JP5828576B2 - A method for producing a polyester decorative board and an oxygen barrier film for producing a polyester decorative board. - Google Patents

Description

  The present invention relates to a polyester decorative board used for various furniture, kitchens, building interior materials and the like, and in particular, there is no risk of polluting the environment, and the polyester decorative board has excellent surface smoothness and excellent scratch resistance. And an oxygen barrier film for producing a polyester decorative board.

  Conventionally, this type of polyester decorative board is obtained by attaching a decorative paper on which a printed pattern such as wood grain is formed on a base material for a decorative board by an adhesive and using a roll press method. After the saturated polyester resin is applied, this surface is coated with an air (oxygen) blocking film, and the unsaturated polyester resin is cured to peel off the air (oxygen) blocking film.

  In general, an unsaturated polyester resin is a mixture of a polyester having an unsaturated group in a molecule obtained by reacting with a polyhydric alcohol in combination with an unsaturated acid and a saturated polybasic acid, and a vinyl monomer acting as a crosslinking agent, A styrene monomer is generally used as a crosslinking agent because it is excellent in crosslinkability (polymerizability) and is easily available and inexpensive (for example, see Patent Document 1).

The invention described in Patent Document 1 aims to improve the service life of the silicone resin shaping mold without being affected by the styrene monomer coming out of the unsaturated polyester resin. Or, there is a possibility that it remains as a trimmer, and this may be released into the air over time from various types of furniture, kitchens, or polyester decorative panels used for building interior materials, etc., and may contaminate the environment. There has been a demand for a polyester decorative board made of an unsaturated polyester resin without such a fear.
On the other hand, the curing of the unsaturated polyester resin is affected by the performance of the air (oxygen) barrier film covering the surface. From the viewpoint of productivity, in order to obtain a high-hardness polyester decorative board in a shorter time, a film having a high air (oxygen) barrier property is required.

JP-A-6-99560

  Then, this invention is providing the manufacturing method of the polyester decorative board and the oxygen barrier film for polyester decorative board manufacture for obtaining the high-hardness polyester decorative board in a short time.

In order to achieve the above object, the inventor of the present invention provides an adhesive layer and a makeup layer on the top surface of a decorative board substrate made of either a wooden substrate or an inorganic substrate. Polyester which laminates a sheet layer in order, applies uncured unsaturated polyester resin on the decorative sheet layer, abuts and cures an oxygen barrier film on the unsaturated polyester resin, and then peels off the oxygen barrier film In the decorative board manufacturing method, the oxygen-blocking film has at least a synthetic resin base material layer and a vapor deposition layer, and further has a surface coat layer on the vapor deposition layer, the surface coat layer comprising polyvinyl alcohol, It is a method for producing a polyester decorative board, wherein the synthetic resin base material layer side of an oxygen barrier film is brought into contact with the unsaturated polyester resin.

According to a fourth aspect of the present invention, there is provided a primer layer at least between the base layer made of synthetic resin and the vapor deposition layer, a surface coat layer on the vapor deposition layer, and the primer layer being an acrylic layer. It is formed from a copolymer of a resin and a urethane resin and an isocyanate, and the surface coat layer contains polyvinyl alcohol .

  In the polyester decorative board of the present invention, by using a film having excellent oxygen barrier properties, inhibition of curing of the polyester resin layer by oxygen can be suppressed, and a high-hardness polyester decorative board can be obtained in a short time.

It is a layer block diagram of a polyester decorative board. It is a layer block diagram which laminated | stacked the oxygen interruption | blocking film on the polyester decorative board. FIG. 3 is a configuration diagram for removing the oxygen barrier film of the present invention from a polyester decorative board.

The above-described present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram showing the layer structure of a polyester decorative board according to an embodiment of the present invention. The polyester decorative board 1 is provided on a decorative board base 2 with an adhesive layer 3 and a decorative sheet layer 4. And then applying an unsaturated polyester resin on the decorative sheet layer 4 and then abutting and curing an oxygen barrier film having an average surface roughness of 0.001 to 0.03 μm on the unsaturated polyester resin. The oxygen barrier film is peeled off to form a polyester resin layer 5.

  As the base material 2 for decorative board, an inorganic base material such as plywood, MDF (medium density fiberboard), particle board or other woody base material, calcium silicate board, asbestos slate board or cement slate board is appropriately selected. Can be used.

  The decorative sheet layer 4 is made of a material such as a printing paper for building materials having a basis weight of 30 to 100 g / m 2, a pure white paper, or a thin paper having a higher interlaminar strength mixed with a synthetic resin, such as titanium oxide. Paper-based materials such as titanium paper mixed with opaque pigments, non-woven fabrics, etc. can be used. Among these materials, titanium paper is most suitable from the viewpoint of suitability for impregnation with unsaturated polyester resin and concealment of the base plate 2 for decorative board. It is. The decorative sheet layer 4 is a layer in which a printed pattern layer (not shown) such as a wood grain pattern, a stone pattern, a cloth pattern, and an abstract pattern is provided on the material. (Not shown) is formed with printing ink by printing means such as gravure printing. In the printing ink, a nitrocellulose-based resin, a cellulose acetate-based resin, an alkyd-based resin, or the like is used alone or as a vehicle, and the resin is colored with organic or inorganic pigments, dyes, glitter pigments, and the like. Agents, extender pigments, stabilizers, plasticizers, solvents and the like are appropriately mixed.

  The base material 2 for decorative plate and the decorative sheet layer 4 are laminated by roll pressing with the adhesive layer 3, and the adhesive layer 3 includes acrylic resin, urethane resin, vinyl acetate-urea resin. A normal emulsion type such as the above is appropriate, and the coating amount may be appropriately determined according to the material of the decorative board substrate 2.

  The polyester resin layer 5 includes an unsaturated polyester to which a polyester having an unsaturated group in the molecule, a monofunctional and / or polyfunctional acrylate monomer, a polymerization initiator, and a polymerization accelerator are added as necessary. Made of resin. The polyester having an unsaturated group in the molecule is obtained by reacting an unsaturated polybasic acid and a polyhydric alcohol, or an unsaturated polybasic acid and a saturated polybasic acid in combination with the polyhydric alcohol.

  Examples of preferred unsaturated polybasic acids include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and dihydromuconic acid. , Γ-unsaturated dibasic acid. These compounds can be used singly or in combination.

Examples of preferable saturated polybasic acids include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroterephthalic acid. , Hexahydroisophthalic acid, succinic acid, malonic acid, or dialkyl esters thereof.
These compounds can be used singly or in combination.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, hydrogenated bisphenol A, and 1,4-cyclohexane. Examples include adducts of dimethanol, 1,4-cyclohexanediol, hydrogenated bisphenol A with alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. These can be used alone or in combination of two or more.

  The polyester having an unsaturated group in the molecule used in the present invention is obtained by condensation reaction of the above acid component and the above polyhydric alcohol component by a known method. The molar ratio with the component is preferably acid component / polyhydric alcohol component = 0.9 to 1.3. The number average molecular weight (Mn) of the polyester is preferably in the range of 1200 to 5000. When the number average molecular weight (Mn) is less than 1200, the mechanical strength of the resin-cured coating film is low, and when it exceeds 5000, the viscosity of the unsaturated polyester resin composition increases, which is not preferable.

  Next, the crosslinking agent used in the present invention will be described. As the cross-linking agent, an acrylate monomer is preferable, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl ( Monofunctional monomers such as (meth) acrylate, or trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butylene glycol di (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, a polyfunctional monomer such as neopentyl glycol di (meth) acrylate. These monomers can be used alone or in combination of two or more. Moreover, since the surface smoothness of the polyester resin layer 5 is obtained and excellent scratch resistance is obtained, the blending amount of the acrylate monomer used in the present invention is 60% by mass or less based on the resin content of the unsaturated polyester resin. As the acrylate monomer, the polyfunctional acrylate is contained in an amount of 50% by mass or more, and the double bond equivalent, that is, the molecular weight per polymerizable double bond is in the range of 50 to 180, preferably 80 Short chain monomers in the range of ~ 150 are suitable. When the polyfunctional acrylate content is less than 50% by mass, the scratch resistance is poor. When the double bond equivalent is less than 50, the surface smoothness and the scratch resistance are poor. Therefore, it is inferior in heat resistance. In addition, a monofunctional acrylate may be appropriately used in consideration of application suitability, curing speed, and the like.

  Moreover, in order to adjust a cure rate, a polymerization initiator, a polymerization accelerator, a polymerization inhibitor, etc. can be used for unsaturated polyester resin.

  Examples of the polymerization initiator added to the unsaturated polyester resin include peroxides such as methyl ethyl ketone peroxide (MEKPO), benzoyl peroxide, hydroperoxide, and radical initiators such as azobisisobutyronitrile. These are appropriately selected from known ones. As the polymerization accelerator, for example, cobalt compounds such as cobalt naphthenate, metal compounds such as vanadium compounds and manganese compounds, and amine compounds such as dimethylnitrile can be used. As the polymerization inhibitor, for example, hydroquinone, trihydroquinone, benzoquinone, trihydrobenzene and the like can be used. In addition, each above-mentioned hardening rate regulator may be used together.

Next, the oxygen barrier film will be described. The oxygen barrier film is used for surely curing the unsaturated polyester resin and smoothing the surface of the cured polyester resin layer 5 to give gloss. The film used for this needs to be a material that has excellent oxygen barrier properties and can be released from the cured polyester resin layer 5.
The oxygen barrier film of the present invention is characterized by having at least a synthetic resin substrate layer and a vapor deposition layer.
The side that comes into contact with the unsaturated moat ester resin may be a synthetic resin base layer or a vapor deposition layer side, but the side that makes contact with the synthetic resin base layer is an unsaturated polyester resin that will be described later. The composition material and by-product generated during curing do not affect the vapor deposition layer and the surface coat layer, which is preferable in that the number of times of use in repeated use can be increased.

Synthetic resin base layers include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl alcohol copolymers, olefinic thermoplastic resins such as mixtures thereof; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, Ester thermoplastic resins such as polyethylene naphthalate-isophthalate copolymer, polycarbonate, and polyarylate; Acrylic thermoplastic resins such as polymethyl methacrylate, ethyl polymethacrylate, and polybutyl acrylate; polyimide, polyurethane, Non-halogen thermoplastic resins such as polystyrene and acrylonitrile-butadiene-styrene resin are exemplified.
The synthetic resin base material layer may be a uniaxial or biaxially oriented sheet, or may be unstretched, but has a high mechanical strength because it is a base material on which a vapor deposition layer described later is formed. A sheet stretched in the biaxial direction is preferable for reasons such as excellent dimensional stability. The thickness of the synthetic resin substrate layer is generally 1 to 100 μm, preferably 5 to 50 μm.

  Examples of the vapor deposition layer include an inorganic vapor deposition layer composed of a metal thin film typified by aluminum, and an inorganic oxide vapor deposition layer composed of an inorganic oxide thin film typified by silicon oxide, magnesium oxide, and aluminum oxide. The vapor deposition layer is formed on the synthetic resin base material layer by a known vapor deposition method such as a vacuum vapor deposition method or a plasma activated chemical reaction vapor deposition method. More preferably, it is an inorganic oxide vapor deposition layer whose vapor deposition layer is transparent.

  A surface coat layer may be provided on the vapor deposition layer for the purpose of further improving the oxygen barrier properties of the vapor deposition layer and suppressing cracks and peeling off of the vapor deposition layer, etc. that occur when the oxygen barrier film is repeatedly used. . The surface coat layer also functions as a protective layer for the vapor deposition layer, and its thickness is suitably about 0.1 to 10 μm.

  Examples of the surface coat layer include polyvinyl alcohol resin (PVA), urethane resin, and polyvinylidene chloride resin. The polyvinyl alcohol-based resin has the general formula R1nM (OR2) m (wherein R1 and R2 are the same or different and are an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an alkyl substituent having 1 to 2 carbon atoms). And a phenyl group having a halogen substituent, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M) Containing at least one alkoxide represented by the formula, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and further by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water and an organic solvent. Examples include compositions prepared by polycondensation. Further, by combining polyvinyl alcohol and an ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance and the like are remarkably improved. A silane coupling agent or the like may be added to the composition. The urethane resin is preferably a two-component curable resin.

  In the present invention, a primer layer may be provided between the synthetic resin substrate layer and the vapor deposition layer. For example, when “surface coat layer / vapor deposition layer / primer layer / synthetic resin base material layer” is used, the adhesion between the synthetic resin base material layer and the vapor deposition layer is improved, and even when the oxygen barrier film is repeatedly used, Cracks and peeling off of the deposited layer can be suppressed.

  Examples of the resin used for such a primer layer include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and the like. These resins can be used alone or in combination. The primer layer can be formed using an appropriate application means such as a roll coating method or a gravure printing method.

  Among these, the primer layer is preferably formed from (i) a copolymer of acrylic resin and urethane resin and (ii) isocyanate. That is, the copolymer of (i) an acrylic resin and a urethane resin is composed of an acrylic polymer component having a hydroxyl group at the terminal (component A), a polyester polyol component having a hydroxyl group at both ends (component B), and a diisocyanate component (component). C) is mixed and reacted to form a prepolymer, and a chain extender (component D) such as diamine is further added to the prepolymer to extend the chain. By this reaction, polyester urethane is formed and an acrylic polymer component is introduced into the molecule to form an acrylic-polyester urethane copolymer having a hydroxyl group at the terminal. The acrylic-polyester urethane copolymer is formed by reacting and curing the terminal hydroxyl group with the isocyanate (ii).

  As the component A, a linear acrylate polymer having a hydroxyl group at the terminal is used. Specifically, linear polymethyl methacrylate (PMMA) having a hydroxyl group at the terminal is preferable because it is excellent in weather resistance (particularly, characteristics against photodegradation) and can be easily copolymerized with urethane. The component A is an acrylic resin component in the copolymer, and those having a molecular weight of 5000 to 7000 (weight average molecular weight) are preferably used because of particularly good weather resistance and adhesiveness. In addition, the component A may be used only having a hydroxyl group at both ends, but a mixture having a conjugated double bond at one end is mixed with the above-mentioned one having a hydroxyl group at both ends. Also good.

  Component B reacts with diisocyanate to form polyester urethane and constitutes a urethane resin component in the copolymer. The component B is a polyester diol having hydroxyl groups at both ends. Examples of the polyester diol include an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof, or an epoxy compound, a condensation product of a dibasic acid and a diol, and a cyclic ester compound. Examples thereof include a derived polyester compound. Examples of the diol include short-chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol; and alicyclic short-chain diols such as 1,4-cyclohexanedimethanol. it can. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. Preferred as the polyester polyol is adipic acid using adipic acid or a mixture of adipic acid and terephthalic acid as the acid component, particularly preferably adipic acid, and 3-methylpentenediol and 1,4-cyclohexanedimethanol as the diol component. Polyester.

  In the primer layer, the urethane resin component formed by the reaction of the component B and the component C gives flexibility to the primer layer and contributes to improvement in adhesion. Moreover, the acrylic resin component which consists of an acrylic polymer contributes to a weather resistance and blocking resistance in the said primer layer. In the urethane resin, the molecular weight of the component B may be within a range in which a urethane resin capable of sufficiently exhibiting flexibility in the primer layer is obtained. Adipic acid or a mixture of adipic acid and terephthalic acid, and 3-methylpentanediol In the case of polyester diol composed of 1,4-cyclohexanedimethanol, 500 to 5000 (weight average molecular weight) is preferable.

  As the component C, an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule is used. Examples of the diisocyanate include tetramethylene diisocyanate, 2,2,4 (2,4,4) -1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4′-cyclohexyl. A diisocyanate etc. can be mentioned. As the diisocyanate component, isophorone diisocyanate is preferable in terms of physical properties and cost. When the above-mentioned components A to C are reacted, the equivalent ratio of the total hydroxyl group (may be an amino group) of the acrylic polymer, polyester polyol and chain extender described below and the isocyanate group is such that the isocyanate group becomes excessive. To.

  When the above three components A, B and C are reacted at 60 to 120 ° C. for about 2 to 10 hours, the isocyanate group of the diisocyanate reacts with the hydroxyl group at the end of the polyester polyol to form a polyester urethane resin component and an acrylic polymer. A compound in which diisocyanate is added to the terminal hydroxyl group is also mixed, and a prepolymer is formed in a state where excess isocyanate group and hydroxyl group remain. As a chain extender, for example, a diamine such as isophorone diamine or hexamethylene diamine is added to this prepolymer, the isocyanate group is reacted with the chain extender, and the chain is extended so that the acrylic polymer component is contained in the polyester urethane molecule. The (i) acrylic-polyester urethane copolymer introduced and having a hydroxyl group at the terminal can be obtained.

  Addition of isocyanate of (ii) to acrylic-polyester urethane copolymer of (i), coating method and coating liquid adjusted to necessary viscosity in consideration of coating amount after drying, gravure coating method, roll The primer layer may be formed by coating by a known coating method such as a coating method. The isocyanate of (ii) is not limited as long as it can be crosslinked and cured by reacting with the hydroxyl group of the acrylic-polyester urethane copolymer of (i). An aliphatic isocyanate can be used, and an aliphatic isocyanate is particularly desirable from the viewpoint of thermal discoloration prevention and weather resistance. Specifically, tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate monomers, dimers, trimers and other multimers, or these And polyisocyanates such as derivatives (adducts) obtained by adding the above isocyanate to a polyol.

In addition, as an application quantity after drying of the said primer layer, it is 0.1-20 micrometers, Preferably it is 0.1-10 micrometers. Moreover, the said primer layer is good also as a layer which added additives, such as fillers, such as a silica powder, a light stabilizer, and a coloring agent, as needed.
Further, in order to obtain the surface smoothness of the polyester resin layer 5, 0.001 to 0.03 μm is appropriate as the average surface roughness (Ra) of the oxygen-blocking film, and considering this, the average surface roughness (Ra) is It is preferably about 0.02 μm. The average surface roughness (Ra) is a value measured according to JIS-B-0601, and the lower limit of the average surface roughness (Ra) is preferably 0, but it is almost as close to 0 as possible. If the average surface roughness (Ra) of the oxygen barrier film used in the present invention is 0.03 μm or less, the polyester resin layer 5 having excellent surface gloss is obtained. be able to.

The oxygen barrier film may be provided with a release layer on one side or both sides as necessary. The reason for this is that when an acrylate monomer is used as a cross-linking agent, the oxygen barrier film and the polyester resin layer 5 are better wetted, making it difficult to peel off. The release layer may be, for example, an acrylic melamine resin applied and dried and baked, or an ionizing radiation curable resin composition applied and cured, and is used for repeated use. It is more preferable to form an ionizing radiation curable resin layer.
As the ionizing radiation curable resin composition, a polymerizable oligomer or a prepolymer is used as a main resin, and a reactive silicone is preferably contained for the purpose of imparting releasability. Moreover, in order to raise heat resistance and a crosslinking density, it is preferable to contain the polyfunctional polymerizable monomer.

The ionizing radiation curable resin refers to a resin having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resins.
Typically, the polymerizable monomer contains 50% by mass or more of a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule.

  As the (meth) acrylate monomer, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  A monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as appropriate for the purpose of reducing the viscosity thereof. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate System oligomers and the like. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  For the purpose of improving heat resistance and crosslinking density, the curable resin in the ionizing radiation curable resin composition preferably contains a polyfunctional (meth) acrylate monomer.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the curable resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.

Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

It is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.
The ionizing radiation curable resin composition preferably further contains reactive silicone. It is because a release silicone improves and the tolerance with respect to repeated continuous use improves by containing reactive silicone in an ionizing radiation curable resin composition.

Here, the reactive silicone means a modified silicone oil in which an organic group is introduced into the side chain or terminal and has reactivity depending on the nature of the introduced organic group. The reactive silicone is specifically modified silicone oil side chain type, modified silicone oil both end type, modified silicone oil one end type, modified silicone oil side chain both end type, etc. Examples thereof include epoxy modification, mercapto modification, carboxyl modification, carbinol modification, phenol modification, methacryl modification, and different functional group modification.
The reactive silicone reacts with and binds to the curable resin when the ionizing radiation curable resin composition is cured. Therefore, when unsaturated polyester resin hardens | cures, it is preferable at the point which does not bleed out to the surface of a decorative board (it does not ooze out).

The amount of the reactive silicone used is in the range of about 0.1 to 50 parts by mass, preferably in the range of about 0.5 to 10 parts by mass per 100 parts by mass of the curable resin. When the usage-amount of reactive silicone is 0.1 mass part or more, peeling with a polyester resin decorative board and an oxygen interruption | blocking film becomes enough, and it can endure use for a long period of time. On the other hand, if the amount of reactive silicone used is 50 parts by mass or less, the unsaturated moat ester resin will not be repelled when the oxygen barrier film and the uncured unsaturated polyester resin layer are brought into contact with each other. A polyester decorative board having a mirror-like surface is obtained without roughening the surface.
To the ionizing radiation curable resin composition, components added as necessary and various additives are homogeneously mixed at predetermined ratios to prepare an ionizing radiation curable resin composition. The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
The ionizing radiation curable resin composition thus prepared is coated on the surface of the synthetic resin base material layer and / or the vapor deposition layer so that the thickness after curing becomes 1 to 20 μm. A release layer can be obtained by coating by a known method such as roll coating, reverse roll coating, comma coating, preferably gravure coating, and irradiation with ionizing radiation. When the thickness after curing is 1 μm or more, a desired function is obtained, and preferably about 2 to 20 μm.

Examples of the ionizing radiation include heat, electron beams, ultraviolet rays, and the like. In particular, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer. It is preferable to cure the uncured resin layer at about ~ 300 kV.
In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases, so when using a base material that deteriorates due to the electron beam as the base material, the penetration depth of the electron beam and the thickness of the uncured resin layer By selecting an accelerating voltage so as to be substantially equal, it is possible to suppress the irradiation of the extra electron beam to the base material, and to minimize the deterioration of the base material due to the excess electron beam. it can.

The irradiation dose is preferably such that the crosslinking density of the curable resin in the release layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

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

The oxygen barrier film was produced as follows. That is, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was prepared, and a primer layer 1 made of a two-component curable urethane resin was provided on one side. Further, an aluminum vapor deposition layer was provided on the primer layer 1. [Average surface roughness (Ra): 0.02 μm]
The film thus obtained is referred to as “deposited PET film”.

A surface coat layer (thickness 0.2 μm (dry state)) made of PVA / silicate system is formed on the vapor-deposited PET film, and a laminate (synthetic resin base material layer (PET) / deposition layer / surface coat layer) Was made. On the synthetic resin base material layer side of the laminate, a release layer for applying and drying and baking acrylic melamine resin was provided.
Next, a urethane-based two-component curable adhesive [manufactured by Chuo Rika Kogyo Co., Ltd .: Rikabond BA-11L / BA-11B] on the entire surface of one side of a 6 mm thick dielight [Daiken Kogyo Co., Ltd .: trade name] = 100 / 2.5] was applied in a wet state by roll coating method, and 10g / scale 2 was applied, and the grain pattern was exposed to 80g / m2 titanium paper that had been gravure-printed with acrylic ink on one side in advance. And then laminating with a laminating roll, followed by pressing with a hot press machine (press temperature 100 ° C., press pressure 100 Kg / cm 2, press time 40 seconds) and cooling, and then on the titanium paper as shown in Table 1. The blended unsaturated polyester resin composition was applied to a thickness of 200 μm, and the oxygen barrier film prepared above was coated thereon, rolled and defoamed with a rubber roll, and at 40 ° C. for 2 hours. Heat and the oxygen barrier film after curing the unsaturated polyester resin composition to obtain a polyester decorative plate of the release to the present invention.

The oxygen-blocking film was changed from that of Example 1 to a release layer, a polyfunctional acrylate resin containing a reactive silicone acrylate was applied, and a release layer (dry thickness 10 μm) cured by electron beam irradiation was provided. Otherwise, a polyester decorative board was obtained in the same manner as in Example 1.
[Comparative Example 1]

Polyester similar to Example 1 except that the oxygen barrier film was changed from that of Example 1 to a biaxially stretched polyethylene terephthalate film (biaxially stretched PET) [20 μm, average surface roughness (Ra) 0.02 μm]. A decorative board was obtained.
[Comparative Example 2]

  A polyester decorative board was obtained in the same manner as in Example 1 except that the oxygen barrier film was changed from that of Example 1 to vinylon [total thickness 40 μm, average surface roughness (Ra) 0.02 μm].

  Measurement of the oxygen permeability of the oxygen barrier films of Example 1 and Comparative Example 1 prepared above and the pencil hardness of the polyester decorative board were evaluated, and the state of the oxygen barrier film after 10 or 30 uses was confirmed. The results are summarized in Table 2.

As is clear from Table 2, the polyester decorative board of Example 1 was superior in Comparative Example 1 to a polyester decorative board excellent in pencil hardness.
Moreover, Example 2 was an oxygen barrier film excellent in the number of service life in addition to the above.

1: Polyester decorative board 2: Base material for decorative board 3: Adhesive layer 4: Cosmetic sheet layer 5: Polyester resin layer 6: Substrate layer made of synthetic resin 7: Vapor deposition layer 8: Oxygen barrier film

Claims (5)

An adhesive layer and a decorative sheet layer are laminated in this order on the top surface of a decorative board substrate made of either a woody base material or an inorganic base material, and an uncured unsaturated polyester resin is applied on the decorative sheet layer. In the method for manufacturing a polyester decorative board, the oxygen barrier film is peeled off at least with a synthetic resin base material layer after the oxygen barrier film is contacted and cured on the unsaturated polyester resin and then peeled off. And a surface coat layer on the vapor deposition layer, the surface coat layer comprising polyvinyl alcohol, and the synthetic resin base material layer side of the oxygen-blocking film is brought into contact with the unsaturated polyester resin A method for producing a polyester decorative board, comprising: The method for producing a polyester decorative board according to claim 1, wherein the oxygen-blocking film has a primer layer between the synthetic resin substrate layer and the vapor deposition layer. The method for producing a polyester decorative board according to claim 1 or 2, wherein the oxygen-blocking film has a release layer made of an ionizing radiation curable resin on one side or both sides . At least a primer layer is provided between the base layer made of synthetic resin and the vapor deposition layer, and further has a surface coat layer on the vapor deposition layer, and the primer layer is a copolymer of an acrylic resin and a urethane resin, and an isocyanate. The oxygen barrier film for producing a polyester decorative board, wherein the surface coat layer contains polyvinyl alcohol . The oxygen barrier film for producing a polyester decorative board according to claim 4, wherein the oxygen barrier film has a release layer made of an ionizing radiation curable resin on one side or both sides .

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