JPH10266071A - Fuse welding spark-proof sheet material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject flame-retardant sheet material excellent in flexibility and see-through effect, and to provide a method for producing the sheet. SOLUTION: A core material of inorganic fibrous woven or nonwoven fabric is partly impregnated with a liquid crosslinking agent capable of dissolving an acrylic derivative, followed by impregnation with a flame-retardant polymerizable monomer composition comprising an acrylic derivative of aryl halide, phosphorus-contg. monomer, liquid crosslinking agent capable of dissolving the acrylic derivative and acrylic polyfunctional oligomer and/or phosphoric ester, and then conducting a polymerization using a radical polymerization initiator to effect curing, thus producing a see-through flame-retardant base sheet. Subsequently, at least one side of the base sheet is provided with a flame-retardant polymerizable monomer composition for flame-retardant face layer sheet comprising the acrylic derivative of aryl halide, phosphorus-contg. monomer and liquid crosslinking agent capable of dissolving the acrylic derivative in a sheet-like way followed by polymerizing the flame-retardant polymerizable monomer composition by the use of a radical polymerization initiator to effect curing, thus obtaining the objective flame-retardant sheet material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet material for preventing fusing welding sparks which is effective for cutting off sparks and fouling generated during fusing welding and a method for producing the same.

[0002]

2. Description of the Related Art As a sheet material for preventing fusing welding sparks, for example, Japanese Patent Application Laid-Open No. 56-105873 discloses a method of using a hydroxide compound of 100 parts by weight or more with respect to 100 parts of an organic polymer, or a compound of 50 parts with respect to 100 parts of an organic polymer. 10 parts by weight or more of inorganic filler solidified at 1000 ° C. or less
A welding spark protection sheet comprising an admixture containing at least part by weight is disclosed.

[0003] However, the welding spark protection sheet disclosed in Japanese Patent Application Laid-Open No. 56-105873 is a sheet in which a hydroxide compound such as aluminum hydroxide is blended in an amount of 100 parts by weight or more with respect to 100 parts by weight of an organic polymer. So that
The resulting welding spark prevention sheet becomes cloudy or opaque, and becomes hard and brittle. Therefore, in order to impart the required strength to the welding spark prevention sheet, the thickness of the welding spark prevention sheet is inevitably increased, and the degree of cloudiness or opacity is further increased. It cannot be used at all in applications that require the ability to see through the interior of a welding curtain or the like. In order to make the inside of the welding spark prevention sheet transparent, the amount of the hydroxide compound and the inorganic filler to be blended in a large amount must be reduced. And the welding spark prevention function is almost lost.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object of the present invention is to provide a flame-retardant fusing welding spark prevention sheet having excellent flexibility and transparency. An object of the present invention is to provide a material and a method for manufacturing the same.

[0005]

According to the first aspect of the present invention,
An acrylic halide of an aryl halide, a phosphorus-containing monomer, a liquid crosslinking agent capable of dissolving the acrylic derivative of an aryl halide, and an acrylic polyfunctional oligomer and / or a phosphate ester in a core material made of an inorganic fiber woven fabric or a nonwoven fabric. The flame-retardant polymerizable monomer composition is impregnated, polymerized, and cured on at least one surface of a transparent flame-retardant base sheet, in which the acrylic derivative of an aryl halide, the phosphorus-containing monomer and the acrylic derivative are dissolved. The gist of the present invention is a fusing welding spark prevention sheet material characterized in that a flame-retardant surface layer sheet obtained by polymerizing and curing a flame-retardant polymerizable monomer composition comprising the obtained liquid crosslinking agent is laminated.

[0006] The invention according to claim 2 is to impregnate a core material made of inorganic fiber woven fabric or nonwoven fabric with a liquid cross-linking agent capable of dissolving an acrylic derivative of an aryl halide, and then apply the acrylic halide of the aryl halide. Impregnating a derivative, a phosphorus-containing monomer, a liquid crosslinking agent capable of dissolving the acrylic derivative, and a flame-retardant polymerizable monomer composition comprising an acrylic polyfunctional oligomer and / or a phosphoric ester, and polymerizing using a radical polymerization initiator Curing to form a flame-retardant base sheet having transparency, and then dissolving the aryl halide acrylic derivative, the phosphorus-containing monomer, and the acrylic derivative on at least one surface of the fire-retardant base sheet A flame-retardant polymerizable monomer composition for a flame-retardant surface layer sheet comprising a liquid crosslinking agent is formed into a sheet, and the flame-retardant polymerizable monomer composition is formed. Using a radical polymerization initiator, polymerization,
The gist of the present invention is a method for producing a fusing welding spark prevention sheet material characterized by being cured.

The inorganic fiber woven fabric or nonwoven fabric used as the core material in the present invention is an acrylic derivative of an aryl halide, a phosphorus-containing monomer, or an acrylic derivative of the above-mentioned aryl halide, even if it is invisible as a single substance. The composite flame-retardant base sheet obtained by impregnating, polymerizing and curing a liquid cross-linking agent capable of dissolving the polymer and a flame-retardant polymerizable monomer composition comprising an acrylic polyfunctional oligomer and / or a phosphoric acid ester can be seen through. The material is not particularly limited as long as it is a plain woven cloth of glass yarn (thickness 0.1 mm, basis weight 100 g / m ² ),
Mats, roving cloths, continuous mats, chopped strand mats, and the like.

[0008] The aryl halide acryl derivative is an aryl halide acryl derivative containing at least one of chlorine, bromine and iodine. Examples thereof include tetrabromobisphenol A-bisacrylate and tetrabromobisphenol. A-Ethylene oxide-added dimethacrylate, trichlorophenyl methacrylate, tribromophenyl methacrylate; or monomers and macromonomers of (meth) acrylates of halogenated phenol, halogenated bisphenol and halogenated arylcarboxylic acid ethylene oxide adducts, Examples include monomers and macromonomers in which a glycidyl ether group is introduced.

The above-mentioned phosphorus-containing monomer is not particularly limited as long as it can be copolymerized with the above-mentioned acrylic derivative of an aryl halide, as long as it contains a phosphorus element in the molecule. -2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-
(Acryloyloxyethyl) acid phosphate, bis-2-chloroethyl vinyl phosphate, and the like, and an acrylic derivative of a phosphoric ester or ether.

The content of the phosphorus-containing monomer is 20 parts by weight or more, preferably 20 to 70 parts by weight, based on 100 parts by weight of the aryl halide acrylic derivative, for both the flame-retardant substrate sheet and the flame-retardant surface layer sheet. It is. This is because if the content of the phosphorus-containing monomer is less than 20 parts by weight, the combustion suppression effect peculiar to phosphorus atoms in the solid layer portion of the flame-retardant substrate sheet and the flame-retardant surface sheet cannot be sufficiently obtained.

The liquid crosslinking agent capable of dissolving the acrylic derivative is not particularly limited. Examples thereof include benzyl (meth) acrylate, 3-methoxybutyl acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl acrylate, Acrylate monomers or macromonomers containing 1 to 3 terminal vinyl groups, such as -ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, neopentyl glycol diacrylate and the like.

As the liquid crosslinking agent capable of dissolving the acrylic derivative, only one kind may be used, but by using two or more kinds in combination, the flame-retardant base sheet and the flame-retardant material can be more effectively used. The physical properties of the surface sheet can be improved. For example, when only one kind of benzyl (meth) acrylate is used, the obtained fusing welding fireworks prevention sheet material tends to be slightly hard, but is used in combination with benzyl (meth) acrylate and 3-methoxybutyl acrylate. Thereby, besides the flexibility of the obtained fusing welding fireworks prevention sheet material is remarkably improved, various effects such as improvement of mechanical properties can be exhibited.

The content of the liquid crosslinking agent capable of dissolving the acrylic derivative is preferably 20 to 100 parts by weight based on 100 parts by weight of the aryl halide acrylic derivative. When the content of the liquid crosslinking agent capable of dissolving the acrylic derivative is less than 20 parts by weight, the solubility of the acrylic derivative is reduced, and when it exceeds 100 parts by weight, the flame retardancy is reduced.

Examples of the phosphate used in the flame-retardant base sheet include halogen-containing phosphates such as trisdichloropropyl phosphate, trischloroethyl phosphate, and tris (β-chloropropyl) phosphate; tricresyl phosphate; Examples include orthophosphates such as nyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate.

The content of the above-mentioned phosphoric ester is 1 to 100 parts by weight of the above-mentioned aryl halide acrylic derivative.
0 parts by weight or more, preferably 10 to 40 parts by weight. If the content of the phosphate is less than 10 parts by weight, the obtained fusing welding spark preventing sheet material cannot have sufficient flexibility.

Examples of the acrylic polyfunctional oligomer include urethane acrylate, epoxy acrylate, polyester acrylate and the like. The content of the acrylic polyfunctional oligomer, relative to acrylic derivatives 100 parts by weight of the aryl halide, preferably 10 parts by weight or more, more preferably 10 to 00 by weight part. If the content of the phosphate is less than 10 parts by weight, the obtained fusing welding fireworks prevention sheet material cannot have sufficient flexibility.

In the invention according to the second aspect, the core material 1 made of an inorganic fiber woven fabric or a non-woven fabric having a light transmitting property,
As shown in FIG. 1, a liquid impregnating agent 5 capable of dissolving the acrylic derivative is impregnated in a first impregnation tank 4. The pre-impregnation amount of the liquid crosslinking agent capable of dissolving the acrylic derivative is preferably the above-mentioned aryl halide acrylic derivative 10
It is 5 to 15 parts by weight with respect to 0 parts by weight.

When the preliminary impregnation amount of the liquid crosslinking agent capable of dissolving the acrylic derivative is less than 5 parts by weight, the effect of the preliminary impregnation of facilitating the impregnation of the core material with the flame-retardant polymerizable monomer composition is sufficiently obtained. If the amount exceeds 15 parts by weight, the ratio of the liquid crosslinking agent in the flame-retardant polymerizable monomer composition becomes too large, and the flexibility of the obtained flame-retardant base material sheet, and thus the fusing welding spark prevention sheet material, is reduced. This is because they cannot be obtained sufficiently.

The core material 1 pre-impregnated with the obtained liquid cross-linking agent 5 capable of dissolving the acrylic derivative is then treated in a second impregnation tank 7 with an acrylic derivative of an aryl halide,
A flame-retardant polymerizable monomer composition 6 comprising a phosphorus-containing monomer, a liquid crosslinking agent capable of dissolving the acrylic derivative, and an acrylic polyfunctional oligomer and / or a phosphoric ester is impregnated.

The flame-retardant polymerizable monomer composition 6 includes:
In order to accelerate the reaction of polymerizing and curing the flame-retardant polymerizable monomer composition, an agent such as a polymerization initiator is blended. Although it does not specifically limit as said polymerization initiator, For example, after mix | blending a photopolymerization initiator and impregnating the flame-retardant polymerizable monomer composition 6 in the 2nd impregnation tank 7, it is set to ultraviolet rays etc. Polymerization and curing are performed by photopolymerization using the actinic ray irradiation device 11 to produce the flame-retardant base sheet 2.

Examples of the photopolymerization initiator include, for example, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like.

The flame-retardant polymerizable monomer composition 6 includes:
In addition to the polymerization initiator, if necessary, a defoaming agent, a wetting agent, a release agent, an antistatic agent, and the like may be added.

The obtained flame-retardant substrate sheet 2 is then
Flame-retardant polymerizable monomer composition 8 comprising an aryl halide acrylic derivative, a phosphorus-containing monomer and a liquid crosslinking agent capable of dissolving the acrylic derivative in a third impregnation tank 9
Is impregnated. Like the flame-retardant polymerizable monomer composition 6, a polymerization initiator and, if necessary, a defoaming agent, a wetting agent, a release agent, an antistatic agent, and the like are added to the flame-retardant polymerizable monomer composition 8. You.

The means for polymerizing and curing the flame-retardant polymerizable monomer composition 8 formed on the flame-retardant base material sheet 2 is the same as that for the flame-retardant polymerizable monomer composition 6, as in the case of the actinic ray. The irradiation device 11 may be used.

Since the fusing welding spark preventing sheet material according to the first aspect of the present invention is constituted as described above, the flame retardant substrate sheet polymerized in the structure of the core material made of inorganic fiber woven fabric or nonwoven fabric. The flame-retardant base material sheet is formed into a flame-retardant base sheet having excellent transparency and excellent flexibility, which is polymerized and cured in this state and is firmly bonded in this state. At least one surface of the sheet is composed of a polymer composed of only a polymerizable monomer exhibiting high compatibility with the above-described flame-retardant base sheet and exhibiting excellent flame-retardancy, and has a flame retardance in a solid phase and a gas phase. Since the transparent flame-retardant surface sheet having an effect is firmly laminated, all of the transparency and transparency, the flexibility, the flame retardancy, and the anti-fusing fireworks prevention property are highly satisfied. Therefore, even in the case of a facility for preventing fusing welding fireworks having a complicated structure for use in a narrow place, the fusing welding fireworks prevention sheet material is excellent in workability, and gives a comfortable feeling of use, Since the workplace using the fusing welding fireworks prevention sheet material can be easily seen through from the outside, thorough safety management can be ensured.

Further, since the method for manufacturing a fusing welding spark preventing sheet material according to the second aspect of the present invention is configured as described above, aluminum hydroxide which impairs the transparency and transparency of the fusing welding spark preventing sheet material. The inorganic flame retardant imparting agent such as is not used by mixing with the organic polymer, the polymer material itself constituting the fusing welding spark prevention sheet material, as described above, only a polymerizable monomer showing excellent flame retardancy The present invention is mainly composed of a polymer consisting of: and has a flame-retarding effect in a solid phase and a gas phase, so that it is possible to provide a fusing welding spark prevention sheet material of stable quality.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

(Examples 1 to 8) Using a device as shown in FIG. 2, a glass yarn plain woven cloth (thickness: 0.1 mm, basis weight: 100 g / m ² ) was used as a core material 1.
The liquid cross-linking agent 5 (a mixture of equal amounts of 3-methoxybutyl acrylate and benzyl methacrylate) in the impregnation tank 4
After pre-impregnation (130 g / m ² ) for 1 minute, the total amount of the first and second impregnation tanks of the flame-retardant polymerizable composition 6 for the flame-retardant base material sheet shown in Table 1 of the second impregnation tank 7 was as shown in Table 1. , And irradiated with ultraviolet rays (ultraviolet intensity: 80 W / cm ² ) from the ultraviolet irradiation device 11 to photopolymerize and harden the flame-retardant polymerizable composition 6 to obtain a flame-retardant group. A material sheet was produced. Further, both sides of the obtained flame-retardant substrate sheet are impregnated with the flame-retardant polymerizable composition 8 for a flame-retardant surface layer sheet in the second impregnation tank 9, and are irradiated with ultraviolet rays from an ultraviolet irradiation device 11. The flammable polymerizable composition 8 was photopolymerized and cured to produce a fusing welding spark prevention sheet material.

The names of the raw materials used as the flame-retardant polymerizable composition 6 for the flame-retardant base sheet and the flame-retardant polymerizable composition 8 for the flame-retardant surface layer sheet are shown below.

[Acrylic Derivative of Aryl Halide] Tetrabromobisphenol A-bisacrylate

[Liquid crosslinking agent] Benzyl methacrylate 3-methoxybutyl acrylate

[Phosphorus-Containing Monomer] Diphenyl-2-methacryloyloxyethyl phosphate

[Phosphate ester] 2-ethylhexyldiphenyl phosphate

[Acrylic polyfunctional monomer] Urethane acrylate

[Photopolymerization initiator] 2-hydroxy-2-methyl-1-phenylpropane
1-on

Comparative Example 1 100 parts by weight of EP rubber, 50 parts by weight of aluminum hydroxide, 10 frit (inorganic powder)
Parts by weight, 1 part by weight of stearic acid (processing aid), 2 parts by weight of paraffin and 30 parts by weight of paraffinic oil are kneaded with a roll, and the thickness is 0.3 m using a calender roll.
m was prepared.

[0037]

[Table 1]

(Comparative Example 2) Using only the flame-retardant polymerizable composition for a flame-retardant surface sheet of Example 8, the flame-retardant polymerizable composition was applied by a solution casting method, and an ultraviolet irradiation apparatus was used. Polymerized by a photopolymerization method with a thickness of 0.3 m
m was prepared.

In order to evaluate the performance of the sheet material for preventing fusing welding sparks obtained in Examples and Comparative Examples, a MIT breaking test, a flame retardancy test, a total light transmittance measurement and a comprehensive evaluation were carried out by the following methods. Tests and evaluations were performed.

1. MIT breaking test: JIS P81
An MIT bending resistance test was performed according to No. 15. The test results show that the greater the number of times, the greater the flexibility of the fusing welding spark prevention sheet material.

2. Flame retardancy test: JIS A 1323
Based on Class C (flame retardancy test method for welding and fusing sparks of building construction sheets), the occurrence of sparks and the presence of through holes harmful to fire prevention were examined. In addition, the thickness of the steel plate for spark generation was 3.2 mm.

3. Total light transmittance measurement: JIS K71
The total light transmittance was measured in accordance with No. 05.

4. Comprehensive evaluation: Comprehensive evaluation based on the results of the above 1 to 3; ：: a remarkable improvement effect is observed;
The improvement effect was recognized, and x: the welding spark protection sheet was hard and the flame retardancy still had a problem.

[0044]

[Table 2]

[0045]

The sheet material for preventing fusing welding spark of the present invention is as follows.
Since it is constructed as described above, it is highly satisfactory in all of transparency, transparency, flexibility, flame retardancy and fusing welding fireworks prevention, excellent workability, and comfortable feeling of use. The work place using the fusing welding fireworks prevention sheet material can be easily seen through from the outside,
Thorough safety management can be ensured. Further, the method for producing a fusing welding spark prevention sheet material of the present invention can produce the fusing welding fire prevention sheet material having excellent performance as described above with a stable quality.

[0046]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a fusing welding spark prevention sheet material according to claim 1.

FIG. 2 is an explanatory view showing an embodiment of a method for producing a fusing welding spark prevention sheet material according to claim 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Core material 2 Flame-retardant base material sheet 3 Flame-retardant surface sheet 4 First impregnation (preliminary impregnation) tank 5 Liquid crosslinking agent 6 Polymerizable monomer composition for flame-retardant base sheet 7 Second impregnation tank 8 Flame retardant Polymerizable monomer composition for functional surface layer sheet 9 Third impregnation tank 10 Transparent release film 11 UV irradiation device 12 Fusing welding spark prevention sheet material

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/263 D06M 15/263 // C08F 290/06 C08F 290/06

Claims (2)

[Claims] An acrylic derivative of an aryl halide, a phosphorus-containing monomer, a liquid crosslinking agent capable of dissolving the acrylic derivative of the aryl halide, and an acrylic polyfunctional oligomer and / or a core material composed of inorganic fiber woven fabric or nonwoven fabric. Or, a flame-retardant polymerizable monomer composition comprising a phosphoric acid ester is impregnated, polymerized, and cured, and at least one surface of a flame-retardant base sheet having transparency, an acrylic derivative of an aryl halide, a phosphorus-containing monomer and the above A fusing welding spark preventing sheet material comprising a flame-retardant surface layer sheet obtained by polymerizing and curing a flame-retardant polymerizable monomer composition comprising a liquid crosslinking agent capable of dissolving an acrylic derivative. 2. A core material made of inorganic fiber woven fabric or nonwoven fabric is partially impregnated with a liquid crosslinking agent capable of dissolving an aryl halide acrylic derivative, and thereafter, an aryl halide acrylic derivative, a phosphorus-containing monomer, Impregnated with a liquid cross-linking agent capable of dissolving the acrylic derivative and a flame-retardant polymerizable monomer composition comprising an acrylic polyfunctional oligomer and / or a phosphoric ester, and polymerized and cured using a radical polymerization initiator to make it transparent A flame-retardant substrate sheet having the following formula (1), and then, on at least one surface of the flame-retardant substrate sheet, an acrylic derivative of an aryl halide, a phosphorus-containing monomer, and a liquid crosslinking agent capable of dissolving the acrylic derivative. Forming a flame-retardant polymerizable monomer composition for a flame-retardant surface sheet into a sheet, and adding the radical-polymerization initiator to the flame-retardant polymerizable monomer composition. A method for producing a fusing welding spark prevention sheet material, wherein the sheet material is used, polymerized, and cured.