JP3336081B2 - Curing sheet for construction work - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curing sheet used for construction work.

[0002]

2. Description of the Related Art Conventionally, when performing construction work, in order to eliminate the occurrence of accidents caused by falling of building members and tools at a construction site, a synthetic woven fabric such as polyester is coated with a coarse woven or knitted fabric. Cured sheet made by impregnating and coating with a polyvinyl chloride paste sol and gelling, or formed using synthetic fiber such as polyester fiber yarn impregnated with a polyvinyl chloride paste sol and gelled. Curing sheets made of coarse woven or knitted fabric are widely used. This curing sheet has excellent strength, good flame resistance, good air permeability, and good high-frequency welder sewing. However, while the cured sheet is a coarse-woven knitted fabric and has good air permeability, dust at the construction site, exhaust gas from automobiles, and the like easily pass along with the air, and thus a large amount of dust and exhaust gas tend to adhere. Further, in the cured sheet, the plasticizer contained in the polyvinyl chloride coating the surface bleeds out partially to the surface during use. For this reason, there is a problem that the surface of the curing sheet has adhesiveness, dust and exhaust gas in the air are easily attached, and the curing sheet is stained and discolored in a short period of time, thereby impairing the beauty of the construction site. In recent years, the deterioration of the beauty of construction sites has been regarded as a serious environmental problem.

When the dirt adhering to the curing sheet was observed under magnification, it was found that there were various things such as sticking and sticking on the sheet surface. After the completion of one construction, the curing sheet is washed to remove dirt. However, the dirt cannot be completely removed, and becomes thin with age and becomes unusable. In recent years, as a countermeasure against this, a method of reducing the adhesion of dust in the air, exhaust gas from automobiles, and the like, and easily removing dirt by washing has been disclosed in Japanese Patent Application Laid-Open No. 3-2.
Japanese Patent No. 49275 discloses a cured sheet in which a cured sheet is coated with a solvent-based fluororesin containing a fluoroolefin and an alkyl vinyl ether copolymer and subjected to a crosslinking treatment. However, this curing sheet has a problem that blocking cannot be prevented. When the rolled raw material processed with the fluororesin is drawn out and cut, the rolled raw material is blocked and becomes a lump, making it extremely difficult to pull out. Furthermore, there is a problem that even if the sheet is moved for cutting and stacking and adjusting the dimensions to determine the position of the eyelet holes, it is difficult to move the sheet due to poor slipping, resulting in poor workability.

When the cut sheet is subjected to high-frequency welder sewing, the tensile strength and elongation of the sewn portion are reduced as compared with a sheet without a fluororesin coating, and there is a problem that the sheet cannot be put to practical use. Further, the antifouling property is better as compared with a sheet without a fluororesin coating, but is not yet sufficient. Further, a coarse base fabric as disclosed in Japanese Utility Model Application Laid-Open No. 4-64590 is impregnated and coated with a thermoplastic synthetic resin film, and a fluororesin film is coated on the coarse net-like sheet in an amount of 5 g to 50 g per square rice.
The bound cured sheet cannot be put to practical use because the tensile strength and elongation of the sewn part are reduced when compared with a sheet without a fluororesin coating when sewn with a high-frequency welder in the same manner as in the prior art described above. There is a problem.

[0005]

Means for Solving the Problems According to the present invention, when a curing sheet is spread on a building construction site, dirt can be reduced, dirt can be easily removed by washing, and the tensile strength and elongation of a high frequency welder sewn portion. The curable sheet used in a building construction site, which does not substantially decrease, has no blocking on the rolled material, has good slippage during sewing, and is excellent in durability, flame resistance and air permeability. The present invention relates to (1) (A) a woven or knitted fabric obtained by weaving or knitting using a fiber yarn impregnated with a polyvinyl chloride-based paste resin sol and gelling, heat-fixed, and heat-fixed at the intersection. (B) a. fluoroolefin, b. fatty acid vinyl ester or a fatty acid isopropenyl ester, c. hydroxy allyl ether and d. more a composition with a carboxyl group-containing monomer as essential components to the copolymer and a curing agent formed by covered with objects crosslinking treatment, building construction for curing sheet. (2) (a) pre-weaving or knitting the textile fabric to a polyvinyl-based paste resin sol chloride impregnated coated treated gel is thermally fixed after the intersection is thermally fixed (B) a. fluoroolefin, b. fatty acid vinyl ester or a fatty acid isopropenyl ester, c. hydroxy allyl ether and d. Curing sheet for architectural work, which is coated with a composition comprising a copolymer containing a ruboxyl group-containing monomer as an essential component and a curing agent and then subjected to a crosslinking treatment (3) The copolymer of the composition to be coated is: a. fluoroolefin 25-75 mole%, b. fatty acid vinyl ester or a fatty acid isopropenyl ester 10-70 mole%, c. hydroxy allyl ether 3 to 40 mol%, d. a carboxyl group-containing monomer 0.1 The curable sheet for building work according to item 1 or 2, which is a copolymer consisting of 0 to 20 mol%, e, and other monomers 0 to 10 mol%. 4. The curing sheet for construction work according to any one of items 1 to 3, which is one or more selected from acrylic acid, vinyl acetic acid, and allyloxy acetic acid. (5) Fluorine-based copolymer composition The amount of coating, 1 g / m
^The curing sheet according to any one of Items 1 to 4, wherein the curing sheet has a weight of ^{2 to} 10 g / m ² . "
About.

[0006]

The feature of the present invention is that the surface of the mesh sheet is covered with a vinyl chloride-based paste resin layer, and a special fluororesin cross-linking coating layer is disposed on the surface of the paste resin coating layer. Since the cured mesh sheet is required to have flame resistance for safety, if it is woven or knitted with ordinary fibers, there is a danger that it will burn due to sparks or the like during welding. Further, the cured mesh sheet is stretched on a construction site and is exposed to sunlight, wind, and rain, so that it needs to have weather resistance. Furthermore, good workability such as spreading is required. Since there is no suitable fiber that satisfies all of these requirements, the surface of the mesh sheet having excellent strength is coated with a vinyl chloride paste resin having excellent flameproofing properties.

[0007] The coating with the vinyl chloride-based paste resin may be covered with a fiber thread and gelled and then woven or knitted, or may be covered with the paste resin after weaving or knitting. Even if the layer coated with this vinyl chloride-based paste resin is gelled, the plasticizer contained bleeds out to the surface, so that the raw material or the like wound on the mesh sheet becomes blocking and lumpy. There is.

For this reason, an anti-blocking layer must be provided on the surface of the paste resin coating layer. However, even if blocking can be prevented with a conventionally used fluororesin-based coating agent, serious defects occur. One of the defects
Means that the tensile strength of the welded seam portion is deteriorated when the high-frequency welder sewing is performed by cutting the raw material.
Further, when the cut mesh sheet is processed into a curing sheet, the workability is significantly reduced due to poor slippage of the sheet.
Such problems have been found that the present invention has a special fluororesin composition having an effect of solving various problems of the paste resin coating layer of the mesh sheet, and all of them have been solved. The composition is different from the one used conventionally, and when used for a mesh sheet, the high frequency welder sewing is very good, and the tensile strength of the welder sewing part is also very excellent, and furthermore, the slip of the coated surface is reduced. Good action with good workability. Further, there is an advantage that dirt is hardly adhered and the adhered matter is easily removed by washing after use, so that it can be reused.

The fluororesin used in the present invention is characterized by using a copolymer comprising fluoroolefin, fatty acid vinyl ester or fatty acid isopropenyl ester, hydroxy group-containing allyl ether and carboxyl group-containing monomer as essential components. Is a fluororesin composition,
In particular, an excellent resin solution is obtained at a low temperature by using one or more of acrylic acid, vinyl acetic acid, and allyloxyacetic acid as the carboxyl group-containing monomer.

The fluoroolefin used in the present invention includes trifluoroethylene, tetrafluoroethylene,
Examples thereof include chlorotrifluoroethylene, hexafluoropropene, and vinylidene fluoride, and chlorotrifluoroethylene and tetrafluoroethylene are preferable from the viewpoint of polymerization reactivity.

The fatty acid vinyl esters include vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl piperic acid, vinyl caprylate, and the like. A value of 3 is preferred. Examples of the fatty acid isopropenyl ester include isopropenyl acetate, isopropenyl propionate and the like, and isopropenyl acetate and the like are preferable from the viewpoint of production.

As the hydroxy group-containing allyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, hydroxypropyl allyl ether and the like can be used.

Further, as the carboxyl group-containing monomer,
Allyl acetic acid, vinyl acetic acid, allyl oxy acetic acid, acrylic acid, methacrylic acid, maleic anhydride and the like are mentioned, and acrylic acid, vinyl acetic acid and allyl oxy acetic acid are preferred.

Other comonomers include acrylic acid or methacrylic acid esters such as hydroxyethyl acrylate, methyl methacrylate and glycidyl methacrylate; acrylamides such as acrylamide and N-methylol acrylamide; ethyl vinyl ether;
Vinyl ether such as butyl vinyl ether is used.

Next, typical copolymers in the present invention include: a. 25-75 mol% of fluoroolefin, b. Fatty acid vinyl ester or a fatty acid isopropenyl ester 10-70 mole%, c. Hydroxyallyl ether 3-40 mol%, d. Carboxyl group-containing monomer 0.1 to 20 mol%, e. Other monomers 0
It is a copolymer consisting of 10 mol%, preferably in the range of 40 to 60 mol%, 20 to 50 mol%, 5 to 30 mol%, 0.3 to 10 mol% and 0 to 8 mol%, respectively.

As the solvent, tetrahydrofuran,
Including cyclic ethers such as dioxane, aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, dimethylformamide, dimethylacetamide and pyridine. Nitrogen solvents, halogen-containing solvents such as 1,1,1-trichloroethane and trichloroethylene are used.

As the curing agent, polyisocyanates are preferred, and blocked polyisocyanates are most preferred.

The coating amount of the fluororesin copolymer composition to the mesh sheet ^{is 1g / m 2 ~10g / m 2} . Preferably it is 1 g / m ^{2 to} 5 g / m ² or less. More preferably, it is 1.5 g / m ^{2 to} 4 g / m ² or less.
If it is 1 g / m ² or less, the antifouling effect is small, and if it is 10 g / m ² or more, the strength of the high-frequency welder sewn portion becomes small, and it is not practical.

[0019]

【Example】

Example 1 Sheet preparation Polyvinyl chloride paste resin (P = 1600) 100
Parts by weight, dioctyl phthalate 50 parts by weight, phosphate plasticizer 10 parts by weight, epoxidized soybean oil 3 parts by weight, B
3 parts by weight of the a-Zn-based stabilizer, 15 parts by weight of Sb ₂ O ₃ , and 6 parts by weight of the gray toner pigment were kneaded with a kneading mixer.
A paste sol having a viscosity of 3,000 cps is obtained. Polyester multifilament yarn 750d / 70f is impregnated and coated with the paste sol through a nozzle, and heated in a heating furnace at 190 ° C for 45 seconds to obtain 1,800de yarn. The thread is woven in a plain weave structure with a length of 52/10 cm and a width of 52/10 cm to obtain a woven fabric having a width of 200 cm. The woven fabric is heated in a heating furnace at 150 ° C. for 60 seconds and heat-fixed. Thus, a sheet coated with polyvinyl chloride was prepared. Coating composition 1356 g of vinyl acetate (VAc) and 41 parts of ethylene glycol monoallyl ether (EGMAE) were placed in a stainless steel autoclave having an internal volume of 10 liters equipped with an electromagnetic stirrer.
3 g, 39 g of vinyl acetic acid, 23.4 g of Parloyl NPP (trade name of Nippon Oil & Fats), and 2533 g of n-butyl acetate are purged with nitrogen gas three times in the autoclave, and degassed. Then chlorotrifluoroethylene (CTFE) 2
After introducing 883 g into the autoclave, the temperature was gradually raised. After polymerization at 40 ° C. for 24 hours, unreacted CT
Remove the FE and open the autoclave. Subsequently, the polymerization liquid was taken out, impurities were removed by washing with water, and dried to obtain 381 g of a copolymer. The molecular weight of the obtained copolymer is 2
2,000 (polystyrene equivalent number average molecular weight) and O
The H value was 56 (KOH mg / g) and the acid value was 6. This copolymer is dissolved in a mixed solvent of butyl acetate / toluene 70/30 to make a resin solution of 50% by weight, and 25 parts by weight of a blocked polyisocyanate as a crosslinking agent is added to 75 parts by weight of the resin solution to form a coating composition. And Curing sheet mesh sheet The above-prepared curing sheet is immersed in a liquid for coating prepared by adding 300 parts by weight of toluene to 100 parts by weight of the coating composition, and squeezed with a mangle to obtain a solids adhesion amount of 3 g / m ^2. ,
After heating at 120 ° C. for 30 seconds, a heating and curing treatment was performed at 150 ° C. for 1 minute, and after cooling, the roll was wound into a roll and wound at 250 m / roll to obtain a mesh sheet for a cured sheet.

Example 2 Preparation of sheet 7 parts by weight of a naphthenic thinner was added to 100 parts by weight of the paste sol having a viscosity of 3,000 cps prepared in Example 1 to prepare a paste sol having a viscosity of 1,200 cps. Polyester multifilament yarn 750d / 70f is 33 lines / inch in length and 33 lines / inch in width and has a width of 2
A 00 cm fabric was woven. The fabric is immersed in the previously prepared paste sol, impregnated and uniformly adhered with a paste sol of 200 g / m ² , heated at 150 ° C. for 30 seconds and further heated for 1 second.
After heating and gelling at 90 ° C. for 60 seconds, after cooling, the sheet is roll-wound, and a rolled sheet is coated with polyvinyl chloride to prepare a cured sheet used for construction work. Coating composition In a 10-liter autoclave, 1205 g of vinyl acetate, 368 g of ethylene glycol monoallyl ether, 30 g of acrylic acid, and 25 g of n-butyl acetate were placed in a 10-liter autoclave in the same manner as in Example 1.
Then, the autoclave was replaced with nitrogen gas three times and degassed. Thereafter, 2,563 g of chlorotrifluoroethylene was introduced into the autoclave, and polymerization was carried out at 40 ° C. for 24 hours. After completion of the reaction, the autoclave was opened to remove unreacted CTFF, and the polymerization solution was washed with water to remove impurities. 325 g after drying
Was obtained. The obtained copolymer had a molecular weight of 19,700 (polystyrene-equivalent number average molecular weight), an OH value of 55 (KOH mg / g), and an acid value of 6. 25 parts by weight of a blocked polyisocyanate was added to 75 parts by weight of a 50% by weight solution of this copolymer in a mixed solvent of butyl acetate / toluene 70/30 to obtain a coating composition. Curing sheet mesh sheet 100 parts by weight of the above coating composition solution was mixed with toluene 350
The sheet prepared above is immersed in the coating solution added by weight, squeezed with a mangle so that the solid content becomes ² g / m ² , heated at 120 ° C. for 30 seconds, and then heat-cured at 150 ° C. for 1 minute. After cooling, the resultant was roll-wound and a roll of 250 m / roll was wound to obtain a mesh sheet.

Comparative Example 1 The sheet of Example 1 is referred to as Comparative Example 1. Comparative Example 2 The sheet of Example 2 is referred to as Comparative Example 2. Comparative Example 3 In place of the coating composition used in Example 1, a 50% solution of a fluoroolefin alkyl-vinyl ether copolymer in methyl ethyl ketone (UM-1 manufactured by Asahi Glass Co., Ltd.) was added to 80 parts by weight of isocyanate (UM-Asahi Glass Co., Ltd.). A coating solution obtained by adding 300 parts by weight of toluene to 100 parts by weight of the solution to which 20 parts by weight was added was used.

Comparative Test In order to clarify the effects of the present invention, performance tests of the examples and comparative examples are shown in Table 1.

[0023]

[Table 1]

Degree of dirt 1 Very large 2 Large 3 Medium 4 Small 5 Very slight

Washing Method The cured sheet was immersed in a water bath of 0.05% anionic synthetic detergent for 4 hours, washed with a roll brush, and further washed with water.
Dry through a dryer at ℃.

Blocking A 250-m roll material roll is pulled out by two people while holding the left and right ends of the sheet, and cut at 5.1 m / sheet. Judgment is made based on the degree of blocking at the time of drawing. 1 The fluororesin peels off due to close contact. 2 There is a sound that the contact comes off when pulled out. 3 There is close contact at the time of pulling out, and considerable power is required and it cannot be pulled out smoothly. 4 Slightly adhered when pulled out, but can be pulled out smoothly. 5 There is no adhesion at all and it can be pulled out smoothly.

Slippage of cut products is difficult. Dimensions are difficult to adjust. Good Dimensions can be adjusted. Good.

The welder sewing conditions high-frequency output 7 k W pressing pressure 4 k gf / cm ² mold size width 20mm length 1,050mm application time 2 seconds heating time of 8 seconds cooling time 2 seconds welder sewing width 20mm overlay

Tensile test Test temperature 23 ° C. Measurement speed 200 mm / min Test piece length 200 mm Width 30 mm

[0030]

The mesh sheet of the present invention has good antifouling properties, does not cause blocking, has good high-frequency welder sewability, has a large tensile strength at the sewn portion, and has excellent slipperiness, so that workability is excellent. .

Claims (5)

(57) [Claims] (A) Weaving or knitting using a fiber yarn impregnated with a polyvinyl chloride-based paste resin sol and gelling, heat-fixed, and heat-fixed at the crossover portion, (B) a. A fluoroolefin, b. Fatty acid vinyl ester or a fatty acid isopropenyl ester, c. Hydroxyallyl ether and d. A curing sheet for building construction, which is coated with a composition comprising a copolymer containing a carboxyl group-containing monomer as an essential component and a curing agent and then subjected to a crosslinking treatment. Wherein (A) pre-weaving or knitting and woven knit to <br/> polyvinyl-based paste resin sol chloride impregnated coated treated gelation by thermal fixing after the intersection with heat (B) a.
A fluoroolefin, b. Fatty acid vinyl ester or a fatty acid isopropenyl ester, c. Hydroxyallyl ether and d. A curing sheet for building construction, which is coated with a composition comprising a copolymer containing a carboxyl group-containing monomer as an essential component and a curing agent and then subjected to a crosslinking treatment. 3. The copolymer of the composition to be coated comprises: a. 25-75 mol% of a fluoroolefin, b. Fatty acid vinyl ester or a fatty acid isopropenyl ester 10-7
0 mol%, c. Hydroxyallyl ether 3-40 mol%, d. Carboxyl group-containing monomer 0.1 to 20 mol%, e. The curing sheet according to claim 1 or 2, which is a copolymer comprising 0 to 10 mol% of other monomers. 4. The curing sheet for building works according to claim 1, wherein the carboxyl group-containing monomer is one or more selected from acrylic acid, vinyl acetic acid, and allyloxy acetic acid. . 5. The coating amount of the fluorine-based copolymer composition is 1
a ^{g / m 2 ~10g / m 2} , claims 1 to have been construction work for curing sheet according to any one of the 4.