KR20200094327A - an adhesive composite and an urethane adhesive with flame resistance and the method of the urethane adhesive - Google Patents

Abstract

The present invention relates to a non-toxic adhesive composition having no harm to a human body and no problem of stability, a moisture-curing one-component urethane adhesive using the non-toxic adhesive composition, and a method of manufacturing the moisture-curing one-component urethane adhesive. According to the present invention, the method of manufacturing the moisture-curing one-component urethane adhesive includes: performing a primary reaction by inserting methylene diisocyanate (MDI) and polypropylene glycol (PPG); performing a secondary reaction by sequentially adding 1,3 butylene glycol (BD); adding dibutyltin dilaurate (DBDTL) to accelerate the reaction; performing stirring after adding a non-toxic adhesive composition; and adding an additive such as an antioxidant, a curing catalyst and the like.

Description

Non-toxic adhesive composition and moisture-curable one-component urethane adhesive using the same and a method for manufacturing the same {an adhesive composite and an urethane adhesive with flame resistance and the method of the urethane adhesive}

The present invention relates to an adhesive composition as a solvent applied to a flame retardant adhesive and an adhesive using the same, and more particularly, to a non-toxic adhesive composition and a moisture-curable one-component urethane adhesive using the same and a method for manufacturing the same.

Adhesives have been used for a variety of marking, retention, protection, sealing and shielding applications. Adhesive tapes generally include a backing or substrate and an adhesive. Pressure sensitive adhesives, a type of adhesive, are particularly useful for many applications.

Polyurethane adhesives are not only suitable for bonding complex structures, but also have excellent adhesion to various materials such as paper, glass, iron plates, and synthetic resins, and physicochemical properties such as chemical resistance, durability, sound absorption, dimensional stability, and elongation. Because of its excellent properties, it is useful as an adhesive for interior and exterior walls and floors of buildings. For example, in a lightweight honeycomb sandwich panel used as a wall of a building, a skin layer made of aluminum, iron, or the like is attached to the upper and lower parts of a honeycomb core made of aluminum, paper, synthetic resin, or the like with a polyurethane adhesive. In addition, a polyurethane sheet is used to adhere a decorative sheet or the like to a substrate such as plywood or particle board to improve the appearance and durability of the panel.

In such an architectural panel, a flame retardant can be easily provided by adding a flame retardant to a core, a substrate, or a skin layer, or by preparing a core, a substrate, etc. with a flame retardant material, but it is practical to impart flame retardancy to the polyurethane adhesive itself Has not been implemented.

The polyurethane adhesive can be divided into two-part type and one-part type. In the case of a two-part polyurethane adhesive, an isocyanate-terminated urethane prepolymer (main component) formed by polymerization of an isocyanate and a long chain polyol, and a mixture of an aromatic amine-based curing agent and a polyol (curing agent component, if necessary, catalysts such as organic metal, lead, etc.) A plasticizer is added) separately, and this is mixed at a construction site according to a prescribed mixing ratio, and then applied to a target object and hardened. These two-part polyurethane adhesives not only need to manage the two components separately, but also need to control the mixing and construction time of the main component and the curing agent component well, and are prone to defects in construction. There is this.

On the other hand, the one-component polyurethane adhesive is a one-component adhesive component by adding a filler, stabilizer, colorant, etc. to a urethane prepolymer obtained by polymerizing polyol and isocyanate, and is a moisture-curable type that is cured by moisture when exposed to the atmosphere. It is an adhesive. Since the one-component polyurethane adhesive is a single composition containing all necessary components, there is an advantage in that it is convenient to use and construct. However, since each component reacts during storage, or because polarity or solubility is different from each other, phase separation of components lacking compatibility is likely to occur, and thus, it is difficult to select each component and manage the mixed composition.

When a conventional flame retardant is mixed with such a polyurethane adhesive composition, the flame retardant is not uniformly dispersed, so that a substantial flame retardant effect cannot be obtained or adhesiveness is deteriorated. In the case of a two-part polyurethane adhesive in which the main agent and the curing agent are separated, since the flame retardant can be relatively stably dispersed, it is known that it is possible to obtain a flame retardant grade 3, but in the case of a one-component moisture-curable polyurethane adhesive, impart flame resistance The situation is going through great difficulties.

Patent Publication No. 10-2016-0096250 (flame-retardant polyurethane adhesive composition and flame-retardant panel for construction using the same, hereinafter prior art) is "50 to 70% by weight of a urethane prepolymer produced by polymerization reaction of polyol and polyisocyanate; curing of the urethane prepolymer 0.1 to 0.5% by weight of a curing agent for accelerating; 4 to 20% by weight of a chlorinated hydrocarbon organic solvent selected from the group consisting of dichloromethane, trichloroethylene and mixtures thereof; and 25 to 45 of expanded graphite having an average diameter of 80 to 300 μm It provides a flame retardant polyurethane adhesive composition containing a weight%, and the moisture content is 1% by weight or less.

In addition, the present inventor has proposed a registered patent 10-1910831 (moisture-curable one-component urethane adhesive with enhanced flame retardancy and a method for manufacturing the same, hereinafter prior art) to solve the above-mentioned problems of the prior art.

The above-described prior art of the present inventor is a moisture-curable one-component urethane adhesive with enhanced flame retardancy, and exhibits an effect of significantly increasing flame retardancy compared to the prior art and the prior art.

In addition, the prior art of the present inventor has the advantage that the effect of the adhesive force does not decrease at all, although the flame retardancy is significantly increased.

However, the above-mentioned prior art has a problem of harmfulness and stability of the human body because it is toxic even after being completed with a one-component urethane adhesive after the work hazard by applying ethylene acetate as a diluting solvent,

The present invention is to provide a non-toxic adhesive composition having no problem of harmfulness and stability to the human body by using a non-toxic solvent, and a moisture-curable one-component urethane adhesive having enhanced flame retardancy using the same and a method for manufacturing the same.

The present invention to solve the above object and needs,

As a solvent used for moisture-curing one-component urethane adhesives,

Isopropyl Myristate, Isopropyl Lanolate, Isopropyl Stearate, Isopropyl Alcohol, Isopropyl Isostearate, Isopropyl Paraben Paraben) or isopropyl palmitate (isopropyl Palmitate) alone or by mixing two or more to provide a non-toxic adhesive composition.

In addition, the present invention is the process of the primary reaction by introducing MDI (methylene diisocyanate) and PPG (polypropylene glycol) (1 step),

The process of performing secondary reaction by sequentially adding 1,3 BD (Butylene Glycol) as a chain extender for strengthening adhesion and crosslinking reaction (2nd step),

Process to accelerate the reaction by adding the reaction catalyst DBDTL (dibutyltin dilaurate) (3 steps),

The process of stirring after introducing the non-toxic adhesive composition of claim 1 (step 4),

Provided is a method for manufacturing a moisture-curable one-component urethane adhesive, which includes performing a process of adding an additive such as an antioxidant and a curing catalyst (step 5).

In addition, the present invention provides a moisture-curable one-component urethane adhesive prepared by the above method.

The above-mentioned prior art has a problem of harmfulness and stability of the human body because it is toxic even after being completed with a one-component urethane adhesive in the future by applying ethylene acetate as a diluting solvent, and later,

The non-toxic adhesive composition as a solvent used for the moisture-curable one-component urethane adhesive according to the present invention has no harmfulness in work and thus ensures stability, and is toxic even after being completed with a one-component urethane adhesive in the future. This has the effect of significantly lowering.

In addition, the moisture-curable one-component urethane adhesive using the non-toxic adhesive composition according to the present invention uses a non-toxic solvent, so there is no problem of harmfulness and stability of the human body, and an adhesive strength is significantly increased.

1 is a flow chart of a method for manufacturing a moisture-curable one-component urethane adhesive using a non-toxic adhesive composition according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a non-toxic adhesive composition as a solvent used in a moisture-curable one-component urethane adhesive.

In addition, the present invention provides a moisture-curable one-component urethane adhesive comprising the non-toxic adhesive composition described above and a method for manufacturing the same.

In addition, the present invention provides a moisture-curable one-component urethane adhesive prepared by the above-described manufacturing method.

The method of manufacturing the moisture-curable one-component urethane adhesive of the present invention is performed by the method described below.

The present invention performs a first reaction process by introducing MDI (methylene diisocyanate) and PPG (polypropylene glycol) into the reaction tank.

The input amount is 100 to 200 parts by weight of PPG (polypropylene glycol) to 100 parts by weight of MDI (methylene diisocyanate). More preferably, it is efficient to mix 140 parts by weight of PPG (polypropylene glycol) to 100 parts by weight of MDI (methylene diisocyanate).

In the case of adding the above material, the reaction vessel temperature is first heated to 50 degrees or more, preferably 60° C., and then MDI is added to completely dissolve it.

In order to synthesize the adhesive of the moisture-curable urethane of the present invention, it is necessary to use most of the prepolymer form due to the reaction of PPG (polypropylene glycol) and MDI (methylene diisocyanate), the main raw materials of urethane.

At this time, it is preferable to use a polypropylene glycol having an OH group having a molecular weight of 1000 to 2000 and a viscosity of 150 to 250 having a bifunctional group.

In the case of MDI (methylene diisocyanate) described above, it is preferable to use a product having a NCO content of 33%, a specific gravity of 1.25, and a purity of 99% or more.

In the present invention, after confirming that MDI is completely dissolved in the above process, PPG (polypropylene glycol), which is a polyol, is gradually added according to the above weight parts.

The above-described MDI (methylene diisocyanate) and PPG (polypropylene glycol) are introduced to perform a primary reaction for 20 to 60 minutes, preferably about 30 minutes.

After performing the above-described process, the present invention performs a secondary reaction by sequentially adding 1,3 BD (Butylene Glycol) as a chain extender for strengthening adhesion and crosslinking reaction. (2 courses)

Preferably, the 1,3 BD (Butylene Glycol) is 0.5 to 5 parts by weight, more preferably 1.5 to 2.5 parts by weight, even more preferably 2.0, based on 100 parts by weight of the primary reaction mixture described above. It is good to mix by weight.

The present invention performs the process of accelerating the reaction by adding the reaction catalyst DBDTL (dibutyltin dilaurate) after the chain extender is added.

The reaction catalyst DBDTL (dibutyltin dilaurate) is 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.03 parts by weight, and even more preferably 0.02 parts by weight based on 100 parts by weight of the primary reaction mixture. to be.

After the reaction catalyst is added, the reaction is performed for 2 hours or more, and preferably 2 hours or 30 minutes.

The present invention performs a process of stirring by introducing a non-toxic adhesive composition as a solvent after the second reaction described above.

Preferably, after the second reaction described above, the reactor temperature is reduced to about 70°C or less, preferably about 60°C, and a non-toxic adhesive composition is added and then stirred.

The technical feature of the present invention is the above-mentioned solvent, which is conventionally applied to ethylene acetate, so that it is toxic even after being completed with a one-component urethane adhesive in the future. It is to produce a moisture-curable one-component urethane adhesive having enhanced flame retardancy by using a non-toxic adhesive composition having no problems of harmfulness and stability as a solvent.

The non-toxic adhesive composition of the present invention is isopropyl Myristate, isopropyl Lanolate, isopropyl Stearate, isopropyl Alcohol, isopropyl isostearate ( It means that isopropyl isostearate, isopropyl paraben or isopropyl palmitate alone.

In addition, the non-toxic adhesive composition of the present invention is isopropyl Myristate, isopropyl Lanolate, isopropyl Stearate, isopropyl Alcohol, isopropyl isostearate (isopropyl isostearate), isopropyl paraben (isopropyl palmitate) means that a mixture of two or more isopropyl palmitate.

The mixing ratio of the non-toxic adhesive composition is 80 to 120 parts by weight of isopropyl lanoleate based on 80 to 120 parts by weight of isopropyl Myristate, 80 to 120 parts by weight of isopropyl stearate Parts, 80 to 120 parts by weight of isopropyl alcohol, 80 to 120 parts by weight of isopropyl isostearate, 80 to 120 parts by weight of isopropyl paraben, isopropyl palmitate ) 80 to 120 parts by weight of the composition is good,

In the above-mentioned non-toxic adhesive composition of the present invention, isopropyl myristate is a compound of isopropanol (a type of alcohol) and myristic acid. Because of its good absorption through the skin, it is used in cosmetics and external medicines such as topical skin ointments. In addition, it is a solubilizer for perfumes, and a bacteria-removing agent parasitic to tooth decay. It is also used as a flea repellent for pets.

Particularly, the present invention not only significantly improves the adhesive strength but also significantly lowers the harmfulness of the human body when preparing the moisture-curable one-component urethane adhesive by adding the above-mentioned non-toxic adhesive composition as a solvent. The environment is improved and worker safety is significantly increased.

The present invention is preferably performed after the second reaction described above, the reactor temperature is reduced to 70° C. or less, preferably about 60° C., and 10-15% of the non-toxic adhesive composition is added, followed by stirring for 15-25 minutes. Again, 10 to 15% of the non-toxic adhesive composition is added, and agitation is performed again for 25 to 35 minutes.

The present invention performs the process of adding the above non-toxic adhesive composition and then performing a stirring process, followed by a process of adding additives such as an antioxidant and a curing catalyst.

The present invention performs the process of adding the above non-toxic adhesive composition and then stirring to complete the reaction, and then adding an additive such as an antioxidant or a curing catalyst while maintaining 55 to 70 degrees, preferably 60 degrees. To complete the process of completing the moisture-curable one-component urethane adhesive.

Antioxidants of the present invention include phenol-based, organic sulfur-based, hindered phenol-based, hindered amine-based, and organic phosphorus-based antioxidants.

Overall, as hindered phenolic antioxidants, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or n-octadecyl-3-(3 And 5-di-tert-butyl-4-hydroxyphenyl)propionate. Examples of the organic phosphorus antioxidant include tris(2,4-di-tert-butylphenyl)phosphite. Among them, from the viewpoint of obtaining high reliability, it is preferable to use a hindered phenolic antioxidant.

In the present invention, the above-mentioned pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or n-octadecyl-3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propionate to 2,6-di-tert-butyl-para-cresol, tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate) ]Methane, 2,4-bis(n-octylcio)-6-(4'-hydroxyl-3',5'-di-tert-butylanilino)-1,3,5-triazine, 2, 4-bis[(oxdilio)methyl]-ortho-cresol, triethylene glycol-bis-3-(3'-t-butyl-4'-hydroxy-5'-methylphenyl)propionate, p-cresol Butyrate reactant, one or more of dicyclopentadiene tri(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite (tris(2,4-di-tert- butylphenyl)phosphite), bis(2,4,-di-tert-butylphenyl)pentaerythritol diphosphite (bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphate) and distearyl pentaerythritol diphosphite (distearyl pentaerythritol diphosphate) contains one or more antioxidants, including more than one, it has the effect of significantly improving the antioxidant effect.

It is preferable that content of antioxidant in the adhesive composition of this invention is 0.05-5 weight part with respect to 100 weight part of reactive MDI (methylene diisocyanate).

When the content of the antioxidant is 0.05 parts by mass or more, the adhesive composition has high reliability after moisture curing, and if it is 5 parts by mass or less, the storage stability of the adhesive composition tends to be excellent.

The curing catalyst of the present invention may be a conventional curing catalyst.

As the amine catalyst used in the curing catalyst of the present invention, amines can be widely used, for example, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, and tri-tert-butyl Monoamines such as amine, triamylamine, trihexylamine, trioctylamine, tri 2-ethylhexylamine, methyl di-2-ethylhexylamine, dibutyl 2-ethylhexylamine, trihexadecylamine, tribenzylamine Polyamines such as tetramethyl 1,2-diaminoethane, tetramethyl 1,3-diaminopropane, tetramethylhexamethylenediamine, and pentamethyl diethylene triamine; triethylenediamine; N-ethyl morpholine, bis(mor) Polynoethyl) ether, bis(2,6-dimethylmorpholinoethyl) ether, bis(3,5-dimethylmorpholinoethyl) ether, bis(3,6-dimethylmorpholinoethyl) ether, 4- And morpholine compounds such as (3,5 dimethylmorpholino)-4'-(3,6-dimethylmorpholino) diethyl ether.

In addition, as the tin catalyst used in the curing catalyst, a known organotin compound can be widely used, for example, divalent organotin compounds such as tin octylate and tin naphthenate; dibutyltin dioctate, dibutyltin Dilaurate, dibutyltin diacetate, dibutyltin dimalate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin dibasatate, dibutyltin oxide, dibutyltin bis(triethoxy Silicates), tetravalent organic tin compounds such as reactants of dibutyltin oxide and phthalic acid esters; tin-based chelators such as dibutyltin bis(acetylacetonate)

And yttrium compounds.

The curing catalyst of the present invention may be used alone or in combination of the above-mentioned amine catalyst and tin catalyst.

The present invention has an effect of significantly improving the efficiency of the curing catalyst by significantly mixing the above-described curing catalyst with cyclohexyl diisocyanate and isophorone diisocyanate, thereby significantly increasing the curing rate.

Although the mixing ratio of the curing catalyst of the present invention is not particularly limited, it is preferable to blend 0.01 to 2 parts by mass of 100 parts by weight of the reactive MDI (methylene diisocyanate),

The present invention thus completed is a moisture-curable urethane adhesive, and is a reactive urethane adhesive in which the NCO functional group of isocyanate remaining in the adhesive reacts with moisture in the air to form a crosslink to generate adhesion.

In particular, the present invention is a urethane adhesive composed of a one-component type, and is composed of an adhesive solid and a solvent (solvent), and in particular, the non-toxic adhesive composition described above as a solvent (solvent) is harmless to the human body and has high safety, thereby significantly improving work efficiency. It is characterized by letting.

The one-component moisture-curable urethane adhesive of the present invention exhibits properties among properties and has a solid content, and in the present invention, the solid content is 70-80% urethane adhesive and 20-30% is composed of a solvent that is a non-toxic adhesive composition. .

The present invention provides a non-toxic adhesive composition having the above-described configuration and function, and a moisture-curable one-component urethane adhesive using the same and a method for manufacturing the same.

The present invention is very useful in the industry of producing, manufacturing, selling, distributing and researching a non-toxic adhesive composition as a solvent used in a moisture-curable one-component urethane adhesive.

In particular, the present invention is very useful in the industry for producing, manufacturing, selling, distributing, and researching a moisture-curable one-component urethane adhesive containing the non-toxic adhesive composition described above.

Claims (3)

As a solvent used for moisture-curing one-component urethane adhesives,
Isopropyl Myristate, Isopropyl Lanolate, Isopropyl Stearate, Isopropyl Alcohol, Isopropyl Isostearate, Isopropyl Paraben paraben) or isopropyl palmitate (isopropyl Palmitate) alone or a mixture of two or more non-toxic adhesive composition.
MDI (Methylene Diisocyanate) and PPG (Polypropylene Glycol) are introduced to perform the first reaction (1 step),
The process of performing the secondary reaction by sequentially adding 1,3 BD (Butylene Glycol) as a chain extender for strengthening adhesion and crosslinking reaction (2 steps),
Process to accelerate the reaction by adding the reaction catalyst DBDTL (dibutyltin dilaurate) (3 steps),
The process of stirring after introducing the non-toxic adhesive composition of claim 1 (step 4),
A method of manufacturing a moisture-curable one-component urethane adhesive, comprising performing a process of adding an additive such as an antioxidant or a curing catalyst (step 5).
A moisture-curable one-component urethane adhesive prepared according to claim 2.

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