JP2005213296A - Energy ray-curable resin composition for synthetic resin floor covering, and synthetic resin flooring material having film composed of the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an energy ray-curable resin composition for a synthetic resin flooring material, wherein the composition can form a film, on a synthetic resin flooring material, which has high abrasion resistance and is tough and durable for a long period of time, and to provide a synthetic resin flooring material having a film composed of the resin composition. <P>SOLUTION: The energy ray-curable resin composition for the synthetic resin flooring material comprises an energy ray-curable monomer or oligomer, a photopolymerization initiator and an inorganic filler having a Mohs hardness of 8 or higher. The synthetic resin floor covering has a film composed of the resin composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an energy ray curable resin composition for a synthetic resin floor material and a synthetic resin floor material having a film made of the composition.

Synthetic resin floors, such as polyvinyl chloride flooring, are widely used as polyvinyl chloride tiles and cushion flooring.
In such flooring, a covering layer made of an energy curable resin composition such as ultraviolet rays is used for synthetic resin flooring, for example, polyvinyl chloride flooring, in order to prevent dirt and protect the base material, and to keep the appearance. Proposed to be on top.

In Patent Document 1, an ultraviolet curable covering material for floor, which is obtained by laminating an ultraviolet curable resin composition with an ultraviolet transmissive film, is attached to a floor material, and is cured by irradiating the film with ultraviolet rays. Although a method for protecting a flooring characterized in that it is integrated with a material is described, it does not mention that an inorganic filler is contained in the ultraviolet curable coating material for flooring.
Patent Document 2 describes a UV curable resin composition comprising a photopolymerizable prepolymer having a carboxylic acid group and / or a carboxylic acid group and a photoinitiator, and this composition can be used as a floor coating. It is described. In this composition, it is described that various additives can be added as desired, but there is no description indicating an inorganic filler as the additive.
In Patent Document 3, an adduct (A) of a polyalkylene oxide-added aromatic epoxy resin and an unsaturated monobasic acid, and a (meth) acrylic acid (B) having an aliphatic ring having a bridge-like bond in the molecule. Is an active energy ray-curable composition for polyvinyl chloride, and an inorganic filler such as silica powder can be used in combination with the resin composition as necessary. By curing the composition, a cured product film can be formed on the substrate, and is particularly effective for coating a PVC flooring. However, this uses a specific resin called an adduct (A) of a polyalkylene oxide-added aromatic epoxy resin and an unsaturated monobasic acid, and the energy ray-curable monomer of the present invention is used. It is not a starting material.

JP 2002-188273 A JP-A-63-225670 Japanese Patent Laid-Open No. 6-279666

  The present invention is for a synthetic resin floor material capable of forming a highly durable and durable film over a long period of time on a synthetic resin floor material without sacrificing contamination resistance. It is an object of the present invention to provide an energy ray curable resin composition and to provide a synthetic resin floor material having a film made of the resin composition.

A first aspect of the present invention is an energy beam curable resin composition for a synthetic resin floor material, comprising an energy beam curable monomer or oligomer, a photopolymerization initiator, and an inorganic filler having a Mohs hardness of 8 or more. About.
A second aspect of the present invention is characterized in that the inorganic filler is spherical and has a diameter of 50 to 100% of the thickness of the surface layer formed from the energy ray-curable resin composition. 1. An energy ray-curable resin composition for a synthetic resin floor material according to 1.
3rd of this invention contains 1-30 weight part of inorganic fillers with respect to 100 weight part of energy-beam curable resin composition which consists of an energy-beam curable monomer or oligomer, and a photoinitiator. The energy ray-curable resin composition for a synthetic resin flooring according to claim 1 or 2.
4th of this invention is related with the synthetic resin flooring characterized by having the membrane | film | coat which consists of an energy-beam curable resin composition for synthetic resin flooring in any one of Claims 1-3.

  Examples of the synthetic resin floor material in the present invention include polyvinyl chloride floor materials, polyolefin floor materials, polyester floor materials, and the like. For example, polyvinyl chloride floor materials include polyvinyl chloride tiles and cushion floor materials. It is a flooring formed using polyvinyl chloride, and examples of the polyvinyl chloride tile include a homogeneous vinyl floor tile and a composition vinyl floor tile. Moreover, as a cushion floor material, the composite vinyl chloride floor sheet etc. which combined the surface layer and the foaming layer can be mentioned.

Examples of the energy ray-curable monomer or oligomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethylacryloyl phosphate, 1,3-butanediol diacrylate, and 1,4-butanediol diester. Acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, or the like or oligomers thereof can be used.
Also, adipic acid / 1,6-hexanediol / acrylic acid reactive organism, phthalic anhydride / propylene oxide / acrylic acid reactive organism, trimellitic acid / diethylene glycol / acrylic acid reactive organism, bisphenol A-epichlorohydrin Type / acrylic acid reactive organism, phenol novolac-epichlorohydrin type / acrylic acid reactive organism, alicyclic type / acrylic acid reactive organism, tolylene diisocyanate / polyester / 2-hydroxyethyl acrylate reactive organism, polyether Acrylate or the like can be used.
These energy ray-curable monomers or oligomers may be used alone, but can also be used as a mixture.

  As a photopolymerization initiator, it has been well known conventionally, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, diethoxyacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone; anthraquinones such as methylanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone; thioxanthone, 2, Thioxanthones such as 4-dichlorothioxanthone and 2,4-diisopropylthioxanthone; Keta such as acetophenone dimethyl ketal and benzyl dimethyl ketal S; benzophenone, 4,4-benzophenones, such as bis-methyl-aminobenzophenone; is azo compounds.

Mohs hardness refers to scratch hardness used to measure the hardness of minerals provided by Mohs, and examples of inorganic fillers with Mohs hardness of 8 or higher include gold sand, osmium, tungsten carbide, boron zirconium, titanium nitride. , Chromium, alumina, silicon carbide, boron carbide, etc., but alumina is particularly preferred because it is readily available.
The inorganic filler is preferably spherical. In particular, when there are needle-like protrusions, the surface film is damaged by walking on the floor or by the wheels of the carrier, etc., which is not preferable because the stain resistance is impaired.
In the present invention, the spherical shape is not necessarily a true spherical shape, and may be fine particles formed by curved surfaces having no needle-like protrusions.
The thickness of the surface layer formed on the synthetic resin flooring is usually 100 to 10 μm, and the inorganic filler in the present invention preferably has a diameter of 5 to 100 μm, particularly preferably 20 to 70 μm. It is necessary that it is not larger than the thickness of the surface layer, and is preferably 50 to 100% with respect to the thickness of the surface layer.
This inorganic filler is added in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of a blend obtained by adding a photopolymerization initiator to an energy ray-curable monomer and / or oligomer. Preferably, 5 to 20 parts by weight is preferable. If the amount is less than 1 part by weight, the effect of adding the inorganic filler is not sufficiently exhibited, and if it is added in excess of 30 parts by weight, the transparency of the coating film is lowered, which may impair the design of the flooring. is there.
In the present invention, in addition to the energy ray-curable monomer or oligomer, the photopolymerization initiator, and the inorganic filler having a Mohs hardness of 8 or more, a plasticizer such as phthalate ester, trimellitic acid ester, chlorinated paraffin, and epoxy plasticizer ; Stabilizers such as metal soap stabilizers, organotin stabilizers, nonmetal stabilizers; antioxidants such as phenolic antioxidants; hydrocarbon lubricants, fatty acid lubricants, higher alcohol lubricants, amides Various synthetic resin compounding agents can be incorporated as required, such as lubricants such as system lubricants.

In forming a film on a synthetic resin floor material using the energy ray-curable resin composition for the synthetic resin floor material of the present invention,
(A) The resin composition is added to a solvent such as ethyl acetate, butyl acetate, xylene, toluene or the like to form a uniform dispersion, and is applied onto a flooring.
(B) Disperse the resin composition in water to form an emulsion or suspension and apply it on the flooring;
(C) The resin composition can be dispersed as powder on the flooring.
Next, an energy ray is irradiated and cured to form a film on the synthetic resin flooring.
Examples of energy rays in the present invention include electron beams, α rays, γ rays, X rays, and ultraviolet rays, and ultraviolet rays are particularly preferable in terms of handling.

  According to the present invention, for a synthetic resin floor material capable of forming a highly durable and durable film over a long period of time on a synthetic resin floor material without sacrificing contamination resistance. An energy ray-curable resin composition could be provided, and a synthetic resin flooring having a film made of the resin composition could be provided.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1
10 g of benzoin as a photopolymerization initiator is added to 30 g of acrylic acid methyl ester and 60 g of acrylic acid methyl ester oligomer, and alumina shown in Table 1 is added to form an ultraviolet curable resin composition, which is coated on a polyvinyl chloride floor tile. The film was applied to a thickness of 30 μm and cured by irradiating with ultraviolet rays using an ultraviolet irradiation device having a high-pressure mercury lamp. Using the obtained samples, the abrasion resistance, heel mark resistance, contamination, and scratch resistance were measured.
About abrasion property, it implemented according to JIS A1453 (Abrasion test method of building materials and building components).
A test load (load applied to the test piece by the wear wheel and the weight) 500 g / single wheel S-42 abrasive paper was used, and an average value of three measurement results was shown.
The heel mark resistance was measured according to JIS K 3920 (floor polish test method).
However, the test was carried out for 10 minutes each in the forward and reverse directions for a total of 30 minutes. The degree of dirt on the sample surface was evaluated before and after dry wiping.
The evaluation criteria were three-level evaluation with ◯>Δ> × based on UV paint samples.
As for 1/10 carbon contamination, carbon diluted to 1/10 with calcium carbonate was sprinkled on a sample (about 50 × 150 mm), lightly rubbed with gauze, the carbon was wiped off, and the degree of contamination was visually evaluated.
Evaluation criteria are: ○: No dirt remains. Δ: Some dirt remains. X: Dirt is remarkable. It was evaluated in three stages.
For scratches, a sandpaper (No. 80: about 45 × 180 mm) with a load of about 35 N was slid over the sample at a speed of 130 mm / min. After being scratched, it was diluted to 1/10 with calcium carbonate. Carbon was rubbed into the wound and the degree of damage was visually evaluated.
The evaluation criteria were three-level evaluation with ◯>Δ> × based on UV paint samples.
The results are shown in Table 1.

Claims (4)

  An energy ray-curable resin composition for a synthetic resin floor material, comprising an energy ray-curable monomer or oligomer, a photopolymerization initiator, and an inorganic filler having a Mohs hardness of 8 or more.   The synthetic resin floor according to claim 1, wherein the inorganic filler is spherical and has a diameter of 50 to 100% of the thickness of the surface layer formed from the energy ray-curable resin composition. Energy ray curable resin composition for materials.   2. An inorganic filler is contained in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of an energy ray curable resin composition comprising an energy ray curable monomer or oligomer and a photopolymerization initiator. Or the energy-beam curable resin composition for synthetic resin flooring of 2 description. A synthetic resin floor material comprising a film made of the energy ray-curable resin composition for a synthetic resin floor material according to any one of claims 1 to 3.