JP2552783B2 - Welding curtain material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a welding curtain material which can prevent a fire from occurring by shutting off sparks generated during welding or fusing work.

[0002]

2. Description of the Related Art Conventionally, as a welding curtain material, a transparent sheet made of a thermoplastic resin such as soft vinyl chloride resin is known (Japanese Patent Laid-Open No. 63-847).
No. 79). However, since this type of welding curtain material is made of a thermoplastic resin, sparks such as slag and spatter generated during burning, welding or fusing work easily penetrate to form holes.

Woven or non-woven fabric of inorganic fiber such as carbon fiber as a welding curtain material capable of preventing penetration of sparks such as slag and spatter generated during welding and fusing work,
Alternatively, a glass fiber woven or non-woven fabric coated with a silicone resin or the like is used.

[0004]

Among the former welding curtain materials made of a transparent sheet made of a thermoplastic resin,
The one made of soft vinyl chloride resin is JIS-A-8952.
It has reached the fire safety evaluation criteria specified in. However, this fire safety evaluation standard is based on the fact that the sheet itself does not burn and spread and does not progress to a fire.Even if a welding curtain material made of a soft vinyl chloride resin sheet is used, no slag or spatter is generated. When touching high-temperature sparks such as, it is likely to melt and form holes. Therefore, there is a risk that a spark may penetrate through the hole and a fire may occur.
-It was not satisfied with the higher fire safety standards specified in A-1323, and the range of use was limited.

The latter of the welding curtain material, which is composed of a woven fabric of inorganic fibers such as carbon fibers, a woven fabric or a non-woven fabric of glass fibers coated with silicone, is described in JIS-A-
Although it satisfies the fire safety evaluation standard stipulated in 1323, it is opaque or cloudy and there is a problem that the other side cannot be seen through. Therefore, a peephole is opened, and a transparent soft vinyl chloride resin sheet is attached to the peephole to form a peephole.However, the time and labor required for that is increased, and there is a risk that the peephole will be pierced by sparks. there were.

In view of the above points, the present invention is not only flame-retardant but also has no transparency even if it touches high-temperature sparks such as slag and spatter, and has transparency. An object of the present invention is to provide a welding curtain material capable of looking through the other side of the curtain without providing a peep window.

[0007]

The welding curtain material of the present invention is a fiber reinforced resin sheet obtained by impregnating a woven fabric or a non-woven fabric made of an inorganic fiber having a light-transmitting property with a flame-retardant thermosetting resin composition and curing it. And a refractive index A of the flame-retardant thermosetting resin composition after curing and a refractive index B of the inorganic fiber satisfy the following expression (1). Yes, and the parallel light transmittance of the fiber reinforced resin sheet is 80% of the total light transmittance.
The above is a feature.

B + 0.015 ≧ A ≧ B−0.005 (1) Regarding the flame-retardant thermosetting resin composition, an acrylic derivative of halogenated aryl or unsaturated containing a halogen element. A polyester resin, a liquid cross-linking agent capable of dissolving the derivative or the unsaturated polyester resin, and a phosphorus-containing monomer, which contains 15 to 50% by weight of a halogen element and 1 to 10% by weight of phosphorus. preferable. Regarding the liquid cross-linking agent, the terminal vinyl group should be 1
It is preferably composed of an acrylic ester monomer or macromonomer containing 3 to 3.

In the conventionally known flame retardants for thermoplastic resins, that is, addition type flame retardants, the refractive index A after curing of the flame retardant thermosetting resin composition is brought close to the refractive index B of the inorganic fiber, and the above formula (1) is used. Is difficult to satisfy. Further, in the case of only the halogen element, it is difficult to obtain sufficient flame retardancy for capturing sparks, and therefore an antimony-based auxiliary agent is generally used together, but the fiber-reinforced resin sheet becomes cloudy and has sufficient transparency. I can't get one. As described above, by using the acrylic derivative of halogenated aryl or the unsaturated polyester resin containing a halogen element in combination with the phosphorus-containing monomer, it becomes easy to obtain flame retardancy without impairing transparency. The halogen element content and the phosphorus content are respectively 1
If it is less than 5% by weight and less than 1%, sufficient flame retardancy cannot be obtained, and conversely, if it exceeds 50% by weight and 10% by weight, respectively, the crosslinking efficiency and flexibility are impaired. It is preferable to set the content rate range.

In the present invention, as the woven or non-woven fabric of inorganic fibers having light transmittance, for example, glass fiber yarn or roving is woven by plain weave, twill weave, satin weave, or glass fiber such as glass fiber chopped strand mat. Examples include non-woven fabric. The inorganic fiber is not limited to the above glass fiber. Any transparent material that withstands a high temperature that does not melt at 1000 ° C. and has transparency may be used, for example, a transparent ceramic fiber made of alumina or the like may be used.

The acryl derivative of an aryl halide is an acryl derivative of an aryl halide containing preferably 20 to 50% by weight of one or more of chlorine, bromine and iodine. For example, tetrabromobisphenol A-bisacrylate. , Tetrabromobisphenol A-ethylene oxide addition dimethacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, trichlorophenyl methacrylate, etc., or halogenated phenol, halogenated bisphenol, halogenated arylcarboxylic acid ethylene oxide adduct, etc. Examples thereof include (meth) acrylic acid ester monomers and their macromonomers. In some cases
These monomers and macromonomers may be partially contained in glycidyl ether.

Examples of unsaturated polyester resins containing halogen elements include unsaturated polyesters containing head acid polyester, tetrachlorophthalic acid, chloromaleic anhydride, tetrabromophthalic acid and the like.

Examples of the liquid crosslinking agent include tetrahydrofurfuryl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-
Terminal vinyl such as ethylhexyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, methoxytriethylene glycol (di) acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, neopentyl glycol diacrylate, ventaerythritol tri (meth) acrylate Base 1
Examples include acrylic ester monomers or macromonomers containing 3 to 3. The amount of this cross-linking agent used is
It is preferably 20 to 80% by weight in the composition. This is because if it is less than 20% by weight, the solubility of the acrylic derivative monomer or unsaturated polyester becomes poor, and if it exceeds 80% by weight, it is difficult to make the refractive index within the above range.

The phosphorus-containing monomer is, for example,
Examples thereof include acrylic derivatives of phosphoric acid esters or ethers such as mono (2-acryloyloxyethyl) acid phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate and bis2-chloroethyl-vinyl phosphate. The amount of the phosphorus-containing monomer used is preferably 10 to 40% by weight in the composition. 1
If it is less than 0% by weight, sufficient flame retardancy cannot be obtained, and 40% by weight
If it exceeds, it is difficult to obtain a refractive index in the above range.

In the present invention, the refractive index of the cured inorganic fiber and flame-retardant thermosetting resin composition is JIS-
It refers to a refractive index of 20 ° C. measured according to K-7105. INDUSTRIAL APPLICABILITY Since the welding curtain material of the present invention is cut into a predetermined width and length and is used as a curtain of a partition system or a hanging system, it is flexible and has a high flexibility, and is subjected to secondary processing. It is preferably good. Therefore, it is preferable to add a softening agent or a flame retardant plasticizer to the flame retardant thermosetting resin composition.

As the softener, for example, polyfunctional oligomer such as urethane acrylate, epoxy acrylate, polyester acrylate is used. As the flame retardant plasticizer, for example, phosphoric acid ester plasticizers such as trisdichloropropyl phosphate, tris monochloropropyl phosphate, tris chloroethyl phosphate, tris tribromophenyl phosphate, triphenyl phosphate are preferably used.

Further, the flame-retardant thermosetting resin composition contains
Conventionally known defoaming agents and humectants are added, and in some cases, conventionally known internal release agents, ultraviolet absorbers, antistatic agents and the like can be added.

For the protection of the eyes, adjusting the light transmittance of the welding curtain material by adding a coloring agent such as dye is no different from the conventional method. The welding curtain material of the present invention is produced by impregnating a woven or non-woven fabric of inorganic fibers having a light-transmitting property with the flame-retardant thermosetting resin composition as described above and curing it. If the air remains in the woven fabric or the nonwoven fabric, the obtained sheet becomes cloudy and does not become a transparent body. Therefore, when impregnating the flame-retardant thermosetting resin composition, it is desirable to pre-impregnate the woven fabric or the non-woven fabric with the liquid crosslinking agent or the low-viscosity monomer of the phosphorus-containing monomer. By doing so, fine air bubbles in the woven or non-woven fabric can be removed almost completely.

As a method for curing the flame-retardant thermosetting resin composition, it is preferable to adopt a photo-curing method using ultraviolet rays or the like. According to photo-curing, the reaction rate is extremely fast, it is economical, and the curing of the resin is started from the surface to which light reaches, and the smoothness of the surface is easily maintained. The reason for this is that since it is cured, peeling of the interface between the inorganic fiber and the resin composition and discontinuity of the interface such as craze can be suppressed to a minimum, and a product with good image clarity can be obtained. As the photo-curing initiator used at this time, conventionally known ones can be used.

[0020]

In the welding curtain material of the present invention, the refractive index A of the thermosetting resin composition used for the fiber reinforced resin sheet after curing and the refractive index B of the inorganic fiber are B + 0.015 ≧ A ≧ By satisfying the relationship of B-0.005, and the parallel light transmittance of the flame-retardant fiber-reinforced resin sheet is 80% or more of the total light transmittance, the fiber-reinforced resin sheet has transparency without clouding. You can maintain and look through the other side of the curtain.

Further, the flame-retardant thermosetting resin composition contains a flame-retarding contributing element such as a halogen element and phosphorus as an ingredient constituting the thermosetting resin, not as an addition type flame retardant. Therefore, the parallel light transmittance of the fiber-reinforced resin sheet is 80% or more of the total light transmittance, and the transparency is maintained without clouding.

[0022]

EXAMPLES Examples of the welding curtain material of the present invention will be described below. (Example 1) As a woven fabric of inorganic fibers having a light transmitting property, a glass yarn plain weave cloth having a refractive index of 1.5555 (width 500 mm, thickness 100 μm, basis weight 100 g / m)
² ) was used, and 100 parts by weight of tetrahydrofurfuryl acrylate, 100 parts of diphenyl-2-methacryloyloxyethyl phosphate, a wetting agent (BYK-26) were used.
62, manufactured by BW-Chemie) and 1 part by weight of a defoaming agent (BYK-A-501, manufactured by BW-Chemie).

To a plain weave glass yarn cloth impregnated with this pre-impregnation liquid, 100 parts by weight of tetrabromobisphenol A-bisacrylate (bromine content 42% by weight),
40 parts by weight of tetrahydrofurfuryl acrylate, bisphenol A-epoxy acrylate (SP-250
0, manufactured by Showa High Polymer Co., Ltd., 20 parts by weight, diphenyl-2-methacryloyloxyethyl phosphate (phosphorus content 8.6
20% by weight, trisdichloropropyl phosphate (flame retardant plasticizer: phosphorus content 7.2% by weight, chlorine content 48.6% by weight), 20 parts by weight, photopolymerization agent (Darocur 1173, manufactured by Merck & Co., Inc.) ) About 2 parts by weight of the basic flame-retardant thermosetting resin composition is added to about 100 g of the cloth to about 2
It was applied and impregnated at a rate of 80 g, and well mixed with a pre-impregnation liquid by a roller. Next, a 125 μm-thick polyethylene terephthalate resin (PET) film was coated on both sides of the film, passed through rollers with 0.5 mm intervals for defoaming, smoothed, and then irradiated with ultraviolet rays for curing. The ultraviolet curing conditions were such that a high-pressure mercury lamp having an intensity of 80 W / cm ² was run at a speed of 1 m / min.

After curing, the PET film is removed to 0.2 m
A transparent fiber-reinforced resin sheet having a thickness of m was obtained. The refractive index of the cured product obtained by curing the entire composition of the basic flame-retardant thermosetting resin composition and the pre-impregnation liquid is 1.5557 (JIS-
K-7105), and the halogen element content in the total composition is 25.4% by weight (chlorine 4.8% by weight, bromine 20.%).
6% by weight) and the phosphorus content was 1.55% by weight.

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1. (Example 2) A yellow transparent sheet was obtained in the same manner as in Example 1 except that 0.2 part by weight of the yellow dye Disazide Yellow was mixed with the basic flame-retardant thermosetting resin composition.

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1. (Example 3) Glass yarn plain weave cloth having a refractive index of 1.5320 (length, width 200 mm, thickness 100 μm, basis weight 1)
200 g / m ²⁾ using, as a basic flame-retardant thermosetting resin composition, an unsaturated polyester comprising a condensation product of dichloro maleic acid and monochloro maleic acid with ethylene glycol (chlorine content, 26 wt%) 100 weight Parts, styrene monomer 40 parts by weight, bis2-chloroethyl-vinyl phosphate (phosphorus content 13.3% by weight, chlorine content 30.4% by weight) 15 parts by weight, photopolymerization agent (Darocur 1173, manufactured by Merck) 1 A transparent fiber-reinforced resin sheet was obtained in the same manner as in Example 1 except that the composition consisting of parts by weight was used.

The cured product obtained by curing the entire composition of the basic flame-retardant thermosetting resin composition and the pre-impregnation liquid has a refractive index of 1.5325 (in accordance with JIS-K-7105). Halogen content in the total composition is 19.6% by weight
(Chlorine 19.6 wt%), Phosphorus content was 1.28 wt%.

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1. (Example 4) The composition of the basic flame-retardant thermosetting resin composition was
Tetrabromobisphenol A-bisacrylate (bromine content 42 parts) 100 parts by weight, tetrahydrofurfuryl acrylate 40 parts by weight, bis2-chloroethyl-vinyl phosphate (chlorine content 30.4% by weight, phosphorus content 13.3% by weight) %) 20 parts by weight and 1.5 parts by weight of a photopolymerization initiator (Darocur 1173, manufactured by Merck & Co., Inc.), and a light yellow transparent fiber-reinforced resin sheet was obtained in the same manner as in Example 1.

The cured product obtained by curing the entire composition of the basic flame-retardant thermosetting resin composition and the pre-impregnation liquid has a refractive index of 1.5688 (according to JIS-K-7105). Halogen content in the total composition is 29.8% by weight
(Chlorine 3.8 wt%, bromine 26.0 wt%) and phosphorus content was 1.6 wt%.

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1. (Example 5) The composition of the basic flame-retardant thermosetting resin composition was
Tetrabromobisphenol A-bis acrylate (bromine content 42 parts) 100 parts by weight, tetrahydrofurfuryl acrylate 40 parts by weight, urethane acrylate (X
P-7000B, manufactured by Nippon Gosei Co., Ltd., 20 parts by weight, polyester acrylate (viscoat 700, manufactured by Osaka Organic Co., Ltd.)
10 parts by weight, bis-2-chloroethyl-vinyl phosphate (chlorine content 30.4% by weight, phosphorus content 13.3% by weight) 20 parts by weight, trisdichloropropyl phosphate (chlorine content 48.6% by weight, phosphorus content) Amount 7.2% by weight)
In the same manner as in Example 1 except that 10 parts and 2 parts of a photopolymerization initiator (Darocur 1173, manufactured by Merck) were used.
A transparent light yellow fiber-reinforced resin sheet was obtained.

The cured product obtained by curing the entire composition of the basic flame-retardant thermosetting resin composition and the pre-impregnation liquid has a refractive index of 1.5512 (according to JIS-K-7105). Halogen content in the total composition is 26.1% by weight
(Chlorine 5.4% by weight, bromine 20.7% by weight) and phosphorus content was 1.67% by weight.

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1. (Comparative Example 1) A flame-retardant test of a welding curtain material (5050-AC35, made by Osaka Seisakusho) made of a commercially available soft vinyl chloride resin sheet was conducted according to JIS-A-13.
23, a B-class test (steel plate thickness 4.
4 mm) and C type test (steel plate thickness 3.2 mm), the curtain material did not ignite, but the spark penetrated the curtain material, and the paper underneath ignited and ignited. (Comparative Example 2) A fiber-reinforced resin sheet was obtained in the same manner as in Example 1 except that a glass yarn plain weave cloth having a refractive index of 1.5320 was used. This sheet is cloudy and opaque,
I couldn't see over there. (Comparative Example 3) The composition of the basic flame-retardant thermosetting resin composition was
100 parts by weight of tetrabromobisphenol A-bisacrylate (bromine content 42% by weight), 40 parts by weight of tetrahydrofurfuryl acrylate, 10 parts of bisphenol A-epoxy acrylate (SP-2500, Showa Polymer Co., Ltd.), photopolymerization initiator (Darocur 1173, manufactured by Merck & Co., Inc.) A fiber reinforced resin sheet was obtained in the same manner as in Example 1 except that the amount was 1.5 parts. The sheet was clouded.

The refractive index of the cured product obtained by curing the entire composition of the basic flame-retardant thermosetting resin composition and the pre-impregnation liquid is 1.5722 (JIS-K-7105 compliant), Halogen content in the total composition is 26.0% by weight
(Bromine 26.0% by weight).

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1. (Comparative Example 4) The composition of the basic flame-retardant thermosetting resin composition was
Tetrabromobisphenol A-bisacrylate 10
0 parts by weight, 40 parts by weight of tetrahydrofurfuryl acrylate, 40 parts by weight of urethane acrylate (XP-7000B, manufactured by Nippon Gosei Co., Ltd.), 20 parts by weight of bis2-chloroethyl-vinyl phosphate, 10 parts of trisbichloropropyl phosphate, initiation of photopolymerization Agent (Darocur 117
A fiber-reinforced resin sheet was obtained in the same manner as in Example 1 except that the amount was 2 parts, and the sheet was clouded, and the other side could not be seen through.

The refractive index of the cured product obtained by curing the entire composition of the basic flame-retardant thermosetting resin composition and the pre-impregnation liquid is 1.5502 (JIS-K-7105 compliant), Halogen content in the total composition is 20.61% by weight
(Chlorine 0.80% by weight, bromine 19.81% by weight) and phosphorus content was 0.32% by weight.

Regarding this sheet, JIS-K-710
5, total light transmittance, parallel light transmittance, parallel light transmittance / total light transmittance and image clarity (comb width 0.5 mm), and JIS-A-1323 Flame retardancy test (class B test: steel plate thickness 4.4 mm,
The results of the C type test: steel plate thickness 3.2 mm) are as shown in Table 1.

[0037]

[Table 1]

As is clear from the above results, in the welding curtain material of the present invention, the refractive index A after curing of the thermosetting resin composition used for the fiber reinforced resin sheet and the refractive index B of the inorganic fiber are , B + 0.015 ≧ A ≧ B
The relationship of -0.005 is satisfied, and the parallel light transmittance of the flame-retardant fiber reinforced resin sheet is 80% or more of the total light transmittance and is transparent.

[0039]

As described above, the welding curtain material of the present invention is not only transparent and capable of seeing through the other side, but also flame-retardant, which is generated during welding or fusing work. A high-temperature spark does not penetrate, and a fire can be prevented.

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Claims (3)

(57) [Claims] 1. A welding curtain material comprising a fiber reinforced resin sheet obtained by impregnating a woven fabric or a non-woven fabric made of an inorganic fiber having a light transmitting property with a flame-retardant thermosetting resin composition and curing the same. The relationship between the refractive index A of the thermosetting resin composition after curing and the refractive index B of the inorganic fiber satisfies the following expression (1), and the parallel light transmittance of the fiber-reinforced resin sheet Is 80% or more of the total light transmittance, a welding curtain material. B + 0.015 ≧ A ≧ B−0.005 (1) 2. A flame-retardant thermosetting resin composition, an unsaturated polyester resin containing an acrylic derivative of halogenated aryl or a halogen element, a liquid cross-linking agent capable of dissolving the derivative or unsaturated polyester resin, and The welding curtain material according to claim 1, which is composed of a phosphorus-containing monomer and contains 15 to 50% by weight of a halogen element and 1 to 10% by weight of phosphorus. 3. The welding curtain material according to claim 2, wherein the liquid crosslinking agent comprises an acrylic ester monomer or macromonomer having 1 to 3 terminal vinyl groups.