JP6795384B2 - Deodorant laminated sheet and deodorant resin mat - Google Patents

Description

The present application relates to a deodorant laminated sheet and a deodorant resin mat. More specifically, the present invention relates to a deodorant laminated sheet having transparency and an excellent deodorizing function on the surface, and a deodorizing resin mat.

The resin mat is laid on the floor to prevent the floor from being scratched by the feet of desks and chairs, to prevent dirt from adhering, or to have appropriate hardness and elasticity, and to have a shape even when deformed. Because it has the property of recovering, it is often used by laying it on the floor or toilet where standing work is done. It is also used by laying it on a desk to improve writing comfort and prevent dirt from adhering.

On the other hand, in recent years, there has been a tendency to demand a sense of cleanliness and coolness in living spaces, and there have been requests such as the odor of excrement from toilets and pets and the odor of keeping pets, so mats laid on the floor There is an increasing demand for products with a deodorant function. Based on these demands, products such as toilet mat covers, table mat covers, desk mat covers, floor mat covers, nap sheets, sports bags, and clothing covers are examples of the use of mat sheets with deodorant functions. Has been developed. For example, Patent Document 1 discloses a sheet provided with a coating film containing a composite hydroxide condensed silicate having deodorizing performance, an amine compound, and titanium oxide on a base sheet.

JP-A-2010-65101

However, the technique disclosed in Patent Document 1 has a problem that the transparency of the obtained sheet is deteriorated and the visibility is inferior because the number of copies of the compound having a deodorizing function is large with respect to the resin component.

Further, in order to increase the transparency, there is a method of making a composition that reduces the number of copies of the compound having a deodorizing function, but in this case, the compound having a deodorizing function is buried in the resin layer and deodorizes. There is a problem that the compound having a function does not appear on the surface of the resin component and the deodorizing performance is deteriorated.

The present application has been made in view of the above-mentioned prior art, and an object of the present application is to provide a deodorant laminated sheet having transparency and an excellent deodorizing function, and a deodorizing resin mat. is there.

As a result of diligent studies, the present inventors have found that the above object can be achieved by setting the relational expression between the compounding ratio of the deodorant to the resin component and the coating film thickness within a predetermined range.

The present application provides one of the means for solving the above problems.
A laminated sheet having a coating film layer composed of a composition containing at least a deodorant and a resin component, wherein the composition is the number of parts S (parts by mass) of the deodorant added to 100 parts by mass of the resin component. A deodorant laminated sheet, wherein the thickness T (μm) of the coating film layer satisfies the following formula (1).
To disclose.
T ≤ 0.3 × S ・ ・ ・ Equation (1)
"Thickness T (μm) of the coating film layer" refers to the thickness after the applied composition is dried and cured.

In the deodorant laminated sheet of the present disclosure, the load length ratio (Rmr (c), C = 50%) on the surface side of the coating film layer is preferably 20% or less.

In the deodorant laminated sheet of the present disclosure, the thickness T (μm) of the coating film layer is preferably 15 μm or less.

In the deodorant laminated sheet of the present disclosure, it is preferable that the resin component contains an acrylate-based resin having curability.

In the deodorant laminated sheet of the present disclosure, it is preferable that the deodorant is an inorganic deodorant.

In the deodorant laminated sheet of the present disclosure, it is preferable that the inorganic deodorant is a porous substance.

The present application provides one of the means for solving the above problems.
A deodorant resin mat having at least the deodorant laminated sheet of the present disclosure,
To disclose.

The form of the deodorant resin mat is not particularly limited, but for example, a form in which a non-slip treatment is applied to the side opposite to the coating film layer of the deodorant laminated sheet, a form in which irregularities are provided to prevent air accumulation, or a form in which irregularities are provided to prevent air accumulation, or , A form in which a base material sheet for imparting cushioning property to the mat is attached. As the base material sheet, for example, a resin sheet having a thickness thicker than that of the base material in the laminated sheet, for example, a resin sheet having a thickness of 0.05 to 10 mm can be used. Moreover, you may use a foamed resin sheet.

According to the present disclosure, it is possible to provide a deodorant laminated sheet having transparency and an excellent deodorant function, and a deodorant resin mat.

Hereinafter, unless otherwise specified, the notation "A to B" for the numerical values A and B shall mean "A or more and B or less". When a unit is attached only to the numerical value B in such a notation, the unit shall be applied to the numerical value A as well.

1. 1. Deodorant Laminated Sheet The deodorized laminated sheet of the present disclosure has a coating film layer composed of a composition containing at least a deodorant and a resin component.

1-1. Coating film layer The coating film layer in the deodorant laminated sheet of the present disclosure comprises a composition containing at least a deodorant and a resin component, and the composition is such that the number of parts of the deodorant added to 100 parts by mass of the resin component S ( It is important that the mass part) and the thickness T (μm) of the coating film layer satisfy the following formula (1). By satisfying the following formula (1), the deodorant contained in the coating film layer is buried in the resin component, the deodorant does not appear on the surface of the resin component, and the deodorizing performance deteriorates. Can be suppressed.
T ≤ 0.3 × S ・ ・ ・ Equation (1)

On the surface side of the coating film layer in the deodorant laminated sheet, the load length ratio (Rmr (c), C = 50%) is preferably 20% or less, more preferably 15% or less. It is more preferably 13% or less. The lower limit of the load length ratio is not particularly specified, but is preferably 0.5% or more, more preferably 1% or more, and further preferably 3% or more. By setting the range of the load length ratio (Rmr (c)) as described above, the balance between the convex portion and the concave portion of the surface shape of the coating film layer becomes preferable, and there are many portions where the deodorant contained is exposed on the surface. The deodorant performance can be improved.

1-1-1. Deodorant The deodorant contained in the coating film layer is not particularly limited, and for example, an inorganic deodorant or an organic deodorant can be used, and these deodorants are used alone. Alternatively, these may be used in combination.

Examples of the inorganic deodorant include a porous substance that adsorbs odor, a metal oxide that decomposes odor, and a combination thereof.

Examples of the porous substance include porous silica, silica gel, magnesium silicate, aluminum silicate, zeolite, sepiolite, activated carbon, activated clay and the like. Of these, it is preferable to use zeolite and / or porous silica having an excellent adsorption ability for ammonia gas. Zeolites have a skeletal structure in which silicon and aluminum are three-dimensionally bonded via oxygen. Further, the porous silica is made of silicon dioxide and has a structure having uniform and regular pores. Molecular-level holes (pores) are opened in these skeletons, and various molecules such as water and organic molecules are taken into the skeleton, so that they are very useful as adsorbents.

Examples of the metal oxide include alumina, zirconium oxide, zinc oxide, iron oxide, titanium dioxide, zirconium phosphate and the like. These metal oxides have the property of deodorizing malodorous gases such as acetic acid, methyl mercaptan, and hydrogen sulfide.

Examples of the organic deodorant include organic nitrogen compounds such as amines and hydrazines, and metal chelated junctions. Of these, polyamine compounds having an amine in the molecule are preferable. As the polyamine compound, any of aliphatic amines, aromatic amines, and alicyclic amines can be used as long as it is a compound having one or more primary amino groups in the molecule. For example, diethylenetriamine, tetraethylenepentamine and the like can be used. Can be mentioned.

Further, the polyamine compound may be supported on an inorganic silicon compound. For example, a polyamine compound supported on porous silicon dioxide, aluminum silicate, or the like can be mentioned. As a method for supporting a polyamine compound, for example, an aqueous solution of the polyamine compound is prepared, porous silicon dioxide is immersed in the aqueous solution, and the mixture is heated and calcined to obtain a silicon dioxide compound supporting the polyamine compound. ..

The number of parts of the deodorant added to the coating film layer is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, based on 100 parts by mass of the resin component of the coating film layer. It is more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more. Further, it is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 35 parts by mass or less. By setting the number of copies of the deodorant to be added as described above, the deodorizing performance can be made preferable, and it is possible to prevent the coating film layer from becoming cloudy and impairing the transparency.

1-1-2. Resin component of the coating film layer The resin component constituting the composition of the coating film layer is preferably a curable resin. Examples of the curable resin include acrylate-based resins obtained by curing a resin composition containing an oligomer component such as urethane acrylate, epoxy acrylate, polyester acrylate, and polyether acrylate. In addition, a monomer component constituting the acrylate-based resin can be added to the resin composition. Further, the above-mentioned oligomer component and monomer component can be modified, and a modified oligomer having an antistatic function and a modified oligomer having an antifouling function such as silicone may be added.

The monomer component of the acrylate-based resin includes a monofunctional monomer and a polyfunctional monomer, and the monofunctional monomer includes 2-hydroxyethyl acrylate (HEA), isobolonyl acrylate (IBXA), and 2-hydroxypropyl acrylate (HPA). , Tetrahydrofurfuryl acrylate (THFA), styrene (St) and the like. Examples of the polyfunctional monomer include 1,6-hexanediol diacrylate (HDDA) and neopentyl glycol diacrylate (NPGDA) as the bifunctional monomer. Polypropylene glycol diacrylate (PPGDA), as a trifunctional monomer, trimethylolpropan triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trimethylol melamine triacrylate (TMMTA), as a tetrafunctional monomer, ditrimethylolpropantetraacrylate ( DTMPTA), pentaerythritol tetraacrylate _(PET 4 A), as 5-functional monomers, dipentaerythritol pentaacrylate (DPPA), as a 6-functional monomers include dipentaerythritol hexaacrylate (DPHA).

In addition, when a curing step is required to form the coating film layer, an initiator is added to the resin composition. As initiators, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydrooxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzophenone derivative, A thioxanthone derivative, dimethylaminoethyl methacrylate and the like can be used, and one of these initiators may be used alone, or two or more thereof may be mixed and used.

The thickness of the coating film layer is preferably 15 μm or less, more preferably 10 μm or less after drying. Further, it is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 1.5 μm or more. By setting the thickness of the coating film layer as described above, the deodorizing performance can be sufficiently exhibited.

1-2. Base material layer The deodorant laminated sheet of the present application is produced, for example, by forming a coating film layer on the base material layer. In this case, the deodorant laminated sheet of the present application has a base material layer and a coating film layer on the base material layer.

The resin used for the base material layer of the deodorant laminated sheet of the present disclosure is not particularly limited, and a known resin can be used. For example, polyvinyl chloride, polyethylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ionomer, acrylic acid ester, methacrylic acid ester and the like can be used. Among them, a polyvinyl chloride-based resin and a polyolefin-based resin can be preferably used, and in particular, a polyvinyl chloride-based resin can be preferably used. Hereinafter, the polyvinyl chloride-based resin and the polyolefin-based resin that can be used for the base material layer will be described.

1-2-1. Polyvinyl chloride-based resin The polyvinyl chloride-based resin that can be used for the base material layer is a homopolymer of vinyl chloride, a polymer of vinyl chloride and a copolymerizable comonomer thereof, and a mixture of these polymers. Say that. The polyvinyl chloride-based resin may be produced by any of known production methods such as a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method, and an emulsion polymerization method.
Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, and dibutyl. Maleic acid esters such as maleate and diethyl maleate, fumaric acid esters such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, cyanite such as acrylonitrile and methacrylonitrile. Polyfunctionality of vinyl halides, α-olefins such as ethylene, propylene and styrene, vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides such as vinylidene halide, diallyl phthalate and ethylene glycol dimethacrylate. Monomer can be mentioned. Of course, the comonomer is not limited to the above. The comonomer is preferably in the range of 30% by weight or less, more preferably 20% by weight or less in the constituent components of the vinyl chloride resin.

The average degree of polymerization of the polyvinyl chloride resin is preferably in the range of 700 to 2500, and more preferably 800 to 1300. Further, two or more kinds having different average degrees of polymerization may be mixed and used. As a mixing method, a method of mixing two or more kinds of resins at the time of film formation processing of a film to be a base material layer is common, but apparently by controlling the polymerization conditions at the time of polymerization of a polyvinyl chloride resin. It may be a method in which two or more kinds of polyvinyl chloride resins having different average degrees of polymerization are mixed.

1-2-2. Plasticizer When a polyvinyl chloride-based resin is used for the base material layer, the polyvinyl chloride-based resin preferably contains a plasticizer. The content of the above plasticizer varies depending on the type of plasticizer, but in general, it is preferably contained in an amount of 5 to 100 parts by mass, preferably 10 to 80 parts by mass, based on 100 parts by mass of the polyvinyl chloride resin. It is more preferable to contain a part. By containing 5 parts by mass or more of the plasticizer, the moldability and processability at the time of producing the base material layer can be improved, and by containing 100 parts by mass or less, the plasticizer can be removed from the base material layer. Sufficient moldability and workability can be improved without bleeding out.

In the present disclosure, the plasticizer that can be used for the polyvinyl chloride resin is not particularly limited, and a known plasticizer can be used. For example, di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diothyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate. Phtalic acid-based plasticizers such as; fatty acid ester plasticizers such as -2-ethylhexyl adipate, di-2-decyl adipate, dibutyl sebatate, -2-ethylhexyl sebatate; tributyl phosphate, tri-2-phosphate Phosphate-based plasticizers such as ethylhexyl, -2-ethylhexyldiphenyl phosphate, tricredyl phosphate; trimellitic acid ester-based plasticizers such as tri-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid; adipic acid-based polyester plasticizer Agent; Polyester-based plasticizer such as phthalic acid-based polyester plasticizer; Telephthalic acid-based plasticizer can be used.

For polyvinyl chloride-based resins, if necessary, known resin additives usually blended in synthetic resins for molding, for example, ultraviolet absorbers, light stabilizers, weather-resistant agents, heat stabilizers, stabilization aids, etc. Various additives such as agents, lubricants, flame retardants, antistatic agents, antibacterial antifungal agents and colorants can be blended.

1-2-3. Polyolefin-based resin Examples of the polyolefin-based resin that can be used for the base material layer include polyethylene-based resin, polypropylene-based resin, and a mixture thereof.

Examples of the polyethylene-based resin include a homopolymer of ethylene, a copolymer of ethylene containing ethylene as a main component and another monomer copolymerizable (low-density polyethylene (LDPE), high-pressure low-density polyethylene, linear). Examples thereof include low-density polyethylene (LLDPE), high-density polyethylene (HDPE), ethylene-α-olefin copolymer (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst, and mixtures thereof.

Examples of the polypropylene-based resin include a propylene homopolymer, a propylene copolymer, a reactor-type polypropylene-based thermoplastic elastomer, and a mixture thereof.

Examples of the propylene copolymer include a random copolymer (random polypropylene) of propylene and ethylene or other α-olefin, a block copolymer (block polypropylene), a block copolymer containing a rubber component, or a graft copolymer. Examples thereof include copolymers. As the other α-olefin copolymerizable with the above propylene, those having 4 to 12 carbon atoms are preferable, and for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4 -Methyl-1-pentene, 1-decene and the like are mentioned, and one kind or a mixture of two or more kinds thereof is used. Usually, the mixing ratio of α-olefin is about 1 to 10% by mass with respect to propylene.

2. 2. Method for Producing Deodorant Laminated Sheet As a method for producing the deodorized laminated sheet of the present disclosure, for example, a method of first producing a base material layer by the method shown below, and then laminating a coating layer on the base material layer. Can be mentioned.

2-1. Preparation of Base Material Layer As a method for preparing the base material layer of the deodorant laminated sheet of the present disclosure, for example, when the above-mentioned polyvinyl chloride-based resin is used, each of the above components is compared with the polyvinyl chloride-based resin. A predetermined amount is added to prepare a polyvinyl chloride-based resin composition, and a method of molding the polyvinyl chloride-based resin composition can be mentioned.

More specifically, first, the raw materials (each component) of the polyvinyl chloride resin composition are blended with a stirrer, and then heated and melted using a known kneader such as a Banbury mixer, a uniaxial extruder, a roll, or a kneader. A polyvinyl chloride resin composition is obtained by kneading with. The polyvinyl chloride-based resin composition thus obtained can be obtained in the form of pellets, particles, flakes, powder or the like. Next, the base material layer of the deodorant laminated sheet can be obtained by molding the obtained polyvinyl chloride resin composition into a sheet with a calendar roll or a T-die molding machine.

The deodorant laminated sheet of the present disclosure may have at least one base material layer obtained by the above method, and the base material layer of the deodorant laminated sheet may be a single layer or a multi-layer. You may. The thickness of the base material layer (in the case of multiple layers, the total thickness of the multiple layers) is not particularly limited, but is 0.03 to 5 mm from the viewpoint of preferable transparency and cushioning property of the sheet. Is preferable, 0.05 to 4 mm is more preferable, and 0.08 to 3 mm is further preferable.

2-2. Lamination of the coating film layer The method of laminating the coating film layer on the base material layer prepared as described above is not particularly limited. First, the raw material (each component) of the curable resin forming the coating film layer is agitated. A resin composition is prepared by blending with, and the resin composition is applied to the surface of the base material layer by a coating method such as a roller coating film, a brush coating, an air spray, or an airless spray, and then cured to laminate the resin composition. be able to. The method for curing the resin composition applied to the surface of the base material layer is not particularly limited, and when the curable resin is a thermosetting resin, it can be cured by heating by a known method. When the curable resin is a photocurable resin, it can be cured by irradiating it with an energy beam such as an electron beam, radiation, or ultraviolet rays by a known method.

3. 3. Deodorant resin mat The deodorant laminated sheet of the present disclosure can be used in various mats as a deodorant resin mat having at least one layer of the deodorant laminated sheet. For example, it can also be used for table mats, desk mats and floor mats.

The deodorant resin mat of the present disclosure is produced by laminating the side of the deodorant laminated sheet opposite to the coating film layer (for example, the base material layer side) to, for example, the base material sheet with an adhesive or an adhesive. be able to. The adhesive and the adhesive are not particularly limited, and known ones can be used.

Hereinafter, it will be described in more detail with reference to Examples. The deodorant laminated sheet and the deodorant resin mat of the present disclosure are not limited to the following examples. The measurement and evaluation in Examples and Comparative Examples were carried out by the methods shown below. The raw materials used in Examples and Comparative Examples are as follows.

[Surface roughness]
Using a laser microscope VK-X100 manufactured by KEYENCE Corporation, a surface observation image of the coating film layer of the obtained deodorant laminated sheet was taken, and the obtained image was analyzed to obtain a load roughness ratio (Rmr) of the roughness curve. (C), c = 50%) was measured.

[transparency]
A printing sheet with a flower pattern is placed on the surface of the base material layer opposite to the coating film layer, and the obtained deodorant laminated sheet is placed on the upper surface of the printing sheet, and the printing sheet is visually observed from the coating film layer side. The pattern was observed and evaluated according to the following evaluation criteria.
◯: The pattern is clearly visible.
Δ: The pattern can be seen.
X: The pattern is blurred and cannot be identified.

[Deodorant]
The obtained deodorant laminated sheet was measured under the following test conditions for the initial concentration of ammonia and the concentration after 20 minutes, and the deodorant performance was calculated by the following formula to obtain the deodorant performance.

<Test conditions>
Sample size: 256 cm ²
Initial concentration: 200 ppm ammonia
Gas filling amount: 500 mL
Measurement time: 20 min
Test temperature: 28 ° C
<Calculation formula>
Deodorant performance = (initial concentration-measured concentration) ÷ initial concentration x 100 (%)
* The higher the number, the higher the deodorant effect.

[Material used for the base material]
Thermoplastic resin: Polyvinyl chloride resin ("Kaneka Vinyl S1001" manufactured by Kaneka Corporation, average degree of polymerization: 1050)
Plasticizer: Phthalate plasticizer (J-PLUS "DOP")
Stabilization aid: Epoxy soybean oil (DIC "M-6")
Stabilizer: Ba-Zn-based stabilizer ("BZ-34C" manufactured by Katsuta Kako Co., Ltd.)
[Material used for the coating film layer]
Resin component: Urethane acrylate-based ultraviolet curable resin composition Initiator: 1-hydrooxycyclohexylphenyl ketone diluent: IPA (isopropyl alcohol) ("IPA" manufactured by Sankyo Chemical Co., Ltd.)
Deodorant: Triple Fresh (Suminoe Textile Co., Ltd .: Porous silica deodorant)

[Preparation of base material layer]
100 parts by mass of polyvinyl chloride resin, 40 parts by mass of phthalate plasticizer, 10 parts by mass of epoxy soybean oil, 2 parts by mass of Ba-Zn stabilizer, and mixed using a Henschel mixer. A base material layer having a thickness of 1.5 mm was formed by setting the cylinder temperature: 140 to 160 ° C. and the die temperature: 175 to 180 ° C. with a T-die molding machine.

[Example 1]
The ultraviolet curable resin composition is blended in an amount of 100 parts by mass and the deodorant triple fresh is added in an amount of 22 parts by mass, and the composition containing the initiator is further diluted with IPA and roll-coated on the base material layer. It was dried at 60 ° C. for 60 seconds and cured with ultraviolet rays at an integrated irradiation dose of 400 mJ.

Under the above conditions, a deodorant laminated sheet having a base material layer thickness of 1.5 mm and a dried coating film layer thickness of 2 μm was prepared and evaluated. The results obtained are shown in Table 1.

[Examples 2 to 5, Comparative Examples 1 to 3]
Examples 2 to 5 and Comparative Examples 1 to 3 under the same conditions as in Example 1 except that the number of parts by mass of the deodorant triple fresh and the thickness of the coating film layer were changed to the parts by mass and the thickness shown in Table 1. A deodorant laminated sheet according to the above was prepared and evaluated. The results obtained are shown in Table 1.

From Table 1, the results of Examples 1 to 5 were obtained in which the deodorizing performance was excellent and the transparency was also excellent. On the other hand, it can be seen that Comparative Examples 1 to 3 do not satisfy the relationship between the number of copies of the deodorant added and the coating film layer thickness specified in the present application, and are inferior in deodorizing performance.

Therefore, it was confirmed that the deodorant laminated sheet of the present disclosure can provide a deodorant laminated sheet having extremely excellent transparency and deodorant properties.

Claims (6)

A laminated sheet having a coating film layer composed of a composition containing at least a deodorant and a resin component.
The composition, the addition parts S of the deodorizing agent to the resin component 100 parts by (parts by weight), the thickness of the coating layer T ([mu] m) is, meets the following formula (1), and the coating A deodorant laminated sheet having a load length ratio (Rmr (c), C = 50%) on the surface side of the film layer of 20% or less .
T ≤ 0.3 × S ・ ・ ・ Equation (1) The deodorant laminated sheet according to claim 1, wherein the thickness T (μm) of the coating film layer is 15 μm or less. The deodorant laminated sheet according to claim 1 or 2 , wherein the resin component contains an acrylate-based resin having curability. The deodorant laminated sheet according to any one of claims 1 to 3 , wherein the deodorant is an inorganic deodorant. The deodorant laminated sheet according to any one of claims 1 to 4 , wherein the inorganic deodorant is a porous substance. A deodorant resin mat having at least the deodorant laminated sheet according to any one of claims 1 to 5 .