CN106626854A - Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board - Google Patents

Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board Download PDF

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Publication number
CN106626854A
CN106626854A CN201611233818.3A CN201611233818A CN106626854A CN 106626854 A CN106626854 A CN 106626854A CN 201611233818 A CN201611233818 A CN 201611233818A CN 106626854 A CN106626854 A CN 106626854A
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China
Prior art keywords
composition
aforementioned
resin
transfer sheet
energy ray
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CN201611233818.3A
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Chinese (zh)
Inventor
土井裕之
小寺恒太郎
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Eike Kogyo K K
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Eike Kogyo K K
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Publication of CN106626854A publication Critical patent/CN106626854A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38242—Contact thermal transfer or sublimation processes characterised by the use of different kinds of energy to effect transfer, e.g. heat and light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Optics & Photonics (AREA)
  • Fluid Mechanics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Disclosed is an active energy ray-curable resin composition which is characterized by containing (A) a urethane acrylate resin or acrylic resin having two radical reactive groups and (B) a urethane acrylate resin or acrylic resin having six or more radical reactive groups. The active energy ray-curable resin composition is also characterized in that the amount of the component (A) is 30-70 parts by weight when the total amount of the component (A) and the component (B) is taken as 100 parts by weight.

Description

Curable with actinic energy ray resin combination, transfer sheet, decorative panel and decorative panel Manufacture method
The application be September in 2010 submit within 30th it is entitled " curable with actinic energy ray resin combination, transfer sheet, The divisional application of 201080043243.3 applications for a patent for invention of the manufacture method of decorative panel and decorative panel ".
The mutual reference of related application
The application advocates the preferential of the Patent 2009-227539 proposed in the Japan Patent Room for 30th in September in 2009 Power, entire contents by reference to and quote in this specification.
Technical field
The present invention relates to it is a kind of for example for the curable with actinic energy ray resin combination of decorative panel purposes, transfer sheet, Decorative panel and its manufacture method.
Background technology
All the time, as raising plaque surface marresistance, resistance to chemical reagents, stain resistance, the means of weatherability, Known following methods：Decorative panel masking liquid of the surface coating comprising curable with actinic energy ray resin or thermmohardening type resin and The method hardened；Masking liquid of the coating comprising these resins, is hardened on the base material with fissility, becomes transfer sheet Afterwards, the hardened coating film for making transfer sheet is overlapped in decorative panel, and by heating pressurization etc., and the surface transfer hardening in the decorative panel is applied The method of film；And, the film being arranged on base material is become semi-hardened state and as transfer sheet, is made the semihard of transfer sheet Change state adhering molding transfer carries out cure process after plaque surface, once again, arranges with aforementioned patience in plaque surface The method of film.The film for particularly hardening by active energy ray has good coating characteristic (marresistance, anti-pollution Property etc.), therefore, the method for plaque surface is arranged on to film various motions (referenced patent document 1-2).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-137942 publications
Patent document 2：Japanese Unexamined Patent Publication 2003-183339 publications
The content of the invention
The invention problem to be solved
But, the film typically with aforementioned patience be in molecule with many reactive functional groups crosslink material and Into, have a case that high crosslink density is more, when the film is directly sealed at decorative panel, due to the densification of film Property, curing shrinkage etc., situation about being significantly deteriorated to the adaptation of plaque surface is more.Additionally, when using transfer sheet Present situation is to arrange prime coat or adhesive phase etc. in the film side of transfer sheet or decorative panel side and guarantee adaptation.
It is an object of the invention to provide one kind is required for priming paint or adhesive and can make active energy ray hardening tree The positively closely sealed curable with actinic energy ray resin combination on melmac layer etc. of the hardening thing of oil/fat composition, The manufacture method of transfer sheet, decorative panel and decorative panel.
Means for solving the problems
The curable with actinic energy ray resin combination of the present invention, it is characterised in that：It is anti-containing 2 free radicals comprising (A) The urethane acrylate resin or acrylic resin and (B) of answering property group contains more than 6 free-radical reactive bases The urethane acrylate resin or acrylic resin of group, is 100 in the total amount of aforementioned (A) composition and aforementioned (B) composition During weight portion, the amount of aforementioned (A) composition is 30-70 weight portions.
By using the curable with actinic energy ray resin combination of the present invention, even if not in the film side of such as transfer sheet Or prime treatment is implemented in decorative panel side, it is also possible to obtain the layer (hardening being made up of curable with actinic energy ray resin combination Thing) adaptation, the good decorative panel of marresistance and resistance to chemical reagents.
The curable with actinic energy ray resin combination of the present invention preferably also includes electric conductivity colloidal sol.
The transfer sheet of the present invention includes：Fissility base material and be formed on aforementioned fissility base material by foregoing active energy The layer of amount line hardened resin composition composition.
The decorative panel of the present invention includes：Melmac layer and be formed on aforementioned melmac layer by front State the layer of the hardening thing composition of curable with actinic energy ray resin combination.
The manufacture method of the decorative panel of the present invention is stacking core, impregnates using thermosetting resin as master on facing paper The resin liquid of composition and dry resin dipping decorative paper and preceding transfer piece, carry out hot forming, and in the heat After pressing formation, aforementioned fissility base material is removed.
Description of the drawings
Composition profile when Fig. 1 is in order to obtain the resistance to chemical reagents decorative panel of the present invention and stacking material.
Fig. 2 is the composition profile of the resistance to chemical reagents decorative panel of the present invention.
Reference
1- fissility base materials；
2- uv-hardening resin compositions；
The hardening thing of 2a- uv-hardening resin compositions；
3- transfer sheets；
6- resin dipping decorative papers；
The resin dipping decorative paper of 6a- hardening；
7- resins impregnate core paper；
The resin dipping core paper of 7a- hardening；
9- resistance to chemical reagents decorative panels.
Specific embodiment
Hereinafter, the present invention is described in detail.It is anti-containing 2 free radicals in (A) composition for using in the present invention The urethane acrylate resin of answering property group react for such as polyalcohol and diisocyanate obtained from isocyanide The acrylate monomer with hydroxyl such as ester compound and hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl Reaction product.(A) weight average molecular weight of composition is preferably 500-1500.
Additionally, in (A) composition for using in the present invention, as the acrylic acid tree containing 2 free-radical reactive groups Fat, the material for for example being formed by the polymer of the derivative of acrylic acid, methacrylic acid or these materials can enumerate example Such as with methyl acrylate, ethyl acrylate, butyl acrylate acrylate, methyl methacrylate, EMA, Polymer of the methacrylates such as butyl methacrylate as principal component.
In (B) composition for using in the present invention, the carbamate propylene containing more than 6 free-radical reactive groups Acid ester resin occurs anti-for such as polyalcohol such as PEPA, PPG, polycarbonate polyol and diisocyanate Isocyanate compound and trimethylolpropane trimethacrylate, pentaerythritol triacrylate, two seasons penta 4 obtained from answering The reaction product of the acrylate monomer with hydroxyl such as alcohol triacrylate.(B) weight average molecular weight of composition is preferably 500-6000。
Additionally, in (B) composition for using in the present invention, as the propylene containing more than 6 free-radical reactive groups Acid resin is the material that the polymer of the derivative for example by acrylic acid, methacrylic acid or these materials is formed, can To enumerate for example with the acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methyl-prop Polymer of the methacrylates such as olefin(e) acid ethyl ester, butyl methacrylate as principal component.
(A) mixed proportion of composition and (B) composition is preferably 70：30-30：70 weight portions (solid state component ratio), (B) into When dividing not enough lower limit, the adaptation, resistance to chemical reagents in the layer being made up of curable with actinic energy ray resin combination easily becomes Difference, when more than the upper limit, adaptation is easily deteriorated.
Relative to all solid state composition of curable with actinic energy ray resin combination, (A) composition and the total amount of (B) composition Ratio (weight ratio) is preferably the scope of 90-100 ﹪.
In the curable with actinic energy ray resin combination of the present invention, preferably in addition to (A) composition and (B) composition, Also it is mixed into electric conductivity colloidal sol.Electric conductivity colloidal sol has the effect that：When decorative panel is manufactured, prevent from being coated with fissility base material The transfer sheet of curable with actinic energy ray resin combination is powered, can prevent in the process of transfer sheet because electrostatic occurs And the dust attachment for causing.Particularly preferred antimony system electric conductivity colloidal sol, the usage amount of electric conductivity colloidal sol is preferably relative to (A) composition (B) weight portion of total 100 of composition is the scope of 8-15 weight portions.When more than 15 weight portion, colour and resistance to chemical reagents energy Easily it is deteriorated, when less than 8 weight portion, it is impossible to obtain sufficient powered preventing effectiveness.
As antimony system electric conductivity colloidal sol, Nissan Chemical Industries Ltd. as commercially available product can be enumerated CELNAX (registration mark) series (zinc antimonates system).As water dispersion sol, there are CX-Z330H, CX-Z330H-F2, or As methyl alcohol dispersion sol, there are CX-Z641M, CX-Z603M, CX-Z603M-F2, CX-Z610M-F2, CX- Z653M-F, CX-Z693M-F, or as isopropanol dispersion sol, have CX-Z210IP, CX-Z210IP-F2 (to be all Trade name), can according to (A) composition, the species of (B) composition, mixed proportion and moderately select and use.
Additionally, in irradiation ultraviolet radiation, preferably in the curable with actinic energy ray resin combination of the present invention, except (A) beyond composition and (B) composition, also it is mixed with light trigger.Light trigger can use such as benzyl ketals, Alpha-hydroxy second Acyl benzene, α-amido acetophenone, acylphosphine oxide, titanocenes based compound, oxime ester etc..As commercially available product, can enumerate IRGACURE 184,369,651,819, DAROCUR 1173 (CIBA SPECIALTY CHEMICALS limited companies system, Trade name) etc..The usage amount of light trigger is 1-10 preferably relative to the weight portion of total 100 of (A) composition and (B) composition Weight portion.When higher than 10 weight portion, hardening envelope is easily coloured, and when less than 1 weight portion, cannot obtain sufficiently hard sometimes Change.
The fissility base for (being for example coated with curable with actinic energy ray resin combination) used in the transfer sheet of the present invention After material on the surface of resin dipping decorative paper to transfer curable with actinic energy ray resin combination by hot forming, can With the base material peeled off, it is possible to use polyester film, polyethylene film, polypropylene film, glassine paper, diacetyl cellulose Film, triacetyl cellulose film, acetylcellulose butyric acid ester film, polyvinyl chloride film, polyvinylidene chloride film, Polyvinyl alcohol film, ethylene vinyl alcohol film, polystyrene film, polycarbonate film, poly-methyl pentene film, polysulfones are thin Film, polyether ketone film, Polyethersulfone membranes, PEI film, Kapton, fluorine resin film, nylon film, propylene The metal formings such as the plastic sheetings such as acyl film, aluminium foil, stainless steel foil, Copper Foil.
When foregoing active energy line hardened resin composition is coated with the surface of aforementioned fissility base material, it is possible to use Known method, such as spraying process, gravure coat method, bar coating, scraper for coating method, pressure roller rubbing method, scraper plate rubbing method, Mould rubbing method, heavy curtain rubbing method etc..Dried coating thickness is preferably 1-100 μm or so.
After the surface coating curable with actinic energy ray resin combination of fissility base material, such as electronics can be irradiated Line, ultraviolet.In irradiation ultraviolet radiation, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, arc, carbon, gold are preferably used Category halide lamp etc., in 100-400nm, the wavelength region of preferred 200-400nm, irradiation has 100-800mJ/cm2Energy Ultraviolet.In the condition hot forming, and the closely sealed of resin dipping decorative paper becomes firm.Furthermore, it is possible to as needed in Harden under blanket of nitrogen.
As the resin dipping decorative paper used in the decorative panel of the present invention, generally well-known decorative panel is adapted for use with With on facing paper using the good melamine formaldehyde resin of thermosetting resin, particularly heat resistance and resistance to abrasion as master The resin liquid dipping decorative paper of composition and the facing paper being dried to obtain.
For core, it is possible to use at the Jing thermosetting resin dippings such as decorative panel brown paper, adhesive-bonded fabric, braid The resin dipping core paper of reason, plywood, MDF (Medium Density Fiberboard：Medium density fibre board (MDF)), wood chip hardboard Etc. wooden system's base material, according to appropriate purposes, desired quality and selected.
Embodiment 1
The urethane acrylates of (A) containing 2 free-radical reactive groups are diluted by the weight portion of methyl ethyl ketone 40 Ester resin UN-2301 (trade names：ART-RESIN, Gen Shang Industries, Inc system, weight average molecular weight 740) 70 weight Part, the urethane acrylate resin UN-904 (trade name of (B) containing 10 free-radical reactive groups：ART- RESIN, Gen Shang Industries, Inc system, weight average molecular weight 4900) 30 weight portions and light trigger IRGACURE184 (CIBA SPECIALTY CHEMICALS limited companies system, trade name) 3 weight portions, obtain ultraviolet Line hardened resin composition (curable with actinic energy ray resin combination).
Then, in OPP (the Oriented Polypropylene of 80 μm of thickness：Oriented polypropylene) be coated with film it is aforementioned Uv-hardening resin composition and cause dry film thickness to be 30 μm, make the exposure intensity be with high-pressure mercury-vapor lamp irradiation ultraviolet radiation 400mJ/cm2, transfer sheet is obtained, cure the week of transfer sheet 1.The transfer sheet 3 as shown in Figure 1, including：OPP film (is peeled off Property base material) 1 and it is formed at the layer 2 formed on the OPP film 1, by uv-hardening resin composition.
In base weight 100g/m2Printing paper on impregnate resin liquid using melamine formaldehyde resin as principal component, enter Row drying and obtain melmac dipping decorative paper.
In base weight 185g/m2Brown paper on impregnate resin liquid using phenol-formaldehyde resin as principal component, done It is dry and obtain phenolic resin dipping core paper.
As shown in Figure 1, by following in turn, 5 phenolic resin dipping core papers 7,1 Zhang San's cymels are laminated Dipping decorative paper 6 and 1 transfer sheet 3, with 132 DEG C of temperature, pressure 70kg/cm2Condition carrying out hot forming, in shaping Afterwards, OPP (Oriented Polypropylene are removed：Oriented polypropylene) film, obtain the resistance to chemical reagents decorative panel shown in Fig. 2 9.In resistance to chemical reagents decorative panel 9,7a is the resin dipping core paper of hardening, and 6a is the resin dipping decorative paper of hardening, and 2a is purple The hardening thing of outside line hardened resin composition.
Embodiment 2
Except using light-cured acrylate (light acrylate) 1,6HX-A (chemistry limited companies of common prosperity society System, molecular weight 226) 70 weight portions as (A) composition, using KAYARAD DPHA (NIPPON PHARMACEUTICAL CO., LTD's system, molecule 878) beyond 30 weight portions are as (B) composition, remaining is implemented amount in the same manner as previous embodiment 1.
Here, light-cured acrylate 1,6HX-A is the acrylic resin comprising 2 free-radical reactive groups.This Outward, KAYARAD DPHA are the acrylic resin comprising 6 free-radical reactive groups.
Embodiment 3
Except (A) composition combined amount (B) composition for 50 weight portions combined amount be 50 weight portions in addition to, remaining with it is front State embodiment 1 similarly to implement.
Embodiment 4
Except using light-cured acrylate 1,6HX-A (chemistry limited company of common prosperity society system, molecular weight 226) 50 Weight portion as (A) composition, using KAYARAD DPHA (NIPPON PHARMACEUTICAL CO., LTD's system, molecular weight 878) 50 weight portions Beyond as (B) composition, remaining is implemented in the same manner as previous embodiment 1.
Embodiment 5
Except (A) composition combined amount (B) composition for 30 weight portions combined amount be 70 weight portions in addition to, remaining with it is front State embodiment 1 similarly to implement.
Embodiment 6
The carbamic acid of (A) containing 2 free-radical reactive groups is diluted by the weight portion of 4-methyl-2 pentanone 20 Ester acrylate UN-2301 (trade names：ART-RESIN, Gen Shang Industries, Inc system) 70 weight portions, (B) Urethane acrylate resin UN-904 (trade name containing 10 free-radical reactive groups：ART-RESIN, root Upper Industries, Inc's system) 30 weight portions, light trigger IRGACURE184 (CIBA SPECIALTY CHEMICALS stocks Part Co., Ltd system, trade name) 5 weight portions, light trigger IRGACURE819 (CIBA SPECIALTY CHEMICALS stocks Part Co., Ltd system, trade name) 1 weight portion and electric conductivity colloidal sol zinc antimonates isopropanol dispersion sol (CELNAX CX-Z210IP-F2, ZnSb2O6：20 ﹪, Nissan Chemical Industries Ltd.'s system, trade name) 12.5 weight portions, come Obtain uv-hardening resin composition.
Then, in OPP (the Oriented Polypropylene of 80 μm of thickness：Oriented polypropylene) be coated with film it is aforementioned Uv-hardening resin composition and cause dry film thickness to be 30 μm, make the exposure intensity be with high-pressure mercury-vapor lamp irradiation ultraviolet radiation 400mJ/cm2, transfer sheet is obtained, cure the week of transfer sheet 1.
In base weight 100g/m2Printing paper on impregnate resin liquid using melamine formaldehyde resin as principal component, enter Row drying and obtain melmac dipping decorative paper.
In base weight 185g/m2Brown paper on impregnate resin liquid using phenol-formaldehyde resin as principal component, done It is dry and obtain phenolic resin dipping core paper.
By following in turn, 5 phenolic resin dipping core papers, 1 Zhang San's cymel dipping decorative papers and 1 are laminated Transfer sheet is opened, with 132 DEG C of temperature, pressure 70kg/cm2Condition carrying out hot forming, after forming, remove OPP (Oriented Polypropylene：Oriented polypropylene) film, obtain resistance to chemical reagents decorative panel.
Embodiment 7
Except using light-cured acrylate 1,6HX-A (chemistry limited company of common prosperity society system, molecular weight 226) 70 Weight portion as (A) composition, using KAYARAD DPHA (NIPPON PHARMACEUTICAL CO., LTD's system, molecular weight 878) 30 weight portions Beyond as (B) composition, remaining is implemented in the same manner as previous embodiment 6.
Embodiment 8
Except (A) composition combined amount (B) composition for 50 weight portions combined amount be 50 weight portions in addition to, remaining with it is front State embodiment 6 similarly to implement.
Embodiment 9
Except using light-cured acrylate 1,6HX-A (chemistry limited company of common prosperity society system, molecular weight 226) 50 Weight portion as (A) composition, using KAYARAD DPHA (NIPPON PHARMACEUTICAL CO., LTD's system, molecular weight 878) 50 weight portions Beyond as (B) composition, remaining is implemented in the same manner as previous embodiment 6.
Embodiment 10
Except (A) composition combined amount (B) composition for 30 weight portions combined amount be 70 weight portions in addition to, remaining with it is front State embodiment 6 similarly to implement.
Embodiment 11
In addition to the combined amount of CX-Z210IP-F2 is 10 weight portions, remaining is implemented in the same manner as previous embodiment 8.
Embodiment 12
In addition to the combined amount of CX-Z210IP-F2 is 15 weight portions, remaining is implemented in the same manner as previous embodiment 8.
Comparative example 1
In addition to except the combined amount of (A) composition, for 0 weight portion (without mixing), the combined amount of (B) composition is 100 weight portions, Remaining is implemented in the same manner as previous embodiment 1.
Comparative example 2
Except (A) composition combined amount (B) composition for 10 weight portions combined amount be 90 weight portions in addition to, remaining with it is front State embodiment 1 similarly to implement.
Comparative example 3
Except (A) composition combined amount (B) composition for 20 weight portions combined amount be 80 weight portions in addition to, remaining with it is front State embodiment 1 similarly to implement.
Comparative example 4
Except (A) composition combined amount (B) composition for 80 weight portions combined amount be 20 weight portions in addition to, remaining with it is front State embodiment 1 similarly to implement.
Comparative example 5
Except (A) composition combined amount (B) composition for 90 weight portions combined amount be 10 weight portions in addition to, remaining with it is front State embodiment 1 similarly to implement.
Comparative example 6
In addition to the combined amount of combined amount (B) composition for 100 weight portions of (A) composition is 0 weight portion (without mixing), Remaining is implemented in the same manner as previous embodiment 1.
By the combination of each embodiment and comparative example, in being displayed in table 1- tables 3.
[table 1]
[table 2]
[table 3]
Then, the decorative panel of each embodiment and comparative example is tested.Test method is as follows.The test of (a)-(c) below is all The test of the adaptation of the layer (transfer printing layer) that evaluation is formed by uv-hardening resin composition.
A () is crosscutting：Cause crosscutting on the surface of decorative panel with cutter, shelled after cellophane tape is attached After, the exfoliated state of transfer printing layer is judged with visually.(according to JISK5400 coating ordinary test methods, × cutting belt method). The metewand of cross-cut test is as follows.
○：The week of transfer sheet 1 is cured in normal temperature and occur without peeling off.
×：Normal temperature cure the week of transfer sheet 1 and attach adhesive tape × major part of cutting part, have stripping.
Peel off in (b) chessboard hole：Peel off (tested according to JISK5400 chessboards hole) by chessboard hole adhesive tape and evaluated.Chess The metewand that disk hole is peeled off is as follows.
○：After the normal temperature curing week of transfer sheet 1, tested and remained more than 95/100.
×：After the normal temperature curing week of transfer sheet 1, tested and remained less than 84/100.
C () is water-fast adaptation：In boiled water, decorative panel is boiled 2 hours, re-dry 2 hours in 100 DEG C of electric furnace Afterwards, cause crosscutting on surface with cutter, after being peeled off after cellophane tape is attached, judge to turn with visually The exfoliated state of print layer.(according to JISK5400 coating ordinary test methods, × cutting belt method).The metewand of water-fast adaptation is such as Under.
○：After the normal temperature curing week of transfer sheet 1, even being tested, also occur without stripping.
×：After the normal temperature curing week of transfer sheet 1, tested, attach adhesive tape × major part of cutting part, have stripping From generation.
(d) resistance to chemical reagents：According to JIS K 6902：1998 stain resistance and the resistance to of various medicines is observed with visually Property.The time of contact of polluter is 16-24 hours.The metewand of resistance to chemical reagents is as follows.
○：Without cosmetic variation on film.
△：Somewhat there is vestige to remain on film, or film discoloration.
×：Significant changes are seen on film.
(e) sheet resistance value：According to JIS K 6911-5-13 (nineteen ninety-five version) using digital ultra-high resistance/small Galvanometer R8340A (Advantest (stock) company), is measured.
The evaluation result of each test, is shown in aforementioned table 1- tables 3.From table 1- tables 3, the decorative panel of each embodiment with than Compare compared with the decorative panel of example, in adaptation, the resistance to chemical reagents of the layer (transfer printing layer) formed by uv-hardening resin composition Aspect, significantly well.

Claims (8)

1. a kind of transfer sheet, it is characterised in that the layer being made up of curable with actinic energy ray resin combination is formed at fissility base On material, the curable with actinic energy ray resin combination includes the carbamate of (A) containing 2 free-radical reactive groups Acrylate or acrylic resin and the urethane acrylates of (B) containing more than 6 free-radical reactive groups Ester resin or acrylic resin, and light trigger, are 100 weight portions in the total amount of aforementioned (A) composition and aforementioned (B) composition When, the amount of aforementioned (A) composition is 30-70 weight portions,
The weight average molecular weight of aforementioned (A) composition is 500-1500,
The weight average molecular weight of aforementioned (B) composition is 500-6000.
2. the transfer sheet described in claim 1, it is characterised in that in the total amount of aforementioned (A) composition and aforementioned (B) composition be 100 weights During amount part, the light trigger is 1-10 weight portions.
3. the transfer sheet described in claim 1, it is characterised in that the curable with actinic energy ray resin combination is also comprising leading Electrical colloidal sol.
4. the transfer sheet described in claim 3, it is characterised in that in the total amount of aforementioned (A) composition and aforementioned (B) composition be 100 weights During amount part, the electric conductivity colloidal sol is 8-15 weight portions.
5. a kind of decorative panel, including melmac layer and be formed on the melmac layer by active-energy The layer of the hardening thing composition of line hardened resin composition, the curable with actinic energy ray resin combination contains 2 comprising (A) The urethane acrylate resin or acrylic resin of individual free-radical reactive group and (B) are free containing more than 6 The urethane acrylate resin or acrylic resin of base reactive group, and light trigger, in aforementioned (A) composition and When the total amount of aforementioned (B) composition is 100 weight portion, the amount of aforementioned (A) composition is 30-70 weight portions,
The weight average molecular weight of aforementioned (A) composition is 500-1500,
The weight average molecular weight of aforementioned (B) composition is 500-6000.
6. the decorative panel described in claim 5, it is characterised in that in the total amount of aforementioned (A) composition and aforementioned (B) composition be 100 weights During amount part, the light trigger is 1-10 weight portions.
7. the decorative panel described in claim 5, it is characterised in that the curable with actinic energy ray resin combination is also comprising leading Electrical colloidal sol.
8. a kind of manufacture method of decorative panel, it is characterised in that：It is laminated core, impregnates with thermosetting resin work on facing paper The transfer sheet described in resin liquid and dry resin dipping decorative paper and claim 1,2,3 or 4 for principal component, enters Row hot forming, and after the hot forming, remove the fissility base material.
CN201611233818.3A 2009-09-30 2010-09-30 Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board Pending CN106626854A (en)

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KR20120079061A (en) 2012-07-11
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Application publication date: 20170510