zone has convex form.
15. wantonly 1 the described ornament materials according to claim 1-3 also further has impermeable layer between ground and low gloss pattern ink lay.
16. ornament materials according to claim 15, ground are the permeability grounds.
17. wantonly 1 described ornament materials according to claim 1-3; stacked on ground have chromatograph, patterned layer and an impermeable layer; have low gloss pattern ink lay and sealer at these above the layer; this sealer is present on this low gloss pattern ink lay and contact with it, and is covered comprising the zone that forms this low gloss pattern ink lay and do not form in the gamut in zone of this low gloss pattern ink lay.
18. ornament materials according to claim 17, wherein patterned layer forms the wood grain decorative pattern, and low gloss pattern ink lay forms the low gloss part of the conduit part in this wood grain decorative pattern.
19. a decorative panel, this decorative panel stick on the substrate by wantonly 1 the described ornament materials with claim 1-18 and form.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP341788/2003 | 2003-09-30 | ||
| JP341789/2003 | 2003-09-30 | ||
| JP2003341788 | 2003-09-30 | ||
| JP426480/2003 | 2003-12-24 | ||
| JP020803/2004 | 2004-01-29 |
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| Publication Number | Publication Date |
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| CN1860028A CN1860028A (en) | 2006-11-08 |
| CN100528558C true CN100528558C (en) | 2009-08-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800284101A Active CN100528558C (en) | 2003-09-30 | 2004-09-30 | Decorating material |
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| CN (1) | CN100528558C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102729680A (en) * | 2011-03-30 | 2012-10-17 | Dic株式会社 | Film for thermal transfer and decoration molded apparatus |
| CN107405889A (en) * | 2014-03-27 | 2017-11-28 | 大日本印刷株式会社 | Sheet material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102182109B (en) * | 2011-05-04 | 2012-07-25 | 富阳荣胜纸业有限公司 | Black paper-making coating and method for producing black paperboard by utilizing same |
| CN102251441B (en) * | 2011-07-07 | 2013-09-04 | 广东玉兰装饰材料有限公司 | Wall paper with deodorizing function and preparation method thereof |
| JP6034440B1 (en) * | 2015-04-28 | 2016-11-30 | 日本写真印刷株式会社 | Decorative sheet, manufacturing method of molded product, and molded product |
| JP6958550B2 (en) * | 2016-05-26 | 2021-11-02 | 凸版印刷株式会社 | Cosmetic material |
| JP7259201B2 (en) * | 2018-01-22 | 2023-04-18 | 凸版印刷株式会社 | makeup sheet |
| CN108508015A (en) * | 2018-03-30 | 2018-09-07 | 无锡尚德太阳能电力有限公司 | Photovoltaic glass plated film resistance to soiling test method |
| EP4249249A3 (en) * | 2019-03-28 | 2023-11-15 | Dai Nippon Printing Co., Ltd. | Decorative material and method for producing same |
| WO2020215845A1 (en) * | 2019-04-26 | 2020-10-29 | 苏州镓祥新材料科技有限公司 | Multi-layer composite color-coated printed metal board, household appliance shell and decorative material |
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2004
- 2004-09-30 CN CNB2004800284101A patent/CN100528558C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102729680A (en) * | 2011-03-30 | 2012-10-17 | Dic株式会社 | Film for thermal transfer and decoration molded apparatus |
| CN107405889A (en) * | 2014-03-27 | 2017-11-28 | 大日本印刷株式会社 | Sheet material |
| US10457025B2 (en) | 2015-03-26 | 2019-10-29 | Dai Nippon Printing Co., Ltd. | Sheet |
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| CN1860028A (en) | 2006-11-08 |
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