JP5697290B1 - Resin composition for floor material welding rod and floor material welding rod - Google Patents

Abstract

The present invention provides a resin composition that can be used in the production of floor welding rods having excellent antifouling performance. A floor welding rod resin composition comprising a vinyl chloride resin and at least one resin-based additive selected from a silicone resin and a fluororesin. [Selection] Figure 1

Description

  The present invention relates to a resin composition for a floor material welding rod and a floor material welding rod obtained from the resin composition, and particularly relates to a floor material welding rod excellent in antifouling performance.

  For example, the floor material such as a long floor sheet made of vinyl chloride resin is protected by, for example, periodically applying wax, but in recent years from the viewpoint of easy maintenance and maintenance-free, the floor surface is covered with urethane resin or ultraviolet rays. The process which coat | covers cured resin is performed. In particular, in hospitals, geriatric health facilities, welfare facilities, schools, and stores, awareness of easy maintenance and maintenance-free is increasing in order to reduce maintenance costs.

  By the way, for welding of the long floor sheet, thermal welding using a welding rod or liquid welding using a seam liquid is mainly performed, but from the viewpoint of construction cost, in most cases, thermal welding using a welding rod is adopted. ing. With the increasing awareness of floor materials as described above, development of new floor material welding rods is required from the viewpoint of easy maintenance and maintenance-free. For example, in JP-A-2005-054001 (Patent Document 1), a specific olefin resin that contributes to stain resistance and scratch resistance and a specific olefin resin that contributes to improvement in welding strength and flexibility are disclosed. It is described that it is possible to provide a welding rod excellent in dirt resistance and scratch resistance while ensuring welding strength by combining.

JP-A-2005-054001

  However, in Patent Document 1, it is necessary to blend two different olefinic resins, and from the viewpoint of construction cost, development of a floor material welding rod containing a general synthetic resin such as vinyl chloride resin is also required. ing. Various floor material manufacturers sell dedicated welding rods together with various floor materials, for example, but there is still room for improvement in the antifouling performance of the welding rods.

  Then, the objective of this invention is providing the resin composition which can be used for manufacture of the flooring welding rod which solves the problem of the said prior art and is excellent in antifouling performance. Another object of the present invention is to provide a floor welding rod excellent in antifouling performance.

  The inventor has found that the antifouling performance of a floor welding rod can be improved by combining vinyl chloride resin with at least one resin-based additive selected from silicone resin and fluororesin, and completes the present invention. It came to.

  That is, the resin composition for a floor welding rod of the present invention is characterized by containing a vinyl chloride resin and at least one resin-based additive selected from a silicone resin and a fluororesin.

  In a preferred example of the resin composition for floor welding rods of the present invention, the resin-based additive is a silicone resin.

  In another preferable example of the resin composition for a floor welding rod of the present invention, the content of the vinyl chloride resin is 40 to 70% by mass, and the content of the resin additive is 3 to 15% by mass. is there.

  In another preferred example of the resin composition for floor welding rods of the present invention, it further comprises at least one filler selected from the group consisting of calcium carbonate, talc and silica, and the average particle size of the filler is 0.2-1 μm.

  In another preferable example of the resin composition for a floor welding rod of the present invention, the content of the vinyl chloride resin is 40 to 70% by mass, and the content of the resin additive is 3 to 15% by mass. Yes, the content of the filler is 1 to 15% by mass.

  Moreover, the floor material welding rod of this invention is obtained from said resin composition for floor material welding rods, It is characterized by the above-mentioned.

  According to the resin composition for a floor welding rod of the present invention, a floor welding rod excellent in antifouling performance by combining vinyl chloride resin with at least one resin-based additive selected from silicone resin and fluororesin. The resin composition which can be used for manufacture of can be provided.

  Moreover, according to the floor material welding rod of this invention, the floor material welding rod which is excellent in antifouling performance can be provided by using the above-mentioned resin composition.

2 is an image showing the surface of a test sample after an antifouling test in Example 1. FIG. 4 is an image showing the surface of a test sample after an antifouling test in Example 3. 6 is an image showing the surface of a test sample after an antifouling test in Example 5. It is an image which shows the surface of the test sample after the antifouling property test in Reference Example 7. 6 is an image showing the surface of a test sample after an antifouling test in Comparative Example 1. It is an image which shows the surface of the test sample after the antifouling property test in comparative example 2.

  Hereinafter, the resin composition for a floor material welding rod of the present invention (hereinafter, also simply referred to as the resin composition of the present invention) will be described in detail. The resin composition for a floor welding rod of the present invention includes a vinyl chloride resin and at least one resin-based additive selected from a silicone resin and a fluororesin. The floor material welding rod is a rod-shaped molded product used when welding a seam of a floor material such as a long floor sheet made of vinyl chloride resin.

  The vinyl chloride resin used in the resin composition of the present invention is a base material, and a known vinyl chloride resin that can be used for a floor welding rod can be used. For example, a vinyl chloride homopolymer, vinyl chloride, and the vinyl chloride A copolymer with a copolymerizable monomer, a graft copolymer obtained by grafting vinyl chloride to a polymer composed of a monomer other than vinyl chloride, and the like are included. It is also possible to prepare a cross-linked vinyl chloride resin by selecting a monomer copolymerizable with vinyl chloride and a backbone portion constituting the graft copolymer. In the present invention, since the antifouling performance can be further improved by completely crosslinking the vinyl chloride resin during welding, a crosslinked vinyl chloride resin is preferred. In addition, these vinyl chloride resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The production method of the cross-linked vinyl chloride resin is not particularly limited, and can be appropriately selected from conventionally known methods. For example, (1) a quaternary ammonium salt, a metal salt of a polyvalent carboxylic acid having two or more carboxyl groups, and an acid anhydride of a polyvalent carboxylic acid having two or more carboxyl groups are added to a vinyl chloride resin. Mixing and heat treatment to cross-link vinyl chloride resin, (2) When vinyl chloride is suspension polymerized or emulsion polymerized in an aqueous medium, a polyfunctional monomer is added to form a polyfunctional monomer. For example, a method of cross-linking can be used.

  In the copolymer of vinyl chloride and a monomer copolymerizable with vinyl chloride, examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, acrylonitrile, styrene, acrylate ester, methacrylate ester, and ethylene. , Propylene, butylene and the like. These monomers copolymerizable with vinyl chloride may be used alone or in combination of two or more.

  In the graft copolymer obtained by grafting vinyl chloride onto a polymer composed of a monomer other than vinyl chloride, examples of the polymer composed of a monomer other than vinyl chloride include polyurethane, ethylene / vinyl acetate copolymer, and polyacrylate. , Polymethacrylate, polyethylene, chlorinated polyethylene and the like. Here, conventionally known techniques can be used for graft copolymerization. For example, when grafting vinyl chloride onto polyurethane, (1) thermoplastic polyurethane and vinyl chloride monomer soluble in vinyl chloride monomer Of a soft thermoplastic resin by suspension polymerization (graft copolymerization) with (2), and (2) impregnating a vinyl chloride resin with a polyol, adding polyisocyanate while stirring the polyurethane, and polyurethane in the vinyl chloride resin A method for producing a polyvinyl chloride-polyurethane composite by forming a resin can be used.

  The vinyl chloride resin preferably has a high degree of polymerization from the viewpoint of further improving the antifouling performance, but considering the economical aspect and the hardness during construction, the degree of polymerization of the vinyl chloride resin is 400 to 2500. Is preferable, and 800 to 1000 is more preferable. Vinyl chloride resins having different degrees of polymerization can be mixed and used. However, if the difference in the degree of polymerization is too large, a sea-island structure is formed between the vinyl chloride resins, which is undesirable. In the present invention, the degree of polymerization of the vinyl chloride resin can be measured according to JIS K 6720-2.

  In the resin composition of the present invention, the content of the vinyl chloride resin is preferably 40 to 70% by mass, and more preferably 50 to 65% by mass.

  The resin composition of the present invention needs to contain at least one resin-based additive selected from a silicone resin and a fluororesin. By using such a resin-based additive, the antifouling performance of the floor material welding rod containing a vinyl chloride resin can be improved. In addition, a silicone resin is preferred from the viewpoint of improving the antifouling performance and molding processability.

  The silicone resin is a polymer having a siloxane bond in the main skeleton, but also includes a graft copolymer obtained by grafting a silane compound to a polymer such as polyacrylate. In the present invention, an organic-inorganic composite resin such as an acrylic silicone copolymer resin is preferable from the viewpoint of combination with a vinyl chloride resin. In addition, as a silicone resin, a commercial item can be used conveniently.

  Examples of the fluororesin include, for example, tetrafluoroethylene resin (polytetrafluoroethylene PTFE), trifluoroethylene chloride resin, hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, and difluorodiethylene chloride resin. Etc. In addition, as a fluororesin, a commercial item can be used conveniently.

  In the resin composition of the present invention, the content of the resin additive is preferably 3 to 15% by mass, and more preferably 5 to 10% by mass. In addition, when using both a silicone resin and a fluororesin, the total amount of these becomes the content of the resin-based additive. When the content of the resin additive is 3% by mass or more, the antifouling performance of the floor material welding rod can be improved more reliably. On the other hand, if the content of the resin-based additive is too high, the welding performance may be lowered. Therefore, the content of the resin-based additive is preferably 15% by mass or less.

  The resin composition of the present invention may contain a filler from the viewpoint of improving workability. Although it does not specifically limit as a filler, A calcium carbonate, a talc, a silica, etc. are mentioned. In addition, from the viewpoint of combining with a vinyl chloride resin, a filler subjected to surface treatment is preferable. For example, the surface treatment with a fatty acid can improve the compatibility in the resin component, and the surface treatment with a silane coupling agent or a titanium coupling agent can improve the adhesion with the resin component. In addition, these fillers may be used individually by 1 type, and may be used in combination of 2 or more type. A commercially available product can be suitably used as the filler.

  The filler used in the resin composition of the present invention usually has an average particle size of 0.1 to 25 μm, and particularly preferably 0.2 to 1 μm. When a filler is used in the resin composition of the present invention, a void is easily generated between the resin component and the filler, dirt is attached to the void, and a welded portion that is a seam of the flooring material is easily contaminated. However, if the average particle diameter of the filler is 1 μm or less, the generation of voids can be suppressed. On the other hand, if the particle size of the filler is too small, the filler may be aggregated and voids may be generated. Therefore, the average particle size of the filler is preferably 0.2 μm or more. In addition, in this invention, the average particle diameter of a filler is an average particle diameter calculated | required in BET specific surface area conversion.

  In the resin composition of this invention, content of a filler is 1-15 mass%, for example, and it is preferable that it is 1-5 mass%. In addition, when using several types of fillers, these total amount becomes content of a filler. If content of a filler is 1 mass% or more, workability | operativity can be improved. On the other hand, if the content of the filler is too high, the antifouling performance and the welding performance may be lowered. Therefore, the content of the filler is preferably 15% by mass or less.

  The resin composition of the present invention is preferably plasticized by including a plasticizer. Although it does not specifically limit as a plasticizer, The contamination by the bleed-out of a plasticizer is also considered. For this reason, a plasticizer which is difficult to bleed on the surface of the welded portion which is the joint of the flooring is preferable. From the viewpoint of combining with vinyl chloride resin, specifically, bis (2-ethylhexyl) phthalate (DOP), diisononyl phthalate Phthalates such as (DINP), trimellitic esters such as trimellitic acid tris (2-ethylhexyl) (TOTM), epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil, adipic acid polyester plastic An agent or the like is preferable. In addition, these plasticizers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the resin composition of this invention, it is preferable that content of a plasticizer is 20-35 mass%. When there is little content of a plasticizer, the softness | flexibility as a welding rod will be impaired, and workability and weld strength will fall. On the other hand, when there is too much content, the surface of a welding part may be contaminated by the bleed-out of a plasticizer.

  In the resin composition of the present invention, a stabilizer, a processing aid, an ultraviolet absorber, an antioxidant, an antistatic agent, an antifogging agent, a pigment, a dye, a crosslinking agent, a flame retardant, an fragrance, Known additives such as lubricants, surfactants, water repellents, and oil repellents may be appropriately selected and blended within a range that does not impair the object of the present invention. Moreover, the resin composition of this invention can be prepared by mixing the said vinyl chloride resin and resin-type additive, and the various additives selected suitably as needed.

  Next, the floor material welding rod of the present invention will be described in detail. The floor material welding rod of the present invention is obtained from the above-described resin composition of the present invention, and can be prepared by, for example, extrusion molding.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Comparative Example 1)
For 100 parts by mass of vinyl chloride resin (trade name TK-1000, manufactured by Shin-Etsu Chemical Co., Ltd.), 43 parts by mass of dioctyl phthalate which is a plasticizer, calcium zinc stabilizer (RX-210, manufactured by ADEKA, product name) 2 .5 parts by mass, and 25 parts by mass of calcium carbonate A (trade name μ-powder 3S, manufactured by Bihoku Powder Chemical Co., Ltd., average particle size 0.27 μm) are mixed uniformly with a Henschel mixer, and then The mixture was supplied to a single screw extruder with a screw of 50 mm, and formed into a round bar shape with a diameter of 3.5 mm under the following conditions to prepare a welding rod.
[Extrusion conditions]
Cylinder temperature: C1 = 130 ° C., C2 = 150 ° C., C3 = 170 ° C.
Head temperature: 165 ° C
Die temperature: 160 ° C
Screw rotation speed: 20rpm
Drawing line speed: 10m / min

(Examples 1 to 6 and Reference Example 7)
A welding rod was produced in the same manner as in Comparative Example 1 except that the raw material according to the formulation of Table 1 was used. In the table, Charline R-170S manufactured by Nissin Chemical Industry Co., Ltd. was used as the silicone resin additive, and Softon 1000 (average particle size: 2.2 μm) manufactured by Bihoku Powder Chemical Co., Ltd. was used as the calcium carbonate B. .

(Comparative Example 2)
A welding rod was produced using a welding rod YS0209 manufactured by Sangetsu Co., Ltd., which is a resin composition. Extrusion conditions are the same as in Comparative Example 1. This resin composition contains vinyl chloride resin as a base material, but does not contain silicone resin or fluororesin.

[Test sample preparation method]
A vinyl chloride flooring was pressure-bonded to a test plate made of marble with double-sided tape, and a groove was made with a grooving cutter. Next, a hot air welding machine in which a welding rod was inserted into the guide member was prepared, and welding was performed along the groove while heating and melting the welding rod with hot air of high temperature (about 410 ° C.). In addition, welding was performed to such an extent that it could be overfilled. Thereafter, the surplus portion was cut with a spatula knife, and the welded portion was smoothly finished to prepare a test sample.

[Anti-fouling test]
The antifouling test was performed in accordance with JIS K 3920. Specifically, a heel mark resistant snell capsule tester is used, and the test sample is attached inside the tester. Thereafter, the tester was rotated at a speed of 50 revolutions per minute with six standard black rubber blocks in the tester. The surface of the test sample after 10,000 rotations was strongly wiped with a cloth that had been wetted and wrung out, and the welded portion was evaluated according to the following evaluation criteria. The results are shown in Table 2. In addition, about Examples 1, 3, 5 and Reference Example 7 and Comparative Examples 1 and 2, the surface images of the test samples after the antifouling test are shown in FIGS.
○: There is almost no rubber contamination, and rubber can be wiped off when wiped with water.
Δ: Rubber contaminates, but when wiped with water, the rubber can be wiped off.
X: Rubber contamination is severe and the rubber cannot be wiped off even when wiped with water.

[Workability test]
The flooring and the welding rod were cured for one day in an ambient atmosphere at room temperature (about 23 ° C.), and then a test sample was prepared as described above. Here, the easiness of finishing when the surplus portion was cut with a spatula knife was evaluated according to the following evaluation criteria. The results are shown in Table 2.
○: The spatula knife blade enters smoothly and finishes smoothly.
Δ: The spatula knife blade escapes a little when cutting, but finishes smoothly.
X: The blade of the spatra knife escapes when cut and does not finish smoothly.

[Welding strength test]
The peel strength between the welding rod and the flooring was measured to evaluate the welding strength. The peel strength was measured using an Instron universal testing machine. Specifically, welding is performed according to the test sample preparation method described above, but a groove having a length of 200 mm is made on a test plate having a width of 20 mm and a length of 200 mm, only 100 mm of which is welded, and the remaining 100 mm is welded. It was set as the unwelded part. Also, the welding rod was not cut off from the end of the welded portion, leaving a 100 mm unwelded portion. Next, the end of the unwelded portion of the welding rod and test plate is sandwiched between chuck portions of a universal testing machine, and the tensile speed is set to 200 mm / min so that the welded portion of the welding rod and test plate is peeled in the direction of 180 °. Pulled. A peel test was performed until the welding rod and the test plate were completely peeled, and the highest value in the test was taken as the peel strength. The measurement results were evaluated according to the following evaluation criteria. The results are shown in Table 2.
○: Peel strength 25N or more (no problem in practice)
Δ: Peel strength 20N or more and less than 25N (although there is no problem in practice, there is a risk of peeling over time)
X: Peel strength less than 20N (welding strength is weak and the welded part is easy to peel off)

Claims (6)

Vinyl chloride resin, saw-containing and at least one resin based additive is selected from silicone resins and fluorine resins, the content of the vinyl chloride resin is 40 to 70 wt%, the content of the resin additive 3 to 15% by mass of a resin composition for a floor welding rod.   The resin composition for a flooring welding rod according to claim 1, wherein the resin-based additive is a silicone resin. Furthermore, at least comprise one filler, according to claim 1 or 2 average particle diameter of the filler is characterized in that it is a 0.2~1μm selected calcium carbonate, from the group consisting of talc and silica Resin composition for flooring welding rods. The content of the vinyl chloride resin is 40 to 70% by mass, the content of the resin-based additive is 3 to 15% by mass, and the content of the filler is 1 to 15% by mass. The resin composition for flooring welding rods according to claim 3 . A vinyl chloride resin, at least one resin-based additive selected from silicone resins and fluororesins, and at least one filler selected from the group consisting of calcium carbonate, talc and silica, and an average of the fillers A resin composition for a floor welding rod, wherein the particle diameter is 0.2 to 1 μm. A floor material welding rod obtained from the resin composition for a floor material welding rod according to any one of claims 1 to 5.