KR102383278B1 - Producing method of flame retardant moisture curing adhesives and textile coating fabric used it - Google Patents

Abstract

The present invention relates to a method for producing a flame-retardant moisture-curing adhesive having excellent adhesive properties, heat resistance, and durability after washing, and a fiber-coated fabric using the same. The flame-retardant moisture-curing adhesive has an NCO content in the range of 1.2 to 4.5% by including and reacting: (A) 5 to 30 wt% of flame retardant polyester polyol; (B) 40 to 65 wt% of polyester polyol; (C) 1 to 10 wt% of polyether polyol; (D) 4 to 20 wt% of a flame retardant diol-based chain extender; and (E) 15 to 35 wt% of isocyanate.

Description

Manufacturing method of flame-retardant moisture-curing adhesive having excellent adhesive properties, heat resistance and durability after washing, and fiber-coated fabric using the same

The present invention provides a flame-retardant moisture-curing adhesive having excellent adhesive properties, heat resistance and durability after washing by containing and reacting a polyester polyol and a polyether polyol with respect to a flame-retardant polyester polyol prepared using a flame-retardant diol, a non-flammable diol, and a polyhydric carboxylic acid. It relates to a manufacturing method and a fiber-coated fabric using the same.

Recently, safety protective clothing that responds to extremely high temperature environments such as steel mills and fire sites is largely classified into industrial and firefighting applications. Industrial thermal clothing is used as a protective clothing to protect workers in industrial sites that handle molten metals, and fire protection clothing refers to non-combustible heat-resistant clothing that can access flames or high-temperature radiant heat.

The heat dissipation clothing for industrial and firefighting is usually composed of a nonwoven fabric made of aramid, a single-layer and multi-layer metal aluminum deposition film, and an adhesive. In addition to this, due to the process using the additive-type flame retardant, problems in processability due to poor adhesion and blooming are caused.

In the flame retardant application field as described above, as the regulation of halogenated flame retardants is accelerating due to environmental and human harm, the development of environmentally friendly and harmless flame retardants is being actively carried out. In order to improve the development and durability problems after washing, research on products with enhanced flame retardancy by applying flame-retardant diols in the polymerization reaction in the form of simply adding flame-retardant additives is in progress. In this case, there is a problem of deterioration of physical properties such as thixotropic properties, tensile strength, and modulus of existing adhesives, and thus the required flame retardancy cannot be obtained.

Accordingly, it is urgently needed to develop a technology to obtain excellent properties and flame retardancy even with a minimum reactive flame retardant by imparting flame retardancy to the polyol chain, which is the basic chain of the adhesive, and applying an additional reactive flame retardant.

Looking at the prior art for improving this problem, in Korean Patent Application Laid-Open No. 10-2008-0019070 (i) a phosphate-organophosphorus compound having a phosphonate bond and a flame-retardant polyester fiber and a flame-retardant polyurethane resin composition including the same , stable to water and heat, has low volatility, has little effect on various physical properties of products in which phosphate-phosphonate compounds are used as materials, is recyclable and imposes little burden on the environment, chlorine or bromine phosphate-phosphonate compounds that do not contain halogen atoms such as; (ii) flame-retardant polyester fibers, in particular, flame-retardant polyester fibers that are stable to water and heat and are durable in washing using a specific organophosphorus compound having a phosphate-phosphonate bond in one molecule; and (iii) a flame retardant polyurethane resin composition, in particular, using a specific organophosphorus compound having a phosphate-phosphonate bond in one molecule, which has excellent flame retardancy and is not substantially affected by the various properties thereof by the phosphorus compound. It is published that enables the advantages of providing a polyurethane resin composition.

In addition, Patent Publication No. 10-2008-0080762 discloses a flame-retardant polyester polyol in which an alcohol to which a halogen element is bound, a dicarboxylic acid, and an esterification bond and polycondensation in the presence of a catalyst and an acid reducing agent, and a method for preparing the same and applying the same As a flame-retardant polyurethane, the flame-retardant polyester polyol according to the present invention has a flame-retardant element bonded to itself, so that an excellent flame-retardant effect can be obtained without using an additive-type flame retardant. Since it can be used without changing the physical properties of foamed and non-foamed urethane while solving the secondary pollution problem, it is said that it can be expected to build an innovative urethane system that replaces the existing additive-type flame retardant.

And the polyester-based polymer polyol having excellent flame retardancy and its manufacturing method in the same Patent Registration No. 10-0867156 uses an aromatic polyester polyol as a base polyol and introduces a tribromostyrene compound when preparing a polymer polyol to introduce flame retardancy. Thus, a novel polyester-based polymer polyol suitable for use in construction fields such as floor waterproofing materials requiring flame retardancy, automobiles, electric/electronic, and aircraft applications was prepared. The obtained polymer polyol is said to be able to improve the disadvantage that the polymer polyol using the existing adipic acid-based polyester polyol burns easily and has excellent dispersion stability.

However, it is confirmed that this flame-retardant polyester polyol has good reactivity at the beginning, but as the size of the chain in the late reaction increases, the reactivity decreases due to steric hindrance, making it difficult to apply.

On the other hand, through Patent No. 10-1709909, the present applicant demonstrates adhesive strength and structural strength using chemical crosslinking of isocyanurate produced as a trimer of diisocyanate, and at the same time exhibits thermal stability and thermal stability of the adhesive itself by increasing the degree of curing. It has excellent chemical stability and can improve heat resistance and weather resistance. It is a 100% solids eco-friendly polyurethane adhesive that does not use a solvent. We have developed a reactive polyurethane hot-melt adhesive that has good physical properties such as adhesion and peel strength, soft touch, and excellent heat resistance for coated fabrics.

Republic of Korea Patent Publication No. 10-2008-0019070 (published on February 29, 2008) Republic of Korea Patent Publication No. 10-2008-0080762 (published on September 05, 2008) Republic of Korea Patent Publication No. 10-0867156 (published on November 06, 2008) Republic of Korea Patent Publication No. 10-1709909 (published on February 24, 2017)

It is an object of the present invention to use a flame retardant diol with excellent structural reactivity when preparing a polyester polyol that forms a urethane reaction in order to solve the deterioration of adhesion and mechanical strength that occurs when a large amount of an additive-type flame retardant is used. By doing so, excellent flame retardancy can be expressed even when a small amount of flame retardant diol is additionally used, and also to provide a method for manufacturing a flame retardant moisture curing adhesive that maintains good touch and heat resistance and improves durability after washing, and a fiber coated fabric using the same will be.

In the method for producing a flame retardant moisture curing adhesive according to the present invention, 20 to 80 parts by weight of a flame retardant diol is dissolved in a range of 100 to 150° C., and then 15 to 75 parts by weight of a dicarboxylic acid is added to the esterification reaction under a catalyst, and then there is a non-flammable 5 to 30% by weight of flame-retardant polyester polyol (A) prepared by adding 5 to 50 parts by weight of diol and polycondensation reaction in the range of 100 to 200° C.; 40 to 65 wt% of a polyester polyol (B) having a number average molecular weight of 2,000 to 3,500; 1 to 10% by weight of polyether polyol (C) having a number average molecular weight of 1,500 to 3,500; Flame-retardant diol-based chain extender (D) 4 to 20% by weight; 15 to 35% by weight of isocyanate (E); It is characterized in that it comprises and reacts in a ratio of NCO content in the range of 1.2 to 4.5%.

The flame-retardant diol used in the preparation of the flame-retardant polyester polyol (A) is BDDPP [bis (diethylene dialchol) phenylphosphate], diethyl phosphate [Diethyl phosphate], 2-benzylamino-propane-1,3-diol [2-Benzylamino -propane-1,3-diol] or a mixture of two or more selected from the group consisting of ethylene glycol [Ethylene glycol], diethylene glycol [Diethylene glycol], propylene glycol [Propylene glycol], 1 ,3-butane diol [1,3-butane diol], 1,4-butane diol [1,4-butane diol], 1,5-pentane diol [1,5-pentane diol], 1,6-hexanediol One or a mixture of two or more selected from [1,6-hexane diol] is used, and the dicarboxylic acid is adipic acid [Adipic acid], terephthalic acid [Terephthalic acid], glutaric acid [Glutaric acid], succinic acid [Succinic] acid], malonic acid [Malonic acid], oxalic acid [Oxalic acid], suberic acid [Severic acid], sebacic acid [Sebacic acid], dimethyl terephalic acid [Dimethyl terephalic acid], DOPO-IA [6-oxide6h-dibenz(c , e) (1,2) oxaphosphorin-Itaconic acid], use one or a mixture of two or more.

The flame-retardant polyester polyol (A) prepared as described above has a hydroxyl value of 75 to 310 mgKOH/g, an acid value of 0.3 to 5.0 mgKOH/g, and a number average molecular weight in the range of 362 to 1497.

In addition, the polyester polyol (B) is poly(1,4-butylene ethylene adipate)-based, poly(ethylene glycol diethylene glycol adipate)-based, poly(ethylene glycol diethylene glycol trimethylol propane adipate)-based , poly(neopentylene adipate), poly(ethylene glycol 1,4-butylene isophthalate adipate), poly(ethylene glycol adipate), poly(hexylene glycol adipate), polycaprolac One or a mixture of two or more selected from among tone systems is used, and the polyether polyol (C) is poly(propylene glycol)-based, poly(ethylene glycol)-based, poly(butylene glycol)-based, poly(tetramethylene glycol) ) or a mixture of two or more selected from the group consisting of

In addition, the flame retardant diol-based chain extender (D) is BDDPP [bis (diethylene dialchol) phenylphosphate], diethyl phosphate [Diethyl phosphate], 2-benzylamino-propane-1,3-diol [2-Benzylamino-propane- 1,3-diol], 1,4-butane diol [1,4-butane diol], 1,5-pentane diol [1,5-pentane diol], 1,6-hexanediol [1,6-haxane diol] ] selected from 1 type or a mixture of 2 or more types, and the isocyanate (E) is p-phenylene diisocyanate (PPDI), 1,6-hexaethylene diisocyanate (HDI), toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), 4,4-diphenylmethane diisocyanate (MDI), 4,4'-methylene dicyclohexyl diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), tetra One or a mixture of two or more selected from methyl xylene diisocyanate (TMXDI) is used.

And the fiber-coated fabric according to the present invention melts the flame-retardant moisture-curing adhesive prepared as above at a temperature of 80 to 120 ℃, is applied to the fiber fabric in an amount of 5 to 30 g/m2, and then at a temperature of 30 to 50 ℃, relative It is manufactured by aging for 12 to 48 hours at a humidity of 50 to 100%. The flame retardancy of the flame-retardant moisture-curing adhesive is V-0 grade (UL94 vertical method), and the fiber-coated fabric is heat-resistant at 260 to 300°C, and peel strength. It is characterized in that it is 5 ~ 22N/5cm.

The flame-retardant moisture-curable adhesive prepared through the present invention uses a flame-retardant diol with excellent structural reactivity when preparing a polyester polyol that forms a urethane reaction to prepare a flame-retardant polyester polyol, and thus a general polyester polyol, polyether polyol, Excellent flame retardancy can be expressed by reacting a flame retardant diol-based chain extender with isocyanate to have an NCO content in the range of 1.2 to 4.5%. Compared to that, it maintains good touch and heat resistance and has the effect of improving durability after washing.

Hereinafter, a method for producing a flame-retardant moisture-curing adhesive having excellent adhesive properties, heat resistance, and durability after washing according to the present invention and a fiber coated fabric using the same will be described, which has ordinary knowledge in the technical field to which the present invention pertains. It is intended to be exemplified to the extent that it can be easily implemented by a person, and this does not mean that the technical spirit and scope of the present invention is limited.

In the method for producing a flame-retardant moisture-curing adhesive according to the present invention, 20 to 80 parts by weight of a flame-retardant diol is dissolved in a range of 100 to 150° C., and then 15 to 75 parts by weight of dicarboxylic acid is added to the esterification reaction under a catalyst, and then there is a non-flammable 5 to 30% by weight of flame-retardant polyester polyol (A) prepared by adding 5 to 50 parts by weight of diol and polycondensation reaction in the range of 100 to 200° C.; 40 to 65 wt% of a polyester polyol (B) having a number average molecular weight of 2,000 to 3,500; 1 to 10% by weight of polyether polyol (C) having a number average molecular weight of 1,500 to 3,500; Flame-retardant diol-based chain extender (D) 4 to 20% by weight; 15 to 35% by weight of isocyanate (E); It contains and reacts in a proportion of NCO content in the range of 1.2 to 4.5%.

In general, when an additive-type flame retardant is applied, excellent flame retardancy can be achieved, but there is a problem of deterioration of flame retardancy and durability after washing due to the blooming phenomenon caused by the use of external additives, a decrease in the strength of the resin, and desorption of the flame retardant during washing. . Accordingly, when a flame-retardant diol is applied, washing durability can be improved by attaching the flame-retardant component directly to the backbone of the resin. Therefore, it is difficult to adjust the thixotropy and viscosity, or there is a problem of poor flexibility during fiber coating. Due to this, it was noted that there is a limit to the amount of flame-retardant diol added to exhibit the expected flame-retardant effect.

Accordingly, in the present invention, flame retardancy is imparted to the polyol forming the urethane reaction and structurally excellent in reactivity to produce flame retardant polyester polyol (A) capable of sufficiently expressing flame retardancy even with a small amount of additionally used flame retardant diol did

The flame-retardant polyester polyol (A) prepared in the present invention is esterified under a catalyst by adding 15 to 75 parts by weight of dicarboxylic acid after dissolving 20 to 80 parts by weight of a flame retardant diol in a range of 100 to 150° C., and then there is a non-flammable It is prepared by adding 5 to 50 parts by weight of diol and polycondensation reaction in the range of 100 to 200°C.

For the production of the flame-retardant polyester polyol (A), for example, after dissolving the flame-retardant diol, dicarboxylic acid is added, and the esterification reaction is carried out at 140° C. for 18 hours under a dibutyltin oxide catalyst, and then denounced as an acid reducer A soft diol is added and reacted at 160° C. for 5 hours to obtain an alcohol-terminated polyol. As a result, a translucent flame-retardant polyester polyol compound having a color APHA of 100 or less, a hydroxyl value of 75 to 310 mgKOH/g, an acid value of 0.3 to 5.0 mgKOH/g, and a number average molecular weight ranging from 362 to 1497 can be obtained.

The flame retardant diol is 1 selected from BDDPP [bis (diethylene dialchol) phenylphosphate], diethyl phosphate [Diethyl phosphate], 2-benzylamino-propane-1,3-diol [2-Benzylamino-propane-1,3-diol] species or a mixture of two or more types, and the nonflammable diol is ethylene glycol [Ethylene glycol], diethylene glycol [Diethylene glycol], propylene glycol [Propylene glycol], 1,3-butanediol [1,3-butane diol], 1,4-butane diol [1,4-butane diol], 1,5-pentane diol [1,5-pentane diol], 1,6-hexane diol [1,6-hexane diol] 1 selected from It is preferable to use the species or a mixture of two or more. In the present invention, when a large amount of flame-retardant diol is applied, the molecular weight and molecular chain length are short, resulting in a rapid polymerization reaction, making it difficult to adjust thixotropy and viscosity, or fiber coating. A nonflammable diol was combined in an appropriate ratio in order to prevent a decrease in flexibility during operation.

That is, when less than 20 parts by weight of the flame-retardant diol is used in the preparation of the flame-retardant polyester polyol (A), sufficient flame retardancy is not expressed. However, it is difficult to maintain adequate flexibility due to low flexibility and flexural strength, especially molecular weight.

And dicarboxylic acids are adipic acid, terephthalic acid, glutaric acid, succinic acid, malonic acid, oxalic acid, suberic acid acid], sebacic acid, dimethyl terephalic acid, DOPO-IA [6-oxide6h-dibenz(c,e)(1,2)oxaphosphorin-Itaconic acid] It is preferable to use a mixture, and the catalyst used in the preparation of the flame-retardant polyester polyol (A) may be a bismuth-based catalyst or a tertiary amine-based catalyst, but dibutyltin oxide) , it is effective for the esterification reaction to use an organometallic catalyst such as dibutyltin dilaurate.

The moisture-curable adhesive of the present invention applies the flame-retardant polyester polyol (A), and the polyester polyol (B) having a number average molecular weight in the range of 2,000 to 3,500 excellent in adhesive strength and a number average molecular weight in the range of 1,500 to 3,500 having good fluidity A mixture of polyether polyol (C) was used. At this time, the polyol is suitable for exhibiting strong adhesion and excellent fluidity and excellent fluidity by mixing 40 to 65% by weight of polyester polyol and 1 to 10% by weight of polyether polyol based on the total weight of the adhesive. It goes without saying that the adhesive strength, viscosity, and feel of the product are deteriorated.

For reference, polyurethane resin is a resin produced on the basis of a urethane bond generated by the reaction of an isocyanate group (-NCO) and a hydroxyl group (-OH) in a polymer, and as a raw material, polyol, isocyanate, chain extender, etc. , various solvents are added and prepared by solution polymerization. Accordingly, the characteristic of polyurethane resin is that the film strength and adhesive strength are large, so it is possible to manufacture a thin coating film. It has excellent cold resistance, and since it is processed without using a plasticizer, there is less workability problem caused by the plasticizer.

Polyol is an active hydrogen compound used to prepare polyurethane by reacting with isocyanate. These polyols are classified according to their molecular weight, and low molecular weight polyols such as ethylene glycol, glycerine, butanediol, trimethylol propane, etc. are used as chain extenders or crosslinking agents, and the average High molecular weight polyols with a molecular weight of up to 8,000 are actually used for the production of polyurethanes.

As described above, various types of polyols are used according to molecular structure, molecular weight, functionality, and OH-value, and they directly affect the physical properties of polyurethane. For example, polyurethane using polyester polyol has higher tensile strength, hardness and elongation than polyurethane using polyether polyol, and has excellent flame retardancy as well as chemical resistance and chemical resistance, so it is strong against oxidation. In addition, while it has excellent adhesion to polyester fabric, it has a hydrolysis property unlike polyether polyol, and thus has a weak water resistance. However, polyurethane using polyether polyol has excellent elasticity and shows excellent durability against acids and alkalis, so it can be used in high temperature and high humidity environments.

For this reason, the polyester polyol (B) used in the present invention is poly(1,4-butylene ethylene adipate)-based, poly(ethylene glycol diethylene glycol adipate)-based, poly(ethylene glycol diethylene glycol trimethylol). Propane adipate), poly(neopentylene adipate), poly(ethylene glycol 1,4-butylene isophthalate adipate), poly(ethylene glycol adipate), poly(hexylene glycol adipate) One or a mixture of two or more selected from the group consisting of poly(propylene glycol), poly(ethylene glycol), poly(butylene glycol), polyether polyol (C) is used. One or a mixture of two or more selected from poly(tetramethylene glycol)-based systems was used.

In addition, the flame retardant diol-based chain extender (D) used in the present invention is BDDPP [bis (diethylene dialchol) phenylphosphate], diethyl phosphate [Diethyl phosphate], 2-benzylamino-propane-1,3-diol [2- Benzylamino-propane-1,3-diol], 1,4-butane diol [1,4-butane diol], 1,5-pentane diol [1,5-pentane diol], 1,6-hexanediol [1, 6-haxane diol] is mixed and reacted using 4 to 20% by weight based on the total weight of the adhesive. Among them, it was investigated that 2-benzylamino-propane-1,3-diol is most preferable for adhesion, mechanical strength, washing durability, and flame retardant properties.

And the isocyanate (E) used in the present invention is p-phenylene diisocyanate (PPDI), 1,6-hexaethylene diisocyanate (HDI), toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI) 1 selected from , 4,4-diphenylmethane diisocyanate (MDI), 4,4'-methylene dicyclohexyl diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), tetramethyl xylene diisocyanate (TMXDI) It is preferable to use a type or a mixture of two or more types. Considering that the diisocyanate is tacky during dip coating and slip properties between fabric filaments, and the resulting flexibility and feel, especially MDI is used as the total weight of the adhesive. It is most preferable to use it in a ratio of 15 to 35% by weight, and accordingly, the flame retardant moisture curing adhesive of the present invention is made in the range of 1.2 to 4.5% of the NCO content.

Next, the fiber coating fabric using the flame retardant moisture curing adhesive according to the manufacturing method of the present invention melts the flame retardant moisture curing adhesive at a temperature of 80 to 120 ° C. It is manufactured by aging for 12 to 48 hours at a temperature of 30 to 50° C. and a relative humidity of 50 to 100%, thereby maximizing heat resistance, adhesive strength, high peel strength, and soft touch. Silver is V-0 grade (UL94 vertical method), and the coated fabric has physical properties with good tactile properties such as heat resistance of 260 to 300°C, and peel strength of 5 to 22N/5cm.

Hereinafter, a method for manufacturing a flame-retardant moisture-curing adhesive according to the present invention and an example in which a fiber-coated fabric using the same will be tested. The present invention will be described through preferred embodiments of

[Example 1] Preparation of flame-retardant polyester polyol (1)

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. The inside of the reactor was purged with nitrogen, 720 g of BDDPP was added, 280 g of adipic acid and 0.2 g of dibutyltin oxide were added, stirred and esterified at 140 ° C. for 18 hours. Then, 18 g of diethylene glycol, an acid reducing agent, was added. After maintaining 160 °C for an hour, the reaction was terminated. The obtained polyester polyol had a hydroxyl value of 100 to 300 mgKOH/g, an acid value of 0.3 to 5.0 mgKOH/g, and a number average molecular weight of 374 to 1,122.

[Example 2] Preparation of flame-retardant polyester polyol (2)

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. The inside of the reactor is purged with nitrogen, 300 g of diethylene glycol is added, 700 g of DOPO-IA and 0.2 g of dibutyltin oxide are added, and the ester reaction is performed at 140 ° C. for 18 hours by adding 10 g of ethylene glycol, an acid reducing agent. After maintaining 160° C. for 5 hours, the reaction was terminated. The obtained polyester polyol had a hydroxyl value of 110 to 295 mgKOH/g, an acid value of 0.3 to 5.0 mgKOH/g, and a number average molecular weight ranging from 380 to 935.

[Example 3] Preparation of flame-retardant polyester polyol (3)

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. The inside of the reactor was purged with nitrogen, 530 g of BDDPP was added, 470 g of DOPO-IA and 0.2 g of dibutyltin oxide were added, stirred at 140° C. for 18 hours, and then 18 g of diethylene glycol, an acid reducing agent, was added. After maintaining 160° C. for an hour, the reaction is terminated. The obtained polyester polyol had a hydroxyl value of 75 to 310 mgKOH/g, an acid value of 0.3 to 5.0 mgKOH/g, and a number average molecular weight ranging from 362 to 1,497.

[Example 4] Preparation of flame-retardant moisture-curing adhesive (1)

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. Purging the reactor with nitrogen, DPE-47 (Dong-A Chemical) 217 g, PPG1000 (Kumho Petrochemical) 33 g, the flame-retardant polyester polyol prepared in Example 1 120 g, CAPA2201A (Solvay Caprolactones) 290 g, 2-Benzylamino-propane-1 , After 80 g of 3-diol is added, it is dissolved at 70° C. for 30 minutes and stirred. Then, 260 g of MDI (Kumho Mitsui) is added, and the reaction is carried out at 85 to 100° C. for 5 hours and then terminated.

[Example 5] Preparation of flame-retardant moisture-curing adhesive (2)

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. The inside of the reactor is purged with nitrogen and DPE-47 (Dong-A Chemical) 219g, PPG1000 (Kumho Petrochemical) 35g, the flame-retardant polyester polyol prepared in Example 2 120g, CAPA2201A (Solvay Caprolactones) 283g, 2-Benzylamino-propane-1 , After 80 g of 3-diol is added, it is dissolved at 70° C. for 30 minutes and stirred. After that, 263 g of MDI (Kumho Mitsui) is added, and the reaction is carried out at 85 to 100° C. for 5 hours and then terminated.

[Example 6] Preparation of flame-retardant moisture-curing adhesive (3)

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. Purging the reactor with nitrogen, DPE-47 (Dong-A Chemical) 225 g, PPG1000 (Kumho Petrochemical) 34 g, the flame-retardant polyester polyol prepared in Example 3 120 g, CAPA2201A (Solvay Caprolactones) 282 g, 2-Benzylamino-propane-1 , After 80 g of 3-diol is added, it is dissolved at 70° C. for 30 minutes and stirred. Then, 259 g of MDI (Kumho Mitsui) is added, and the reaction is carried out at 85 to 100° C. for 5 hours and then terminated.

[Comparative Example 1]

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. The inside of the reactor was purged with nitrogen, DPE-47 (Dong-A Chemical) 196g, PPG1000 (Kumho Petrochemical) 27g, CAPA2201A (Solvay Caprolactones) 243g, 2-Benzylamino-propane-1,3-diol 200g was added, and at 70℃ Dissolve for 30 minutes and stir. After that, 334 g of MDI (Kumho Mitsui) is added, and the reaction is carried out at 85 to 100° C. for 5 hours and then terminated.

[Comparative Example 2]

A thermometer, stirrer, impeller, and cooling condenser are installed in the 4-neck round glass flask reactor. After purging the reactor with nitrogen, 264 g of DPE-47 (Dong-A Chemical), 40 g of PPG1000 (Kumho Petrochemical), and 330 g of CAPA2201A (Solvay Caprolactones) were added and stirred at 70° C. for 30 minutes to dissolve, and then MDI (Kumho Mitsui) 166 g is added and the reaction proceeds at 85 ~ 100 ℃ for 5 hours. After completion of the reaction, 200 g of resorcinol bis diphenyl phosphate (RDP) is added, and the reaction is terminated after stirring at 90° C. for 1 hr.

The blending amounts (unit: g) of the components for the moisture-curing adhesives respectively carried out in Examples 4 to 6 and Comparative Examples 1 and 2 are shown in [Table 1] below.

division Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 (A) flame retardant polyester polyol (Example 1) 120 0 0 0 0 (A) flame retardant polyester polyol (Example 2) 0 120 0 0 0 (A) flame retardant polyester polyol (Example 3) 0 0 120 0 0 (B) DPE-47 217 219 225 196 264 (B) CAPA2201A 290 283 282 243 330 (C) PPG1000 33 35 34 27 40 (D) flame retardant diol 80 80 80 200 0 (E) MDI 260 263 259 260 166 Additive Flame Retardant (RDP) 0 0 0 0 200

[Experimental example]

The results of measuring the physical properties of the moisture-curing adhesives performed in Examples 4 to 6 and Comparative Examples 1 and 2, respectively, are shown in [Table 2] below.

division Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Peel strength (N/5cm) 15 12 13 19 8 Flame retardant (UL94) V-0 V-0 V-0 V-0 V-0 Heat resistance (thermal deformation, ℃) 230 220 250 190 160 Flame retardant (NFPA 701) Pass Pass Pass Pass Pass Flame retardant after washing (NFPA 701) Pass Pass Pass Fail Fail touch ◎ ○ ○ X △

- Adhesive strength

Poly Dewspo 50D was used as a test piece for the adhesive strength (peel strength) test of the hot melt adhesive. After melting at a temperature of 100℃, the hot melt adhesive was transferred to the surface of the fabric so that the application amount was about 5 ~ 30g/m2 using #152 Gravure roll. did At this time, 5 specimens were used and the universal tensile testing machine owned by our company was used for the testing machine. The breaking load of the tester and the test piece was set to within 5 to 85% of the capacity, and after bonding, it was aged for 12 hours at a temperature of 40°C and a relative humidity of 70%, and then carried out 5 times.

- Flame retardant

Based on the UL94 vertical method, a specimen having a width of 1.3 cm and a length of 12 cm was prepared in a similar manner to that of a heat-resistant specimen, and the flame retardancy was confirmed during vertical contacting.

- Heat resistance (thermal deformation)

The flame-retardant moisture-curing adhesive is used to prepare a specimen having a thickness of 5 to 30 μm, a width of 2 cm, and a length of 10 cm, and the temperature is raised by 5° C. for 5 minutes under a load of 10 g inside the oven, and the thermal deformation and cutting temperature of the film are measured.

- Tactile

The flame-retardant moisture curing adhesive and the aramid fabric were combined to select 10 experts and measure the average value of the touch (◎: very good, ○: good, △: normal, ×: poor).

As the experimental results of [Table 2], when comparing the experimental results of Examples 4 to 6 and Comparative Examples 1 and 2, the moisture curing adhesive according to Examples 4 to 6 has adhesive strength, flame retardancy, heat resistance, touch, etc. In all measurement items, it exhibited superior physical properties than the moisture-curing adhesives performed in Comparative Examples 1 and 2, respectively.

Therefore, the flame-retardant moisture-curing adhesive prepared as in the present invention has excellent adhesive properties, heat resistance and durability after washing, so it can be substituted, deformed and changed in various ways within the scope of the present invention without departing from the technical spirit of the present invention. Since it has the advantage of being easy, it can be used for various purposes and forms, such as coated on the surface of various textile materials, as well as clothes, automobiles, and construction materials, or bonded in the form of a film.

Claims (10)

After dissolving 20 to 80 parts by weight of a flame retardant diol in the range of 100 to 150°C, 15 to 75 parts by weight of a dicarboxylic acid is added to the esterification reaction under a catalyst, and then 5 to 50 parts by weight of a nonflammable diol is added thereto in the range of 100 to 200°C 5 to 30% by weight of flame-retardant polyester polyol (A) prepared in a polycondensation reaction;
Poly(1,4-butylene ethylene adipate) type, poly(ethylene glycol diethylene glycol adipate) type, poly(ethylene glycol diethylene glycol trimethylol propane adipate) type, poly(neopentylene adipate) type , poly(ethylene glycol 1,4-butylene isophthalate adipate), poly(ethylene glycol adipate), poly(hexylene glycol adipate), polycaprolactone, one or more selected from the group consisting of 40 to 65 wt% of a mixed number average molecular weight of 2,000 to 3,500 polyester polyol (B);
Polyether with a number average molecular weight of 1,500 to 3,500 in which one or two or more selected from poly (propylene glycol), poly (ethylene glycol), poly (butylene glycol), and poly (tetramethylene glycol) systems are mixed 1 to 10% by weight of polyol (C);
Flame-retardant diol-based chain extender (D) 4 to 20% by weight;
15 to 35% by weight of isocyanate (E);
A method for producing a flame-retardant moisture-curing adhesive, characterized in that it contains and reacts in a ratio of 1.2 to 4.5% of NCO content. According to claim 1,
The flame retardant diol is 1 selected from BDDPP [bis (diethylene dialchol) phenylphosphate], diethyl phosphate [Diethyl phosphate], 2-benzylamino-propane-1,3-diol [2-Benzylamino-propane-1,3-diol] species or a mixture of two or more types, and the nonflammable diol is ethylene glycol [Ethylene glycol], diethylene glycol [Diethylene glycol], propylene glycol [Propylene glycol], 1,3-butanediol [1,3-butane diol], 1,4-butane diol [1,4-butane diol], 1,5-pentane diol [1,5-pentane diol], 1,6-hexane diol [1,6-hexane diol] 1 selected from A method for producing a flame-retardant moisture-curing adhesive, characterized in that the species or a mixture of two or more types is used. According to claim 1,
The dicarboxylic acid is adipic acid [Adipic acid], terephthalic acid [Terephthalic acid], glutaric acid [Glutaric acid], succinic acid [Succinic acid], malonic acid [Malonic acid], oxalic acid [Oxalic acid], suberic acid [Suberic acid] acid], sebacic acid, dimethyl terephalic acid, DOPO-IA [[6-oxide6h-dibenz(c,e)(1,2)oxaphosphorin-Itaconic acid] A method for producing a flame-retardant moisture-curing adhesive, characterized in that it is used by mixing the above. According to claim 1,
The flame-retardant polyester polyol (A) has a hydroxyl value of 75 to 310 mgKOH/g, an acid value of 0.3 to 5.0 mgKOH/g, and a number average molecular weight of 362 to 1,497. delete delete According to claim 1,
The flame retardant diol-based chain extender (D) is BDDPP [bis (diethylene dialchol) phenylphosphate], diethyl phosphate [Diethyl phosphate], 2-benzylamino-propane-1,3-diol [2-Benzylamino-propane-1, 3-diol], 1,4-butane diol [1,4-butane diol], 1,5-pentane diol [1,5-pentane diol], 1,6-hexanediol [1,6-haxane diol] A method for producing a flame-retardant moisture-curing adhesive, characterized in that the selected one or two or more are mixed and used. According to claim 1,
The isocyanate (E) is p-phenylene diisocyanate (PPDI), 1,6-hexaethylene diisocyanate (HDI), toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), 4,4- One or two or more selected from diphenylmethane diisocyanate (MDI), 4,4'-methylene dicyclohexyl diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), and tetramethyl xylene diisocyanate (TMXDI) A method for producing a flame-retardant moisture-curing adhesive, characterized in that it is used by mixing. The flame retardant moisture curing adhesive prepared in any one of claims 1 to 4, 7, and 8 is melted at a temperature of 80 to 120° C. and applied to the fiber fabric in an amount of 5 to 30 g/m2. Next, a fiber-coated fabric, characterized in that it is manufactured by aging for 12 to 48 hours at a temperature of 30 to 50° C. and a relative humidity of 50 to 100%. 10. The method of claim 9,
The flame retardancy of the flame-retardant moisture-curing adhesive is V-0 grade (UL94 vertical method), and the coated fabric has a heat resistance of 260 ~ 300℃, and a peel strength of 5 ~ 22N/5cm.