JP4831369B2 - Method for producing 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. It is about.

  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.
JP-A-6-99560

  Therefore, the present invention is to provide a polyester decorative board which has no risk of polluting the environment, has excellent smoothness and scratch resistance.

In order to achieve the above object, the inventor of the present invention includes a step of applying an adhesive layer to the entire upper surface of a decorative board substrate and a printing pattern layer printed on one surface in advance. A step of laminating the formed decorative sheet layer on the adhesive layer so that the printed pattern layer is exposed; and an oxygen-blocking film is applied to the unsaturated polyester after applying an unsaturated polyester resin on the decorative sheet layer. In the manufacturing method of the polyester decorative board comprising the steps of contacting the resin and integrally curing and then peeling the oxygen blocking film to form a polyester resin layer, wherein the oxygen blocking film is a biaxially stretched polyethylene made from the unsaturated polyester resin with consisting terephthalate film is an acrylate monomer of the polyester and the crosslinking agent having an unsaturated group in the molecule, before Acrylate monomer, a polyfunctional acrylate containing at least 50 mass%, and a short-chain monomers in the range of the double bond equivalent of 50 to 180,
The polyester resin layer has the following characteristics: (1) Average surface roughness (Ra): 0.3 μm or less (2) Hardness: Pencil hardness is 5H or more.

  Since the polyester decorative board of the present invention is made of an unsaturated polyester resin that does not use a styrene monomer as a cross-linking agent, there is no risk of contaminating the environment, and it has excellent pencil hardness and excellent surface smoothness. There is an effect.

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 an unsaturated polyester resin is applied on the decorative sheet layer 4, and then an oxygen blocking film having an average surface roughness of 0.001 to 0.03 μm is brought into contact with the unsaturated polyester resin to be integrated. After the curing, the oxygen blocking film is peeled off to form the polyester resin layer 5. The polyester resin layer 5 is formed of an unsaturated polyester resin comprising a polyester having an unsaturated group in the molecule and a monofunctional and / or polyfunctional acrylate monomer as a crosslinking agent. The polyester resin layer 5 formed by using an unsaturated polyester resin is a styrene monomer or dimer which is feared in an unsaturated polyester resin using a styrene monomer as a crosslinking agent, or It is possible to obtain an environmentally friendly polyester decorative board that does not release trimmer into the air over time, and a polyester decorative board excellent in glossiness and scratch resistance.

  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 may be made of 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 whose interlaminar strength is enhanced by mixing a synthetic resin, titanium oxide, etc. Paper-based materials such as titanium paper mixed with non-transparent pigments, non-woven fabrics, etc. can be used. Among the above materials, titanium paper is the most preferable in terms of suitability for impregnation with unsaturated polyester resin and concealment of the base plate 2 for decorative board. Is appropriate. 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 blocking film will be described. The oxygen blocking film is used for surely curing the unsaturated polyester resin and smoothing the surface of the cured polyester resin layer 5 to give it gloss. The film used for this is not particularly limited as long as it has excellent oxygen barrier properties and can be released from the cured polyester resin layer 5, in order to obtain the surface smoothness of the polyester resin layer 5. It is appropriate to mold with a film having an average surface roughness (Ra) of 0.001 to 0.03 μm, and taking this into consideration, the average surface roughness (Ra) is approximately 0.02 μm. A polyester film (polyethylene terephthalate film) is most suitable. 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) is 0.03 μm or less, the polyester resin layer 5 having excellent surface gloss is defined as 0.001 μm in meaning. Obtainable. The oxygen blocking film may be subjected to a release treatment on one side or both sides as necessary. This is because, in the present invention, since an acrylate monomer is used as a cross-linking agent, the oxygen blocking film and the polyester resin layer 5 are better wetted and may not be easily peeled off. . As the mold release treatment, for example, an acrylic melamine resin may be applied, dried and baked.

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

A urethane-based two-component curable adhesive [manufactured by Chuo Rika Kogyo Co., Ltd .: Ricabond BA-11L / BA-11B = 100 on the entire surface of one side of a 6 mm thick die light [manufactured by Daiken Kogyo Co., Ltd .: trade name] /2.5] is applied in a wet state by a roll coating method and 10 g / scale ^{2 is} applied, and the wood grain pattern expresses 80 g / m ² of titanium paper which is gravure-printed with acrylic ink on one side in advance. After laminating with a laminating roll as described above, after pressing with a hot press machine (press temperature 100 ° C., press pressure 100 Kg / cm ² , press time 40 seconds) and cooling, the titanium paper shown in Table 1 was used. An unsaturated polyester resin composition containing A was applied to a thickness of 200 μm, and a 100 μm-thick biaxially stretched polyethylene terephthalate film [manufactured by Teijin Limited: average surface roughness] (Ra): 0.02 μm], rolled with a rubber roll, defoamed, heated at 40 ° C. for 2 hours to cure the unsaturated polyester resin composition, and then peeled off the biaxially stretched polyethylene terephthalate film. Thus, a polyester decorative board of the present invention was obtained.

[Comparative Example 1]
A polyester decorative board as a comparative example was obtained in the same manner as in Example 1 except that the unsaturated polyester resin composition having the composition of B in Table 1 was used.

  For the polyester decorative board of Example 1 and Comparative Example 1 produced above, the pencil hardness and surface roughness were evaluated, and the reflection of the fluorescent lamp was visually evaluated. The results are summarized in Table 2. Indicated.

  As is apparent from Table 2, the polyester decorative board of Example 1 is superior in pencil hardness and has a small average surface roughness (Ra) and excellent surface smoothness as compared with Comparative Example 1, so that The lamp shape can be seen accurately.

It is a layer block diagram which shows one Example of the polyester decorative board concerning this invention schematically.

Explanation of symbols

1 polyester decorative board 2 base material for decorative board 3 adhesive layer 4 decorative sheet layer 5 polyester resin layer

Claims (1)

A step of applying an adhesive layer on the entire upper surface of the base material for decorative plate, and a decorative sheet layer on which a printed pattern layer has been printed in advance on one surface is placed on the adhesive layer so that the printed pattern layer is exposed. A step of laminating, and after applying an unsaturated polyester resin on the decorative sheet layer, the oxygen blocking film is brought into contact with the unsaturated polyester resin and integrally cured, and then the oxygen blocking film is peeled off. In the method for producing a polyester decorative board comprising a step of forming a polyester resin layer, the oxygen blocking film comprises a biaxially stretched polyethylene terephthalate film, and the unsaturated polyester resin is crosslinked with a polyester having an unsaturated group in the molecule. An acrylate monomer as an agent,
The acrylate monomer is a short-chain monomer containing a polyfunctional acrylate of 50% by mass or more and having a double bond equivalent in the range of 50 to 180,
The method for producing a polyester decorative board, wherein the polyester resin layer has the following characteristics.
(1) Average surface roughness (Ra): 0.3 μm or less (2) Hardness: Pencil hardness of 5H or more

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