KR101188321B1 - Eco-friendly moisture-curing polyurethane resin composition and a method thereof - Google Patents

Abstract

The present invention relates to a moisture-curable (one-component) polyurethane resin composition, the composition comprising a bifunctional or more than two functional isocyanate compound and a polyol as an active ingredient, in addition to the chain to improve the adhesion and mechanical properties And extenders, crosslinkers, diluents, catalysts, and the like, and may further include functional additives, hygroscopics, fillers, and the like to obtain storage stability reinforcement and extender effects.
Moisture-curable (one-component) polyurethane resin composition according to the present invention has good adhesion, shorten the solidification time, excellent workability as well as less harmful to the human body as a medicinal solvent, due to skin irritation or environmental hormone Eco-friendly with little impact, it can be applied to various industries such as automobile, aircraft, high speed train, ship, building, house interior / floor elastic adhesive, building paint, adhesive, sealing agent (CAS).

Description

ECO-FRIENDLY MOISTURE-CURING POLYURETHANE RESIN COMPOSITION AND A METHOD THEREOF}

The present invention relates to a moisture-curable polyurethane resin composition for an environment-friendly elastic adhesive and a method for producing the same, and more particularly comprises a bifunctional or more isocyanate compound and a polyol as an active ingredient, in addition to the adhesive and mechanical properties Moisture-curable (one-component) polyurethane resin composition containing a chain extender, a crosslinking agent, a diluent, a catalyst, and the like, and further comprising a functional additive, a moisture absorbent, a filler, and the like to obtain storage stability reinforcement and an increase effect. And to a method for producing the same.

Structural elastic adhesives used for fixing windshields such as automobiles, aircrafts, high-speed trains, ships, etc., which are subject to strong air pressure and vibration caused by high-speed movement, or high-rise buildings exposed to strong natural environments such as typhoons, improve adhesion strength. In addition to the mechanical properties such as water resistance, weather resistance, thermal shock resistance improvement of long-term use stability, such as the ability to bond different materials with different properties, insulation, dielectric properties and conductivity is required.

Polyurethane-based elastic adhesive has a rigid structure (isocyanate bond structure) and a soft structure (polyol bond structure) in the internal structure, and excellent durability compared to other adhesives due to repeated repeated cycles of cold and hot, there is no irritating smell Rather, it is characterized by low noise generation.

As an adhesive for house interiors / floors, acrylic resins or epoxy resins have been used so far, but recently, polyurethanes have been used.

On the other hand, it is a vinyl chloride (PVC) tile / widely used as a building cladding material for schools, hospitals, offices, and mansions because of its advantages of easy construction, flooring and durability, and easy cleaning when contaminated. Sheet adhesives have generally been used two-component urethane and epoxy adhesives. However, since the two-component adhesive has the trouble of mixing the main agent and the curing agent, and there is a possibility of defects caused by the mixing ratio of the main / hardener or the mixing method error, the development of the one-component adhesive has recently been progressed.

In particular, the epoxy resin adhesive has a lot of restrictions on the construction conditions, such as the use of an amine-based curing agent, the smell is irritating and civil complaints from the residents as well as the surrounding people.

In addition, air pollution prevention and green movements such as new house / new school syndrome have boomed across the society, and organic solvent-based paints, adhesives, and sealing agents have used large amounts of aromatic diluents such as toluene and xylene. and the use of Sealants (CAS) are extremely regulated, and the development of eco-friendly CAS products such as solvent-free, water-based, high solids, and medicinal solvents is promising.

In response to this desire, in recent years, diluents for CAS have been used, such as ethyl acetate and butyl acetate, which have good solubility and relatively low toxicity.However, when a CAS product using an acetate diluent is applied to concrete, the ester compound is decomposed by alkaline substances. Therefore, calcium acetate, which is a white crystalline substance, is precipitated by reacting with calcium carbonate used as a filler, thereby causing a problem of damaging aesthetics.

After all, the present invention has been made to solve the above problems, the main object of the present invention is a structural paint, housing interior / flooring material that is severely subjected to strong air pressure and vibration as well as building paints, adhesives, sealing agents, etc. It is to provide a moisture-curable polyurethane resin composition for an environment-friendly elastic adhesive can be used and a method for producing the same.

In order to achieve the above object, the present invention provides a moisture-curable (one-component) polyurethane resin composition for an environment-friendly elastic adhesive and its manufacturing method.

Moisture-curable (one-component) polyurethane resin composition for an environment-friendly elastic adhesive of the present invention comprises a bifunctional or more than two functional isocyanate compound and a polyol as an active ingredient, in addition to the chain extender to improve the adhesion and mechanical properties , A crosslinking agent, a diluent, a catalyst, and the like, and further, a functional additive, a moisture absorbent, a filler, and the like may be further mixed to obtain storage stability reinforcement and an increase effect.

The moisture-curable (one-component) polyurethane resin composition for an eco-friendly elastic adhesive according to the present invention has a short solidification time, single-sided coating and sealing adhesion, and has excellent adhesive strength to a wide range of adhesive materials.

In addition, the moisture-curable (one-component) polyurethane resin composition for an eco-friendly elastic adhesive of the present invention is a medicinal solvent type, which emits little harmful organic compounds and is environmentally friendly with little effect on the human body by skin irritation or environmental hormones. As it reacts with moisture in the air and hardens, structural properties can be expressed, so structural elastic adhesives used for fixing windshields of automobiles, aircrafts, high-speed trains, ships, buildings, etc., as well as elastic adhesives for interior / floor materials of houses and buildings It is applicable to various industrial fields such as paints, adhesives and sealants.

Hereinafter, the present invention will be described in detail.

The present invention provides a moisture-curable (one-component) polyurethane resin composition for an environment-friendly elastic adhesive.

The moisture hardening type (one-component) polyurethane resin composition of this invention contains a bifunctional or more isocyanate compound and a polyol as an active ingredient.

The bifunctional or higher isocyanate compound is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI) aromatic isocyanates such as p-Phenylene Diisocyanate; It is preferable to use one or more selected from aliphatic isocyanates such as hexamethylene diisocyanate (HMDI), hydrogenated diphenylmethane diisocyanate (MDI), and isophorone diisocyanate, and more preferably. Is at least one selected from diphenylmethane diisocyanate (MDI) and polymeric diphenylmethane diisocyanate (MDI).

In addition, the polyol is an ester polyol (polycondensate of 3-methyl-1,5-pentanediol (3-methyl-1,5-pentanediol and adipic acid)), bifunctional polypropylene glycol (Polypropylene glycol, PPG), bifunctional polybutadien glycol (PBG), and bifunctional polyisoprene glycol (Polyisoprene glycol, PIG) is preferably at least one selected from.

In this case, the difunctional isocyanate compound and the polyol may be prepared and used as a prepolymer according to a method of synthesizing a conventionally known polyurethane.

Synthesis of the prepolymer in the present invention is a hydroxyl such as polyols, chain extenders, crosslinking agents and the like contained in the mole of the isocyanate compound and the curing agent so that the equivalent ratio (NCO / OH) of the isocyanate group and the hydroxyl group is in the range of 0.8 to 2.6 It is to be designed by adjusting the molar ratio of practical skills. At this time, when the isocyanate ratio is too high or too low, the mechanical properties required as the elastic adhesive are not obtained.

In the preparation of the polyurethane-based prepolymer according to the present invention, the polyol is preferably used by mixing polybutadiene glycol (PBG) or polyisoprene glycol (PIG) with polypropylene glycol (PPG), polybutadiene glycol (PBG) Alternatively, the double bonds present in the polyisoprene glycol (PIG) form a new double bond with the substrate, thereby increasing adhesion, and at the same time, a hard segment and a bifunctional polyol composed of difunctional isocyanate groups. It is possible to prepare an elastic adhesive in which soft segments composed of groups are hybridized uniformly.

In addition, when polybutadiene glycol (PBG) and polyisoprene glycol (PIG) are mixed with polypropylene glycol (PPG), the deterioration of polyethylene (PE) pipe can be significantly improved, and more preferably, polybutadiene glycol (PBG) or / and polyisopreneglycol (PIG) is preferably mixed with polypropylene glycol (PPG), where the incorporation rate of polybutadiene glycol (PBG) or polyisopreneglycol (PIG) is determined by the weight of polypropylene glycol (PPG) 1 to 15% is preferred. If the polybutadiene glycol (PBG) or polyisoprene glycol (PIG) incorporation rate is less than 1%, the adhesion promoting effect with the substrate is insufficient, and if it exceeds 15%, there is a risk of deteriorating the polyethylene hot water pipe.

In addition, the moisture-curable (one-component) polyurethane resin composition according to the present invention may change the physical properties according to the intended use, for this purpose, at least one selected from a chain extender, a crosslinking agent, a diluent, a catalyst, etc. when preparing the prepolymer. It may further include.

In the present invention, the chain extender is added to change the strength and hardness (elasticity) of the moisture-curable (one-component) polyurethane resin composition, and it is preferable to use one having two or more active hydrogen functional groups. Low molecular weight diols having 12 or more carbon atoms are mainly used, and 2-butyl-2-ethylpropane-1,3-diol having a hydroxyl group at both ends with a molecular weight of 1,000 to 3,000 is used as 2-Butyl-2-ethylpropane-1,3 -diol) and adipic acid is a polycondensation product of the alkylene side chain polyesterpolyol (Polyesterpolyol) is good to use. The polyesterpolyol having an alkylene side chain (Polyesterpolyol) is excellent in resistance to hydrolysis due to its molecular structure, and is easy to handle since it has a viscosity of 1 to 30 cps at room temperature.

At this time, the polyester polyol as a chain extender may be used alone or in the form of a mixture with other diols having 12 or less carbon atoms, the mixing ratio is preferably used 1 to 30% based on the polyol weight.

In addition, in the present invention, a crosslinking agent having 3 or 4 functional groups may be used to improve crosslinking between chains to increase mechanical strength. The crosslinking agent used in the present invention is glycerol, trimethylolpropane, pentaerythritol, trihydroxycyclohexane, tetra (2-hydroxyethyl) ethylenediamine, tetra (2-hydroxypropyl) having three or more active hydrogen functional groups. Ethylenediamine and oligomeric polyoxyalkylenepolyols having 3 to 4 functional groups. The crosslinking agent is used alone or in admixture with the polyol in the form of a mixture, where the mixing ratio is preferably 1 to 30% based on the polyol weight.

In the present invention, at least one of trimellitate ester, benzoic acid ester, ethylcyclohexane, 2,2,4-trimethyl-1,3-pentanediol diisobutylate and dimethyl carbonate (DMC) as a diluent. Can be used. The diluent is added to adjust the viscosity of the composition according to the intended use, of which ethylcyclohexane, 2,2,4-trimethyl-1,3-pentanediol diisobutylate is restricted in the environmental regulations, etc. When the elastic adhesive is installed, the self-leveling property is good even at low temperatures. In addition, when dimethyl carbonate (DMC) is used as the diluent, carbon dioxide and methyl alcohol are formed even when hydrolysis occurs in an alkaline atmosphere of calcium carbonate or concrete, and thus no crystalline substance is precipitated. In this case, the amount of the diluent is preferably 1 to 30% by weight of the polyol.

In addition, the present invention may include a catalyst. The catalyst is used to promote the reaction in the cold season, such as winter, tertiary amine, imidazole organometallic compound system is preferred. In this case, the amount is preferably 0.001 to 3.0% by weight of the polyol.

In addition, the composition of the present invention may be further mixed with a functional additive, a moisture absorbent, a filler and the like to increase the storage stability and obtain a reinforcing and increasing effect.

As the functional additive in the present invention, one or more selected from flame retardants, latent hardeners, antioxidants, dispersants, antifoaming agents, dyes, pigments, and the like are included.

Examples of the flame retardant include tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3-dichloropropine) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate Red antimony trioxide, arsenic trioxide, ammonium polyphosphate, and the like may be used in an amount of 5 to 25% by weight of the polyol. In addition, the latent curing agent may be catamine-based, aldimine-based, incosol-based, enamine-based, etc. The antioxidants include sodium / potassium / lithium halides, copper halides, hindered phenol, hydroquinone, etc. It should be controlled stoichiometrically according to the free-NCO% designed in the synthesis of the polymer. If the amount of the latent hardener is added less than the stoichiometric amount of free-NCO%, storage and curing delay phenomenon of the polyurethane resin composition occurs, and if it is added more than the stoichiometric amount, the economical efficiency is lowered. It is preferable to use at 3%.

In addition, the dispersant may be used a phosphate ester, a nonionic surfactant, an anionic surfactant, and the antifoaming agent may be a silicone-based and non-silicone-based. In addition, nigrosine may be used as the organic dye, and titanium dioxide, cadmium sulfide, cadmium selenide sulfide, phthalocyanine ultramarine blue, and carbon black may be used as pigments, and these may be 0.1 to 0.5% based on the polyol weight, respectively. It is preferable to use as.

In addition, in the present invention, the moisture absorbent may use zeolite (molecular sieve), silica, magnesium oxide, calcium oxide, barium oxide, incosol, toluidine isocyanate (TI), etc., and the amount of the moisture absorbent is 2 to 10% by weight of the polyol. good.

Further, fillers usable in the present invention include slag, silica fume, calcium carbonate, barium sulfate, and the like, which is preferably used at 2 to 35% by weight of the polyol.

The present invention also provides a method for producing a moisture-curable (one-component) polyurethane resin composition for an environment-friendly elastic adhesive.

The moisture-curable (one-component) polyurethane resin composition for an eco-friendly elastic adhesive according to the present invention is suitable for the use of paints, adhesives, and sealing agents by means well known in the art, and according to the purpose of use, viscosity, housework It is preferable to synthesize | combine time, workability, and hardening time suitably, and to mix a functional raw material with the synthesized prepolymer, and apply it directly to a use place, and to harden | cure by moisture in air | atmosphere.

In addition, the present invention can be added to the prepolymer containing an isocyanate optional diluents, catalysts and the like so that the mixture is easily mixed and physical properties.

In addition, functional additives, moisture absorbents, fillers, and the like, which are commonly used for storage stability, reinforcement, and an increase effect of the composition, may be further included, but are not limited to the kind and addition method thereof.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1.

950 g of bifunctional polypropylene glycol (PPG, Mn = 2,000), 50 g of bifunctional polyisopreneglycol (PIG, Mn = 2,500) and 421.5 g of diphenylmethane diisocyanate (MDI) are placed in a flask and The polyurethane prepolymer was prepared by reacting under a nitrogen stream for 3 hours.

To 250 g of the polyurethane prepolymer prepared above, 450 g of calcium carbonate, 450 g of dimethyl carbonate as a diluent, 10 g of clodall silica, 10 g of 3-glycidoxypropyltrimethoxysilane as a coupling agent, dibutyl tin dired ( DBTDL) 1.0 g and 1 g of dehydrating paratoluidine sulfonyl isocyanate (PTSI) were placed in a 5 L flask and stirred for 30 minutes, followed by degassing under reduced pressure at 50 to 100 hPa to obtain a moisture-curable (1 part type) polyureteran resin composition for an elastic adhesive. Got.

Example 2.

Polycondensate of 950 g of bifunctional polypropylene glycol (PPG, Mn = 2,000) with ester polyol (3-methyl-1,5-pentanediol) and adipic acid ) 25 g, 50 g of bifunctional polybutadiene glycol (PBG, Mn = 2,000) and 422.1 g of diphenylmethane diisocyanate (MDI) were placed in a flask and reacted under a nitrogen stream at 90 ° C. for 3 hours to prepare a polyurethane prepolymer. It was.

To 100 g of the polyurethane prepolymer prepared above, 90 g of calcium carbonate, 20 g of surface treated calcium carbonate, 1 g of paratoluidine sulfonyl isocyanate (PTSI), 2,2,4-trimethyl-1,3-pentanediol as a diluent 40 g of diisobutylate was placed in a 5 L flask and stirred for 30 minutes, followed by degassing under reduced pressure at 50 to 100 hPa to obtain a moisture-curable (1 part type) polyureteran resin composition for an elastic adhesive.

Experimental Example 1. Measurement of viscosity, pot life, hardness, tensile strength and tear strength

The resin compositions prepared in Examples 1 and 2 were measured using a Brookfile viscometer at room temperature for viscosity and pot life (times twice the initial viscosity), and after curing for 24 hours in a constant temperature room at 25 ° C. Hardness, tensile strength and tear strength were measured according to KS F ISO 3211.

Experimental Example 2. Adhesion Strength Measurement

The resin composition prepared in Examples 1 and 2 was applied to the slate plate with a comb-type trowel so that the coating amount was 550 g / m 2, and the wood soundproof flooring was bonded and left at 23 ° C. and 55% RH for 7 days, followed by peeling off the flooring. The adhesion state was evaluated in four steps as follows.

◎: Damage to the flooring material,

○: Damage to flooring material + Slate contact surface,

△: broken slate contact surface,

×: easily peeled off from the slate contact surface

Experimental Example 3. Measurement of Tensile Elongation

After splitting the cross-linked polyethylene (PE) pipe having a diameter of 7 mm and a length of 10 cm in half and cutting it into a dumbbell No. 3 type, the resin composition prepared in Examples 1 and 2 was applied to the center surface of each test body and cured at 23 ° C. for 1 day. Then, the resultant was allowed to stand at 140 ° C. air circulation rate 5 times / hour in a forced circulation oven for 600 hours and then taken out and stored at 23 ° C. indoor to measure the tensile elongation at a rate of 50 mm / min.

Tensile Elongation (%) = [Test specimen length at breakdown-initial specimen length) / Initial specimen length] × 100

The experimental results are shown in Table 1 below.

Evaluation item unit Example 1 Example 2 Assessment Methods Viscosity cps 10000 18000 Brookfiled Housework time min 35 32 Brookfiled Shore D - 45 85 KSFISO3211 The tensile strength N / mm < 2 & 25 53 KSFISO3211 Phosphorus strength N / mm 32 95 KSFISO3211 Adhesive strength - ○ ◎ - Tensile Elongation % 190 40 KSFISO3211

As described above, specific portions of the contents of the present invention have been described in detail, and for those skilled in the art, these specific techniques are merely preferred embodiments, and the scope of the present invention is not limited thereto. Will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (5)

To a one-component moisture-curable polyurethane resin composition for elastic adhesive comprising a bifunctional or more isocyanate compound and a polyol as an active ingredient, and further comprising at least one selected from a chain extender, a crosslinking agent, a diluent and a catalyst. In
Toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI), p-phenylene isocyanate (pDI) At least one bifunctional or higher isocyanate compound and ester selected from phenylene diisocyanate, hexamethylene diisocyanate (HMDI), hydrogenated diphenylmethane diisocyanate (MDI), and isophorone diisocyanate Polyols (polycondensates of 3-methyl-1,5-pentanediol and adipic acid), bifunctional polypropylene glycol (PPG), bifunctional At least one polyol selected from the group consisting of polybutadien glycol (PBG), and bifunctional polyisoprene glycol (PIG) is an example. Prepared and used as a pre-polymer, and mixed so that the equivalent ratio (NCO / OH) of the isocyanate group and hydroxyl group of the prepolymer is in the range of 0.8 to 2.6,
In addition to 2,2,4-trimethyl-1,3-pentanediol diisobutylate, dimethyl carbonate (DMC) and a diluent selected from these mixtures, characterized in that it comprises 1 to 30% by weight of the polyol Moisture-curable polyurethane resin composition for an eco-friendly one-component elastic adhesive. delete delete delete delete