JP2008000973A - Decorative material for building material and flooring material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material for building materials which is made of a vinyl chloride resin with VOC generation reduced while maintaining good characteristics of a conventional decorative material for building materials and a flooring material including a low cost, processability, design, printing aptitude, lamination strength, and fire retardancy and a flooring material using the decorative material. <P>SOLUTION: A transparent vinyl chloride resin sheet 4 is hot-pressed on the pattern 2 and/or 3 surface of a colored vinyl chloride resin sheet 1 with the patterns 2 and/or 3 printed to form the decorative material for building materials. The patterns 2 and/or 3 are formed by using water base inks using an aqueous urethane resin as a binder. In the decorative material, the measured value of volatile organic compounds (VOC) measured by a gas chromatography method is below 3 mg/m<SP>2</SP>. The flooring material using the decorative material is provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a decorative material for building materials made of vinyl chloride resin, and more particularly to a decorative material for building materials and a floor material that can suppress the generation of volatile organic compounds from furniture, flooring, and the like.

  Conventionally, as a surface decoration material used for floor surfaces of furniture, houses, etc., a decorative material for building materials made of laminated vinyl chloride resin sheets (hereinafter, “constructive material for building materials” may be simply referred to as “decorative material”). ) Is used. This decorative material for building materials made of vinyl chloride resin is formed by laminating a colored vinyl chloride resin sheet as a base material and a transparent vinyl chloride resin sheet as a top layer by a hot melt laminating method called doubling. . Also, conventional decorative materials for building materials made of vinyl chloride resin are decorated with patterns such as wood grain using oil-based ink containing organic solvent, are inexpensive, workability, various resistances, laminate strength, printability and Because of its excellent design and flame retardancy, which is a characteristic of vinyl chloride resin, it is widely used as a surface decoration material for furniture and flooring.

  However, recently, due to problems such as sick house syndrome, it has been demanded to reduce the amount of volatile organic compounds (VOC) generated mainly from interior materials of building materials.

  However, conventional decorative materials for building materials use oil-based inks containing organic solvents as inks for patterning, and toluene, methyl ethyl ketone, xylene, methyl isobutyl ketone, ethyl acetate, butyl acetate, cyclohexanone are used as components of the organic solvent. Or since isophorone etc. are used, the solvent which remained in the product generate | occur | produces as a large amount of VOC from the product obtained using these.

  So far, various materials and methods have been studied for the decorative material for building materials in order to suppress the occurrence of these VOCs. For example, a method of making the base material made of a non-vinyl chloride resin such as an olefin resin has been proposed (Patent Document 1). By changing the base material from vinyl chloride resin to olefin resin, the amount of organic solvent absorbed from the ink to the base material can be reduced, and the solvent remaining in the decorative material for building materials as a whole can be reduced. However, a non-vinyl chloride resin decorative material is less expensive because the cost is higher than that of a vinyl chloride resin decorative material. Moreover, the said decorative material is also inferior in workability and is not excellent in a flame retardance.

There is also a method in which the ink used to form the pattern of the decorative material made of vinyl chloride resin is changed from oil-based ink to water-based ink. However, since vinyl chloride resin emulsions and ethylene-vinyl acetate resin emulsions are generally used as binders for water-based inks, cosmetics with patterns formed with conventional water-based inks may have poor ink printability. Problems such as a decrease in the laminate strength of the base material and the top layer over time occurred frequently.
JP 2000-127306 A

  Therefore, the object of the present invention is to generate VOCs while maintaining the excellent properties such as low cost, processability, various resistances, laminate strength, printability, designability and flame retardancy of conventional building materials. An object of the present invention is to provide a vinyl chloride resin-made decorative material for building materials and a flooring material using the decorative material.

The above problems are solved by the present invention described below. That is, the present invention is obtained by thermocompression bonding the transparent vinyl chloride resin sheet 4 to the pattern 2 and / or 3 side of the colored vinyl chloride resin sheet 1 on which the pattern 2 and / or 3 is printed. A decorative material for building materials, wherein 3 is formed of a water-based ink having a water-based urethane resin as a binder, and a measured value of a volatile organic compound (VOC) by gas chromatography is less than 3 mg / m ² and the decorative material Is a flooring material that is bonded to the substrate surface. The aqueous urethane resin is preferably a self-emulsifying urethane resin. Moreover, it is preferable that the said water-based urethane resin is a urethane resin whose terminal is an isocyanate group.

  According to the present invention, the conventional decorative material for building materials is inexpensive, and VOC is generated while maintaining excellent properties such as processability, various resistances, laminate strength, printability, designability and flame retardancy. It is possible to provide a reduced decorative material for building materials made of vinyl chloride resin and a flooring material using the decorative material.

Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view schematically showing a basic layer structure of a decorative material for building materials of the present invention. As shown in FIG. 1, the decorative material for building materials of the present invention is obtained by thermocompression bonding a transparent vinyl chloride resin sheet 4 on the pattern 2 and / or 3 side of the colored vinyl chloride resin sheet 1 on which the pattern 2 and / or 3 is printed. The pattern 2 and / or 3 is formed of a water-based ink having a water-based urethane resin as a binder, and the measured value of a volatile organic compound (VOC) by gas chromatography is less than 3 mg / m ^2. It is said.

  The colored vinyl chloride resin sheet 1 constituting the present invention is made from a colored vinyl chloride resin composition as a raw material and formed into a sheet by a known processing method such as a calendar method or an extrusion molding method. Although the thickness of the said sheet | seat 1 is not specifically limited, 50-800 micrometers is preferable in consideration of workability and various tolerance.

  The colored vinyl chloride resin composition is mainly composed of a vinyl chloride resin, a plasticizer, a colorant and a stabilizer, and is the same as the colored vinyl chloride resin composition used in conventional cosmetics for building materials. Is used. The colored vinyl chloride resin composition may be a soft, semi-rigid or hard material containing 0 to 40% by mass of a plasticizer in the composition, preferably considering the workability and resistance. This is a semi-rigid colored vinyl chloride resin composition containing 5 to 30% by mass of a plasticizer in the product.

  The sheet 1 is provided for imparting designability to the decorative material for building materials, and is provided for bonding with a backer or base material such as wooden, rubber or steel, and is usually appropriately colored to conceal the base. ing.

  The patterns 2 and / or 3 are obtained by a known printing method such as gravure printing, flexographic printing or screen printing using an ink obtained by adding a water-based urethane resin as a main binder and adding a pigment, a solvent, or the like thereto. Formed by applying patterns of ~ 5 colors. Mainly, the design 2 is imparted to the decorative material by solid-printing the design 2 and printing the design 3. By using a water-based urethane resin as the main binder of ink, generation of VOC from the decorative material can be suppressed. The binder also includes a composition in which an aqueous acrylic resin or a vinyl chloride resin emulsion is added as a modifier.

  The aqueous urethane resin is required to have pigment dispersibility, printability, adhesion to a vinyl chloride resin sheet, water resistance, and the like. Therefore, for example, a colloidal dispersion of an ester urethane resin and / or an ether urethane resin, a water-soluble type and / or an emulsion type can be used as the aqueous urethane resin, and a self-emulsifying type urethane resin is particularly preferable. Can be used. Furthermore, it is preferable to use a urethane resin whose terminal is an isocyanate group as the water-based urethane resin from the viewpoint of improvement of water resistance and various resistances of the ink.

  The aqueous urethane resin is prepared, for example, by the following method. In an organic solvent that does not react with the isocyanate group (NCO), for example, a ketone solvent, the polyisocyanate and the polyol are reacted at a ratio of NCO / OH> 1, thereby obtaining a urethane resin having a terminal isocyanate group. At this time, when a polyol, polyamine or amino acid having an anionic group such as dimethylolpropionic acid is used as a part of the polyol, a urethane resin having a carboxyl group or a sulfone group pendant in the main chain is obtained. Next, after removing the solvent of the reaction solution and adding the reaction product to alkaline water such as ammonia, the anionic group of the urethane resin is neutralized with ammonia or the like to obtain a hydrophilic urethane resin. The urethane resin thus obtained can be made water-soluble or self-emulsifiable depending on the amount of the anionic group.

  In this case, the terminal isocyanate group reacts with water and the isocyanate group may be lost. After the urethane resin is produced, the isocyanate group is stabilized in an organic solvent (ketone, etc.) solution (block). It is necessary to keep it. This block is performed by, for example, addition reaction of phenols such as phenol and cresol with an isocyanate group.

  As the polyisocyanate used in the production of the urethane resin, various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, tolylene diisocyanate, isopropylene diisocyanate, xylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate can be used.

  Examples of the polyol used in the production of the urethane resin include low molecular glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol, and polyether polyols, polyester polyols, polycarbonate polyols, and polybutadienes. Polyols usually used for the production of urethane resins such as polymer polyols such as glycols can be mentioned.

  Examples of the polyol, polyamine or amino acid having an anionic group used in the production of the urethane resin include, in addition to 2,2-dimethylolpropionic acid, for example, 2,2-dimethylolbutyric acid, dimethylolalkanoic acid. Diamine type amino acids such as diaminobenzoic acid or monoamine type amino acids such as aspartic acid. The polyol, polyamine or amino acid having an anionic group gives an anionic group such as a carboxyl group or a sulfone group to the urethane resin, and also has an action of adjusting the molecular weight of the urethane resin to stop the reaction in the synthesis of the urethane resin.

  Examples of the alkali for neutralizing the urethane resin include ammonia, for example, monomethylamine, diethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, monoethanolamine, dimethylethanol. And organic amines such as amine, diethylethanolamine, morpholine or 2-amino-2-methyl-1-propanol, inorganic alkalis such as sodium hydroxide or lithium hydroxide, etc. Used in combination. The alkali is preferably ammonia or amine which suppresses the generation of VOC and is easily dissociated and volatilized by heat from the viewpoint of maintaining the physical properties of the film after drying.

  The above-mentioned water-based urethane resin is manufactured and used by itself, for example, from Daiichi Kogyo Seiyaku Co., Ltd. under the trade names “Superflex 107M”, “Superflex 150”, etc., and used in the present invention. Can do.

  As the solvent for the ink used in the present invention, water is desirable in order to suppress the occurrence of VOC. However, for the purpose of improving the drying property of the ink, the printability, or the leveling of the ink film, an alcohol having a low carbon number, such as methanol or ethanol. Or isopropyl alcohol etc. can be used together with water. Furthermore, a minimum amount of a monoether of diol, such as methoxypropanol, ethoxypropanol, etc., can also be used as a solvent for the ink.

  In addition to the ink used in the present invention, an antifoaming agent, a viscosity modifier, a filler, and the like can be added.

  The transparent vinyl chloride resin sheet 4 constituting the present invention is made from a transparent vinyl chloride resin composition as a raw material and formed into a sheet by a known processing method such as a calendar method or an extrusion molding method. The thickness of the sheet 4 is not particularly limited, but is preferably 50 to 800 μm in consideration of workability and various resistances.

  The transparent vinyl chloride resin composition is mainly composed of a vinyl chloride resin, a plasticizer, an antistatic agent and a stabilizer, and is similar to the transparent vinyl chloride resin composition used in conventional cosmetics for building materials. Things are used. The transparent vinyl chloride resin composition may be a soft, semi-rigid or hard material containing 0 to 40% by mass of a plasticizer in the composition as the sheet 4, and preferably has processability and resistance. Considering this, it is a semi-rigid transparent vinyl chloride resin composition containing 5 to 30% by mass of a plasticizer in the composition.

  The sheet 4 includes a translucent one in addition to a transparent one, and a surface embossed, and further, a coating agent or UV coat containing a protective film such as a polyethylene terephthalate film or an aqueous urethane resin on the sheet 4 A protective layer such as an agent may be applied.

  Sheet 4 imparts design properties to the decorative material for building materials, and also maintains various physical properties required for building materials such as furniture and flooring, especially surface properties such as scratch resistance, abrasion resistance, and contamination resistance. To be provided.

  The decorative material for building material of the present invention is produced by laminating a transparent vinyl chloride resin sheet 4 on the pattern surface of the colored vinyl chloride resin sheet 1 and laminating by a known laminating method, for example, a hot melt laminating method.

As a method for measuring VOC remaining in the decorative material for building materials of the present invention, a gas chromatographic method can be used. The VOC measurement by the gas chromatographic method described above is performed by taking a certain area of the decorative material for building materials, finely cutting it, sealing it in an Erlenmeyer flask, leaving it to stand at 80 ° C. for 20 minutes, and then evaporating it by gas chromatography. This is done by measuring. The decorative material for building materials of the present invention is characterized in that the VOC measured by the above method is less than 3 mg / m ² .

  The flooring of the present invention is obtained by sticking the decorative material of the present invention to the surface of the base material of the flooring. As the base material of the flooring material, any of the conventional base materials of flooring materials such as vinyl chloride resin, rubber, wood and cloth can be used. The method for attaching the decorative material to the substrate is the same as in the prior art. Such a flooring of the present invention is also low VOC as described above.

Next, the present invention will be described more specifically with reference to examples and comparative examples.
[Ink formulation]
Water, 25% by mass aqueous ammonia, antifoaming agent (trade name: BYK020, manufactured by Big Chemie Japan), pigment (trade name: cyanine blue 7629G, manufactured by Dainichi Seika Kogyo Co., Ltd.), the following resins A to D and viscosities as binders A regulator (trade name: SN thickener 619, manufactured by San Nopco) was blended in the ratios shown in Table 1 and dispersed with a paint shaker for 60 minutes to obtain a water-based ink. The above inks were designated as water-based inks 1 to 4, respectively.

Said resin A thru | or D show the following each, respectively.
(1) Resin A: Colloidally dispersed anionic urethane resin (trade name: Superflex 107M, solid content 25% by mass, manufactured by Daiichi Kogyo Seiyaku).
(2) Resin B: Colloidally dispersed anionic urethane resin (trade name: Superflex 150, solid content 30% by mass, manufactured by Daiichi Kogyo Seiyaku).
(3) Resin C: Vinyl chloride-acrylic copolymer resin emulsion (trade name: VINYBRAN 619, solid content 54 mass%, manufactured by Nissin Chemical Industry).
(4) Resin D: Vinyl chloride-vinyl acetate copolymer resin emulsion (trade name: Vinibrand 601, solid content 50% by mass, manufactured by Nissin Chemical Industry).

[Manufacture of decorative materials for building materials]
A colored vinyl chloride resin sheet having a thickness of 90 μm containing 25% by mass of a plasticizer is prepared in the sheet, and the aqueous ink 1 listed in Table 1 is applied to the sheet with a gravure printing machine at a coating amount of Wet 4 g / m ² . After coating, the pattern surface was formed by drying at a drying temperature of 35 ° C. for about 2 minutes. Next, a transparent vinyl chloride resin sheet having a thickness of 100 μm containing 25% by mass of a plasticizer in the sheet is superimposed on the pattern surface of the colored vinyl chloride resin sheet, and a thickness of polyethylene terephthalate is further formed on the transparent vinyl chloride resin sheet. A protective film having a thickness of 25 μm was stacked. Then, using a hot roll machine, the colored vinyl chloride resin sheet and the transparent vinyl chloride resin sheet are heat laminated under the conditions of a temperature of 200 ° C., a speed of 10 m / min, and a pressure of 1 kg / cm ^2. A decorative material for building materials that can be used was obtained. The decorative material for building materials is referred to as Example 1.

  Using the water-based inks 2 to 4 in place of the water-based ink 1, building materials for building materials were prepared under the same conditions as described above. The decorative material for building material prepared with Ink 2 was used in Example 2, the decorative material for building material prepared with Ink 3 was set as Comparative Example 2, and the decorative material for building material prepared with Ink 4 was set as Comparative Example 3.

  A cosmetic material for building materials was prepared under the same conditions as described above using an oil-based ink containing methyl ethyl ketone and toluene as solvents instead of the water-based ink 1, and this cosmetic material was used as Comparative Example 1.

[Evaluation results]
The decorative materials for building materials of Examples and Comparative Examples and the inks used for the decorative materials were evaluated.
The evaluation conditions are as follows. The following symbols indicate that “◯” is “excellent”, “Δ” is “good”, and “x” is “bad”.
(1) Ink drying property: After gravure printing a water-based ink on a substrate, the ink drying property was evaluated by touch.
○: Dry in less than 1 minute.
Δ: Dry in 1 minute or more and less than 2 minutes.
X: Dried in 2 minutes or more.
(2) Transferability of ink: The transferability of the ink was evaluated by visually observing a pattern surface obtained by gravure printing on a water-based ink.
○: Good transferability.
Δ: Transferability is slightly good.
X: Transferability is poor.
(3) Adhesiveness of ink: After pressure-bonding a 12 mm wide cellophane tape to a gravure-printed pattern surface, it was strongly peeled at an angle of 90 degrees to evaluate the adhesiveness of the ink.
○: Does not peel.
Δ: Partially peeled off.
X: The entire surface is peeled off.
(4) Laminate strength of decorative materials for building materials: The sheet after thermocompression bonding is cut into a width of 24 mm and a length of 100 mm to create a test piece, and after peeling a part of the adhesive part, it is peeled from the peeled part using a tensile tester The laminate strength was measured under the conditions of an angle of 180 degrees, a pulling speed of 300 mm / min, and a full scale of 50 N.
○: Laminate strength is 20 N / 24 mm or more.
Δ: Laminate strength is 10 N / 24 mm or more and less than 20 N / 24 mm.
X: Laminate strength is less than 10 N / 24 mm.
(5) Organic solvent remaining in the decorative material for building materials: The sheet after thermocompression bonding was taken in a certain area, cut into small pieces, and then put into an Erlenmeyer flask and sealed. Thereafter, the mixture was allowed to stand at 80 ° C. for 20 minutes, and the evaporated organic solvent (VOC) was measured by gas chromatography.
○: Organic solvent is less than 3 mg / m ² .
Δ: The organic solvent is 3 mg / m ² or more and less than 5 mg / m ² .
X: The organic solvent is 5 mg / m ² or more.
The above evaluation results are shown in Table 2.

  The decorative material of Comparative Example 1 has various resistances, but there are many residual solvents in the decorative material, and VOC cannot be reduced. The decorative material of Comparative Example 2 or 3 has little residual solvent in the decorative material and can greatly reduce VOC, but has poor practicality because of poor ink adhesion and transferability. The decorative material of Example 1 or 2 is a low VOC decorative material for building materials having good adhesion and transferability of ink, good laminate strength of the decorative material, and suppressing residual solvent in the decorative material.

  According to the present invention, the occurrence of VOCs is reduced while maintaining excellent properties such as processability, designability, printability, bonding strength, and flame retardancy at low cost of conventional decorative materials for building materials. A decorative material for building materials made of vinyl chloride resin and a flooring using the decorative material can be provided. Therefore, the decorative material for building materials of the present invention is useful as a surface decoration material for building materials such as furniture and flooring.

The schematic cross section which shows the basic layer structure of the decorative material for building materials of this invention schematically.

Explanation of symbols

1: Colored vinyl chloride resin sheet 2: Pattern 3: Pattern 4: Transparent vinyl chloride resin sheet

Claims (4)

The transparent vinyl chloride resin sheet (4) is thermocompression bonded to the pattern (2,3) surface of the colored vinyl chloride resin sheet (1) printed with the pattern (2,3). A decorative material for building materials, which is formed of a water-based ink having a water-based urethane resin as a binder, and has a measured value of a volatile organic compound (VOC) by a gas chromatographic method of less than 3 mg / m ² .   The building material decorative material according to claim 1, wherein the water-based urethane resin is a self-emulsifying urethane resin.   The building material decorative material according to claim 1 or 2, wherein the water-based urethane resin is an isocyanate-based urethane resin. A flooring material comprising the decorative material according to any one of claims 1 to 3 bonded to a surface of a base material.

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