KR101714744B1 - Eco friendly phosphorus based flame retardant pressure-sensitive adhesive composition and method for manufacturing the same - Google Patents

Abstract

(Meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, from 55% by weight to 89% by weight, based on 100 parts by weight of the total of (A) 0.5 to 10% by weight of the phosphorus emulsifier, 10 to 30% And 0.5% by weight to 5% by weight of a (meth) acrylic monomer having a carboxyl group, based on 100 parts by weight of the acrylic emulsion; And (B) 5 to 30 parts by weight of a phosphorus-containing flame retardant additive, and a process for producing the flame retardant pressure-sensitive adhesive composition. Such a flame retardant pressure-sensitive adhesive composition can be applied to products such as interior and exterior materials for architectural use, decorative sheets, automobile interior and exterior materials, etc., while having excellent environment-friendliness and excellent flame retardancy, adhesive property and substrate adhesion.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame-retardant pressure-sensitive adhesive composition and a method for producing the same,

The present invention relates to a phosphorus-based flame retardant pressure-sensitive adhesive composition and a method for producing the same.

The types and characteristics of the pressure-sensitive adhesives vary widely, and thus the range of application is wide. Among these various types of pressure-sensitive adhesives, the pressure-sensitive adhesives containing an organic material as a main component are easy to process and have excellent adhesive properties and are particularly closely applied to real life. However, a pressure-sensitive adhesive containing an organic material as a main component has a disadvantage that thermal characteristics and combustion resistance characteristics are poor. The weak burning characteristics of the adhesive may not only be an increase in life and property damage in an emergency such as a fire, but may also cause a fire itself.

Therefore, the pressure-sensitive adhesives used in household appliances and heat-generating devices, interior and exterior materials of automobiles, and interior and exterior materials of buildings to be careful of fire occurrence are required to have flame retardant properties.

On the other hand, a general flame retardant tackifier can physically improve the flame retardancy by mixing the additive flame retardant with the pressure-sensitive adhesive composition, or chemically flame retardancy can be improved by causing a reaction between the pressure-sensitive adhesive composition and the reactive type flame retardant.

Among them, the pressure sensitive adhesive containing the additive type flame retardant may include a nitrogen type, a halogen type metal hydroxide type, an antimony type flame retardant and the like, and in particular, a halogen type flame retardant and an antimony type flame retardant have excellent flame retardancy and are widely used.

However, the halogen-based and antimony-based flame retardants have a problem that they can generate harmful substances when they are used in a pressure-sensitive adhesive. In particular, halogen-based flame retardants are becoming increasingly restricted in many countries because dioxins and furans, which are highly toxic carcinogens, can form during combustion and disposal. Moreover, in Europe, products containing flame retardants containing halogen and antimony have recently been subject to regulations such as not giving an "eco label", and it is urgent to develop a product that can replace them.

Therefore, there is an increasing need for the development of non-halogen-based and non-antimony-based flame retardants which are not only excellent in flame retardancy but can exhibit excellent adhesive property and adhesion to substrates with low harmfulness.

(Patent Document 0001) Korean Patent Publication No. 10-2007-0010393

An object of the present invention is to provide a flame retardant pressure-sensitive adhesive composition which can reduce the use of volatile organic solvents by including an acrylic emulsion and a method for producing the same.

Another object of the present invention is to provide a flame retardant pressure-sensitive adhesive composition which is environmentally friendly and excellent in transparency, and which can increase flame retardancy while minimizing the amount of addition-type flame retardant, and a method for producing the same.

The above and other objects of the present invention can be achieved by the present invention described below.

(A) 0.5 to 10% by weight of a phosphorus emulsifier, 10 to 30% by weight of a phosphorus (meth) acrylic monomer, 55% by weight of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, 100 parts by weight of an acrylic emulsion comprising a copolymer of (meth) acrylic monomer having a carboxyl group and 0.5% by weight to 5% by weight of an acrylic emulsion; And (B) 5 to 30 parts by weight of a phosphorus-containing flame retardant additive.

The phosphorus emulsifier may be a phosphate ester compound represented by the following general formula (1)

[Chemical Formula 1]

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylaryl group having 6 to 20 carbon atoms, R ₂ is hydrogen or -CH ₂ CH ₂ OR ₁ , and n is an integer of 1 to 20.

The phosphorus (meth) acrylic monomer may be a compound represented by the following formula (2)

(2)

In Formula 2, R ₃ is hydrogen or a methyl group; m is an integer from 0 to 10; p is an integer from 0 to 3; q is an integer from 0 to 3; X and Y are each independently a substituted or unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon having 5 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms .

The (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably an acrylic monomer having 2 to 10 carbon atoms such as 2-ethylhexyl acrylate, butyl acrylate, lauryl methacrylate, isooctyl acrylate, isobutyl acrylate, methacrylate, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, acrylonitrile, and vinyl acetate.

The copolymer may further include at least one of a (meth) acrylic monomer having a hydroxy group and a polyfunctional (meth) acrylic monomer.

The (meth) acrylic monomer having a hydroxy group may include at least one of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

The polyfunctional (meth) acrylic monomer may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, Di (meth) acrylate, allyl methacrylate, and the like.

The (meth) acrylic monomer having a carboxyl group may include at least one of (meth) acrylic acid, itaconic acid and maleic acid.

The flame-retardant pressure-sensitive adhesive composition may further include a tackifier resin.

The phosphorus flame retardant is selected from the group consisting of phosphorus-nitrogen intumescent FR, cyclic phosphonate, isopropylated triaryl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, tricresyl phosphate, triphenyl phosphate, butylated triaryl phosphate , Resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), ammonium polyphosphate, and phosphorous polyol.

Another embodiment of the present invention is a composition comprising 0.5 to 10% by weight of a phosphorus emulsifier, 10 to 30% by weight of a phosphorus (meth) acrylic monomer, 55 to 89% by weight of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms And 0.5 to 5% by weight of a (meth) acrylic monomer having a carboxyl group, to prepare an acrylic emulsion; And 5 parts by weight to 30 parts by weight of an addition type phosphorus flame retardant to 100 parts by weight of the acrylic emulsion prepared above; And a method for producing the flame retardant pressure-sensitive adhesive composition.

The step of preparing the acrylic emulsion by the emulsion polymerization includes preparing a reaction solution by stirring ion-exchanged water, a pH buffer substance and an aqueous catalyst solution in a reactor, reacting the reaction solution and the mixture, and then neutralizing the mixture with ammonia water can do.

The flame retardant pressure-sensitive adhesive composition according to the embodiments of the present invention can realize excellent flame retardance, transparency, adhesive property, and substrate adhesion while having excellent environmental friendliness. Further, such a flame retardant pressure-sensitive adhesive composition can be applied to products such as interior and exterior materials for construction, decorative sheets, and automobile interior and exterior materials.

1 shows an exemplary polymerization apparatus for producing a flame retardant pressure-sensitive adhesive composition according to an embodiment of the present invention.

(A) 0.5 to 10% by weight of a phosphorus emulsifier, 10 to 30% by weight of a phosphorus (meth) acrylic monomer, 55% by weight of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, 100 parts by weight of an acrylic emulsion comprising a copolymer of (meth) acrylic monomer having a carboxyl group and 0.5% by weight to 5% by weight of an acrylic emulsion; And (B) 5 to 30 parts by weight of a phosphorus-containing flame retardant additive.

Thus, the flame retardant pressure-sensitive adhesive composition of one embodiment has excellent flame retardancy, adhesive property, and substrate adhesion while having excellent environmental friendliness through the above-described constitution, and can be applied to products such as interior and exterior materials for architectural use, decorative sheets, automobile interior and exterior materials .

The flame retardant pressure-sensitive adhesive composition of one embodiment is a phosphorus-based pressure-sensitive adhesive composition, and at the same time is a non-halogen and non-antimony flame retardant pressure-sensitive adhesive composition. Such a flame retardant pressure-sensitive adhesive composition can prevent carcinogens such as dioxins and furans, which are generated when a halogen-based flame retardant or an antimony-based flame retardant is burned, and is thus excellent in environmental friendliness and can meet strict environmental regulations.

The flame-retardant pressure-sensitive adhesive composition of one embodiment includes an acrylic emulsion, wherein the acrylic emulsion is a mixture of a phosphorus emulsifier, a phosphorus (meth) acrylic monomer, a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, ) Acrylic monomer (hereinafter sometimes simply referred to as " copolymer "). In this case, the flame-retardant pressure-sensitive adhesive composition can be formed of an aqueous dispersion type pressure-sensitive adhesive which does not use an organic solvent, thereby being more environmentally friendly. In addition, the copolymer can impart excellent tackiness and flame retardancy to the flame-retardant pressure-sensitive adhesive composition. Thus, the flame retardant pressure-sensitive adhesive composition of one embodiment can achieve a good level of flame retardancy and tackiness while reducing the amount of the additive type phosphorus flame retardant to be described later.

As used herein, the term (meth) acrylic monomer means an acrylic monomer and / or a methacrylic monomer.

The phosphorus-based emulsifier contained in the copolymer is a phosphorus-based anionic emulsifier, which not only imparts flame retardancy to the copolymer but also imparts physical stability in the production of an acrylic emulsion.

Specifically, the phosphorus emulsifier may be a phosphate ester compound including a mono-ester, a di-ester, and a tri-ester, and such a phosphate ester compound may be, for example, a phosphoric acid and its salt.

More specifically, the phosphorus emulsifier may be a phosphate ester compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylaryl group having 6 to 20 carbon atoms, R ₂ is hydrogen or -CH ₂ CH ₂ OR ₁ , and n is an integer of 1 to 20.

When such a phosphorus emulsifier is used, the copolymer not only has excellent flame retardancy, but also improves the particle stability by imparting physical stability during production of the acrylic emulsion.

The phosphorus emulsifier is contained in the copolymer in an amount of 0.5 wt% to 10 wt%. If the content of the phosphorus emulsifier is less than 0.5% by weight, the copolymer may have a low particle stability and a large aggregation amount in polymerization may occur. When the content of the phosphorus-based emulsifier exceeds 10% by weight, the flame retardancy is improved but the water resistance is lowered and the viscosity is increased.

The phosphorus (meth) acrylic monomer can increase the phosphorus content of the copolymer to improve the flame retardancy and impart excellent tackiness. Thus, the flame retardant pressure-sensitive adhesive composition of one embodiment can achieve a good level of flame retardancy and tackiness while reducing the amount of the additive type phosphorus flame retardant to be described later.

Specifically, the phosphorus (meth) acrylic monomer may be a compound represented by the following formula (2).

 (2)

In Formula 2, R ₃ is hydrogen or a methyl group, m is an integer from 0 to 10, p is an integer from 0 to 3, q is an integer from 0 to 3, X and Y are C 1 -C each independently Substituted or unsubstituted aliphatic hydrocarbons having 5 to 20 carbon atoms, substituted or unsubstituted alicyclic hydrocarbons having 5 to 20 carbon atoms, or substituted or unsubstituted aromatic hydrocarbons having 6 to 20 carbon atoms.

Specifically, X and Y may each independently be a substituted or unsubstituted aliphatic hydrocarbon having 1 to 6 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms. In this case, the flame retardancy and adhesion properties of the flame-retardant pressure-sensitive adhesive composition can be further improved.

More specifically, the phosphorus (meth) acryl monomer may be selected from the group consisting of dimethyl (methacryloyloxymethyl) phosphonate, dimethyl (methacryloyloxyethyl) phosphonate, dimethyl (acryloyloxymethyl) (Methacryloyloxymethyl) phosphonate, diethyl (methacryloyloxymethyl) phosphonate, diethyl (methacryloyloxymethyl) phosphonate, diethyl (Methacryloyloxyethyl) phosphonate, dipropyl (methacryloyloxyethyl) phosphonate, dipropyl (methacryloyloxyethyl) phosphonate, and dipropyl And may include one or more. The phosphorus (meth) acrylic monomer may be used alone or in combination of two or more. Such phosphorus (meth) acrylic monomers are excellent in compatibility with other components contained in the acrylic emulsion, and thus can achieve more excellent tackiness.

The phosphorus (meth) acryl monomer is included in the copolymer in an amount of 10% by weight to 30% by weight. If the content of the phosphorus (meth) acrylic monomer is less than 10% by weight, the effect of improving the flame retardancy is insignificant. If the content of the phosphorus (meth) acrylic monomer is more than 30% by weight, the viscosity may excessively increase and the initial adhesion may be lowered.

In one embodiment, the phosphorus (meth) acrylic monomer may be included in the copolymer in an amount of 10% to 20% by weight. Within this range, the copolymer and the emulsion containing it can be excellent in viscosity, flame retardancy and initial adhesion.

The (meth) acrylic monomer having an alkyl group of 1 to 14 carbon atoms serves to impart the adhesive property to the copolymer and the acrylic emulsion containing the copolymer. When the (meth) acrylic monomer having more than 14 carbon atoms is used, the cohesive force of the copolymer may excessively decrease.

Specifically, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably a monomer having an alkyl group of 1 to 14 carbon atoms such as 2-ethylhexyl acrylate, butyl acrylate, lauryl methacrylate, isooctyl acrylate, isobutyl acrylate, And at least one of acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, acrylonitrile, and vinyl acetate. The (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms may be used singly or as a mixture of two or more kinds. In this case, the cohesive force of the copolymer can be improved while at the same time an excellent initial adhesion can be realized.

In one embodiment, the (meth) acrylic monomer having an alkyl group of 1 to 14 carbon atoms may include, for example, 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate and vinyl acetate. In this case, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms can be further improved in compatibility with other components contained in the copolymer. As a result, the compatibility and cohesion of the copolymer and the emulsion containing the copolymer are further improved, and at the same time, the initial adhesion can be further improved.

The (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is contained in an amount of 55 to 89% by weight in the copolymer. If the content of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is less than 55% by weight, the initial adhesive strength may be lowered. If the content of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is more than 89% by weight, heat resistance may be deteriorated.

In one embodiment, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms can be contained in an amount of 70 to 85% by weight in the copolymer. Within the above range, the copolymer and the emulsion containing it may have excellent initial adhesion and heat resistance.

In one embodiment, the copolymer is obtained by copolymerizing the phosphorus compound represented by the above-mentioned formula (1), the phosphorus (meth) acrylic monomer represented by the formula (2) and the (meth) acrylic monomer having an alkyl group with the carbon number of 1 to 14 in the above- Synergy effect is generated by using together. In other words, the phosphorus-based compound of formula (1) and the phosphorus-based (meth) acrylic monomer of formula (2) described above are excellent not only in compatibility between the two, but also in compatibility with a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms This is very good. In this case, the copolymer and the acrylic emulsion containing the copolymer are excellent in flame retardancy and adhesiveness of the copolymer itself, as well as being formed in a suitable range of viscosity, and thus are excellent in handleability. In addition, not only the uniformity and dispersibility of the acrylic emulsion can be enhanced, but also the transparency of the pressure-sensitive adhesive can be realized at a superior level.

The (meth) acrylic monomer having a carboxyl group serves to increase the cohesive force of the copolymer and to provide a crosslinking point necessary for curing. As a result, the flame retardant pressure-sensitive adhesive composition of one embodiment not only improves the degree of curing, but also improves tackiness and cohesion.

Specifically, the (meth) acrylic monomer having a carboxyl group may include at least one of (meth) acrylic acid, itaconic acid and maleic acid. In this case, the flame-retardant pressure-sensitive adhesive composition can further improve the degree of curing.

The content of the (meth) acrylic monomer having a carboxyl group may be 0.5% by weight to 5% by weight of the copolymer. When the content of the (meth) acrylic monomer having a carboxyl group is less than 0.5% by weight, the polymerization degree may be lowered. When the content of the (meth) acrylic monomer having a carboxyl group is more than 5% by weight, the viscosity during neutralization sharply increases and aging may occur depending on the temperature.

In one embodiment, the (meth) acrylic monomer having a carboxyl group may be included in the copolymer in an amount of from 0.5% to 3% by weight. Within this range, the degree of polymerization, degree of crosslinking and water resistance of the copolymer and the emulsion containing it can be further improved.

The copolymer contained in the flame retardant pressure-sensitive adhesive composition of one embodiment includes the phosphorus-based emulsifier, the phosphorus (meth) acrylic monomer, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms and the (meth) acrylic monomer having a carboxyl group; (Meth) acrylic monomer having a hydroxy group or a polyfunctional (meth) acrylic monomer. In this case, the flame-retardant pressure-sensitive adhesive composition can further improve the adhesive property.

The (meth) acrylic monomer having a hydroxy group can further improve the curability of the copolymer by providing a hydroxyl group as a functional group upon curing.

Specifically, the (meth) acrylic monomer having a hydroxy group may include at least one of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. In this case, not only the supply and the supply of raw materials are easy, but also the reactivity can be further improved.

In one embodiment, the (meth) acrylic monomer having a hydroxy group may be included in the copolymer in an amount of 0 wt% to 10 wt%, for example, 0.1 wt% to 5 wt%. Within the above range, the flame-retardant pressure-sensitive adhesive composition can further improve the heat resistance, the adhesive holding force and the water resistance.

The polyfunctional (meth) acrylic monomer can further improve the crosslinking degree of the copolymer and can realize excellent adhesive property.

Specifically, the polyfunctional (meth) acrylic monomers are selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di Diol di (meth) acrylate, and allyl methacrylate. The polyfunctional (meth) acrylic monomer may be used alone or in combination of two or more. In this case, the reactivity and the adhesive property can be further improved.

In one embodiment, the multifunctional (meth) acrylic monomer may be included in the copolymer in an amount of 0 wt% to 5 wt%, for example, 0.1 wt% to 5 wt%, and 0.1 wt% to 3 wt%. Within the above range, the flame-retardant pressure-sensitive adhesive composition can further improve the heat resistance, adhesive holding power and water resistance, while keeping the cohesive force in an appropriate range, thereby improving handling properties.

The flame retardant pressure-sensitive adhesive composition of one embodiment includes an acrylic emulsion prepared by emulsion polymerization of a mixture containing the monomers contained in the copolymer in the above-mentioned ratio, as described above.

In this case, the acrylic emulsion may contain an initiator used in the emulsion polymerization. Specifically, the initiator is not particularly limited as an initiator for emulsion polymerization by a conventional emulsion polymerization method, and any conventional emulsion polymerization initiator may be used. As the initiator, for example, at least one of potassium persulfate, sodium persulfate and ammonium persulfate may be used.

In one embodiment, the amount of initiator used may be from 0.1% to 1% by weight based on the total acrylic emulsion. In this case, the degree of polymerization and the molecular weight of the copolymer can be adjusted to an appropriate range.

In addition, the acrylic emulsion may be an aqueous solvent as a dispersion medium in emulsion polymerization. The kind of the dispersion medium is not particularly limited, but when an aqueous solvent is used, the use of the organic solvent of the flame-retardant pressure-sensitive adhesive composition can be omitted or reduced. For example, the dispersion medium may be water, ion-exchanged water, distilled water, or the like. In this case, the environmental friendliness of the flame-retardant pressure-sensitive adhesive composition can be further improved.

In one embodiment, when the ion exchange water is used as the dispersion medium, the compatibility with the components contained in the above-mentioned flame retardant pressure-sensitive adhesive composition can be further improved.

In addition, the acrylic emulsion may further include a pH buffer substance used in emulsion polymerization. Specifically, the type of the pH buffer material is not particularly limited, and may be, for example, at least one of sodium bicarbonate, sodium acetate, and potassium bicarbonate.

In one embodiment, the amount of the pH buffer material used may be from 0.01 wt% to 1 wt% with respect to the total acrylic emulsion. In this case, the particle size of the copolymer can be uniformly formed, and the polymerization degree can be further improved.

In addition, the acrylic emulsion may contain ammonia water (specifically, 10 to 30%, for example, 28%) as a neutralizing agent used in emulsion polymerization. In this case, the final pH of the acrylic emulsion can be adjusted.

In one embodiment, the amount of ammonia water (28%) may be used in a range in which the pH of the acrylic emulsion is adjusted to 7.0 to 7.5.

In addition, the acrylic emulsion can be used without any limitations in the emulsion polymerization, if necessary, in usual emulsion polymerization such as defoaming agent, leveling agent, thickener, preservative, freezing stabilizer, plasticizer, pigment and filler.

The flame retardant pressure sensitive adhesive composition of one embodiment may further comprise a tackifier. These tackifiers act to control the tacking performance of the flame retardant tackifier composition.

Specifically, the tackifier may be selected from the group consisting of rosin resin, hydrogenated rosin resin, terpene resin, styrene-added terpene resin, terpene phenol resin, phenol resin and petroleum resin. In this case, the adhesive property of the flame-retardant pressure-sensitive adhesive composition can be further improved.

In one embodiment, the tackifier may be used in an amount of 0 to 30 parts by weight, for example, 1 to 30 parts by weight and 1 to 20 parts by weight based on 100 parts by weight of the acrylic emulsion. In this case, the adhesive property of the flame-retardant pressure-sensitive adhesive composition can be further improved.

The flame retardant pressure-sensitive adhesive composition of one embodiment contains a phosphorus-based flame retardant, so that the flame retardancy can be further improved.

The content of the phosphorus flame retardant is in the range of 5 to 30 parts by weight based on 100 parts by weight of the acrylic emulsion. When the phosphorus flame retardant content is less than 5 parts by weight, the flame retardancy is deteriorated. When the phosphorus flame retardant content exceeds 30 parts by weight, the pressure-sensitive adhesive property of the pressure-sensitive adhesive decreases, and the adhesion of the base material deteriorates.

Specifically, the content of the phosphorus-based flame retardant may be, for example, 5 parts by weight to 25 parts by weight, 5 parts by weight to 15 parts by weight, or 5 parts by weight to 10 parts by weight based on 100 parts by weight of the emulsion. In this case, the content of the added phosphorus flame retardant can be further reduced, and the production efficiency can be improved. Further, it is possible to more effectively prevent the blooming phenomenon and maintain the flame retardancy in an excellent range.

Specifically, the phosphorus flame retardant is selected from the group consisting of phosphorus-nitrogen intumescent FR, cyclic phosphonate, isopropylated triaryl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, triclosyl phosphate, triphenyl phosphate, At least one selected from the group consisting of polyaryl phosphates, resorcinol bis (diphenyl phosphates), bisphenol A bis (diphenyl phosphates), ammonium polyphosphates and phosphorous polyols can be used. The phosphorus-based flame retardant may be used alone or in combination of two or more. When a phosphorus-based flame retardant is used in the above range, the compatibility with the acrylic emulsion is excellent, the adhesion property of the flame-retardant pressure-sensitive adhesive composition is further improved, and the content of the flame retardant can be minimized.

Another embodiment of the present invention relates to a method for producing the above-mentioned flame retardant pressure-sensitive adhesive composition.

Specifically, a method for producing a flame-retardant pressure-sensitive adhesive composition according to an embodiment comprises 0.5 to 10% by weight of a phosphorus emulsifier, 10 to 30% by weight of a phosphorus-based (meth) acrylic monomer, (meth) acrylic monomer having an alkyl group of 1 to 14 By weight of a mixture containing 55% by weight to 89% by weight of a (meth) acrylic monomer having a carboxyl group and 0.5% by weight to 5% by weight of a (meth) acrylic monomer having a carboxyl group to prepare an acrylic emulsion; And 5 parts by weight to 30 parts by weight of an addition type phosphorus flame retardant to 100 parts by weight of the acrylic emulsion prepared above; .

In one embodiment, the step of emulsion-polymerizing the above-mentioned mixture to prepare an acrylic emulsion can be, for example, a semi-batch emulsion polymerization method.

Hereinafter, the manufacturing method of one embodiment of the present invention will be described with reference to the exemplary emulsion polymerization apparatus of Fig.

Specifically, in the semi-batch emulsion polymerization method, the ion exchanged water and the pH buffer material are added to the reactor 10, and the mixture is mixed with the stirrer and the nitrogen gas introduced from the nitrogen gas storage unit 20 is introduced. The reactor temperature is raised to 80 to 85 캜, and when the reactor temperature reaches a certain temperature, a catalyst aqueous solution is added and the reaction solution is prepared by stirring. In this case, uniformity of the copolymer particles produced through emulsion polymerization can be further improved.

Next, an appropriate amount of ion-exchanged water is added to a mixture of a phosphorus emulsifier, a phosphorus (meth) acryl monomer, a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms and a (meth) acrylic monomer having a carboxyl group, Add to the prepared reaction solution. The reaction solution may be slowly added for about 180 to 240 minutes and then aged for one hour so that all the unreacted monomers can be polymerized. In this case, the uniformity and the generation rate of the copolymer particles can be further improved.

Ammonia water may be added to the aged mixture to adjust the pH to 7.0 to 7.5 so that an acrylic emulsion can be finally prepared. In this case, the adhesive property of the acrylic emulsion thus prepared and the stability to the user can be further improved.

When the acrylic emulsion is prepared by the above-described method, the emulsion can further improve the reactivity and particle uniformity, thereby realizing excellent adhesive property.

The flame retardant pressure-sensitive adhesive composition according to the present invention can be prepared by mixing 5 to 30 parts by weight of the phosphorus-based flame retardant described above with 100 parts by weight of the acrylic emulsion prepared by the above-mentioned production method.

The flame-retardant pressure-sensitive adhesive composition according to the present invention may further contain additives such as a defoaming agent, a leveling agent, a thickener, an antiseptic, a freezing stabilizer, a plasticizer, a pigment and a filler.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

Example 1

19 g of ion-exchanged water and 0.3 g of sodium acetate were simultaneously added to the reactor, and the temperature of the reactor was raised to 80 캜. When the temperature of the reactor reached 80 캜, a solution prepared by dissolving 0.3 g of ammonium persulfate in 1.0 g of ion-exchanged water was added to the reactor and stirred for 3 minutes. After 3 minutes, 16 g of ion-exchanged water and 0.6 g of phosphorus anion emulsifier (RHODAFAC RS-610, RHODIA), 29 g of 2-ethylhexyl acrylate, 8 g of butyl acrylate, 12 g of ethyl acrylate, 6 g of methyl methacrylate, , 1.7 g of SIPOMER PAM-100 (Phosphate esters of polyethylene glycol monomethacrylate) and 0.5 g of methacrylic acid was added to the reactor over a period of 180 to 240 minutes, followed by aging for 1 hour. Ammonia water (28%) was added to the reactor to adjust the pH of the reactant to 7.0 to prepare an acrylic emulsion.

A flame-retardant pressure-sensitive adhesive composition was prepared by mixing 15 parts by weight of an addition type phosphorus flame retardant (cyclic phosphonate) to 100 parts by weight of the acrylic emulsion.

Example 2

Phosphorus monomer SIPOMER PAM-100: An experiment was carried out in the same manner as in Example 1 except that SIPOMER PAM-200 was used instead of Phosphate esters of polyethylene glycol monomethacrylate.

Example 3

An experiment was carried out in the same manner as in Example 1 except that LIGHT ESTER P-1M (2-Methacryloyloxyethyl acid phoshate) was used instead of the phosphorus monomer SIPOMER PAM-100.

Component (unit: parts by weight) Example 1 Example 2 Example 3 Ion-exchange water 40.6 40.6 40.6 Sodium acetate 0.3 0.3 0.3 Phosphorus anion emulsifier (RHODAFAC RS-610) 2.0 2.0 2.0 Ammonium persulfate 0.5 0.5 0.5 2-ethylhexyl acrylate 25.0 25.0 25.0 Butyl acrylate 10.0 10.0 10.0 Ethyl acrylate 6.0 6.0 6.0 Methyl methacrylate 5.0 5.0 5.0 Vinyl acetate 3.0 3.0 3.0 SIPOMER PAM-100 7.0 SIPOMER PAM-200 7.0 LIGHT ESTER P-1M 7.0 Acrylic acid 0.6 0.6 0.6 TOTAL 100 100 100 Phosphorous flame retardant (cyclic phosphonate) 15 15 15

Comparative Example 1

An experiment was conducted in the same manner as in Example 1 except that butyl acrylate was used in place of the phosphorus monomer SIPOMER PAM-100.

Comparative Example 2

An experiment was carried out in the same manner as in Example 1 except that RHODAPEX CO-436, a non-phosphorous anionic emulsifier, was used in place of phosphorous anionic emulsifier (RHODAFAC RS-610).

Comparative Example 3

An experiment was conducted in the same manner as in Comparative Example 2 except that butyl acrylate was used in place of the phosphorus monomer SIPOMER PAM-100.

The components used in Comparative Examples 1 to 3 are shown in Table 2 below.

Component (unit: parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Ion-exchange water 40.6 40.6 40.6 Sodium acetate 0.3 0.3 0.3 Phosphorus anion emulsifier (RHODAFAC RS-610) 2.0 0 0 Anionic emulsifier (RHODAPEX CO-436) 0 2.0 2.0 Ammonium persulfate 0.5 0.5 0.5 2-ethylhexyl acrylate 25.0 25.0 25.0 Butyl acrylate 17.0 10.0 17.0 Ethyl acrylate 6.0 6.0 6.0 Methyl methacrylate 5.0 5.0 5.0 Vinyl acetate 3.0 3.0 3.0 PAM-100 0 7.0 0 Acrylic acid 0.6 0.6 0.6 TOTAL 100 100 100 Phosphorous flame retardant (cyclic phosphonate) 15 15 15

≪ Evaluation of physical properties &

The properties of the flame-retardant pressure-sensitive adhesive compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated in accordance with KS T 1028: 2009. The flammability test was carried out in accordance with UL-94 regulations. Table 3 shows the results of physical property evaluation.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 adhesiveness
(kgf / in) 1140 1120 1250 1240 1100 1115 retention 0mm 0mm 0mm 0.5mm 0.5mm 0.5mm ball tack
(ball #) 6 6 5 6 6 6 Flammability VTM-1 VTM-1 VTM-0 Not gradable Not gradable Not gradable

It can be seen from Table 3 that the flame retardant pressure-sensitive adhesive compositions of Examples 1 to 3 of the present invention had the same physical properties as those of the pressure-sensitive adhesives of Comparative Examples 1 to 3, which do not contain phosphorus-based emulsifiers and phosphorus monomers, I could.

Claims (10)

(A) from 0.5 to 10% by weight of a phosphorus emulsifier, from 10 to 30% by weight of a phosphorus (meth) acryl monomer, from 55 to 85% by weight of a (meth) acrylic monomer having an alkyl group having from 1 to 14 carbon atoms, 100 parts by weight of an acrylic emulsion containing 0.5 to 5% by weight of a (meth) acrylic monomer having a copolymer; And
(B) 5 to 30 parts by weight of an addition type phosphorus flame retardant,
Wherein the phosphorus-based emulsifier is a phosphate ester compound represented by the following formula (1), and the phosphorus-based (meth) acrylic monomer is a compound represented by the following formula (2)
[Chemical Formula 1]

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylaryl group having 6 to 20 carbon atoms, R ₂ is hydrogen or -CH ₂ CH ₂ OR ₁ , and n is an integer of 1 to 20;
(2)

In Formula 2, R ₃ is hydrogen or a methyl group; m is an integer from 0 to 10; p is an integer from 0 to 3; q is an integer from 0 to 3; X and Y are each independently a substituted or unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon having 5 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms .
delete delete The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylic monomer having an alkyl group of 1 to 14 carbon atoms is at least one selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, lauryl methacrylate, isooctyl acrylate, Acrylate, methacrylate, ethyl methacrylate, ethyl methacrylate, and butyl methacrylate,
Wherein the flame-retardant pressure-sensitive adhesive composition further comprises at least one of styrene, acrylonitrile and vinyl acetate.
[3] The copolymer according to claim 1, wherein the copolymer further comprises at least one of a (meth) acrylic monomer having a hydroxy group and a polyfunctional (meth) acrylic monomer;
The (meth) acrylic monomer having a hydroxy group includes at least one of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate,
The polyfunctional (meth) acrylic monomer may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, Di (meth) acrylate, and allyl methacrylate.
The flame-retardant pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylic monomer having a carboxyl group comprises at least one of (meth) acrylic acid, itaconic acid and maleic acid.
The flame-retardant pressure-sensitive adhesive composition according to claim 1, wherein the flame-retardant pressure-sensitive adhesive composition further comprises a tackifier resin.
The phosphor according to claim 1, wherein the phosphorus flame retardant is selected from the group consisting of cyclic phosphonate, isopropylated triaryl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, tricyclyl phosphate, triphenyl phosphate, butylated triaryl phosphate, Wherein the flame retardant adhesive composition comprises at least one selected from the group consisting of sodium bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), ammonium polyphosphate, and phosphorus polyol.
(Meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, and from 55 to 85% by weight of a (meth) acrylic monomer having a carboxy group, ) Acrylic monomer in an amount of 0.5% by weight to 5% by weight to prepare an acrylic emulsion; And
Mixing 5 parts by weight to 30 parts by weight of the additive phosphorus flame retardant with 100 parts by weight of the acrylic emulsion prepared above; Lt; / RTI >
Wherein the phosphorus-based emulsifier is a phosphate ester compound represented by the following formula (1), and the phosphorus-based (meth) acrylic monomer is a compound represented by the following formula (2)
[Chemical Formula 1]

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkylaryl group having 6 to 20 carbon atoms, R ₂ is hydrogen or -CH ₂ CH ₂ OR ₁ , and n is an integer of 1 to 20;
(2)

In Formula 2, R ₃ is hydrogen or a methyl group; m is an integer from 0 to 10; p is an integer from 0 to 3; q is an integer from 0 to 3; X and Y are each independently a substituted or unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon having 5 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms .
The method according to claim 9, wherein the step of preparing the acrylic emulsion by the emulsion polymerization comprises: preparing a reaction solution by stirring ion-exchanged water, a pH buffer substance and an aqueous catalyst solution in a reactor, reacting the reaction solution with the mixture, And neutralizing the resultant with ammonia water.

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