JPH0765271B2 - Method for producing antifouling curing sheet - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an antifouling curing sheet for use in construction work sheets, safety nets, scattering prevention nets, etc. The present invention relates to an antifouling processing method for a vinyl chloride resin-coated curing sheet having excellent washing durability.

(Prior art) The mesh fabric coated with vinyl chloride resin is well known as a curing sheet for construction work and civil engineering work, and is currently supplied mainly by a lease method. These curing sheets are manufactured by coating a polyamide or polyester yarn with a vinyl chloride-based paste resin as a core yarn and then weaving it with a polyamide or polyester yarn, and then adding a vinyl chloride resin to the woven fabric. There is a type that impregnates and coats. Regarding the durability of the curing sheet when used, the former is superior because the fabric texture points are firmly fused and fixed.

The reason why vinyl chloride resin is widely used as a coating resin for curing sheets is that it is low in cost, excellent in processability, excellent in light / weather resistance and chemical resistance, and also in flameproof performance. It can be easily obtained by adding a flameproofing agent and that high-frequency welder sewing is possible.

(Problems to be Solved by the Invention) The curing sheet obtained by weaving the vinyl chloride resin-coated yarn has many advantages as a curing sheet.
Since the vinyl chloride resin-coated yarn has a high friction coefficient, it has the disadvantage of poor weavability. When it is exposed to the outdoors for a long time, it sticks to the sheet surface due to elution of the plasticizer to the surface. It has the disadvantage that it is easy to get dirty because it shows good properties. For this reason, at the present time, when the construction work is completed, the leasing company does the washing and reuses it. Various processing methods have been proposed in order to solve this defect that dirt easily adheres, but no method has been found that is satisfactory in all aspects such as antifouling performance, durability, processability, and cost. Is the reality. The present invention is to solve the above problems,
It is an object of the present invention to provide a method capable of improving the weaving property, producing a stain-proofing sheet having less dirt adherence and excellent durability.

(Means for Solving Problems) As a result of earnest research to solve such problems, the present inventors have found that curing with less dirt adhesion during use and excellent dirt removability during washing. As a method for producing a sheet, the inventors have found that this can be achieved by applying a composition solution consisting of a mineral oil, an emulsifier, dimethylpolysiloxane and a fluorine-based water repellent and antifouling agent to a vinyl chloride resin-coated yarn, and arrived at the present invention. Is.

That is, according to the present invention, the fiber yarn is coated with a vinyl chloride paste resin sol for gelation treatment to obtain a vinyl chloride resin-coated fiber yarn. Second step of applying a composition solution comprising 30-80 parts by weight, an emulsifier 3-15 parts by weight, dimethylpolysiloxane 1-10 parts by weight and a fluorine-based water repellent agent 1-10 parts by weight, and further heat-treated after weaving And a method for producing an antifouling curing sheet, which comprises the third step of fusion-fixing the fabric texture points with a vinyl chloride resin.

Hereinafter, the method of the present invention will be described in detail.

First, the fiber yarn in the present invention is composed of natural or synthetic fiber yarn, inorganic fiber yarn and mixed yarn thereof, and both short fiber and long fiber can be used. In particular, polyamide and polyester long fiber yarns are often used because of their excellent strength.

Next, the vinyl chloride paste resin sol is composed of a vinyl chloride paste resin, a dialkyl phthalate plasticizer (such as dioctyl phthalate, dibutyl phthalate, etc.) and a diluting solvent. The kneading is performed by using an open type heating type mixing roll or a Banbury mixer. Incidentally, in order to impart flameproofness to the vinyl chloride resin, an inorganic flameproofing agent such as antimony trioxide or aluminum hydroxide may be appropriately added. Next, an example of prescription of vinyl chloride paste resin sol is shown for reference.

20 to 60 parts of phthalate plasticizer to 100 parts by weight of vinyl chloride paste resin (hereinafter, simply referred to as “parts”), and methyl isobutyl ketone /
Add 5-10 parts of naphthenic thinner = 1/1 and knead with an open type heating type mixing roll to obtain an organosol with an apparent viscosity of 50-500 CPS. Using this organosol, the fiber yarn is coated, heated and gelled. Further, in order to achieve the object of the present invention, the average thickness of the vinyl chloride resin coating layer is 10 μm or more, preferably 50-1000 μm. The vinyl chloride resin in the present invention includes vinyl chloride homopolymers, vinyl chloride / vinyl acetate, vinyl chloride / acrylic acid ester and vinyl chloride / vinylidene chloride copolymers, as well as homopolymers. Mixtures of copolymers are also included.

Next, as a method for coating the fiber yarn with the vinyl chloride resin, after impregnating the yarn into the vinyl chloride paste resin sol, the resin concentration and the nip pressure are adjusted by a roll so that the target adhesion amount is obtained. Method and after impregnating the yarn,
There is a method of selecting a nozzle hole diameter suitable for the target adhesion amount and adhering the resin sol by squeezing the nozzle hole. Any method may be used as long as it is uniformly applied to the yarn. After coating the yarn with vinyl chloride resin, heat treatment is applied to gel the resin. The heat treatment condition is preferably a temperature of 130 to 200 ° C. for 15 seconds to 10 minutes.

Next, the vinyl chloride resin-coated yarn is woven, but since the yarn has a high friction coefficient, it is necessary to impart smoothness to the yarn with an oil agent or the like. Therefore, a composition solution consisting of mineral oil, an emulsifier, dimethylpolysiloxane and a fluorine-based water repellent and antifouling agent is used.

The mineral oil used herein is a mixture of straight-chain aliphatic hydrocarbon compounds having a stearyl group, a cetyl group, an oleyl group and the like. Other compounds that provide smoothness include refined paraffin and higher fatty acid esters, which may be used for the same purpose as mineral oil.

As the emulsifier, all commonly used emulsifiers can be used, but in a W / O type emulsion in which oil is dispersed in water, a water-soluble emulsifier is preferably used. That is, a nonionic surfactant such as an ethylene oxide adduct of vegetable oil, an ethylene oxide adduct of higher alcohol, an ethylene oxide adduct of alkylphenol, an ethylene oxide adduct of higher fatty acid, or an anionic surfactant such as a sulfate of vegetable oil is used. Often used.

Next, dimethylpolysiloxane is the most common of the organopolysiloxanes, and imparts smoothness, water repellency and anti-tack property of vinyl chloride coated yarn. Therefore, in addition to dimethylpolysiloxane, the methyl group is a phenyl group,
It goes without saying that those partially substituted with a hydroxyl group or the like or copolymers thereof can also be used.

Further, in order to impart the antifouling property of the present invention, a fluorine-based water repellent antifouling agent is added to the above composition solution.

The water repellent and antifouling agent in the present invention is a polymer composed of perfluoroalkyl-containing methacrylate and perfluoroalkyl-containing acrylate, and the critical surface tension of the perfluoroalkyl group in the side chain is extremely low. Difficult to get wet with liquids and solids with large
It has the property of being resistant to dirt. Hereinafter, typical ones of the perfluoroalkyl-containing polymers used in the present invention are shown below.

CF ₃ (CF ₂ ) ₆ CH _2- A, CF ₃ (CF ₂ ) CH _2- M, (CF ₃ ) ₂ CF-A, CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₂ CH ₂ CH ₃ ) CH ₂ CH _2- A, (CF ₃ ) ₂ CH-
A, (CF ₃ ) ₂ CH-M, HCF ₂ (CH ₂ ) ₇ CH ₂ -A, HCF ₂ (CF ₂ ) ₉ CH _2-
A, CF ₃ (CF ₂ ) ₂ CH _2- A, (CF ₃ ) CFO (CH ₂ ) _2- A, HCF ₂ (CF ₂ ) ₃ CH _2- A, (CF ₃ ) ₂ CFO (CH ₂ ) ₅ -A A and M represent repeating units of acrylate and methacrylate, respectively. Further, the water repellent antifouling agent of the present invention includes those having acrylic amide, isocyanate, etc. in the main chain in addition to acrylate and methacrylate.

In the composition solution, the proportion of mineral oil is 30-80 parts, the proportion of emulsifier is 3-15 parts, the proportion of dimethylpolysiloxane is 1-10 parts, and the proportion of fluorinated water repellent agent is 1-10 parts. . If the proportion of mineral oil is less than 30 parts, weaving becomes difficult due to lack of smoothness, and if it exceeds 80 parts, emulsification becomes difficult and the stability of the composition solution deteriorates. If the proportion of the emulsifier is less than 3 parts, emulsification is difficult, and if it exceeds 15 parts, smoothness is poor and weaving is difficult. If the proportion of dimethylpolysiloxane is less than 1 part, the smoothness, water repellency and anti-tack effect are not observed, and if it exceeds 10 parts, the vinyl chloride resin coating layer is not fused and fixed between the woven fabric structures even after heat treatment. . If the ratio of the fluorine-based water repellent antifouling agent is less than 1 part, the antifouling effect is poor, and if it is more than 10 parts, the antifouling effect does not change,
On the contrary, the smoothness is insufficient and the weavability is deteriorated.

In order to satisfy both the smoothness and the antifouling property of the vinyl chloride resin-coated fiber yarn, the above composition is added to the surface of the vinyl chloride resin-coated yarn in a solid content of 0.1-10% by weight (hereinafter, weight% is simply referred to as%). It is preferable to add it so as to be in the range of (abbreviated).
If it is less than 0.1%, the effect of smoothness and antifouling property is small, while if it exceeds 10%, the cost becomes high and the vinyl chloride resin coating layer is hard to be firmly fused and fixed to the woven structure points.

Next, as the yarn of the curing sheet, 210-2420 denier yarn is preferably used although it varies depending on the use such as a safety net and a scattering prevention net. Also, regarding the fabric density, it is preferable that the fabric is manufactured with an appropriate fabric design in consideration of the sheet weight, strength and cost.

Next, after weaving, heat treatment is performed using a heat setter. As heat treatment conditions, the vinyl chloride-coated yarn texture points of the warp and weft are fused and fixed in a temperature range of 130 to 200 ° C and a heat treatment time of 15 seconds to 15 minutes. If the temperature is lower than 130 ° C, the microstructure points do not fuse, and if it exceeds 200 ° C, the vinyl chloride resin decomposes, so the temperature range of 130-200 ° C is preferable. In addition, if the heat treatment time is shorter than 15 seconds, fusion of microstructure points is insufficient, while if it is longer than 15 minutes, deterioration of the vinyl chloride resin becomes a problem.

As described above, the conventional vinyl chloride resin-coated curing sheet is liable to be soiled and is less likely to be soiled, whereas the method of the present invention is less likely to be soiled during use and is washable. It has excellent stain removability. In the present invention, the smoothing treatment and the antifouling treatment are simultaneously performed in the yarn state before weaving. However, the smoothing treatment may be performed before the weaving, and the antifouling treatment may be performed after the sheet is formed. Needless to say.

Specific examples of the present invention will be described below with reference to examples.

(Example) Example 1 Polyester multifilament yarn 1000D / 96F was impregnated with a vinyl chloride resin composition solution shown in the following Formulation 1, and after uniformly applying 700% by weight of the yarn weight to the resin, 150 ° C ×
Heat treatment was carried out for 3 minutes to obtain a vinyl chloride resin-coated yarn.

(Formulation 1) Vinyl chloride resin paste resin (emulsion polymer, degree of polymerization 13
50, Particle size 1.2μ, Latex concentration 21%) 100 parts Dioctyl phthalate 40 parts (Plasticizer) Antimony trioxide 15 parts (Flame retardant) Methyl isobutyl ketone / naphthenic thinner (VOL
Ratio 1/1) 10 parts (diluent) The resin coating layer of the obtained vinyl chloride resin coated yarn has an average of 60
It was 0 μ.

Next, using the vinyl chloride resin-coated yarn, a composition solution (an aqueous solution in which 900 parts of water was added to 100 parts of the composition) shown in the following Table 1, Formulation 2-5 was padded, and a squeezing ratio of 50 was used.
% (Solid content of 4% per yarn weight was given, and after drying, weaving was performed using this yarn. (Garment density: 21 warps / 2.5
4 cm, 20 wefts / 2.54 cm) Then, this fabric is heat-treated at a temperature of 180 ° C for 1 minute with a heat setter to fuse and fix the texture points of the fabric made of vinyl chloride resin coated filaments, and cure for construction work. Created a sheet.

A stain test was performed using the obtained curing sheet for construction work. Regarding the test conditions, the above-mentioned sheet was put into a stain compound shown below, stirred 100 times a day, allowed to stand for 3 months, and then the state of stain was observed.

(Dirt compound structure) Peat moss 38% Cement 17% Kaolin clay 17% Silica 17% Carbon black 1.75% Iron oxide 0.5% Mineral oil (A heavy oil) 8.75% Also, this sheet was repeatedly washed under the washing conditions shown below. Again, perform the dirt test under the same conditions as above,
The state of dirt was observed. The results are shown in Table 1.

(Washing conditions) Score roll 0.5 g / sodium carbonate 0.5 g / It was immersed in the above solution at room temperature for 6 hours and then brushed with a cleaning brush. (Repetition number: 5 times) As is clear from Table 1, the curing sheet obtained by the present invention has excellent antifouling property and durability as compared with the conventional products, and is required for the curing sheet. It also had a flameproof property and a welder property.

(Effects of the Invention) The present invention has the above-mentioned structure, and it is difficult to remove the stains even after being left for a long period of time. Since it can reduce adhesion, it can be used in a wider field.

Moreover, even if it is repeatedly washed, the antifouling effect does not decrease and it is durable, and the workability and cost of the high-frequency welder can be maintained at about the same level as conventional ones.

Claims (1)

[Claims] 1. A first step of obtaining a vinyl chloride resin-coated fiber yarn by subjecting the fiber yarn to a gelation treatment with a vinyl chloride paste resin sol, the vinyl chloride resin-coated fiber yarn comprising:
30-80 parts by weight of mineral oil, 3-15 parts by weight of emulsifier, 1-10 parts by weight of dimethylpolysiloxane and fluorinated water and water repellent agent 1-
An antifouling curing sheet comprising a second step of applying a composition solution consisting of 10 parts by weight, a third step of weaving and then heat-treating, and fixing and fixing the fabric texture points with vinyl chloride resin. Manufacturing method.