KR102042249B1 - Expandable resin particles having semi-fireproof performance and method for manufacturing the same - Google Patents

Abstract

Expandable resin particles having semi-fireproof performance and a manufacturing method thereof, according to one embodiment of the present invention, may include a step of spraying expanded graphite powder on the thermoplastic expandable resin particles. The present invention can improve the adhesion in the process of coating fireproof materials.

Description

Expandable resin particles having semi-fireproof performance and method for manufacturing the same

The present invention relates to a foamable resin particle having a semi-non-flammable performance and a method for producing the same, and more particularly, to a method for producing the foamable resin particles having a semi-non-flammable performance.

Expandable polystyrene (EPS) is produced by adding a foaming agent to a polystyrene resin, and is subjected to a processing process such as foaming and molding to become styrofoam. Styrofoam is widely used in various industrial fields such as packaging materials, insulation materials, sound absorbing materials, building materials, etc., because of its lightness and excellent thermal insulation, sound insulation, water resistance and cushioning properties.

Meanwhile, according to the Enforcement Decree of the Building Act, the building material having more than six non-combustible finish materials should be used for buildings having six or more floors. However, polystyrene foam has a disadvantage in that it is weak in heat, and various methods for improving the heat resistance and flame resistance of polystyrene foam have been attempted.

As part of the prior art, Korean Patent No. 10-1332431 discloses a flame retardant foam in which a styrene resin, a char-generated thermoplastic resin, and an inorganic foam particle are mixed to extrude a mixed composition, and the extruded pellets are aqueous suspended in a reactor to impregnate a foaming agent. Disclosed is a method for producing polystyrene beads, and Korean Laid-Open Patent Publication No. 10-2015-0173148 discloses a melt containing a blowing agent, which is extruded through a die plate of an extruder having a hole of 1 to 2.5 mm, and then granulated in water. Disclosed is a method for producing expandable polystyrene particles having a polystyrene particle having a particle size of 1.5 to 4.0 mm and containing pores having a size of 0.1 to 100 μm.

However, most of the flame-retardant expanded polystyrene prepared according to the prior arts have a flame retardant performance of less than semi-combustible (grade 3 flame retardant), and products that satisfy the semi-combustible (flame retardant grade 2) performance have not been published until now. In addition, the expanded polystyrene foam having a flame retardancy produced according to the prior art has a limit that the mechanical properties, including lowering the fusion of the molded article is lowered due to molecular weight reduction, decomposition of additives, etc. during the manufacturing process.

가열하여 열가소성 수지 입자에 표면에 불연 단열성 막을 형성시키고 있다.In addition, Korean Patent Laid-Open Publication No. 10-2012-0061364 discloses a method for preparing expanded resin particles in which non-flammable and insulating films are formed on thermoplastic foamed resin particles.

By heating, a non-combustible heat insulating film is formed on the surface of the thermoplastic resin particles.

Korean Patent Publication No. 10-2015-0173148 Korean Patent Publication No. 10-2012-0061364 Korean Patent Publication No. 10-2012-0005122

One aspect of the present invention provides a foamed resin particles having a semi-combustible performance by coating a non-combustible material on the foamed resin particles in a state before foaming, and a method of manufacturing the same.

Another aspect of the present invention provides a foamable resin particle having a semi-combustible performance that can improve the adhesion in the coating process of a non-combustible material and a method of manufacturing the same.

The technical problem of the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Foamable resin particles having a semi-non-flammable performance according to an embodiment of the present invention and a method for producing the same may include the step of spraying the expanded graphite powder on the thermoplastic foamable resin particles.

In the spraying the expanded graphite powder on the thermoplastic foamable resin particles, 51 to 100 parts by weight of the expanded graphite powder having a particle diameter of 150 ~ 300μm to 100 parts by weight of the thermoplastic foamable resin particles having a particle diameter of 0.2mm ~ 3.0mm ,

Stirring the thermoplastic expandable resin particles sprayed with the expanded graphite powder at 30 to 3000 rpm to form a flame retardant coating layer on the surface layer of the expandable resin particles; And

Further comprising mixing and coating 0.05 to 50 parts by weight of the adhesive resin selected from the group consisting of epoxy, phenol, vinyl acetate and combinations of at least two kinds of materials to the resin particle surface layer,

The flame retardant coating layer, the intermediate layer consisting of the expanded graphite powder; And an outer layer laminated on upper and lower surfaces of the intermediate layer, the outer layer including linear low density polyethylene (LLDPE),

The outer layer further comprises a functional additive including low density polyethylene (LDPE) and synthetic silica,

An adhesive composition is applied between the intermediate layer and the outer layer,

The adhesive composition, 40 to 80 parts by weight of thermoplastic resin, 5 to 40 parts by weight of tackifying resin, 1 to 5 parts by weight of rosin, 1 to 10 parts by weight of plasticizer, 1 to 10 parts by weight of filler, 0.1 to 1 parts by weight of antioxidant And 0.1 to 5 parts by weight of nanosilica.

According to one aspect of the present invention described above, the present invention can adhesively coat a large amount of heat-insulating and non-combustible materials on the fine spherical particles of the foamed resin particles that are not foamed, and the coated materials are not detached during the foaming process. Without uniform coating, the flame retardancy of the foamable resin can be improved.

DETAILED DESCRIPTION The following detailed description of the invention refers to the accompanying drawings that show, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein may be embodied in other embodiments without departing from the spirit and scope of the invention in connection with the embodiments. In addition, it is to be understood that the location or arrangement of individual components within each disclosed embodiment may be changed without departing from the spirit and scope of the invention. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention, if properly described, is defined only by the appended claims, along with the full range of equivalents to which such claims are entitled.

Hereinafter, preferred embodiments of the present invention will be described in more detail.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to thermoplastic resin particles and foamed particles in which a non-flammable and heat insulating film is formed. The resin particles used can be used as a resin that can be foamed by forming the particles into a thermoplastic resin softened by heat, and is not limited in the type of resin, foaming agent and foaming method.

Thermoplastic resins that can be used in the present invention include, for example, olefin resins, polyester resins, aromatic vinyl resins, acrylic resins, vinyl chloride resins, and homopolymers or hybrid polymers of two or more kinds thereof may be used. . α-olefin polymers include 1-butene, 1-pentene, 1-hexene and 1-octene, ethylene-propylene interpolymers, Ethylene-propylene-dicyclo-pentadiene interpolymers, ethylene-propylene-1,4-hexadiene and the like. Acrylic acid and -aromatic vinyl-based interpolymers include styrene- (meth) acrylic acid interpolymers, styrene-methyl (meth) acrylate interpolymers, styrene-maleic anhydride interpolymers, styrene-butadiene interpolymers, methyl methacrylate, meta Ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and aromatic vinyl monoamine p-methylstyrene, 2,4-dimethylstyrene, p-methoxystyrene , pn-butylstyrene, pt-butylstyrene, p-chlorostyrene, 2,4,6-tribromostyrene, o-chlorostyrene, m-chlorostyrene, styrenesulfonic acid, sodium styrene sulfonate, styrene, α-methylstyrene The mixed polymer with o-methyl styrene and m-methyl styrene, and the vinyl chloride polymer include, for example, vinyl acrylates, vinyl caproate, and vinyl carboxylates having 2 to 8 carbon atoms such as methyl acrylate and methyl methacrylate. Ethylene, Olefins such as 1-pentene, arylglycidyl ether, glycidyl methacrylate, isobutyl vinyl, octyl vinyl, and the like and hybrid polymers, and the present invention is limited to polymers of thermoplastic resins as described above. It is not.

The present invention is to form a non-flammable and heat insulating film on the surface layer of the foamable thermoplastic resin particles having a particle size of 0.2 mm to 3.0 mm in the non-foamed state prepared by the polymerization method or the extrusion method. Specifically, the thermoplastic foamability of the particle diameter of 0.2 mm to 3.0 mm Spraying 51 to 100 parts by weight of expanded graphite powder having a particle size of 150 to 300 μm to 100 parts by weight of resin particles, and stirring the thermoplastic expandable resin particles sprayed with the expanded graphite powder at 30 to 3000 rpm to be flame retardant to the surface layer of the expandable resin particles. It may comprise the step of forming a coating layer.

In order to give further improved flame retardant performance to a resin particle, a well-known flame retardant can be contained in a particle surface layer. For example, it can select from a halogen compound, an antimony oxide, a phosphorus compound, and a chlorine compound, and can use 1 type individually or in mixture of 2 or more types. The flame retardant may be coated by spraying on the resin particles before coating the non-flammable and heat insulating powder, or by mixing and coating the powder, or by spraying on the resin particles in a step in which the powder penetration fusion coating is completed. In some cases, the powder may be mixed and coated on a binder after the penetration fusion coating of the powder is completed. The flame retardant composition ratio is 0.1 to 2 parts by weight of hexabromo cyclododecane (HBCD), which is a halogen compound, and 0.1 to 10 parts by weight of antimony oxide, which is 0.1 to 10 parts by weight. It is 1-10 weight part and 0,1-10 weight part is preferable for paraffin chloride (70 weight% chlorine) which is a chlorine-type flame retardant.

The non-flammable, heat-insulating powder and flame retardant of the present invention may penetrate into the particle surface layer and perform steam molding, thermoforming, and extrusion molding of the resin particles coated with fusion. If it is a resin particle which does not foam as a final purpose, it can shape | mold by foaming again in a desired magnification. For example, the foamed polystyrene resin particles may be first foamed at 30 to 50 times and then steamed or thermoformed through a secondary foaming process at a desired magnification. 50 parts by weight may be sprayed onto 100 parts by weight of the foamed resin particles, and the coating may be repeatedly fused. In addition, it can be molded by repeatedly adhesive coating while spraying 0.05 to 50 parts by weight of the adhesive resin binder to the non-flammable heat insulating powder and sprayed onto the foamed resin particles. The adhesive resin binder may be selected from the group consisting of epoxy, phenol, vinyl acetate, and combinations of at least two kinds thereof. The nonflammable and heat insulating powder thus prepared penetrates into the particle surface layer and the molded article of the fused coated foamed resin particles has excellent nonflammable and heat insulating properties.

In addition, it is possible to coat with an adhesive resin binder as necessary to improve the moldability and adhesion to the resin particles of the powder penetration fusion coating is completed. The amount of the binder to be used is 0.1 to 20 parts by weight (based on solids) of the weight of the coated resin particles, and the amount of the binder is preferably used to 0.1 to 10 parts by weight (based on the solids). If it is less than 0.1 part by weight, the effect is weak, and if it is 10 parts by weight or more, there is a disadvantage in that flame retardancy is reduced and manufacturing cost is increased.

The coating amount of the non-flammable and heat insulating powder is 51 to 100 parts by weight, preferably 51 to 70 parts by weight based on 100 parts by weight of the expandable resin particles. If it is more than this range, the mechanical properties of the final molded product is lowered, the effect of increasing the nonflammability and heat insulation is insignificant.

In the present invention, the powder is preferably selected from non-combustible powders and powders that improve thermal insulation properties, and the ratio of 5: 1 to 10: 1 for non-combustible purposes is 1: 2 to 1: 4 for thermal insulation purposes. It is preferable to mix and use. The powder used in the present invention is sprayed onto the resin particle surface layer without being heated, and the powder penetrates into the resin particle surface layer to form a nonflammable and heat insulating film. Can be used.

After spraying the flame-retardant expanded graphite powder, a hot melt resin binder may be sprayed. Since the melted and injected resin binder has a function of curing, adhering and coating, the non-combustible and heat-insulating powder penetrates into the coated resin particles and improves the action of fusion coating. The resin binders that can be used are melted and cured by non-combustible and heat-insulating powder and heat, and can be adhesively coated on resin particles which are to be coated together with non-combustible and heat-insulating powder. It can be selected from the group consisting of a system and a combination of at least two kinds of these.

Hereinafter, the configuration and the effect thereof of the expandable resin particles having a semi-non-flammable performance of the present invention through specific examples and comparative examples will be described in more detail. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

Example 1

50 parts by weight of expanded graphite powder was sprayed onto 100 kg of expandable polystyrene particles (SH Energy Chemical SE-2000) before foaming, and then stirred at 1000 rpm to prepare expandable resin particles having a semi-combustible performance.

On the other hand, Comparative Examples 1 and 2 were prepared in the same manner as in Example 1, but was prepared by spraying 30, 40 parts by weight of expanded graphite powder, respectively, Examples 2, 3, 4 were prepared in the same manner as in Example 1, but expanded Graphite powder was prepared by spraying differently at 60, 70, and 80 parts by weight, respectively.

As can be seen from the above table, when the expanded graphite powder is sprayed to 50 parts by weight or less, it can be seen that the semi-non-combustible performance standards are insufficient.When the expanded graphite powder is sprayed to 70 parts by weight or more, the semi-non-combustible performance standards are met but sprayed. It can be seen that the improvement effect is insignificant compared to Example 1 relative to the amount.

On the other hand, in some other embodiments, the flame-retardant coating layer formed on the surface layer of the expandable resin particles according to the present invention is an intermediate layer consisting of expanded graphite powder, respectively laminated on the upper and lower surfaces of the intermediate layer, an outer layer comprising linear low density polyethylene (LLDPE) It may include.

The intermediate layer may preferably be made of 100 parts by weight of expanded graphite powder, but may be used in combination with ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), LLDPE, mLLDPE, and the like. Even in this case, the intermediate layer preferably contains at least 50 parts by weight of expanded graphite powder for sufficient flame retardancy improvement.

전후) 이상에서는 재료가 산화되고, 강도가 낮아 취급시 부주의로 인한 파손이 쉽다는 문제점이 있다. 본 발명은 이러한 문제를 해결하기 위하여 외부층에 개량된 기능성 첨가제가 혼합되는 것을 특징으로 하며, 이는 이하에서 자세히 설명한다. At this time, when the coating layer is formed of the expanded graphite powder alone, the critical temperature (typically 400) in the oxidative atmosphere (air, carbon dioxide, water, etc.)

Before and after), there is a problem that the material is oxidized, and the strength is low, so that damage caused by careless handling is easy. The present invention is characterized in that the improved functional additive is mixed in the outer layer to solve this problem, which will be described in detail below.

In some other embodiments, the intermediate layer may be a mixture of 50 to 70 parts by weight of expanded graphite powder and 30 to 50 parts by weight of downconversion phosphor powder that is excited from ultraviolet light and emits red visible or infrared light. have.

Down conversion phosphor refers to the interaction between photons and media that absorb light with high energy wavelengths (photons) and emit light with low energy wavelengths. That is, the downconversion phosphor may be a phosphor that absorbs ultraviolet rays having a high energy wavelength in the light source when it is irradiated, and is excited from the absorbed ultraviolet rays and emits visible or infrared rays having an energy wavelength lower than that of the ultraviolet rays.

The downconversion phosphor according to the present invention may be either a ceramic phosphor or an organic phosphor material in an inorganic form.

The ceramic phosphor in the inorganic form may include a Y ₂ O ₂ S: Eu phosphor or a Y ₂ O ₃ : Eu phosphor. That is, the flame-retardant coating layer formed on the surface layer of the expandable resin particles according to an embodiment of the present invention, the expanded graphite powder and the Y ₂ O ₂ S: Eu phosphor or any one of the down-conversion phosphor Y ₂ O ₃ : Eu phosphor It may include an intermediate layer contained in the form of a powder.

The Y ₂ O ₂ S: Eu ceramic phosphor is a structure in which Y ₂ O ₂ S is doped with europium (Eu) as an activator. Y ₂ O ₂ S: Eu ceramic phosphor powder is a downconversion phosphor that absorbs ultraviolet rays of about 220-400 nm wavelength and emits red visible light (630 nm = 1.97 eV) and infrared light (713 nm = 1.74 eV). The Y ₂ O ₃ : Eu ceramic phosphor powder is a structure in which yttrium trioxide (Y ₂ O ₃ ) is doped with europium (Eu) as an activator. In particular, Y ₂ O ₂ S: Eu ceramic phosphor powder can be obtained by the antibacterial and antiseptic effect due to the sulfur (S) component contained in the phosphor.

Inorganic ceramic phosphor powder can absorb light of about 360nm wavelength very effectively, and it is excited from absorbed ultraviolet rays and emits not only the main emission wavelength (red visible) of about 630nm but also the long wavelength of 713nm (infrared). By doing so, the infrared divergence effect is excellent.

,7′'-dimethyloctyloxy)-1,4-phenylenevinylene]) 중 어느 하나일 수 있다. On the other hand, the organic phosphor is PPV (Poly (1,4-phenylene vinylene)), Poly (thiophenes), Poly (2,5-pyridinevinylene), PFO (Polyfluorenes), BODIPY (boron-dipyrromethene) fluorophore, dithienotropylium, ABPX (aminobenzopyrano) -xanthene) induced structure and MEH-PPV (poly (2-methhoxy-5- (2-ethylhexyloxy) -1,4-pheneylenevinylene) derived from PPV) and MDMO-PPV (Poly [2-methoxy-5- ( 3

, 7 ′ '-dimethyloctyloxy) -1,4-phenylenevinylene]).

That is, the foamable resin particles prepared according to the method of manufacturing the expandable resin particles according to an embodiment of the present invention may be formed with a flame-retardant coating layer containing any one of downconverting phosphors of an organic phosphor or an inorganic phosphor in powder form. However, the type of the phosphor is not limited to the above-described example, and may further include various organic materials or inorganic materials emitting red visible light or near infrared light.

As described above, the flame-retardant coating layer formed on the surface layer of the expandable resin particles according to an embodiment of the present invention, the expanded graphite powder and the down-conversion phosphor of any one of the Y ₂ O ₂ S: Eu phosphor or Y ₂ O ₃ : Eu phosphor Comprises an intermediate layer contained in powder form, and the Y ₂ O ₂ S: Eu ceramic phosphor powder or Y ₂ O ₃ : Eu ceramic phosphor powder contained in the intermediate layer absorbs ultraviolet light, which is a relatively high energy wavelength, It can emit red visible or infrared light.

Accordingly, after the flame-retardant coating layer according to an embodiment of the present invention is formed on the surface layer of the expandable resin particles, when the light source is irradiated to the expandable resin particles, the downconversion phosphor formed on the intermediate layer absorbs ultraviolet rays and emits red visible light. It is easy to visually identify whether the temporary flame retardant coating layer is evenly formed on the surface of the expandable resin particles.

The linear low density polyethylene (LLDPE) constituting the outer layer serves to impart tensile strength and workability to the flame retardant coating layer. In one embodiment, a metallocene-based linear low density polyethylene (mLLDPE) may be used. The weight average molecular weight (Mw) of the LLDPE is 90,000 to 110,000, the molecular weight distribution (GPC) is 2.5 to 2.8, the density is 0.918 or less, generally having a density of 0.912 ~ 0.928g / cm 3 can be used.

In addition, the outer layer may further include 0.1 to 20 parts by weight of POP (polyolefin elastomer) or POE (polyolefin elastomer) based on 100 parts by weight of the linear low density polyethylene (LLDPE).

On the other hand, as mentioned above, the outer layer further includes 0.1 to 10 parts by weight of the functional additives to 100 parts by weight of the linear low density polyethylene (LLDPE) functional additives to improve physical properties such as opening properties and slip properties. In this case, the functional additive may include low density polyethylene (LDPE) and synthetic silica, and may further include a dispersant, an antioxidant, and the like, as necessary.

The low density polyethylene of the functional additive serves as a solvent for the other components of the additive, the synthetic silica serves to improve the overall opening and slip properties of the packaging material, 5 ~ 30 compared to 100 parts by weight of the low density polyethylene (LDPE) It is preferable to use by weight. When the content of the synthetic silica is less than 5 parts by weight, it is difficult to improve the opening properties and slip properties, and when it is more than 30 parts by weight, the physical properties of the packaging material may be lowered.

At this time, the average particle size of the synthetic silica is preferably 13 ~ 17㎛. In general, the particle size of the additive component used in the packaging material is 5 ~ 7㎛, the present invention is expanded graphite powder alone using synthetic silica having a large particle size of about 2 times the existing of 13 ~ 17㎛ as an additive component Even if an intermediate | middle layer is comprised, workability, such as opening property and slipperiness | lubricacy, can be prevented from falling.

In addition, the silica particles may be used in general, all commonly used silica particles, preferably silica particles surface-treated with a silicone oil may be used to further increase the miscibility.

In this case, the silicone oil is not particularly limited and known ones may be used without limitation, and specifically, dimethyl silicone oil, methylphenol silicone oil, and methyl hydrogen silicone oil. silicone oil), amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, carbinol modified silicone oil, polyether modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil and the like.

The viscosity of the silicone oil is not particularly limited, but it is preferable to use 20 to 500 cSt. If the viscosity is smaller than this, the silicone oil tends to be volatile, and if larger, the treatment tends to be uneven.

The method of surface treatment with silicone oil is not particularly limited, but a wet method of dissolving silicone oil in a solvent such as toluene, dispersing silica particles in the solvent and evaporating the solvent to attach the silicone oil to the surface of the silica particles, A dry method of spraying silicone oil on the silica particles to attach the silicone oil to the surface of the silica particles, and performing a predetermined heat treatment may be used.

The content of the silicone oil adhering to the surface of the silica particles is preferably 2 to 4% by weight based on the silica particles. When smaller than this, it is difficult to play a role of increasing the degree of miscibility, and when larger than this, the silicon particles may aggregate.

Meanwhile, the additive may further include 1 to 5 parts by weight of a dispersant based on 100 parts by weight of low density polyethylene (LDPE), and the dispersant may help to disperse the synthetic silica well, and is generally used for various packaging materials. Dispersants may be used.

In addition, the additive may further comprise 0.1 to 3 parts by weight of antioxidant based on 100 parts by weight of low density polyethylene (LDPE).

The flame-retardant coating layer of the three-layer structure having such a configuration can be manufactured by co-extrusion, etc., the thickness of the intermediate layer occupies 40-60% of the total coating layer thickness, the thickness of the upper and lower outer layers are each 20-30 of the total coating layer thickness Will take%.

Hereinafter, the configuration and the effects thereof of the flame retardant coating layer having a three-layer structure of the present invention through specific examples and comparative examples will be described in more detail. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

[Examples and Comparative Examples]

의 용융 압출온도에서 공압출 방식으로 용융압출하였다. 이후 냉각 온도에서 냉각시켜 중간층과 상하 외부층의 두께비가 2:1:1인 3층 구조의 난연성 코팅층을 제조하였다. 1) The intermediate layer is composed of the expanded graphite powder alone, the outer layer is prepared by kneading in a screw mixer in the composition of Table 1, 130 ~ 180

Melt extrusion was carried out by co-extrusion method at the melt extrusion temperature. After cooling at a cooling temperature to prepare a flame-retardant coating layer of a three-layer structure having a thickness ratio of the middle layer and the upper and lower outer layers of 2: 1: 1.

까지 가열한 후, 개방 상태에서 점도 50cSt의 디메틸 실리콘 오일을 실리카 입자의 12wt% 가량 첨가하였다. 이후 유체 노즐을 이용하여 분무한 후, 분위기와 온도를 유지한 상태에서 1시간 교반하여 실리콘 오일이 표면 처리된 실리카 입자를 얻었다.2) On the other hand, in the case of Example 2, the silica particles were placed in a mixer vessel in a nitrogen atmosphere while stirring and 270

After heating to, dimethyl silicone oil having a viscosity of 50 cSt was added at about 12 wt% of the silica particles in an open state. Thereafter, after spraying using a fluid nozzle, the mixture was stirred for 1 hour while maintaining the atmosphere and temperature to obtain silica particles having the silicone oil surface treated.

Experimental Example

The sheets prepared in Examples and Comparative Examples were cut to prepare specimens, and measured and evaluated for the following physical properties. Tensile strength was measured by ASTM D638.

As shown in Table 3, the coating layer of the three-layer structure of the present invention has a high elongation and restoring force to significantly improve the flame retardancy and at the same time improve the openness and slip properties has a high workability.

On the other hand, the adhesive composition according to the present invention may be applied between the layers forming the flame retardant coating layer according to the present invention.

Adhesive composition according to an embodiment of the present invention, the adhesive composition formed between each layer to bond the layer and the layer, 40 to 80 parts by weight of thermoplastic resin, 5 to 40 parts by weight of tackifier resin, 1 to 5 rosin It includes weight part, plasticizer 1-10 weight part, filler 1-10 weight part, and antioxidant 0.1-1 weight part. The present invention is a hot melt adhesive composition, in detail look at each component below.

The thermoplastic resin serves as a main component of the composition to control adhesion and cohesion. If the type includes a vinyl group or a hydroxyl group, the type thereof is not particularly limited, and examples thereof include ethylene vinyl acetate copolymer, polyvinylacetate, polyvinyl alcohol, ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, and polyurethane. It may be composed of any one or more selected from the group consisting of.

The content of the thermoplastic resin is preferably 40 to 80 parts by weight based on the total composition. If the content is less than 40 parts by weight, the melt viscosity is high and the melt flow index is low, the workability is very poor, if the content is more than 80 parts by weight it is difficult to exert sufficient adhesive force to be applied directly to the fabric.

The tackifier resin is a low molecular weight resin, lowers the melt viscosity to improve workability, improves the initial wettability of adhesion and adhesion of the adhesive on the surface of the adherend, and enables control of the solidification time.

The tackifying resin is not particularly limited in kind, but is preferably a petroleum resin. More specifically, the tackifier resin may be composed of one or more selected from the group consisting of aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, aromatic hydrocarbon-modified aliphatic hydrocarbon resins, and hydrogenated hydrocarbon resins.

The aliphatic hydrocarbon resins are commercial products such as Hikorez A-1100, Hikorez A-1100S, Hikorez C-1100, Hikorez R-1100, Hikorez R-1100S, and the like. In addition, alicyclic hydrocarbon resins include hydrocarbon resins containing dicyclopentadiene (DCPD) as monomers, and aromatic hydrocarbon resins are commercially available from Kolon Oil Co., Ltd. of Hikotack P-110S, Hikotack P-120, Hikotack P-120HS, Hikotack P-120S, Hikotack P-140, Hikotack P-140M, Hikotack P-150, Hikotack P-160, Hikotack P-90, Hikotack P-90S, Hirenol PL-1000, Hirenol PL-400. In addition, aromatic hydrocarbon-modified aliphatic hydrocarbon resins include Hikorez T-1080, Hikorez T-1100, etc. of Kolon Oils. Hydrogenated hydrocarbon resins can also be subdivided into hydrogenated aliphatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, and the like, and commercially available from Kolon Oil, Sukorez D-300, Sukorez D-390, Sukorez SU-100, Sukorez SU-110, Sukorez SU-120, Sukorez SU-130 and Sukorez SU-90.

The tackifier resin is preferably a hydrocarbon resin having 4 to 10 carbon atoms in the monomer, and specifically, a C5 aliphatic resin, a C9 aromatic resin, a C5 / C9 aliphatic / aromatic copolymer resin, or the like may be used.

In addition, the tackifying resin of the present invention is more preferably characterized in that the hydrogenated hydrocarbon resin containing a dicyclopentadiene as a monomer, commercially available from Sukorez D-300, Sukorez D-390, Kolon Emulsifier (Korea), Sukorez SU-100, Sukorez SU-110, Sukorez SU-120, SukorezSU-130 and Sukorez SU-90.

On the other hand, the adhesive composition of the present invention is preferably used by mixing the biodegradable hypoallergenic resin together with the various petroleum resins described above.

The biodegradable hypoallergenic resin may be prepared by melt-mixing a monomer of a polymer into a biodegradable polymer, and polylactic acid is preferably used as the biodegradable polymer.

The polylactic acid is a polyester synthesized by polycondensation of lactate or ring-opening polymerization of lactide, and has a medium physical property between polyamide and polyethylene terephthalate, and is mainly made of natural vegetable sugar components obtained from potatoes and corn. Biodegradability is high, but generally has high hardness, low elasticity, and poor durability.

The biodegradable polymer is melt-mixed with the same polymer monomer, wherein the biodegradable polymer is partially bonded with the monomer to cause chain breakage, thereby lowering the overall number average molecular weight. As the number average molecular weight falls, the physical properties that can be used as an adhesive are exhibited, and the workability is increased.

With respect to 100 parts by weight of the polylactic acid, the lactic acid monomer may be mixed 20 to 30 parts by weight. When the monomer is mixed in less than 20 parts by weight, the number average molecular weight is high and hard to be used as a pressure-sensitive adhesive, when the monomer exceeds 40 parts by weight migration may occur on the surface and may also be difficult to use as an adhesive.

It is preferable that the mixing ratio of the petroleum resin and the biodegradable hypoallergenic resin is 1 to 2: 1 (w / w). When the mixing ratio of the petroleum resin is too high, the biodegradable hypoallergenic effect is less likely to occur. If the mixing ratio is too high, economic efficiency may be lowered and the overall adhesive effect may be lowered.

In addition, the content of the tackifying resin is preferably 5 to 40 parts by weight relative to the total composition. If the content is less than 5 parts by weight, the effect of lowering the melt viscosity due to the addition of the tackifying resin is insufficient, and there is a fear that the increase in the melt flow index is not so large that the workability may not be satisfactorily reached, and the content is more than 30 parts by weight. If the melt flow index increase rate due to the excess of the tackifier resin is not large, the economical efficiency is lowered and the content of the thermoplastic polymer is relatively reduced, thereby reducing the overall physical properties of the composition.

The rosin acts to improve the overall adhesion of the adhesive composition and is harmless to the human body and acts as a natural preservative. The content of the rosin is preferably 1 to 5 parts by weight based on the total composition. If the content is less than 1 part by weight, it is difficult to obtain an effect of improving the adhesive strength, and if the content exceeds 5 parts by weight, there is a problem in that the adhesion is increased during processing and processing into the product becomes difficult.

The plasticizer is used to impart flexibility and adhesion to the polymer, and the type of plasticizer according to the present invention is not particularly limited, and for example, sorbitol, ethylene glycol, glycerin, glycerin diacetate, and pentaerythritol It may consist of one or more selected from the group consisting of.

The amount of the plasticizer is preferably 1 to 10 parts by weight based on the total composition. If the content is less than 1 part by weight, the effect of the addition of the plasticizer is insignificant. If the content is more than 10 parts by weight, the economical efficiency may be reduced by excessive use of the plasticizer, and there is a concern that the overall physical properties of the adhesive may be lowered.

The filler is used to control the reinforcement and flow of the composition. The type of filler is not particularly limited, and for example, calcium carbonate, clay, bentonite, calcium stearate or the like can be used.

On the other hand, the adhesive composition of this invention is easy to generate | occur | produce bad smell and bacteria on application environment. Therefore, in order to reduce the odor and bacteria generation while controlling the reinforcement and flow of the adhesive composition, it is preferable to use a mixture of stone powder and pulp powder as a filler. Stone powder can achieve high strength without using additives due to the compactness of the particles, and the cracking of the adhesive hardly occurs even when the temperature change is large due to low volumetric strain according to the surrounding environment.

The stone powder may be used in the form of powder of various rocks such as loess, marble, ganban stone, granite, jadeite, preferably characterized in that the loess has various functions such as antibacterial, anti-fungal, UV emission.

The pulp powder serves to agglomerate the stone powders while sucking the liquid components, to improve the miscibility and improve the cohesion between the components. At this time, the stone powder and the pulp powder is preferably mixed in a ratio of about 7: 3 to 8: 2 (w / w).

The content of the filler is preferably 1 to 10 parts by weight based on the total composition. If the content is less than 1 part by weight, the effect of adding the filler is insignificant, and if the content is more than 10 parts by weight, there is a concern that the overall physical properties of the adhesive may be lowered.

The antioxidant is intended to improve the change in viscosity, yellowing, deterioration of adhesion and degradation of durability due to oxidation and decomposition, and the type thereof is not particularly limited, and specifically, phenols, aromatic amines, citric acid, or ascorbic acid may be used. Can be.

The content of the antioxidant is preferably 0.1 to 1 parts by weight relative to the total composition. If the content is less than 0.1 parts by weight, the effect of the addition of the antioxidant is inadequate, and if the content is more than 1 part by weight, not only the economy of the adhesive is lowered but also the overall physical properties may be lowered.

In addition, the adhesive composition of the present invention may further include nano silica that can improve the adhesion of the adhesive composition. At this time, the content of the nano silica is preferably 0.1 to 5 parts by weight, and the size of the nano silica (primary particles) is preferably 100 nm or less.

If the content of the nano-silica is less than 0.1 parts by weight, the effect of the addition of nano-silica is insignificant, and if the content exceeds 5 parts by weight, not only the adhesive force is lowered but also a bad phenomenon that blooming (blooming) occurs on the surface of the adhesive over time May occur.

Hereinafter, the configuration of the present invention and its effects through specific examples and comparative examples will be described in more detail. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

Example 1

에서 용융혼련시켜 접착제 조성물을 제조한 후 펠렛 타입으로 성형하였다. 이때, 상기 생분해성 저자극 수지는 폴리락트산 100중량부에 락트산 단량체 2.5중량부를 160

로 5분동안 용융혼합하여 제조하였다.60 parts by weight of ethylene-vinylacetate copolymer, 25 parts by weight of Sukorez D-300, 3 parts by weight of rosin, 5 parts by weight of ethylene glycol, 4 parts by weight of ocherite, 2 parts by weight of pulp powder and 1 part by weight of ascorbic acid

Melt kneading at to prepare an adhesive composition and then molded into pellets. At this time, the biodegradable hypoallergenic resin is 2.5 parts by weight of lactic acid monomer 160 parts by weight of polylactic acid 160

It was prepared by melt mixing for 5 minutes.

 Example 2

에서 용융혼련시켜 접착제 조성물을 제조한 후 펠렛 타입으로 성형하였다. 이때, 상기 생분해성 저자극 수지는 폴리락트산 100중량부에 락트산 단량체 2.5중량부를 160

로 5분동안 용융혼합하여 제조하였다.60 parts by weight of ethylene-vinylacetate copolymer, 15 parts by weight of Sukorez D-300, 10 parts by weight of biodegradable hypoallergenic resin, 3 parts by weight of rosin, 5 parts by weight of ethylene glycol, 4 parts by weight of loess, 2 parts by weight of pulp powder and ascorb 170 ~ 180 by mixing 1 part by weight of acid

Melt kneading at to prepare an adhesive composition and then molded into pellets. At this time, the biodegradable hypoallergenic resin is 2.5 parts by weight of lactic acid monomer 160 parts by weight of polylactic acid 160

It was prepared by melt mixing for 5 minutes.

Example 3

Except for adding 1 part by weight of nanosilica, it was prepared in the same manner as in Example 1, and was made as Example 3.

 [Comparative Example]

It was used after removing the backing paper from the conventional TPU hot melt film.

Experimental Example

(1) Mesh adhesive strength

에서 용융 도포한 후, 130

에서 30초 동안 60㎏f/㎠의 압력으로 프레스 작업을 진행하고 메쉬접착강도(㎏f/㎠)를 측정하였다. In order to evaluate the mesh adhesive strength of the hot melt adhesive, the adhesive pellet quantified between two sheets of fabric was applied.

After melt coating at 130

Press work at a pressure of 60 kgf / ㎠ for 30 seconds at and measured the mesh adhesive strength (kgf / ㎠).

 (2) Melt Flow Index

에서 약 5분간 녹였다. 3㎏의 추를 얹고 10분간 실린더를 통해 통과되는 접착제의 중량(g)을 측정하였다.Fill the heating cylinder of the melt flow rate meter with the pellet-type adhesive 160

Dissolved for about 5 minutes. The weight (g) of the adhesive passed through the cylinder for 10 minutes was measured by putting a weight of 3 kg.

As can be seen from the table, it was confirmed that the adhesive composition of the present invention has improved adhesion and flow index than the existing product, even when using a biodegradable hypoallergenic resin it was confirmed that the adhesion and flow index does not fall significantly. Also, when the nano-silica is mixed, the flow index can be seen to increase significantly.

Although described above with reference to the embodiments, those skilled in the art will understand that various modifications and changes can be made without departing from the spirit and scope of the invention as set forth in the claims below. Could be.

Claims (2)

Spraying expanded graphite powder on the thermoplastic expandable resin particles,
In the spraying the expanded graphite powder to the thermoplastic foamable resin particles, 51 to 100 parts by weight of the expanded graphite powder having a particle size of 150 ~ 300μm to 100 parts by weight of the thermoplastic foamable resin particles having a particle diameter of 0.2mm ~ 3.0mm ,
Stirring the thermoplastic expandable resin particles sprayed with the expanded graphite powder at 30 to 3000 rpm to form a flame retardant coating layer on the surface layer of the expandable resin particles; And
Further comprising mixing and coating 0.05-50 parts by weight of the adhesive resin selected from the group consisting of epoxy, phenol, vinyl acetate and combinations of at least two kinds of materials to the resin particle surface layer,
The flame retardant coating layer, the intermediate layer consisting of the expanded graphite powder; And an outer layer stacked on top and bottom surfaces of the intermediate layer, the outer layer including linear low density polyethylene (LLDPE),
The outer layer further comprises a functional additive comprising low density polyethylene (LDPE) and synthetic silica,
An adhesive composition is applied between the intermediate layer and the outer layer,
The adhesive composition, 40 to 80 parts by weight of thermoplastic resin, 5 to 40 parts by weight of tackifying resin, 1 to 5 parts by weight of rosin, 1 to 10 parts by weight of plasticizer, 1 to 10 parts by weight of filler, 0.1 to 1 parts by weight of antioxidant And 0.1 to 5 parts by weight of nano-silica, characterized in that the method for producing expandable resin particles having a semi-combustible performance.
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