Bio-plasticizer containing wallpaper

Abstract

To provide a wallpaper containing a bio-derived component as a plasticizer.SOLUTION: This wallpaper can be obtained without yellowing by using a glycerol fatty acid ester as a bio-plasticizer and using far-infrared radiation as a heating method in a foaming step. The wallpaper thus obtained exhibits physical properties superior to those of conventional wallpapers in a stretch test and a surface reinforcement test.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to wallpaper using bio-derived components as plasticizers. [Background technology]

[0002] BACKGROUND ART Resin wallpaper has been widely used to aesthetically finish the interior surfaces of buildings and also to provide water resistance, weather resistance, and the like. Among these, polyvinyl chloride laminated wallpaper is widely used, which consists of a laminate of a substrate and a resin layer, with the resin layer being a foamed polyvinyl chloride resin layer made from a material containing polyvinyl chloride resin, a phthalate ester plasticizer, and a foaming agent.

[0003] Meanwhile, in recent years, with the increasing demand for environmental friendliness, it has been considered to use bio-derived components as constituents of wallpaper as a building material. Among the bio-derived components that are being considered as candidates for use as plasticizers are epoxy-based plasticizers and non-phthalate-based plasticizers, but none have yet been found that meet the properties required for commercialization.

[0004] Patent Document 1 describes a flame-retardant wallpaper produced by mixing 50 parts by weight of diisononyl phthalate (DINP) as a plasticizer with 100 parts by weight of polyvinyl chloride to form a polyvinyl chloride paste. Patent Document 2 describes wallpaper in which the expandable polyvinyl chloride resin layer contains polyvinyl chloride resin with an average degree of polymerization of more than 1200 and 1600 or less, and diisononyl phthalate (DINP) as a plasticizer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-212900 [Patent Document 2] JP 2020-158924 A Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, although bio-derived ingredients have been proposed as candidates for use as plasticizers, they cannot be made into a paste, such as epoxy-based plasticizers, and it is therefore impossible to adopt materials that are unsuitable for the wallpaper manufacturing process.

[0007] On the other hand, even if non-phthalate plasticizers, which do not cause any particular problems during the manufacturing process, are used, yellowing occurs when heated during manufacturing, which has an adverse effect on the color printed on the surface of the wallpaper, and therefore the product has not yet been commercialized. [Means for solving the problem]

[0008] The invention described in claim 1 is Wallpaper containing at least polyvinyl chloride resin, a plasticizer, and a foaming agent, the plasticizer is a bioplasticizer containing a glycerin fatty acid ester as a component, The heating method in the step of foaming the foaming agent is far infrared radiation. This wallpaper is characterized by the above.

[0009] The average degree of polymerization of the polyvinyl chloride resin used in the polyvinyl chloride resin layer is 700 to 1200, preferably 750 to 1100. If the average degree of polymerization is less than 700, the wallpaper becomes soft and the design is impaired, which is undesirable. On the other hand, if it exceeds 1200, the foaming property becomes extremely poor, the surface smoothness is impaired, and commercialization becomes difficult. Furthermore, to obtain good stretchability, an average degree of polymerization of 900 to 1100 is more preferable. The average degree of polymerization can be measured according to "JIS K6720-2:1999 Plastics - Vinyl chloride homopolymer and copolymer (PVC) - Part 2: Preparation of test specimens and determination of properties."

[0010] When a polyvinyl chloride resin for paste processing is used as the polyvinyl chloride resin, it becomes easy to laminate a polyvinyl chloride resin layer on a substrate by paste coating, and it becomes possible to produce a variety of foamed products by blending a large amount of various compounding agents using inexpensive equipment, and it is further suitable and preferable for producing a wide variety of products in small quantities.

[0011] Polyvinyl chloride resin for paste processing is made by precisely controlling the particle size, and consists of primary particles that are spherical and uniform in size, with an average particle size of, for example, 0.1 to several μm. Polyvinyl chloride resin for paste processing becomes a paste with good fluidity when a plasticizer is added, and can be molded at room temperature. It is then heated and melted to become wallpaper. Because it can be molded at room temperature in a state with good fluidity, it is possible to keep equipment costs and energy costs low.

[0012] As the plasticizer, glycerin fatty acid esters are preferred, and among them, BIOCIZER manufactured by Riken Vitamin Co., Ltd. is particularly preferred. Among bio-based plasticizers, these have properties that make them suitable for wallpaper production, and by selecting the heating method described below, it is possible to avoid yellowing, which has been a concern in the past.

[0013] The amount of bioplasticizer to be blended with polyvinyl chloride resin is about 35 to 60 parts, but preferably 40 to 55 parts when used alone. When used alone, if it is less than 40 parts, some surface roughness will occur and the design will not be guaranteed, and if it is more than 55 parts, depending on the amount of calcium carbonate, the viscosity will drop significantly and the paste viscosity will be 1000 CPs or less for Type B, which will cause problems with the coating process. Although it can be used in combination with phthalate-based plasticizers, it is preferable to use a blend of 51% or more bioplasticizers, or to use them alone.

[0014] Wallpaper is heated twice during the manufacturing process, during the drying and foaming processes, and we have discovered that yellowing can be suppressed by using a different heating method during the foaming process. While hot air is typically used for both the drying and foaming processes, in this invention, far-infrared radiation is used for the heating method during the foaming process. As a result, we have achieved wallpaper that suppresses yellowing, even when using bioplasticizers.

[0015] For heating with far infrared rays, a sheath heater, ceramic heater, carbon heater, etc. may be used. These may be used alone or in combination of two or more. It is preferable to adjust the temperature inside the furnace to 120 to 300°C in order to soften the polyvinyl chloride resin layer and decompose the foaming agent. In order to form a denser foam, it is preferable to provide a temperature gradient in the furnace. If the temperature inside the furnace exceeds 300°C, the plasticizer may volatilize, causing the product to harden, or heat deterioration may cause discoloration, which is undesirable.

[0016] The invention described in claim 2 is Color difference ΔE* in the L*a*b* color space, based on the case where diisononyl phthalate is used as the plasticizer ab The value of is less than or equal to 1.0, The wallpaper according to claim 1.

[0017] The wallpaper obtained by the invention described in claim 2 is one in which yellowing is suppressed as described above. The specific measurement values ​​are calculated based on the L* (lightness) / a* (redness) / b* (yellowness) (illuminant D65) measured with a spectrophotometer manufactured by Konica Minolta, CM3600A, and the values ​​of ΔL*, Δa*, and Δb* are calculated using the values ​​of the conventional product as the standard, and the color difference ΔE* ab This results in wallpapers with extremely excellent values ​​of 1.0 or less.

[0018] The invention described in claim 3 is The 100% breaking strength in the Sangetsu stretch standard test is 4.5 mm or more. The wallpaper according to claim 2.

[0019] The wallpaper obtained by the invention described in claim 3 also has superior stretchability compared to conventional products. In accordance with Sangetsu stretchability testing standards, measurements were taken using a Toyo Seiki Strograph E3-L testing machine with five samples taken lengthwise and widthwise (n=5). The results showed that the 100% breaking strength was 4.5mm or more, demonstrating that the wallpaper has better stretchability than conventional products.

[0020] The invention described in claim 4 is 21 to 29.5 wt% of a base material; a resin layer comprising 29 to 40% by weight of the polyvinyl chloride resin, 13 to 22% by weight of the bioplasticizer, 1 to 4% by weight of a foaming agent, 4 to 30% by weight of a filler, 4 to 5.6% by weight of a colorant, and 0.9 to 1.2% by weight of a stabilizer; The wallpaper according to claim 3 comprises:

[0021] The substrate is 65 to 85 g / m 2 It has a weight per unit of 65g / m 2 If the thickness is less than this, the wallpaper will peel less easily (peel resistance) when replaced, which is undesirable. On the other hand, the thickness of the substrate is not particularly limited, but it is preferably 0.11±0.10 mm, and from the viewpoint of rigidity, the thickness is preferably 0.11±0.05 mm. The weight percentage of the substrate in the wallpaper will vary depending on the weight of the polyvinyl chloride resin layer, but is preferably 21 to 29.5 weight%.

[0022] Examples of the substrate include paper, fabric, nonwoven fabric, synthetic resin sheet (including synthetic resin film), and composite materials thereof. Examples of paper include various paper materials such as coated paper, kenaf paper, plain paper, recycled paper, Japanese paper, fine paper, crepe paper, glassine paper, tracing paper, cast paper, coated paper, and synthetic paper. Examples of fabric include knitted fabrics and woven fabrics made of natural fibers, synthetic fibers, semi-synthetic fibers, recycled fibers, and the like. Examples of nonwoven fabric include nonwoven fabrics made of natural fibers, synthetic fibers, semi-synthetic fibers, recycled fibers, and the like. Examples of synthetic resin sheets include sheets made of synthetic resins such as polyolefins such as polyethylene terephthalate, polyethylene, and polypropylene, polyvinyl chloride resin, olefin-based thermoplastic elastomers, and ABS resin.

[0023] The polyvinyl chloride resin layer is formed by foaming a layer made of polyvinyl chloride resin and then embossing it. The weight of the polyvinyl chloride resin layer is 150 to 250 g / m 2 and 250 g / m 2 If it exceeds this, it may not be possible to meet the fireproof certification standard of "semi-non-combustible wallpaper", which is not desirable. 2 If the thickness is less than this, the unevenness will be small when embossed, resulting in poor design properties, which is undesirable.

[0024] The polyvinyl chloride resin layer contains 0.5 to 1.5% by weight of the foaming agent. If the amount of the foaming agent is more than 1.5% by weight, the surface may become rough, collapse, or have poor surface strength. From the viewpoint of design and hiding power, the addition amount is preferably 0.5% by weight or more.

[0025] The foaming agent is not particularly limited, and examples thereof include azodicarbonamide (ADCA) and oxybisbenzenesulfonylhydrazide (OBSH). These may be used alone or in combination of two or more.

[0026] The polyvinyl chloride resin layer contains 9 to 30% by weight of filler. If the filler content is more than 30% by weight, the wallpaper's ability to conform to the substrate and its surface strength will be impaired. Furthermore, from the viewpoint of the hiding power and flame retardancy of the wallpaper, it is preferable that the polyvinyl chloride resin layer contains 9% by weight or more of filler.

[0027] The filler is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium silicate, etc. These may be used alone or in combination of two or more.

[0028] The polyvinyl chloride resin layer contains 3 to 10% by weight of a colorant. If the colorant content is less than 3% by weight, the polyvinyl chloride resin layer will yellow when heated, which is undesirable. If the colorant content is 10% by weight or more, the hiding power of the wallpaper will improve, but costs will increase, which is undesirable. Therefore, from the viewpoint of achieving both resistance to yellowing when heated and cost, the colorant content is preferably 3% by weight or more and 10% by weight or less.

[0029] The coloring agent is not particularly limited, and examples thereof include titanium oxide, zinc oxide (zinc white), lithopone, and white lead. These may be used alone or in combination. In addition, when the wallpaper is to be colored, carbon black and red, yellow, and blue organic pigments may be used as appropriate.

[0030] The stabilizer is not particularly limited, and examples thereof include organic phosphorus compounds, organic tin stabilizers such as dibutyltin laurate, dibutyltin maleate, and dibutyltin mercapto, lead stabilizers such as lead stearate and lead benzoate, calcium zinc stabilizers, barium zinc stabilizers, inorganic stabilizers such as hydrotalcite and zeolite, etc. These may be used alone or in combination of two or more.

[0031] The content of the stabilizer is not particularly limited, but from the viewpoint of thermal stability and cost, it is more preferably 0.5% by weight or more and 1.5% by weight or less.

[0032] Furthermore, in addition to the plasticizer, foaming agent, filler, colorant, and stabilizer, a diluent for adjusting the fluidity of the paste-like polyvinyl chloride resin for paste processing can be appropriately added to the polyvinyl chloride resin for paste processing. [Effects of the Invention]

[0033] The present invention has made it possible to produce wallpaper using bio-derived plasticizers, which was previously considered difficult, and has also made possible a means of avoiding the yellowing that inhibits color development during printing. In addition to considering the above environmental issues, the wallpaper of the present invention was found to have superior performance beyond expectations in stretchability tests and surface strengthening tests compared to conventional products that use conventional petroleum-derived plasticizers. [Brief explanation of the drawings]

[0034] [Figure 1] FIG. 1 is a flow chart showing the manufacturing process of wallpaper of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0035] Hereinafter, embodiments of the present invention will be described. However, each specific description is one example of realizing the present invention, and the present invention is not limited to these specific examples. Any other specific examples that can realize the technical idea of ​​the present invention are also included in the present invention. [Example]

[0036] An example of a production method suitable for the present invention will be described below. 100 parts by weight of polyvinyl chloride resin (Tosoh Corporation's Ryuron Paste K94Z) was blended with 42.9 parts by weight of a glycerin fatty acid ester with a biomass content of 74.8 (Riken Vitamin Co., Ltd.'s BIOCIZER) as a plasticizer, 29.9 parts by weight of calcium carbonate (Bihoku Funka Kogyo Co., Ltd.'s BF200S) as a filler, 14.1 parts by weight of titanium oxide (Sakai Chemical Industry Co., Ltd.'s TITONE R-25) as a colorant, 3.1 parts by weight of zinc carboxylate (Daikyo Kasei Kogyo Co., Ltd.'s LFX-97JY) as a stabilizer, 3 parts by weight of azodicarbonamide (ADCA) (Eiwa Kasei Kogyo Co., Ltd.'s Vinihole AC#93) as a foaming agent, and 8.10 parts by weight of nonane (Oxazol S) as a diluent, and kneaded to prepare a blended raw material. The mixed raw materials were applied to a wood pulp paper (CP65 manufactured by Chuetsu Pulp Industries Co., Ltd.) as a substrate to obtain a coated substrate, which was then dried, embossed, printed, foamed and embossed, and cut to produce wallpaper. The amount of the base material was 71.7 parts by weight per 100 parts by weight of the polyvinyl chloride resin. [Example]

[0037] The degree of discoloration was measured for the product of the present invention and the conventional product. The L*, a*, and b* values ​​were measured under the following conditions based on the heating method, plasticizer, and measurement date in the foaming process. The ΔL*, Δa*, and Δb* values ​​were calculated based on the hot air heating / DINP values, and the color difference ΔE* compared to the standard was calculated. ab was obtained as a result.

[0038] The production and measurement were carried out under the following conditions. <Heating conditions> The method of the present invention (far infrared rays) Drying process 220~226℃ / 13.15 seconds (hot air) Foaming process: 230-245℃ / 25.35 seconds (far infrared) Conventional method (hot air) Drying process 150℃ / 30 seconds (hot air) Foaming process: 225℃ / 55 seconds (hot air) <Color measurement> Konica Minolta CM3600A spectrophotometer L* (lightness) / a* (redness) / b* (yellowness) (illuminant D65) <Test product blend ratio (wt%)>

[0039] [Table 1] <Color difference data of test products>

[0040] [Table 2]

[0041] Although the wallpaper of the present invention uses a bioplasticizer, the color change is suppressed to the same extent as that of conventional DINP, and it has been found to be a valuable product. When a bioplasticizer is used that is heated with hot air, the degree of yellowing varies greatly depending on the storage period, in addition to the non-uniformity between lots due to the natural ingredients. In this regard, the product of the present invention, which uses a bioplasticizer of similarly natural origin but in which yellowing itself is suppressed, allows for the production of a stable, valuable product without regard to lot size or storage period, which is another advantage of the present invention. [Example]

[0042] The physical properties of the present invention and the conventional product were compared by a stretchability test. The test was carried out under the following conditions: Inspection method and conditions Sangetsu stretchability test standard Inspection machine: Toyo Seiki Strograph E3-L Inspection Part Number 1. RE55013 (Bio-Cloth: the present invention) 2.SP9710 3.General combination products Sampling count: n=5 vertically and horizontally <Test product blend ratio (wt%)>

[0043] [Table 3] <Stretch test data of test item>

[0044] [Table 4]

[0045] The wallpaper of the present invention had superior stretchability compared to conventional products in all values ​​of breakage initiation, 80% breakage, and 100% breakage. [Example]

[0046] The physical properties of the present invention and the conventional product were compared by a surface strengthening test. The test was carried out under the following conditions: Inspection method and conditions: Complies with the surface strengthening test standards established by the Wallpaper Industry Association Inspection machine: Toyo Seiki dye fastness friction tester Inspection Part Number 1. RE55013 (Bio-Cloth: the present invention) 2.SP9710 3.General combination products Sampling count: n=3 vertically and horizontally The compounding ratio of the test product was the same as in Example 3. <Surface strengthening test data for test items>

[0047] [Table 5]

[0048] The surface strengthening test established by the Wallpaper Industry Association was conducted, and the number of times the tape was returned to its original position before grade 2 or lower occurred was recorded. As a result, RE55013, which required the most number of times the tape was returned to its original position before grade 2 occurred, was found to have the highest surface strength performance of the three product numbers. [Industrial Applicability]

[0049] The present invention provides wallpaper with high commercial value, which is an environmentally friendly product in both production and disposal, is comparable to conventional products in terms of color development inhibition due to yellowing, and has superior physical properties compared to conventional products using petroleum-derived plasticizers.

Claims

1. Wallpaper containing at least polyvinyl chloride resin, a plasticizer, and a foaming agent, the plasticizer is a bioplasticizer containing glycerin fatty acid ester as a main component, The heating method in the step of foaming the foaming agent is far infrared radiation. Wallpaper characterized by:

2. Color difference ΔE* in the L*a*b* color space, based on the case where diisononyl phthalate is used as the plasticizer ab The wallpaper according to claim 1 , wherein the value of is 1.0 or less.

3. 3. Wallpaper according to claim 2, which has a 100% breaking strength of 4.5 mm or more in the Sangetsu Stretchability Standard Test.

4. 21 to 29.5 wt. % of a base material; a resin layer comprising 29 to 40% by weight of the polyvinyl chloride resin, 13 to 22% by weight of the bioplasticizer, 1 to 4% by weight of a foaming agent, 4 to 30% by weight of a filler, 4 to 5.6% by weight of a colorant, and 0.5 to 1.5% by weight of a stabilizer; 4. The wallpaper according to claim 3, comprising:

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