JP2003300298A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet wherein a harmful organic solvent such as toluene remains little after printing, which can thus contribute to settlement of a problem of indoor environmental pollution and which hardly causes blocking on the occasion of winding up and storage, the bulge of a surface after manufacture, or the like. <P>SOLUTION: The decorative sheet has a printed layer 2 formed of the printing ink of which the solvent content is a mixture of isobutyl acetate, butanone, ethyl acetate and 2-methyl-4-pentanone. A mixture of an acrylic resin and a vinyl chloride - vinyl acetate copolymer, or the like, can be used suitably as the resin content of the printing ink. Even when an amorphous polyester resin easily affected by toluene is used as a base sheet 1, the resin is hardly affected by the mixed solvent and thus the decorative sheet wherein the solvent remains very little can be obtained. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior and exterior materials such as wall materials, floor materials, and ceiling materials for buildings such as houses, furniture, furniture,
The present invention relates to a decorative sheet for use in surface makeup such as furniture, exterior materials for household appliances and home appliances, and interior / exterior materials for transportation equipment such as automobiles.Especially, residual harmful organic solvents such as toluene are extremely The present invention relates to a decorative sheet which has few health problems and is less likely to cause blocking during storage after winding after printing.

[0002]

2. Description of the Related Art As a conventional decorative sheet, a base sheet made of a colored polyvinyl chloride resin film is printed with a pattern by a gravure printing method or the like, and the printed surface is made of a transparent polyvinyl chloride resin film. The most common one is a laminate of the above-mentioned substrate sheets. In recent years, in consideration of environmental issues, etc., instead of polyvinyl chloride resin, polyolefin resin such as polypropylene resin, amorphous polyester resin such as copolyester resin, acrylic resin such as polymethylmethacrylate resin, etc. A decorative sheet using a non-halogen type thermoplastic resin such as a resin has also been developed and put into practical use (JP-A-6-198831, JP-A-8-99391, JP-A-11-34269, etc.).

When printing a pattern on a base sheet,
It is necessary to select a printing ink having excellent adhesion to the base sheet so that the printed layer does not peel off from the base sheet during long-term use of the decorative sheet. Under these circumstances, in the conventional decorative sheet, toluene, which has high solubility in various resins as the resin component (binder) of the printing ink and excellent wettability to various base sheet materials, is used as a solvent component. It was common to use printing inks containing as one of the main components of the.

However, since the above-mentioned toluene has an extremely high affinity with various resins, even if the printing ink containing the toluene is printed on the substrate sheet and the printing layer is dried with hot air or the like, the toluene is completely removed. It is extremely difficult to remove. Therefore, in recent years, in a room where this decorative sheet is used as a building interior material, furniture material, etc., residual toluene gradually volatilizes and pollutes the indoor air, adversely affecting the health of residents and the like. Is becoming a problem.

Further, there is a problem that if the film is stored in a wound state after printing, blocking may occur due to the action of the residual solvent. Further, in a decorative sheet having a multilayer structure in which a second base material sheet made of a thermoplastic resin is laminated on the printed surface, the residual solvent is gradually volatilized after lamination to generate bubbles at the lamination interface, and In some cases, it may cause swelling of the sheet surface, deterioration of design property due to shining bubbles or the like, or deterioration of interlayer adhesion due to easy peeling caused by bubbles.

[0006] In particular, the amorphous polyester resin, which is regarded as a promising non-halogen-based material excellent in three-dimensional moldability such as vacuum molding, has a particularly high affinity with toluene, so that toluene is not easily added during printing. Since it has a property of being easily taken in, and has a large amount of residual solvent despite the drying treatment after printing, the above-mentioned blocking and swelling are particularly likely to occur, and there are strong voices of concern from the viewpoint of indoor environment pollution.

In order to solve such a problem, instead of toluene or the like, toxicity is low and health concerns are small, and even if some remains in the printing layer, blocking is less likely to occur during winding and storage. Proposal of a decorative sheet using printing ink with a solvent component mainly composed of alcohol and alcohol solvent,
It has already been done (JP 2001-38849 A, JP 2001-191472 A, etc.).

However, since the water and alcohol solvents have poor solubility in various resins, the types of resins that can be used as the resin component of the printing ink are limited, and the wettability to the base sheet is poor. However, it is extremely difficult to select a resin component that is satisfactory in all aspects such as adhesion to a substrate sheet, weather resistance, printability and the like. In addition, since water has a large specific heat and evaporation heat and consumes a large amount of heat for evaporation and drying, it puts a load on the printing press and is not necessarily a perfect solution in terms of energy consumption. could not say it all.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems in the prior art, and its object is to retain harmful organic solvents such as toluene after printing. The present invention is to provide a decorative sheet that contributes to solving the problem of indoor environment pollution, and that is unlikely to cause blocking during winding storage and swelling of the surface after manufacturing.

[0010]

The decorative sheet of the present invention comprises:
In a decorative sheet having a printed layer on at least one side of a base sheet, the printed layer is formed by a printing ink containing a solvent mixture of isobutyl acetate, butanone, ethyl acetate and 2-methyl-4-pentanone. It is characterized by.

Particularly, in the above decorative sheet, the solvent content is 12 to 20% by weight of isobutyl acetate, 24 to 32% by weight of butanone, 24 to 32% by weight of ethyl acetate and 2% by weight.
-Methyl-4-pentanone consisting of a mixture of 24-32% by weight.

Particularly, in the decorative sheet, the resin component of the printing ink is one selected from acrylic resin, urethane resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin and nitrification cotton resin. Alternatively, it is a mixture of two or more kinds.

In particular, in the above decorative sheet, the resin component of the printing ink is an acrylic resin and vinyl chloride-
It is characterized by being a mixture with a vinyl acetate copolymer resin.

Further, in particular, in the decorative sheet, the base sheet is made of a thermoplastic resin.

Further, in particular, in the decorative sheet, the base sheet is made of an amorphous polyester resin.

Further, in particular, the decorative sheet is characterized in that a second base material sheet made of a thermoplastic resin is laminated on the printed layer surface of the base material sheet.

Further, in particular, in the above decorative sheet, the second base sheet is made of a polyolefin resin.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The decorative sheet of the present invention comprises a base sheet 1 and a print layer 2 provided on at least one side thereof, as shown in FIG. 1, for forming the print layer 2 by printing. The printing ink used in is an isobutyl acetate (abbreviated as IBA) which is an organic solvent other than toluene as a solvent component.
C), butanone (also known as methyl ethyl ketone, abbreviation ME)
K), ethyl acetate (abbreviation EAC) and 2-methyl-4-
Pentanone (also known as methyl isobutyl ketone, abbreviation MIB
It is a printing ink using a mixture of K).

By adopting the solvent component consisting of the above mixture, sufficient solubility with respect to the resin component of the printing ink can be obtained without using toluene, and the wettability with respect to the base sheet 1 is also satisfactory. The drying property is better than that in the case of using toluene, and the solvent component can be sufficiently removed in the drying step after printing.

Therefore, the decorative sheet of the present invention has a reduced residual solvent and does not substantially contain toluene, which is highly harmful, so that there is no risk of health damage due to indoor environmental pollution as in conventional decorative sheets. . Moreover, the occurrence of blocking during winding and storage of the base material sheet 1 after printing is prevented, and even when the second base material sheet 4 is laminated on the printing layer 2 side, residual solvent No bubbles are generated at the laminated interface due to vaporization, and there is no concern about swelling, silver eyes, or deterioration of interlayer adhesion.

The mixing ratio of each component in the solvent component may be appropriately designed in consideration of the solubility in the resin component, the wettability with respect to the base sheet 1, the drying property, and the like.
Generally, the compounding amount is within a range of 12 to 20% by weight of isobutyl acetate, 24 to 32% by weight of butanone, 24 to 32% by weight of ethyl acetate and 24 to 32% by weight of 2-methyl-4-pentanone. Most desirable.

The resin content of the printing ink is not particularly limited in the present invention, but the solubility in the mixed solvent, the adhesion to various base sheet 1 and the printing layer 2 of the decorative sheet are not limited. Considering weather resistance and the like, it is desirable to use one kind or a mixture of two or more kinds selected from acrylic resin, urethane resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin and nitrified cotton resin. . Among them, a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin has excellent solubility in the above mixed solvent, and particularly good adhesion to the base material sheet 1 made of a polyolefin resin, a polyester resin, or the like. It is most desirable because it has excellent flexibility and weather resistance.

The printing inks mentioned above are generally colored by the addition of suitable colorants. The colorant is not particularly limited in the present invention, and examples thereof include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, iron black, navy blue, cobalt blue, and azo, lake, and anthraquinone. In general, organic pigments such as quinacridone-based, phthalocyanine-based, isoindolinone-based, dioxazine-based, and the like, metal powder pigments such as aluminum powder and bronze powder, titanium oxide-coated mica, bismuth chloride chloride, etc. In some cases, pearlescent pigments are used.

In addition, if necessary, various types of extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, stabilizers, curing agents, curing accelerators or curing retarders, etc. It is also possible to appropriately add the additive.

The method for forming the printing layer 2 is not particularly limited in the present invention, and for example, a gravure printing method, an offset printing method, a gravure offset printing method,
Conventionally known printing methods such as a dry offset printing method, a screen printing method, a flexographic printing method, a relief printing method, and an inkjet printing method, and in the case of a solid surface, in addition to the above various printing methods, for example, a gravure coating method, a roll Various coating methods such as a coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method and a flow coating method can also be applied.

Prior to the formation of the printing layer 2, if necessary, for example, a corona discharge treatment, an ozone treatment, a flame treatment, an ionizing radiation treatment, an acid treatment, or the like on the printed surface of the substrate sheet 1.
By performing surface treatment such as alkali treatment, anchor treatment or primer treatment, the adhesion of the printed layer 2 to the printed surface of the base sheet 1 can be improved.

The type of the pattern formed by the print layer 2 is not particularly limited in the present invention, and for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometrical figure, a character or symbol, or a plurality of them. A combination of species is optional as desired.
Further, in the case of simply coloring or adjusting the color, a plain solid color may be used.

In the case where the intended decorative sheet requires concealment with respect to color and defects on the surface of the adherend substrate, the substrate sheet 1 is transparent or lacks concealment. In such a case, a hiding layer can be provided as a part of the printing layer 2. The material for forming the hiding layer and the method for forming the hiding layer are similar to those of the printing layer 2 described above, but in order to obtain good hiding property, at least an inorganic pigment having a high hiding property such as titanium oxide or iron oxide is used. Is desirable.
Further, by coloring the hiding layer in an appropriate color,
The print layer 2 can also serve as a background color.

The decorative sheet of the present invention has a single-layer structure (the base sheet is 1
Since it is only a layer, it may be a decorative sheet called as described above), or as shown in FIG. 1, a second substrate sheet 4 may be laminated on the printed layer 2 side, or If necessary, another substrate sheet (not shown) after the third layer may be further laminated on the printed layer 2 side or the opposite side of the substrate sheet 1.
The decorative sheet may have a multi-layered structure, and can be appropriately designed depending on the purpose of use and the required quality of the decorative sheet.

At that time, the printed layer 2 may be provided on both surfaces of the base sheet 1 as well as on one side, or at least one of the second and subsequent base sheets 4 may be provided as well as the first base sheet 1. A printing layer (not shown) may be provided on one side or both sides, and when forming these printing layers, it is desirable to use a printing ink using a mixed solvent having a formulation specified in the present invention as a solvent component.

The material of the base material sheet 1 and the second base material sheet 4 is not particularly limited in the present invention. For example, thin paper, titanium paper, high quality paper, resin impregnated paper, resin mixed paper, paper interval Made of paper such as reinforced paper, woven or non-woven fabric made of natural fiber or synthetic fiber, thermoplastic resin such as polyolefin, polyester, acrylic, polyamide, styrene, polyvinyl, and fibrin derivative It is possible to use a film or sheet, a metal foil such as an aluminum foil, a veneer obtained by thinly slicing wood, a mixture of two or more kinds thereof, a composite, a laminate, or the like. In addition,
Needless to say, when the printing layer 2 is sandwiched by a plurality of base material sheets 1 and 4, the base material sheet on either side thereof should be transparent or translucent so that the printing layer 2 can be seen through.

Among the various materials mentioned above, the effect of the present invention is most remarkably exhibited when at least the substrate sheet 1 to be the printing material of the printing layer 2 is made of a thermoplastic resin. Thermoplastic resins generally have a particularly low affinity with water and alcohol solvents, and good adhesion cannot be obtained with water-based or alcohol-based printing inks, while
The affinity with petroleum-based or aromatic solvents such as toluene is extremely high, and when a printing ink containing such a solvent is used, the solvent content is likely to remain, whereas the mixed solvent specified in the present invention is used as a solvent. The printing ink used as a component has sufficient wettability and adhesiveness to the base material sheet 1 made of a thermoplastic resin, but does not so much attack the base material sheet 1 that the solvent content does not easily remain. Because it is.

This effect is particularly remarkable when the substrate sheet 1 made of an amorphous polyester resin is used. Amorphous polyester resin has thermal and mechanical properties similar to polyvinyl chloride resin, which is the most popular material for decorative sheets, and is a substitute for polyvinyl chloride resin especially in vacuum forming applications. Although it is regarded as a promising material, it cannot be printed with water-based or alcohol-based printing inks because it is extremely hydrophobic, while it is extremely susceptible to petroleum-based or aromatic solvents such as toluene. This is because when printing with a printing ink containing this, blocking due to poor drying and swelling after lamination are likely to occur, and it was difficult to manufacture the decorative sheet itself.

The printing ink containing the mixed solvent specified in the present invention as the solvent component has good wettability and adhesion to the amorphous polyester resin, but does not substantially attack the amorphous polyester resin. Therefore, swelling of the base material sheet 1 during printing hardly occurs, and since it is easily dried well in the drying process, the residual solvent is extremely small, and problems such as blocking and swelling do not occur, and good quality makeup can be obtained. The sheet can be easily manufactured. In addition, since residual solvents such as toluene are extremely small in general, there is no problem of indoor environmental pollution during use of the decorative sheet as a building material, furniture material, or the like.

The base material sheet 1 made of the above-mentioned amorphous polyester resin is extruded into a sheet under the molding conditions that do not crystallize a general-purpose crystalline polyester resin such as polyethylene terephthalate resin (so-called A -PET sheet) and a sheet formed of a resin (so-called copolyester resin) in which various copolymerization components for suppressing crystallization are copolymerized in the basic skeleton of the above crystalline polyester resin. And any of these can be used for the purposes of the present invention.

The above A-PET sheet is made of a polyethylene terephthalate resin which is pure or nearly pure, and specifically, "Teijin Tetoron Sheet (A-PET)" manufactured by Teijin Limited and "Toyobo Co., Ltd." The commercially available products such as "TOYOBO PETMAX sheet A series" and "Kanebo A-PET sheet" manufactured by Kanebo Co., Ltd. can be mentioned.

On the other hand, the latter so-called copolyester resin sheet is a long-chain aliphatic such as sebacic acid, eicoic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid as a dicarboxylic acid component in the ethylene terephthalate skeleton. Dicarboxylic acid and / or alicyclic dicarboxylic acid is introduced, and / or polyether diol and / or alicyclic diol such as polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol are introduced as diol components. There are things.

Among them, the most typical one is commonly known as PET-G.
Is a commercially available cyclohexanedimethanol copolymerized polyethylene terephthalate resin, and as a resin formed into a sheet, for example, "NAGASE A-PET" manufactured by Nagase & Co., Ltd., "Rivestar" manufactured by Riken Technos Co., Ltd., etc. Can be mentioned as a commercially available product.

The thickness of the base sheet 1 is not particularly limited,
The same thickness as that of the conventional decorative sheet of the same kind can be used. However, if it is too thin, it tends to break during printing or laminating on a substrate to be adhered, while if it is too thick, it loses flexibility and bending workability, vacuum formability, etc. are reduced. Since it is economical, it is generally preferable to set the thickness within the range of about 20 to 200 μm.
Above all, it is most desirable to set the thickness to about 50 to 150 μm.

The base sheet 1 may include, for example, a colorant, a filler, an antioxidant, a Shiga line-of-sight absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, if necessary. It is also possible to add one or more selected from various additives such as antibacterial agents and antifungal agents. In particular, when the target decorative sheet is required to have concealing properties such as color and defects on the surface of the adherend substrate, the base sheet 1 may be made of, for example, titanium oxide, zinc oxide, iron oxide, carbon black, or the like. It is desirable that the base sheet 1 has a colored hiding property by adding a hiding color pigment.

In the decorative sheet of the form shown in FIG. 1,
The material of the second base material sheet 4 to be laminated on the print layer 2 of the base material sheet 1 is not particularly limited as long as it has transparency that allows the print layer 2 to be seen through, but is generally thermoplastic. It is desirable to use a film or sheet made of resin. The type of the thermoplastic resin is not particularly limited, but a polyolefin resin, a polyester resin, an acrylic resin or the like is preferable, and from the viewpoint of surface physical properties such as solvent resistance and scratch resistance and economical efficiency, the polyolefin resin is preferable. Is most desirable.

The type of the above polyolefin resin is not particularly limited, and various homopolymers such as polyethylene, polypropylene, polybutene, polymethylpentene, etc., ethylene-α-olefin copolymers, ethylene-acetic acid, etc. Vinyl copolymer or its saponification product, ethylene-
(Meth) acrylic acid (ester) copolymer, ethylene-
Examples thereof include olefin copolymer resins such as unsaturated carboxylic acid copolymer metal neutralized products (so-called ionomers).

Most preferred among them are polypropylene resins, that is, homopolymers or copolymers containing polypropylene as a main component, and specifically, for example, homopolypropylene resin, random polypropylene resin, block polypropylene resin, etc., alone or appropriately blended. Alternatively, a resin or the like in which atactic polypropylene is appropriately blended can be used.

Further, it may be a copolymer containing an olefinic monomer other than propylene, for example, having a polypropylene crystal part and having 2 to 2 carbon atoms other than propylene.
0 α-olefins, preferably ethylene, butene-
15 mol% of one or more comonomers of 1,4-methylpentene-1, hexene-1 or octene-1
The propylene-alpha-olefin copolymer etc. which are contained above can be illustrated. Also, low density polyethylene, ethylene-α-olefin copolymers, ethylene-propylene copolymer rubbers, ethylene-propylene-non-conjugated diene copolymer rubbers, styrene-butadiene copolymers, which are usually used for softening polypropylene resins. A modifier such as rubber or a hydrogenated product thereof can also be added as appropriate.

The second base material sheet 4 does not necessarily need to be completely colorless and transparent, and is semitransparent or colored as long as at least the printing layer 2 therebelow is transparent enough to be seen through. It may be transparent, and may be colored within the range by adding a dye or a pigment. Also,
Depending on the intended use of the decorative sheet, if necessary, for example, antioxidant, light stabilizer, heat stabilizer, plasticizer, lubricant, antistatic agent, flame retardant, extender pigment, filler, antibacterial agent, antifungal agent. , One or more conventionally known additives such as a gloss adjusting agent, an anti-friction agent and the like may be added.

The thickness of the second base material sheet 4 is not particularly limited, and can be, for example, the same as in the case of a conventional general decorative sheet having a multilayer structure. Generally, the thicker the second base sheet 4 is, the more advantageous it is in terms of surface physical properties such as abrasion resistance and solvent resistance, weather resistance, a feeling of painting and a feeling of depth, and designability such as embossing depth. On the other hand, it is disadvantageous in terms of flexibility and flexibility as a decorative sheet, particularly post-processability such as lapping processability and vacuum formability, so that a thickness range that balances both is selected. Specifically, depending on the intended use of the decorative sheet, the required quality, the type of resin used, etc., it is generally selected from the range of about 20 to 200 μm, and a particularly preferable range is about 50 to 150 μm.

The method for laminating the base material sheet 1 and the second base material sheet 4 is not particularly limited in the present invention, and for example, a dry laminating method or a wet laminating method via an appropriate adhesive layer 3 is used. A heat laminating method with or without an adhesive layer 3, a sand laminating method with an extruded layer of a thermoplastic resin that is heated and melted, and a thermoplastic resin that is to form the second base sheet 4 is heated and melted. It can be carried out by arbitrarily selecting from various conventionally known laminating methods such as an extrusion laminating method of simultaneously extruding into a sheet and laminating.

In the extrusion laminating method, when the adhesiveness between the base sheet 1 and the second base sheet 4 is poor, a heat-sensitive adhesive anchor layer is previously formed on the printed layer 2 side of the base sheet 1. (Not shown) is provided and / or the constituent resin of the second base sheet 4 and a separately prepared thermo-adhesive resin are co-extrusion laminated to form the base sheet 1 and the second base sheet. By sandwiching the heat-adhesive resin layer as the adhesive layer 3 with the material sheet 4, the interlayer adhesion can be improved.

The surface of the second base sheet 4 may be provided with a recessed pattern 6 by embossing a desired appropriate pattern, if necessary, as in the conventional decorative sheet. The type of the concave pattern 6 is not particularly limited, and may be various patterns such as wood grain (particularly wood grain conduit groove pattern), stone pattern, cloth pattern, Japanese paper pattern, geometric pattern pattern, etc. ,
Alternatively, for example, a matte pattern such as a grain pattern or a satin pattern, a hairline pattern, a suede pattern, or a leather pattern may be used. Further, by synchronizing these concave patterns 6 with the pattern of the printing layer 2, it is possible to further improve the design.

The method of forming the recessed pattern 6 is not particularly limited, but the mechanical embossing method using a metal embossing plate is the most general method, and the second base sheet 4 is formed on the base sheet 1.
After laminating, the embossing may be performed, or the laminating may be performed simultaneously with the laminating by a thermal lamination simultaneous embossing method (so-called doubling embossing method), an extrusion laminating simultaneous embossing method, or the like. Also, the concave pattern 6
If necessary, the concave portion may be filled with a coloring agent by a method such as a wiping method.

A surface protective layer 5 may be provided on the second base sheet 4 in order to impart more excellent surface properties to the surface of the decorative sheet of the present invention. The constituent material of the surface protective layer 5 is not particularly limited, but in general, a coating capable of forming a coating film having excellent surface physical properties such as abrasion resistance, scratch resistance, solvent resistance, and stain resistance can be formed and cured. It is desirable to use a coating material containing a conductive resin as a main component. Specifically, for example, thermosetting resins such as melamine-based resins, epoxy-based resins, aminoalkyd-based resins, urethane-based resins, acrylic-based resins, polyester-based resins, and ionizing radiation-curable resins such as (meth) acrylate-based resins. Resin etc. can be used conveniently. Further, if necessary, various additives such as a luster modifier, an anti-friction agent, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent, a fungicide, an ultraviolet absorber, and a light stabilizer are appropriately added. You can also

The decorative sheet of the present invention is generally the same as the conventional decorative sheet, for example, the surface of various adhered substrates such as wood-based substrates, inorganic-based substrates, metal-based substrates, synthetic resin-based substrates and the like. It is attached (laminated) to and used as a decorative material. The back surface of the decorative sheet of the present invention (the back surface of the base material sheet 1) in order to secure the adhesiveness during the attachment.
Alternatively, a primer layer (not shown) made of a resin composition having excellent adhesiveness with a general-purpose laminating adhesive may be provided.

Examples of the primer layer include urethane type, acrylic type, ethylene-vinyl acetate copolymer type,
Among various conventionally known primer agents such as a vinyl chloride-vinyl acetate copolymer system, one selected according to the material of the base sheet 1 is used. Note that, for example, silica,
By adding inorganic powder such as alumina, calcium carbonate, barium sulfate, etc., the roughening of the surface of the primer layer can prevent blocking during the winding and storage of the decorative sheet, and also as an adhesive for laminating due to the anchoring effect. It is also effective in improving the adhesiveness of.

[0054]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples of the decorative sheet of the present invention.

Example 1 Isobutyl acetate (IBAC) 16% by weight and butanone (MEK) 28% by weight as solvent components were formed on the surface of a colored amorphous polyester resin film (“Rivestar” manufactured by RIKEN TECHNOS CORPORATION) having a thickness of 100 μm. Ethyl acetate (EAC) 2
8% by weight and 2-methyl-4-pentanone (MIBK)
Using acrylic-vinyl chloride acetate resin-based printing ink with 28 wt% mixed solvent, wood grain pattern is printed by gravure printing method, dried in-line, and then rolled into a roll. I kept it. A few days later, this printing raw sheet was unwound, and a two-component curing type urethane resin-based dry laminating adhesive was applied to the printing layer surface,
A 70 μm thick transparent polypropylene resin film was laminated, and finally a surface protective layer made of a two-component curing type urethane resin was formed on the surface of the film to prepare a decorative sheet of the present invention.

Comparative Example 1 In the above-mentioned Example 1, the printing ink used for printing a wood grain pattern was prepared by using a mixed solvent of isobutyl acetate 25% by weight, butanone 25% by weight, ethyl acetate 25% by weight and toluene 25% by weight as a solvent component. Other than that, a printing raw sheet was prepared under the same conditions as in Example 1 above, and a decorative sheet was further prepared.

Comparative Example 2 In Comparative Example 1 described above, the drying after printing was performed by adding an additional drying step under the same conditions to the in-line drying, and otherwise under the same conditions as in Comparative Example 1 above. An original printing sheet was prepared, and a decorative sheet was further prepared.

Comparative Evaluation For the printed original sheets of Example 1 and Comparative Examples 1 and 2 above, the amount of residual solvent was measured by gas chromatography at the time of storage for 1 week at room temperature after printing, and the presence or absence of blocking was measured. Then, the quality of the ink inking state and the presence or absence of hot wrinkles were visually evaluated. The results are shown in the table below.

List of Evaluation Results of Printed Fabric Sheet Example 1 Comparative Example 1 Comparative Example 2 Residual Solvent Amount EAC 25 20 15 MEK 170 85 85 65 MIBK 200 0 0 IBAC 100 250 250 190 Toluene 0 300 230 Total 495 655 500 No Blocking Yes some Yes inking good good good Netsushiwa No No Yes Note) residual solvent content of the unit: mg / m ²

When the decorative sheets of Example 1 and Comparative Examples 1 and 2 were evaluated, the quality of the decorative sheet of Example 1 was good, but the decorative sheet of Comparative Example 1 had blisters and silver eyes. In addition to the above, the interlayer adhesion strength was not stable, and the decorative sheet of Comparative Example 2 was poorly laminated due to the hot wrinkles of the original printed sheet.

[0061]

As described in detail above, the decorative sheet of the present invention uses a specific mixed solvent containing no toluene as a solvent component of the printing ink, thereby substantially removing harmful toluene as a residual solvent. Not only it does not contain, but the total amount of residual solvent can be reduced, which can contribute to solving the indoor environment pollution problem. At the same time, blocking of the printed original sheet during winding and storage, swelling due to vaporization of residual solvent and silvering when a second substrate sheet is laminated on the printed surface, decrease in interlayer adhesion strength, etc. In addition, since it is not necessary to particularly strengthen the drying conditions after printing in order to reduce the total amount of such residual solvent, the occurrence of hot wrinkles in the drying process is also prevented, and a good-quality decorative sheet can be easily manufactured. It has an excellent effect that it can be manufactured.

[Brief description of drawings]

FIG. 1 is a side sectional view showing an embodiment of a decorative sheet of the present invention.

[Explanation of symbols]

1 Base sheet 2 printing layers 3 Adhesive layer 4 Second substrate sheet 5 Surface protection layer 6 concave pattern

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AK01A AK01C AK03C AK15B                       AK15J AK22B AK22J AK25B                       AK41A AK41B AK51B AL01B                       AT00A BA02 BA03 BA07                       BA10A BA10C GB08 HB31B                       JA12A JB16A JB16C JK06                       JL06                 4J039 AB02 AD05 AD08 AD10 AE04                       AE06 BC16 BC20 BE12 EA45                       EA48 FA02

Claims (8)

[Claims] 1. A decorative sheet having a printed layer on at least one side of a substrate sheet, wherein the printed layer is formed by a printing ink containing a solvent mixture of isobutyl acetate, butanone, ethyl acetate and 2-methyl-4-pentanone. A decorative sheet that is formed. 2. The solvent content is isobutyl acetate 12 to 20.
% By weight, butanone 24-32% by weight, ethyl acetate 24-
32% by weight and 2-methyl-4-pentanone 24-32
The decorative sheet according to claim 1, wherein the decorative sheet is composed of a mixture of weight%. 3. The resin component of the printing ink is one or a mixture of two or more selected from acrylic resins, urethane resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins and nitrification cotton resins. The decorative sheet according to claim 1 or 2, wherein 4. The decorative sheet according to claim 3, wherein the resin component of the printing ink is a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. 5. The decorative sheet according to claim 1, wherein the base sheet is made of a thermoplastic resin. 6. The decorative sheet according to claim 5, wherein the base sheet is made of an amorphous polyester resin. 7. The decorative sheet according to claim 1, wherein a second base material sheet made of a thermoplastic resin is laminated on the printed layer surface of the base material sheet. 8. The decorative sheet according to claim 7, wherein the second base sheet is made of a polyolefin resin.