JPH11302979A - Flame-retardant laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant laminate having excellent water resistance, weather resistance and flame retardancy and suitable for outdoor uses as various kinds of tents. SOLUTION: This flame-retardant laminate is produced by forming the layer of a resin composition comprising (1) 100 pts.wt. of an urethane-based resin, (2) 5-50 pts.wt. of a flame retardancy-imparting agent containing an ammonium polyphosphate compound and/or a (iso)cyanuric acid derivative, (3) 1-30 pts.wt. of an inorganic hydrate-based flame retardance auxiliary, and (4) 0.1-20 pts.wt. of one or more of an aziridine compound, a carbodiimide compound, an oxazoline compound and a coupling agent on a fibrous substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an outdoor eaves tent, a house-shaped tent, a awning tent, a car top sheet,
The present invention relates to a fiber sheet structure suitable for use as a construction mesh sheet or the like. More specifically, the present invention relates to a flame-retardant laminate excellent in flame-retardant durability such as water resistance and weather resistance and suitable for the above-mentioned applications.

[0002]

2. Description of the Related Art Various production methods are known for a fiber sheet structure used for a car top sheet, a construction mesh sheet, and the like.
No. 8995 discloses a method in which a polyester fiber cloth is subjected to a pre-adhesion treatment, and the pre-treated surface is coated with a polyvinyl chloride resin. The polyvinyl chloride resin-coated structure obtained by this method is excellent in flexibility, durability and flame retardancy, but generates harmful hydrogen chloride gas due to the polyvinyl chloride resin during combustion. However, this is a major problem.

In order to solve this problem, use of a resin containing no halogen element has been studied. In such a resin system, in order to impart flame retardancy thereto, a method of adding an inorganic compound such as aluminum hydroxide or magnesium hydroxide, a method of adding red phosphorus, and the like are known. In order to obtain satisfactory flame retardancy, a large amount of an inorganic compound is added, so that the coating structure obtained therefrom has a drawback of inferior flexibility and durability, and in the latter, red phosphorus becomes dark brown. Because of coloring, there was a disadvantage that the variety of colors was poor.

[0004] Japanese Patent Application Laid-Open No. 6-340815 discloses a method in which ammonium polyphosphate coated with melamine and a specific nitrogen-containing organic compound are added to a thermoplastic resin. Although melamine coating is an effective means for improving the water resistance of ammonium polyphosphate, it has a drawback that the flame retardancy decreases over time under severe use conditions such as outdoors. In particular, when a urethane-based resin is used as a thermoplastic resin, its properties greatly change depending on its chemical structure.For example, in the case of a polyester-based urethane resin, the flame retardancy can be easily improved, but the water resistance is poor. Yes, and the polyether-based urethane resin has the disadvantage that it has excellent water resistance but tends to be inferior in weather resistance, and therefore satisfies the flame retardancy, water resistance, and weather resistance. Flame retardant laminates have not yet been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention is intended for use in outdoor eaves tents, house tents, awning tents, car hood sheets, construction mesh sheets, and the like, even under severe use conditions such as outdoors. , Less damage due to resin layer peeling, falling off, etc.
Moreover, it aims to provide a flame-retardant laminate that is easy to dispose and incinerate.

[0006]

The flame-retardant laminate according to the present invention comprises a fibrous base fabric and a flame-retardant urethane-based resin layer formed on at least one surface of the laminate. The urethane-based resin layer is composed of (1) 100 parts by weight of a urethane-based resin and (2) at least one selected from an ammonium polyphosphate-based compound and an (iso) cyanuric acid derivative compound.
5 to 50 parts by weight of a flame retardant imparting agent containing a seed;
0.1 to 20% by weight containing 30 parts by weight of an inorganic hydrate-based flame retardant aid and (4) at least one selected from an aziridine-based compound, a carbodiimide-based compound, an oxazoline-based compound, and a coupling agent And a crosslinking agent.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The fibrous base fabric used in the flame-retardant laminate of the present invention is a natural fiber such as cotton or hemp, an inorganic fiber such as glass fiber, a regenerated fiber such as viscose rayon, cupra or the like. Selected from semi-synthetic fibers, such as di- and triacetate fibers, and synthetic fibers, such as nylon 6, nylon 66, polyester (such as polyethylene terephthalate) fibers, aromatic polyamide fibers, acrylic fibers, and polyolefin fibers. And at least one fabric.

[0008] The fibers in the base fabric may be in any shape such as a spun short fiber yarn, a long fiber yarn, a split yarn, and a tape yarn. Further, the base fabric structure may be any of a woven fabric, a knitted fabric, a nonwoven fabric or a composite thereof. Further, there is no particular limitation on the knitting structure of the base cloth, but, for example, at least each of the coarse cloth knitted woven fabric constituted by the yarns including the warp and the weft arranged in parallel with a gap between the yarns, and Non-coarse cloth-like knitted fabric (a knitted fabric in which substantially no gap is formed between yarns).

The basis weight of the coarse cloth knitted fabric is 30 to 700.
g / m ² , and the open area ratio of the coarse cloth knitted fabric is 10 to 9 with respect to the area of the coarse cloth knitted fabric.
It is preferably about 5%. When the fibrous base fabric is a non-coarse cloth-like knitted fabric, its structure, basis weight, thickness, etc. are not limited, but depending on the purpose of use, plain weave, twill weave, circular knit,
Knitted fabrics such as weft knitting and warp knitting can be selected, and the basis weight is preferably about 50 to 1000 g / m ² .

For the purpose of imparting water resistance and water absorption preventing property to the base cloth, for example, a wax emulsion, a wax emulsion containing a resin binder,
Water-repellent pretreatment may be performed in advance by a method of spraying or dipping an emulsion of a silicone compound and a solution thereof, or the like.

As the urethane resin used for the flame retardant laminate of the present invention, a resin obtained by reacting a polyol with a diisocyanate can be used. As the polyol used for the synthesis of the urethane resin,
Polyester polyols having both hydroxyl groups, polyether polyols, polycarbonate diols and the like can be used. As the diisocyanate, aromatic diisocyanates such as 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylene diisocyanate, and isophorone diisocyanate, and aliphatic diisocyanates can be used. In particular, a polycarbonate-based urethane resin obtained by using a polycarbonate-based diol as a polyol component and an aliphatic diisocyanate as a diisocyanate component has high weather resistance and durability, and is suitable for the present invention.

[0012] For the purpose of imparting flame retardancy to the flame retardant laminate of the present invention, a flame retardant is added. As the flame retardant, ammonium polyphosphate compounds,
And at least one selected from (iso) cyanuric acid derivative compounds. As the ammonium polyphosphate-based compound, a condensation product of ammonium orthophosphate and urea is preferably used. Ammonium polyphosphate may be used as it is, or may be used whose surface is coated with melamine or microencapsulated.

The (iso) cyanuric acid derivative compounds include melamine, melamine sulfate, melamine phosphate, melamine polyphosphate, methylol melamine, trimethyl cyanurate, triethyl cyanurate, ammeline, ammelide, and 2,4,6-triamine. Cyanuric acid derivatives such as oxycyanidins can be used. Also, isoammeline, isomeramine, isoammelide,
Isocyanuric acid derivatives such as trimethylcarbodiimide, triethylcarbodiimide, and tricarbimide can be used. In particular, melamine isocyanurate obtained by reacting melamine with isocyanuric acid can be suitably used in the present invention.

For the purpose of enhancing the flame retardancy, if necessary, the flame retardant may further contain a phosphorus compound other than ammonium phosphate, such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trioctyl phosphate, and the like. Phosphoric esters such as phenyl phosphate, tricresyl phosphate, and octyl diphenyl phosphate; condensed phosphoric esters such as polyphosphate having a high molecular weight; Cyanamide derivatives such as dicine, guanidine, guanidine sulfamate, guanidine phosphate, and diguanide; and urea, dimethylol urea, diacetyl urea, trimethyl urea, N-benzoyl urea,
And urea derivatives such as guanylurea phosphate
More than one species may be included.

The addition amount of the flame retardant is preferably 5 to 50 parts by weight based on 100 parts by weight of the urethane resin solids. If the addition amount of the flame retardant is less than 5 parts by weight, it is not possible to obtain a laminate having sufficient flame retardancy,
On the other hand, if it exceeds 50 parts by weight, a laminate having sufficient durability cannot be obtained, and the cost increases.

The flame-retardant urethane resin layer of the laminate of the present invention contains an inorganic hydrate as a flame-retardant aid. As the inorganic hydrate, an inorganic compound containing water of crystallization is preferably used. In particular, it is preferable to use magnesium hydroxide, aluminum hydroxide, sodium tetraborate, magnesium phosphate, sodium diphosphate, zinc phosphate, or a combination of at least one of these. The addition amount of the flame retardant aid is preferably 1 to 30 parts by weight based on 100 parts by weight of the urethane resin solid content. If the amount is less than 1 part by weight,
Insufficient flame-retardant effect cannot be obtained, and it is 3
If the amount exceeds 0 parts by weight, the strength of the urethane-based resin layer will be greatly reduced.

Further, a crosslinking agent containing at least one selected from an aziridine compound, a carbodiimide compound, an oxazoline compound, and a coupling agent is added to the urethane resin layer as an essential component. These cross-linking agents have the effect of suppressing a decrease in the water resistance, weather resistance, and resin strength of the urethane resin, and improving the water resistance and bleed resistance of the flame retardant. The aziridine compound used in the present invention may be any compound having an aziridinyl group in the molecule, and a compound having two aziridinyl groups in the molecule, for example, diphenylmethane-bis-4-4'-N -N'-diethylene urea,
And a compound containing three aziridinyl groups in the molecule,
For example, 2,2-bishydroxymethylbutanol-
Tris [3- (1-aziridinyl) propionate] and the like are used.

The carbodiimide compound used in the present invention is obtained by reacting an organic diisocyanate in the presence of a catalyst that promotes carbodiimidation, such as a phosphorene compound, a metal carbonyl complex compound, and a phosphoric ester. Those obtained are preferably used. Specifically, dipropylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, di-P-toluoylcarbodiimide, triisopropylbenzene polycarbodiimide, and the like can be used. In particular, polyfunctional carbodiimides such as triisopropylbenzene polycarbodiimide are preferably used because of their excellent durability.

As the oxazoline compound used in the present invention, a compound derived and produced from oxazole obtained by decarboxylation of oxazole-4-carboxylic acid is preferably used. For example, 2-oxazoline, 4
A polyfunctional oxazoline polymer obtained by grafting an oxazolyl group to a polymer such as -methyl-2-oxazoline, 2,2'-bis (2-oxazoline), and styrene or an acrylic compound is used. in particular,
Polyfunctional oxazolines such as 2,2'-bis (2-oxazoline) have excellent durability and are therefore preferably used in the present invention.

The coupling agent used in the present invention is at least one selected from a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a zirconaluminum coupling agent. Those consisting of seeds are preferably used. Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; epoxysilanes such as γ-glycidoxypropylmethyldiethoxysilane And γ-glycidoxypropyltriethoxysilane and the like; vinylsilanes,
For example, vinyltriethoxysilane and vinyltris (β-methoxyethoxy) silane; and mercaptosilanes such as γ-mercaptopropyltrimethoxysilane.

Examples of the titanium-based coupling agent include alkoxys such as tetraisopropoxytitanium, tetra-n-butoxytitanium and tetrakis (2-ethylhexoxy) titanium; acylates such as tri-n
-Butoxytitanium stearate and isopropoxytitanium tristearate. Examples of the zirconium-based coupling agent include tetrabutyl zirconate, tetra (triethanolamine) zirconate, and tetraisopropyl zirconate. Examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropylate. In addition, examples of the zirconaluminum-based coupling agent include tetrapropyl zircoaluminate.

Among these, from the viewpoints of water resistance and weather resistance, it is particularly preferable to use epoxy silane such as γ-glycidoxypropylmethyldiethoxysilane and γ-glycidoxypropyltriethoxysilane. These crosslinking agents may be used alone or in combination of two or more. The amount of the cross-linking agent added is
It is preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 0 parts by weight. If the amount is less than 0.1 part by weight, the resulting urethane resin layer has insufficient water resistance and flame retardancy, and if it exceeds 20 parts by weight, the flexibility of the product is impaired. The problem arises.

In the fiber sheet structure of the present invention, the urethane resin layer comprises a urethane resin, a flame retardant,
An emulsion, a solution containing a flame retardant aid and a crosslinking agent,
It is formed by coating or dipping a fibrous base fabric with the solid composition, or by laminating a film obtained by calendering a mixture of the above components on the base fabric. In the urethane-based resin layer composition, an ultraviolet absorber, an antioxidant,
One or more of a crosslinking agent, an inorganic filler, a pigment, a thickener, and an antifoaming agent may be appropriately added.

The weight of the urethane resin layer adhered to the fibrous base fabric is preferably 30 to 800 g / m ² ,
More preferably, it is 50 to 500 g / m ² . When the adhesion weight of the urethane-based resin layer is less than 30 g / m ² , the flame retardancy of the laminate of the present invention may be insufficient, and when the urethane-based resin adhesion amount exceeds 800 g / m ² , it is obtained. The flexibility of the laminate may be insufficient.

[0025]

The present invention will be described more specifically with reference to the following examples. The measuring method used for evaluating the performance of the product is as follows. Flex resistance According to the Scott method of JIS L-1096, the test piece was subjected to a frequency of 1,0 under the conditions of a gripping distance of 2 cm and a pressing load of 1 kgf.
A bending test was performed 00 times, and the result was visually evaluated. The burning resistance hot water resistance test (3 days immersed in 70 ° C. warm water) before and after the test pieces were subjected to a combustion test according to the following two methods, and its performance was evaluated. (1) 45 degree flame retardant test: A- of JIS L-1091
According to the method 1 or the method A-2, the carbonized area, the carbonized distance,
The residual flame time and residual gin time were measured. If the criteria are satisfied, it will be judged that the flameproof category 3 has passed. (2) Oxygen index method: The flammable oxygen limit was measured according to JIS K-7201.

Example 1 A flame-retardant laminate was produced by the following steps. As a fibrous base fabric, It was used. As the impregnating liquid for forming the urethane resin layer,
Aqueous emulsion (solid content: 40%) of urethane resin synthesized by reaction of polycarbonate polyol and aliphatic diisocyanate, and melamine isocyanate obtained by reaction of melamine and isocyanuric acid as a flame retardant An emulsion having the following composition containing nurate was used. Urethane resin (solid content: 40% by weight) 100 parts by weight Melamine isocyanurate 10 parts by weight Aluminum hydroxide 8 parts by weight Diphenylmethane-bis-4-4'-NN'-diethyleneurea 2 parts by weight Pigment (Dainippon Ink (Ryudai-W69, manufactured by Co., Ltd.) 3 parts by weight Ultraviolet absorber (Tinuvin 765, manufactured by Ciba-Geigy) 0.5 part by weight The composition of the impregnating liquid is shown in Table 1. The amounts of the (iso) cyanuric acid derivative, inorganic hydrate, and aziridine-based crosslinking agent in the above composition were 25% by weight, 20% by weight, and 5% by weight, respectively, based on the weight of the urethane-based resin solid content. . The fibrous base fabric is immersed in the urethane resin-containing impregnating solution, squeezed with a mangle, dried at 100 ° C.,
Heat treatment at 40 ° C, resin adhesion amount (solid content) is 140g
/ M ² of the flame-retardant laminate. The obtained flame retardant laminate was subjected to the test. Table 2 shows the test results.

Example 2 A flame-retardant laminate was prepared in the same manner as in Example 1, and subjected to the above-mentioned test. However, 4 parts by weight of a coupling agent (γ-glycidoxypropyltriethoxysilane) was added instead of the aziridine-based crosslinking agent. At this time, the amount of the crosslinking agent added was 10% by weight based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Example 3 A flame-retardant laminate was prepared in the same manner as in Example 1, and was subjected to the test. However, instead of the aziridine-based crosslinking agent, 8 parts by weight of a carbodiimide-based crosslinking agent (triisopropylbenzene polycarbodiimide) was added. At this time, the amount of the crosslinking agent added is 20 to the weight of the urethane resin solid content.
% By weight. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Example 4 A flame-retardant laminate was prepared in the same manner as in Example 1 and subjected to the above-mentioned test. However, instead of the aziridine-based crosslinking agent, 8 parts by weight of an oxazoline-based crosslinking agent (2,2′-bis (2-oxazoline)) was added. At this time, the amount of the crosslinking agent added was 20% by weight based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Example 5 A flame-retardant laminate was prepared in the same manner as in Example 1, and was subjected to the test. However, instead of the melamine isocyanurate, ammonium polyphosphate (average molecular weight 10,000) obtained by condensing ammonium orthophosphate and urea 1
0 parts by weight were added. Further, 2 parts by weight of a coupling agent (γ-glycidoxypropyltriethoxysilane) was added instead of the aziridine-based crosslinking agent. At this time, the addition amounts of ammonium polyphosphate and the crosslinking agent were 25% by weight and 5% by weight, respectively, based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Example 6 A flame-retardant laminate was prepared in the same manner as in Example 1, and was subjected to the test. However, in place of the melamine isocyanurate, 5 parts by weight of (iso) cyanuric acid and ammonium polyphosphate (average molecular weight 10,000) were added.
Further, 2 parts by weight of a carbodiimide-based compound (triisopropylbenzene polycarbodiimide) was added in place of the aziridine-based crosslinking agent. At this time, the total addition amount of the flame retardant and the crosslinking agent was 25% by weight and 5% by weight, respectively, based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Example 7 A flame-retardant laminate was prepared in the same manner as in Example 1, and was subjected to the test. However, in place of the aziridine-based crosslinking agent, 4 parts by weight of an oxazoline-based crosslinking agent (2,2′-bis (2-oxazoline)) and 4 parts by weight of a coupling agent (γ-glycidoxypropyltriethoxysilane) were added. . At this time, the addition amount of the two types of cross-linking agents was 10% by weight with respect to the weight of the urethane resin solid content, and the total addition amount was 20% by weight. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Example 8 A flame-retardant laminate was prepared in the same manner as in Example 1, and was subjected to the test. However, 12 parts by weight of magnesium phosphate was added in place of the aluminum hydroxide. At this time, the amount of the flame retardant auxiliary added is 3 to the weight of the urethane resin solid content.
It was 0% by weight. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Comparative Example 1 A flame-retardant laminate was prepared in the same manner as in Example 1, and was subjected to the test. However, the aziridine-based crosslinking agent was not added. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Comparative Example 2 A flame-retardant laminate was prepared in the same manner as in Example 1 and subjected to the above-mentioned test. However, the amount of the melamine isocyanurate was 40 parts by weight. At this time, the amount of melamine isocyanurate added was 100% by weight based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Comparative Example 3 A flame-retardant laminate was produced in the same manner as in Example 1 and subjected to the above-mentioned test. However, the amount of the melamine isocyanurate was 1 part by weight. At this time, the amount of melamine isocyanurate added was 2.5% by weight based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Comparative Example 4 A flame-retardant laminate was produced in the same manner as in Example 1, and subjected to the above-mentioned test. However, the addition amount of the aziridine-based crosslinking agent is 2
Changed to 4 parts by weight. At this time, the amount of the crosslinking agent added was 60% by weight based on the weight of the urethane resin solid content.
The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Comparative Example 5 A flame-retardant laminate was prepared in the same manner as in Example 1 and subjected to the above-mentioned test. However, the addition amount of the aluminum hydroxide is 4
Changed to 0 parts by weight. At this time, the amount of the flame retardant auxiliary added is
It was 100% by weight based on the weight of the urethane resin solid content. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

Comparative Example 6 A flame-retardant laminate was prepared in the same manner as in Example 1 and subjected to the above-mentioned test. However, the aluminum hydroxide was not added. The composition of the impregnating liquid is shown in Table 1, and the test results of the obtained flame retardant laminate are shown in Table 2.

[0040]

[Table 1]

[0041]

[Table 2]

As is clear from Tables 1 and 2, at least one selected from an aziridine compound, a carbodiimide compound, an oxazoline compound, and a coupling agent is used.
By adding at least one kind of crosslinking agent as an essential component, a flame retardant imparting agent containing at least one selected from ammonium polyphosphate and an (iso) cyanuric acid derivative, and a flame retardant urethane containing a flame retardant auxiliary agent The flame retardancy of the resin layer was significantly improved.

[0043]

The flame-retardant laminate obtained by the present invention is excellent in durability, flexibility and flame retardancy, and is particularly suitable for outdoor use for sunshades, house-shaped tents, automobile tops, and meshes for architectural curing. It is suitable for such uses. In addition, this flame-retardant laminate has the advantage that it can be easily incinerated and disposed of and has no adverse effect on the environment.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/32 C08K 3/32 5/29 5/29 5/3412 5/3412 5/3477 5/3477 5/353 5/353 5/54 5/54 5/56 5/56 C08L 75/04 C08L 75/04 D06M 13/292 D06M 13/292 13/364 13/364

Claims (1)

[Claims] 1. A flame-retardant urethane-based resin layer formed on at least one surface of a fibrous base cloth, wherein the flame-retardant urethane-based resin layer comprises (1) 100 parts by weight of a urethane-based resin Resin, 5 to 50 parts by weight of a flame retardant containing at least one selected from (2) ammonium polyphosphate compound and (iso) cyanuric acid derivative compound, and (3) 1 to 30 parts by weight An inorganic hydrate-based flame retardant auxiliary,
And (4) 0.1 to 20 parts by weight of a crosslinking agent containing at least one selected from an aziridine compound, a carbodiimide compound, an oxazoline compound, and a coupling agent. Laminate.