JP3035944B2 - Slow-flammable synthetic resin composition and fiber coated therewith - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flame retardant synthetic resin composition and a fiber coated with the composition.

<Conventional technology> As vehicle interior materials become more sophisticated, vehicle seats are also being made into fabrics, and fabric bases for vehicles are produced by coating a synthetic resin emulsion, a synthetic resin aqueous solution, etc. on a fiber base material such as woven fabric, pile moquette fabric, or knitted fabric. It is widely used to improve the dimensional stability of the fiber base material, adjust the hand, adhere the pile, provide seam fatigue resistance, impart flame retardancy, etc. is there.

For this purpose, conventionally self-crosslinking by heating and drying,
An acrylic resin that forms a crosslinked structure and has a melting start temperature after heating and drying of 150 ° C. or higher is used.

<Problems to be Solved by the Invention> However, the fibers obtained by coating the above-mentioned conventional acrylic resin on the fiber base material have a drawback that the burning rate is high.

<Means for Solving the Problems> Accordingly, the present inventors have conducted intensive studies in view of the above-mentioned circumstances, and found that the synthetic resin has a cross-linked structure or is capable of forming a cross-linked structure, and after the cross-linked structure is formed. The present inventors have found that fibers coated with an acrylic resin having a melting start temperature within a specific temperature range have a lower burning rate than conventional fibers coated with the acrylic resin, thereby completing the present invention.

That is, the present invention has a melting start temperature of 70 to
The present invention provides a flame retardant synthetic resin composition for coating comprising 140 ° C., a non-crosslinked acrylic resin having a functional group capable of forming a crosslinked structure, and a fiber coated with the composition. .

The non-crosslinked acrylic resin of the present invention has a functional group capable of forming a crosslinked structure in the resin, has not yet been crosslinked, and has an initial melting temperature of 70 to 140 ° C after the crosslinked structure is formed. Refers to resin.

In this case, examples of the functional group capable of forming a crosslinked structure include an N-methylol group and a glycidyl group.

The acrylic resin having a functional group capable of forming a crosslinked structure according to the present invention needs to have a melting start temperature of 70 to 140 ° C, preferably 70 to 100 ° C after forming the crosslinked structure.
The melting start temperature of the acrylic resin can be measured by, for example, a Koka type floe tester.

The form of the acrylic resin is not particularly limited, for example, powder, granular, liquid, emulsion,
Although any form such as an aqueous solution form and a melt form can be used, an emulsion form is preferable since pollution is less likely to occur and the workability of coating processing is excellent.

The method for producing the acrylic resin emulsion may be any known and commonly used production method, and is not particularly limited. For example, α, β having a (meth) acryloyl group
An ethylenically unsaturated carboxylic acid (A), an α, β-ethylenically unsaturated monomer having a crosslinkable functional group and a (meth) acryloyl group or a derivative thereof (B) and the monomer (A), Α, β-ethylenically unsaturated monomers having a (meth) acryloyl group other than (B) and derivatives thereof (C)
Is carried out in water at 20 to 90 ° C. for 30 minutes to 24 hours using a polymerization initiator, a chain transfer agent, an emulsifier, a protective colloid and the like, if necessary. The monomers (A), (B) and (C) can be added, dropped, and reacted into the reaction vessel by various methods such as batch, division and continuous.

The copolymerization ratio of the monomers (A), (B) and (C) is not particularly limited, but usually, the total monomer weight is 100%.
(A) 0.1 to 10 parts by weight, (B) 05 to 5.0
Parts by weight, (C) 99.4 to 85.0 parts by weight.

Examples of the α, β-ethylenically unsaturated carboxylic acid (A) having a (meth) acryloyl group include (meth) acrylic acid.

Α, β-ethylenically unsaturated monomer having a crosslinkable functional group and a (meth) acryloyl group or a derivative thereof (B)
As N-methoxymethyl (meth) acrylamide, N-butoxymethylacrylamide, N-methylol (meth) acrylamide, diacetone (meth)
Acrylamide, glycidyl (meth) acrylamide,
Glycidyl (meth) acrylate and the like can be mentioned.

Examples of the α, β-ethylenically unsaturated monomer having a (meth) acryloyl group other than the monomers (A) and (B) or the derivative (C) thereof include, for example, methyl (meth) acrylate, Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylonitrile and the like can be mentioned, and these can be used alone or in combination of two or more.

As the polymerization initiator, for example, ammonium persulfate,
Inorganic or organic peroxides such as persulfates such as potassium persulfate and sodium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, azobisisovaleronitrile, etc. No.

Further, a radical polymerization system based on an oxidation-reduction reaction in which a reducing substance such as sodium metabisulfite, sodium bisulfite or sodium rongalite is used in combination with the water-soluble polymerization initiator may be used.

Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, carbon tetrachloride and the like. The amount used where the chain transfer agent is used is usually
When the total monomer weight is 100 parts by weight, the amount is 0 to 0.3 parts by weight.

As the emulsifier, for example, any of nonionic, anionic and cationic may be used, and hydrocarbon surfactants such as polyethylene glycol nonylphenol ether and sodium dodecylbenzene sulfonate, polyethylene glycol perfluoroalkyl ether, perfluoroalkyl carboxylic acid Examples thereof include fluorine-based surfactants such as sodium and perfluoroalkanesulfonamide, and silicone-based surfactants such as silicone. The amount of the emulsifier to be used is generally 0.1 to 10 parts by weight, when the total monomer weight is 100 parts by weight.

In the production of the acrylic resin, after completion of the polymerization, if necessary, removal of unreacted monomers by stripping, concentration, etc., solid content adjustment, or pH adjustment by addition of sodium hydroxide, triethylamine, ammonia, etc. You may.

In addition, as the synthetic resin in the composition of the present invention, if the melting start temperature falls within the range of 70 to 140 ° C as a whole, the other synthetic resins whose melting start temperature is out of the range of 80 to 140 ° C are synthesized as described above. It can be used in combination with resin. Similarly, various flame retardants such as antimony trioxide and halogen can be used in combination for the purpose of imparting flame retardancy.

The flame retardant synthetic resin composition of the present invention has a workability of 50%.
It is preferable to adjust so as to be 00 to 20000 CPS.

As described above, the flame retardant synthetic resin composition of the present invention can be obtained.

The flame retardant synthetic resin composition of the present invention can obtain a flame retardant fiber by coating or impregnating a fiber base material.

Examples of the form of the fiber base include various forms such as yarn, knitted fabric, woven fabric, and non-woven fabric. Examples of the type of the fiber base include synthetic fibers such as nylon, acrylic, and polyester, rayon, viscose rayon, and cellulose acetate. And natural fibers such as cotton and silk, and a mixed fiber thereof. Among them, polyester, mixed woven fabric, polyester pile moquette fabric, polyester moquette fabric and the like are preferable.

As a method for applying or impregnating the synthetic resin composition of the present invention to a fiber base material, for example, a doctor knife method, a roll coating method, a spray method, or an ordinary processing method such as an impregnation method may be applied. Although it is possible, the coating method is preferable to the impregnation method.

The coating amount or amount of impregnation into the fiber substrate in the slow-retardant synthetic resin composition is usually in the dry weight, the fiber base material surface area 1 m ² per 30
150150 g, preferably 50-130 g.

By foaming, the composition of the present invention has a very low penetration into the fiber base material in the application step, and as a result, shows a soft feeling, and the adhesiveness is equal to or higher than that of the non-foamed coat. Sex can be obtained.

The foaming method may be either chemical foaming or mechanical foaming, but mechanical foaming is preferred.

Examples of the mechanical foaming method include a continuous foaming device such as a high-speed blade stirrer, an Oak mixer, and a static mixer. The expansion ratio is not particularly limited,
Usually it is 1.1 to 5 times. In this foaming, A
A small amount of a foam stabilizer such as a BS resin or ammonium stearate may be added.

As a method of crosslinking the composition of the present invention containing the synthetic resin capable of forming a crosslinked structure applied or impregnated on a fiber base material, for example, infrared rays, far infrared rays, ultraviolet rays,
A method of irradiating an active energy ray such as an electron beam or radiation,
Examples include a method of drying by heating in a heating oven or the like,
When a composition containing an acrylic resin capable of forming the preferred crosslinked structure is used as the composition of the present invention, a method of heating and drying is preferred from the viewpoint of workability and economy.

The heating and drying conditions are not particularly limited, but, for example, those capable of forming a crosslinked structure are at or above the temperature required to form a crosslinked structure, and those having a crosslinked structure are at or above the melting start temperature, specifically, 90-150 ° C, preferably 1
00-150 ° C.

In the case of using the foamed composition of the present invention, if the base material is sufficiently melted with crosslinking at a temperature equal to or higher than the melting start temperature of the synthetic resin in the composition after coating it on the fiber base material, it becomes flexible. A processed fiber having excellent properties can be obtained.

<Example> Hereinafter, the present invention will be described specifically with reference to examples. Unless otherwise specified, “%” indicates “% by weight” and “parts” indicates “parts by weight”.

Example 1 65 parts of deionized water was placed in a stainless steel reaction vessel, and 1.5 parts of sodium dodecylbenzenesulfonate and 3.5 parts of polyoxyethylene nonylphenol ether were dissolved. Then 50 parts of butyl acrylate, 35 parts of ethyl acrylate, 7 parts of methyl methacrylate, 3 parts of acrylic acid, 5 parts of N-methylolacrylamide and lauryl mercaptan
0.3 parts were mixed to prepare a monomer mixture. 5 parts of this monomer mixture was charged into a reaction vessel, and then heated to 35 ° C. in a nitrogen stream. A catalyst aqueous solution in which 05 parts of ammonium persulfate was dissolved in 10 parts of deionized water, sodium metabisulfite
0.5 parts of a catalyst aqueous solution obtained by dissolving 0.5 parts in 10 parts of deionized water
Five parts were charged into a reaction vessel, and the temperature was raised to 70 ° C. to initiate polymerization.

After the temperature was raised to 70 ° C., the remaining 95 parts of the monomer mixture and the respective catalyst aqueous solutions were separately added dropwise over 180 minutes while maintaining the same temperature to complete the polymerization.

Thereafter, the mixture was cooled to 30 ° C. and adjusted to pH 5 by adding 0.5 parts of 28% aqueous ammonia and 2 parts of deionized water.

The solid content of the aqueous copolymer dispersion A-1 obtained here was 5%.
4.9%, BM Brookfield viscometer (rotor No.
4, the viscosity at 25 ° C. at 60 rpm) was 520 CPS. Using a 20-mil applicator, the copolymer aqueous dispersion A-1 was spread on a glass plate and dried at 140 ° C. for 5 minutes to obtain a copolymer film. This copolymer film was cut into a suitable size to obtain a sample. Using this sample, the melting start temperature was measured with a Koka type flow tester (CFT-500A, manufactured by Shimadzu Corporation) under the conditions of a die (nozzle) 1 mm x 1 mm, a load of 20 kg, and a heating rate of 3.0 ° C / min. As a result, the temperature was 104 ° C.

Bon Coat 375 was added to 100 parts of the aqueous copolymer dispersion A-1.
0 [Acrylic emulsion type thickener manufactured by Dainippon Ink and Chemicals, Inc., solid content 23%] 3 parts and 28% ammonia water 1.
Five parts were added and mixed well to obtain a coating composition. Next, this composition was coated on the back side of a 400 g / m ² polyester moquette fabric using a doctor knife so that the coating amount at the time of drying was 70 g / m ^2. After drying for minutes, a coated fabric was obtained.

The following burning rate test was performed on this coated fabric. The results are shown in Table 1.

Burning rate: MVSS-302 is the vertical burning rate of the processed fabric.
Was measured. (Indicated by the average value of n = 10.) Comparative Example 1 Except for using a monomer mixture obtained by removing 0.3 parts of lauryl mercaptan from the mixture of the monomer used in Example 1 and the chain transfer example, it was completely the same as Example 1. By performing the same operation, an aqueous copolymer dispersion B-1 was obtained.

The solid content of the copolymer aqueous dispersion B-1 is 55.3%, the viscosity at 25 ° C. is 465 CPS, and the melting start temperature after crosslinking of the copolymer is
174 ° C.

A coating composition was obtained in exactly the same manner as in Example 1 except that A-2 was used in place of the copolymer aqueous dispersion A-1, and a coated fabric was obtained in exactly the same manner.

The same test as in Example 1 was performed using this coated fabric. The results are shown in Table 1.

Example 2 A mixture of the monomer of Example 1 and a chain transfer agent was mixed with 50 parts of butyl acrylate, 35 parts of ethyl acrylate, 9 parts of methyl methacrylate, 3 parts of acrylic acid, 3 parts of N-methylolacrylamide and 3 parts of lauryl mercaptan. Example 1 except that the mixture was changed to a mixture of a monomer and a chain transfer agent consisting of 0.1 part.
The same operation as described above was performed to obtain a copolymer aqueous dispersion A-2.

The solid content of the copolymer aqueous dispersion A-2 is 55.0%, the viscosity at 25 ° C is 465 CPS, and the melting start temperature after crosslinking of the copolymer is
95 ° C.

A coating composition was obtained in exactly the same manner as in Example 1 except that A-2 was used in place of the copolymer aqueous dispersion A-1, and a coated fabric was obtained in exactly the same manner.

The same test as in Example 1 was performed using this coated fabric. The results are shown in Table 1.

Example 3 A mixture of the monomer of Example 1 and a chain transfer agent was mixed with 50 parts of butyl acrylate, 35 parts of ethyl acrylate, 11.5 parts of acrylonitrile, 3 parts of acrylic acid, and 0.5 part of glycidyl methacrylate. The same procedure as in Example 1 was carried out except that the aqueous dispersion A-3 was changed to A-3.
I got

The solid content of the copolymer aqueous dispersion A-3 is 55.3%, the viscosity at 25 ° C is 290 CPS, and the melting start temperature after crosslinking of the copolymer is
81 ° C.

A coating composition was obtained in exactly the same manner as in Example 1 except that A-3 was used in place of the aqueous copolymer dispersion A-1, and a coated fabric was obtained in exactly the same manner.

The same test as in Example 1 was performed using this coated fabric. The results are shown in Table 1.

Example 4 A mixture of the monomer and the chain transfer agent of Example 1 was mixed with 50 parts of butyl acrylate, 35 parts of ethyl acrylate, 7 parts of acrylonitrile, 3 parts of acrylic acid, and glycidyl methacrylate 5
The same procedure as in Example 1 was carried out except that the mixture was changed to a mixture of a monomer consisting of 1 part by weight and 0.3 part of lauryl mercaptan, with a chain transfer agent, to obtain an aqueous copolymer dispersion A-4.

The solid content of the copolymer aqueous dispersion A-4 is 54.7%, the viscosity at 25 ° C is 425 CPS, and the melting start temperature after crosslinking of the copolymer is
107 ° C.

A coating composition was obtained in exactly the same manner as in Example 1 except that A-4 was used instead of the copolymer aqueous dispersion A-1, and a coated fabric was obtained in exactly the same manner.

The same test as in Example 1 was performed using this coated fabric. The results are shown in Table 1.

As is clear from Table 1, the burned rate of the processed fabric coated with the composition of the present invention is significantly lower than that of the conventional coated fabric.

Example 5 100 parts of the aqueous copolymer dispersion A-2 used in Example 2,
22 parts of water, 3 parts of ammonium stearate solution (foam stabilizer, 20% of active ingredient), 3 parts of Boncoat 3750, and 1 part of 28% aqueous ammonia were thoroughly mixed to obtain a coating composition.
BM Brookfield viscometer (Rotor N
o.4, rotation speed 60 rpm) at 25 ° C was 5300 CPS.

The composition was rotated at 10 rpm using a home hand mixer.
The mixture was stirred at 00 rpm for 3 minutes and foamed at a magnification of 1.5 parts.

Then, the foamed composition was dried at a coating amount of 70 g / m ^2.
Using a doctor knife to coat the back of the 540 g / m ² polyester pile moquette fabric so that
The coated fabric was dried at 140 ° C. for 5 minutes in a box-shaped hot air circulation dryer.

The following physical property tests were performed on the coated fabric. The results are shown in Table 2.

Burning rate: According to the same method as described above.

Pile adhesiveness: Nitto double-sided tape (# 501) is affixed to the front side (pile surface) of the processed fabric by a length of 10 cm, placed on a glass plate of 1 cm thickness, and pressed back and forth with a 2 kg iron roller five times. Then, it is peeled 180 degrees by hand for 1 second under the conditions of 20 ° C. and 60% RH, and the pile is observed. Evaluation was made based on the average value of the number of piles that were repeatedly removed five times in the same test.

Judgment criteria 5th grade: No pile missing.

Grade 4 １〜 1-5.

Grade 3 ... 6 to 10 pieces.

Second grade: 〃 11 to 20 pcs.

Grade 1 ... 21 or more.

COMPARATIVE EXAMPLE 2 A mixture of the monomer of Example 1 and a chain transfer agent was obtained by simply adding 50 parts of butyl acrylate, 35 parts of ethyl acrylate, 7 parts of methyl methacrylate, 3 parts of acrylic acid and 5 parts of glycidyl methacrylate. The same procedure as in Example 1 was carried out except that the mixture was changed to a monomer mixture, to obtain a copolymer aqueous dispersion B.
-2 was obtained.

The solid content of the copolymer aqueous dispersion B-2 is 55.0%, the viscosity at 25 ° C. is 480 CPS, and the melting start temperature after crosslinking of the copolymer is
189 ° C.

Instead of the copolymer aqueous dispersion A-2 of Example 5, B-2
Was obtained in the same manner as in Example 5 except that the above-mentioned was used, and the same physical property test was performed. The results are shown in Table 2.

Example 6 A coated woven fabric was obtained in exactly the same manner as in Example 5 except that the expansion ratio of the composition was changed to 3 times, and the same physical property tests were performed. The results are shown in Table 2.

As is clear from Table 2, the processed woven fabric obtained by foaming and coating the composition of the present invention not only has a remarkably low burning rate but also a significantly superior pile adhesiveness as compared with the conventional coated woven fabric. I understand.

Example 7 60 parts of the aqueous copolymer dispersion A-2 of Example 2, 22 parts of Flameguard VF-106 (a flame retardant manufactured by Dainippon Ink and Chemicals, Inc., active ingredient 60%), 4 parts of Boncoat 3750, 28%
1 part of aqueous ammonia was added and stirred well to obtain a coating composition. Next, this composition is applied in an amount of 120 g when dried.
/ m ² using a doctor knife to coat the back of a 270 g / m ² polyester interwoven fabric, and dried in a box-shaped hot air circulating drier at 140 ° C. for 5 minutes to obtain a coated fabric. .

The following physical property tests were performed on the coated fabric. The results are shown in Table 3.

Burning rate: According to the same method as described above.

Seam fatigue: Take two or more pairs of coated fabrics, 100 mm wide x 100 mm long, from the vertical and horizontal directions.
The same size slab urethane foam (density)
0.02 ± 0.002, thickness 5mm) on the backing cloth (nylon non-woven fabric 40g /
m ² ), but with the two composites facing together,
Sewing a 10 mm plate from the end of the long side, and make two or more sets of test specimens in each of the vertical and horizontal directions.

Next, two sets of test pieces are attached using an Amsula-type woven fabric abrasion test material, and the state of slippage of the seam after 2500 times of repeated pulling with a load of 3 kg is examined.

Comparative Example 3 A coated fabric was obtained in the same manner as in Example 7 except that the aqueous copolymer dispersion B-2 was used instead of the aqueous copolymer dispersion A-2, and the same physical property tests were performed. The results are shown in Table 3.

<Effect of the Invention> The fiber coated with the flame retardant synthetic resin composition of the present invention has an effect of significantly lowering the burning rate as compared with a fiber coated with a conventional coating synthetic resin.

The slow-flammable synthetic resin composition of the present invention exhibits the above-mentioned effects.In addition to a backing agent for a fabric sheet, nonwoven fabric, paper, leather, wood, metal coating, impregnation into fibers and fabrics, a binder for fur, Adhesive, hydrophobizing agent, as an elasticizing component or a crushing (crushing) preventing component in the building industry (for example, an additive to a concrete mixture and an asphalt mixture), a vehicle for various paints, an external paint, aerosol paint for home use, and the like. Can be used for Also, lime powder, wood powder, glass fiber, asbestos, paper,
It can also be used as a binder for plastics, rubber scraps, ceramic materials and the like. Furthermore, as a softener in the production of elastic films, foils and yarns, as an aid in the textile printing and yarn industries, as an additive in synthetic resin dispersions, as a sizing agent, as a leather finishing agent, etc. Can be used for applications.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // D06M 101: 32 (56) References JP-A-57-108114 (JP, A) JP-A-52-102363 (JP, A) JP-A-48-29841 (JP, A) JP-A-3-174483 (JP, A) JP-T-62-500384 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C09D 1/00-201/10

Claims (5)

(57) [Claims] The melting start temperature after forming a crosslinked structure is 70 to 140.
C. and a non-crosslinked acrylic resin having a functional group capable of forming a crosslinked structure, comprising a non-crosslinked acrylic resin for coating. 2. An acrylic resin comprising an α, β-ethylenically unsaturated carboxylic acid (A) having a (meth) acryloyl group and an α, β-ethylenic acid having a crosslinkable functional group and a (meth) acryloyl group. Unsaturated monomers or derivatives thereof (B) and (meth) other than the monomers (A) and (B)
The flame retardant synthetic resin composition for coating according to claim 1, which is a copolymer of an α, β-ethylenically unsaturated monomer having an acryloyl group or a derivative thereof (C). 3. An acrylic resin comprising 0.1 to 10 parts by weight of an α, β-ethylenically unsaturated carboxylic acid (A) having a (meth) acryloyl group, based on 100 parts by weight of all monomers, a crosslinkable functional group. , Β- having a group and a (meth) acryloyl group
Ethylenically unsaturated monomer or its derivative (B) 0.5 to 5.0
Parts by weight and (meth) other than the monomers (A) and (B)
The flame retardant synthetic resin composition for coating according to claim 2, which is a copolymer of 99.4 to 85.0 parts by weight of an α, β-ethylenically unsaturated carboxylic acid monomer having an acryloyl group or a derivative thereof (C). 4. A fiber coated with the flame retardant synthetic resin composition for coating according to claim 1. 5. The flame retardant synthetic resin composition for coating,
The fiber according to claim 4, which is foamed.