KR101050266B1 - Photoluminescent molding composition using thermoplastic polyurethane elastomer and its manufacturing method - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding composition using a thermoplastic polyurethane. Specifically, a soft, low shrinkage thermoplastic polyurethane resin is synthesized and cured, and then pulverized and dried using a grinder and activated alkali with rare earth metal ions. It is a molding composition blended with an inorganic photoluminescent pigment, which is a complex of earth metal aluminate, and injected into an injection molding machine. It is a photoluminescent molding composition that has a low shrinkage rate and can be processed with thermoplastic. It can be used.
[Index]
Thermoplastic Polyurethane (TPU), elastomer, Shore hardness, photoluminescent pigment, weather resistance

Description

Luminous composite materials with thermoplastic Polyurethane Elastomer and a method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding composition using a thermoplastic polyurethane. Specifically, a soft, low shrinkage thermoplastic polyurethane resin is synthesized and cured, and then pulverized and dried using a grinder and activated alkali with rare earth metal ions. The present invention relates to a molding composition in which an inorganic photoluminescent pigment, which is a earth metal aluminate composite, is blended and injected into an injection molding machine.

Thermoplastic polyurethanes (hereinafter referred to as 'TPU') have long been known. These materials are widely used industrially because they have excellent mechanical properties and are processed with thermoplastic and have low price. TPU is synthesized with linear polyols (mostly polyester polyols or polyether polyols), diisocyanates and chain extenders. The TPU formation reaction can be reacted by adding a catalyst to improve the reaction rate. In order to control the properties of the formed product, including materials such as fillers, adjuvants, plasticizers, etc., to control the cold resistance, heat resistance, hydrolysis resistance, solvent resistance and the like. TPU can exhibit a variety of physical properties according to the type of raw materials and additives used in this way, as well as various uses thereof, and various compositions are being commercialized to meet the new demands of consumers.

TPU injection molded articles are used for mechanical parts, sneakers, ski shoes, and the like, and TPU extruded molded articles are used for hydraulic, pneumatic hoses, tubes, belts, films and sheets.

U.S. Patent No. 326818 introduces that thermoplastic polyurethanes prepared using methylene diisocyanate, polycarbonate polyols and polyether polyols first reacted with low molecular weight diols improve hydrolysis resistance, flowability and processability.

EP 034455 describes that TPUs with Shore A hardness of 60 to 80 can be obtained using plasticizers containing certain phthalates and phosphates.

EP 0695786 describes the addition of inorganic fillers to produce soft TPUs based on certain polyether / polyester mixtures and plasticizers comprising alkylsulfonic acid esters or benzylbutyl phthalate.

The methods are to change the reaction process or to produce a TPU by using a plasticizer. The US patent is excellent in formability, but it is difficult to produce a soft TPU, and the European Patents use a plasticizer to impart softness. Therefore, problems such as poor surface quality due to the surface migration of the plasticizer has a problem to be applied to various applications as a molding. The TPUs are products that are designed only for adjusting properties, and are not molded products including a phosphorescent pigment that can secure visibility even at night to impart functionality.

Accordingly, the present invention is to solve the problems of the prior art included in the prior art is soft and excellent in elastic modulus and excellent weatherability can be applied outdoors, luminous time and excellent luminous flux to ensure visibility even at night It is to provide a thermoplastic polyurethane photoluminescent molding composition having excellent injection moldability using a pigment.

TPU in the present invention in order to achieve the above object

1) diisocyanate compounds;

2) at least one compound selected from polyester polyols and polyether polyols having a number average molecular weight of 1000 to 6500; And

3) consisting of chain extenders (mainly in diol form) having a molecular weight of 60 to 600,

It consists of a blend of thermoplastic polyurethanes having a Shore A hardness of 60 to 75 by DIN 53 505 measuring method.

Where TPU is

a) continuously mixing a portion of the diisocyanate compound with at least one compound selected from hydroxyl-terminated linear polyester polyols and polyether polyols in a ratio of NCO: OH equivalent ratio of 2.0: 1 to 5.0: 1,

b) continuously reacting the mixture produced in step a) in a reactor for at least 3 hours at 75 ° C. until the conversion rate is at least 95% based on the polyol to form the isocyanate terminated prepolymer

c) The resulting mixture is then cooled to below 50 ° C. and then reacted with one or more chain extension diols having a molecular weight of 60 to 600, with a total NCO: OH equivalence ratio of 0.9: 1 to 1.1: 1 at 50 ° C. for 3 hours. It is obtained through a multi-step reaction consisting of the steps of forming a TPU by the above reaction,

It relates to a TPU molding composition which can be processed into a thermoplastic with a low shrinkage of less than 2.5% according to the DIN 16770 Part 3 measurement method and a Shore A hardness of 60 to 75 according to the DIN 53505 method.

The TPU is pulverized using a pulverizer after curing and sufficiently dried at 105 ° C. for at least 2 hours, and then blended with a flame retardant, an antibacterial agent, an antioxidant, a phosphorescent pigment, and injected into an injection molding machine to produce a molded article.

Examples of the diisocyanate compounds include aliphatic diisocyanates (eg hexamethylene diisocyanate), alicyclic diisocyanates (eg isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2, 4-cyclohexane diisocyanate and 1-methyl-2,60-cyclohexane diisocyanate), as well as diisocyanates with good weather resistance, such as a mixture of the corresponding isomers.

It is preferable to use a polyester diol, a polyether diol, or a mixture thereof as the linear polyol at the hydroxyl end.

Polyester diols are obtained, for example, from dicarboxylic acids and polyhydric alcohols comprising from 2 to 12 carbon atoms, preferably from 4 to 6 carbon atoms. Examples of dicarboxylic acids include aliphatic dicarboxylic acids (eg succinic acid, glutamic acid, adipic acid, suberic acid, azelaic acid and sebacic acid). Examples of polyhydric alcohols include glycols having 2 to 6 carbon atoms (for example, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, and dipropylene glycol). The number average molecular weight of the polyester diol which is a condensation product prepared using the dicarboxylic acid and the polyhydric alcohol in the form of a mixture of each or each other is 1000 to 6500. When the polyol having a number average molecular weight of less than 1000 is used, the adhesion to the workpiece is poor, and when the number average molecular weight is more than 6500, it is not preferable because the work occurs because of the breaking during molding.

The polyether diol is obtained through the reaction of at least one alkylene oxide containing 2 to 4 carbon atoms in the alkylene radical and a starting molecule containing at least one active oxygen. Examples of alkylene oxides include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide. Starting molecules include water, aminoalcohols such as N-alkyl-diethanolamine, diols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol. It is preferable that the number average molecular weight of a linear polyether diol is 1000-6500. When the polyol having a number average molecular weight of less than 1000 is used, it is difficult to ensure softness, and when the number average molecular weight is more than 6500, it is not preferable because the workability is poor due to the breaking during molding.

The chain extender is a diol, possibly a small amount of diamine with a diol and a molecular weight of 60 to 600, preferably an aliphatic diol containing 2 to 14 carbon atoms, and the maximum amount of diamine is such as to obtain a product which can be processed into thermoplastic. Should be Overall, the NCO: OH equivalence ratio should be prepared by adjusting the ratio of 0.9: 1 to 1.1: 1.When the equivalence ratio is less than 0.9, the water resistance becomes poor due to the presence of unreacted aminediol in the TPU, and when the equivalence ratio exceeds 1.1, the TPU It is not preferable because unreacted isocyanate groups remain in the storage, which leads to poor storage stability and changes in physical properties such that adhesion to the coating material changes with time.

Suitable reaction catalysts include tertiary amines as well as organic compounds of metals (eg titanate esters, iron compounds) or tin compounds (eg dibutyltin diacetate, dibutyltin dilaurate). Preferred catalysts are metal organic compounds and tin compounds.

Flame Retardant is generally divided into halogen-based and phosphorus-based, and can be classified into additive type (non-reactive type) and reactive type, and in the present invention, non-toxic and dehydrogenation and dehydration in fire. An additive-type phosphorus-based flame retardant for forming a carbonized layer was used, and as the additive-type phosphorus-based flame retardant, tris (2,4-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate (aka: TCPP) or tris (2- Chloroethyl) phosphate (aka TCEP) may be used.

In addition, antimicrobial agents may be added and blended for the purpose of antibacterial and fungi from fungi or fungi, and antimicrobial agents include phenolic, organotin, organic mercury, triazine, quaternary ammonia salt, halogenated sulfonyl pyridine, Phentan-based, organic copper-based, organic nitrogen-based, iodine-based, silver-based, chloronaphthalin, dihydrobiethylamine petacphenol, pentacrolaulet, etc. may be used, but in the present invention, BIT (1, 2-Bezisothiazolin-3-one) was used.

The photoluminescent pigment blends 30 to 70 wt% of the inorganic photoluminescent pigment, which is an alkaline earth metal aluminate composite activated with rare earth metal ions, to 20 to 60 wt% of the TPU. When the phosphorescent pigment is used at less than 30% by weight, the density of the phosphorescent pigment is not low to obtain an afterglow effect. When the phosphorescent pigment is used at more than 70% by weight, the density of the phosphorescent pigment is so high that it is difficult to uniformly disperse it in a stable state. Rare earth metal ions in the present invention is at least one activated alkaline earth metal alumine selected from the group consisting of europium (Eu), gadolinium (Gd), dysprosium (Dy), terbium (Tb) and ytternium (Yb) Inorganic photoluminescent pigments, which are acid complexes, are used. The alkaline earth metal aluminate complex is a complex of salts consisting of aluminum oxide and calcium oxide, strontium oxide or magnesium oxide, Al ₂ O ₃ CaO, Al ₂ O ₃ MgO, SrAl ₂ O ₄ , SrAl ₂ O ₄ And complexes of salts such as (OH) and Al ₂ O ₃ CaOSrOB ₂ O ₃ .

In addition, antioxidants, wetting dispersants, antifoaming agents and antisettling agents are used as additives to improve the proper processability. Compounds used as antioxidants, wetting dispersants, antifoams and anti-settling agents are no different from those used in the prior art and are prepared using mixtures with compounds already known in the art.

As described above, the present invention is excellent in forming a flexible thermoplastic polyurethane elastomer, and has excellent afterglow brightness and weather resistance, so that visibility can be secured at night when applied to outdoor molded structures, and the manufacturing process is simple and productive. It is possible to improve, and to provide sufficient flame retardancy and at the same time to prevent the propagation of fire in the case of fire and has an antibacterial performance is a useful invention that can be widely used as an environmentally friendly molding material.

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In a four-necked flask equipped with a condenser, a stirrer, and a thermometer, 1 mole of poly-3methyl-1,5-pentanediol adipate having a number average molecular weight of 3000 was 3.5 moles of 4,4'-difetylmethane diisocyanate and dibutyl tin dilau After adding 150 ppm of a rate (based on polyester), the reaction was carried out at 75 ° C. for about 3 hours to prepare a urethane prepolymer. Subsequently, 2.5 mol of a chain extender 1,4-butanediol was added thereto, and reacted at 50 ° C. for about 3 hours. An antioxidant, a wet dispersant, an antifoaming agent, and an antisettling agent were added to prepare a thermoplastic polyurethane elastomer, which was then poured into a mold and cured. It was ground through and dried to granulate.

In a device similar to Example 1, 1 mol of poly-3methyl-1,5-pentanediol adipate having a number average molecular weight of 5000 is 2.5 mol of 4,4'-difetylmethane diisocyanate and 150 ppm of dibutyltin dilaurate (poly After the addition of ester), the reaction was performed at 75 ° C. for about 3 hours to prepare a urethane prepolymer. Subsequently, 1 mole of a chain extender 1,4-butanediol was added thereto, and reacted at 50 ° C. for about 3 hours. An antioxidant, a wet dispersant, an antifoaming agent, and an antisettling agent were added to prepare a thermoplastic polyurethane elastomer, which was then poured into a mold and cured. It was ground through and dried to granulate.

In a device similar to Example 1, 1 mol of poly-3methyl-1,5-pentanediol adipate having a number average molecular weight of 2000 was 3.5 mol of 4,4'-difetylmethane diisocyanate and 150 ppm of dibutyl tin dilaurate (poly After the addition of ester), the reaction was performed at 75 ° C. for about 3 hours to prepare a urethane prepolymer. Subsequently, 2.5 mol of a chain extender 1,4-butanediol was added thereto, and reacted at 50 ° C. for about 3 hours. An antioxidant, a wet dispersant, an antifoaming agent, and an antisettling agent were added to prepare a thermoplastic polyurethane elastomer, which was then poured into a mold and cured. It was ground through and dried to granulate.

In a device similar to Example 1, 1 mol of poly-3methyl-1,5-pentanediol adipate having a number average molecular weight of 2000 was 3.5 mol of 4,4'-difetylmethane diisocyanate and 150 ppm of dibutyl tin dilaurate (poly After the addition of ester), the reaction was performed at 75 ° C. for about 3 hours to prepare a urethane prepolymer. Subsequently, 2.5 moles of chain extender isophorone diamine was added and reacted at 50 ° C. for about 3 hours, and an antioxidant, a wet dispersant, an antifoaming agent, and an antisettling agent were added to prepare a thermoplastic polyurethane elastomer, which was then poured into a mold and cured. Grinded, dried and granulated.

Comparative Example 1

Except for using the chain extender 1,4-butanediol in Example 2, it was prepared in the same manner as in Example 2.

Comparative Example 2

Except for using the chain extender 1,4-butanediol in Example 3, it was prepared in the same manner as in Example 3.

Injection molding

The prepared TPU granules, photoluminescent pigments, flame retardants, and antibacterial agents were blended as shown in Table 1, and melted in a D 60 injection molding machine manufactured by Mannesmann, which was then molded into a rod or plate.

Experimental Example

1. Shore hardness was measured according to DIN 53 505 and 100% modulus was measured according to DIN 53 504. Shrinkage important for evaluating injection molding processability was measured in a similar way to DIN 16 770 (Part 3). The relative longitudinal shrinkage after annealing (80 ° C./12 hours) is listed in Table 1 as a percentage of the molded length.

2. Afterglow effect test

After the molded specimen was stored for 72 hours by blocking the light in the room, the irradiance was measured after irradiating for 4 minutes at a roughness of 200 lux in a dark room.

3. Weather resistance test

The weather resistance was evaluated by exposing the molded specimens for 1000 hours in the open air, blocking the light in the room, storing it for 72 hours, and irradiating for 4 minutes at the intensity of 200 lux in the dark room, measuring the afterglow luminance, and then measuring the color difference (△ E). .

4. Antimicrobial test

The antimicrobial test was carried out using E. coli ( Escherichia coli ATCC 8739) and Pseudomonas aeruginosa ATCC 15442 as a strain and cultured for 24 hours by pressure-adhesive method. Evaluated by calculating the reduction rate of bacteria.

5. Flame retardancy test

Flame retardancy was measured according to the flame retardancy test method of building interior materials and structures of KSF 2271, and the evaluation was evaluated as flame retardant class 1, 2, and 3.

As shown in Table 1, in Examples 1 to 3, the moldability, hardness, elastic modulus, shrinkage ratio, and the like were excellent in softness, and were excellent in afterglow brightness and weather resistance. On the other hand, Comparative Examples 1 and 2 showed poor moldability due to not using a chain extender, hardness was too low and sticky, and the moldability was extremely deteriorated due to the rubbery property as in the elastic modulus and shrinkage value. In addition, the afterglow brightness and the weather resistance of the comparative examples were somewhat reduced in comparison with the examples. It was confirmed that the antimicrobial properties and flame retardancy depend on the amount of the flame retardant and the antimicrobial agent used.

Claims (8)

a) diisocyanate compounds;
At least one compound selected from linear polyester polyols and polyether polyols having a number average molecular weight of 1000 to 6500; And
A chain extender having a number average molecular weight of 60 to 600,
30 to 70% by weight of thermoplastic polyurethane, characterized in that the NCO: OH equivalent ratio of the prepared compound is 0.9: 1 to 1.1: 1, Shore A hardness is 60 to 75 and
b) 30 to 70% by weight of inorganic phosphorescent pigments, which are alkaline earth metal aluminate complexes activated with rare earth metal ions
Thermoplastic polyurethane photoluminescent molding composition comprising a.
The method of claim 1,
The diisocyanate compound is a thermoplastic polyurethane photoluminescent molding composition, characterized in that at least one compound selected from the group consisting of hydroxyl polyester terminal polyol and polyether polyol. The method of claim 1,
The inorganic photoluminescent pigment, which is an alkaline earth metal aluminate composite activated with rare earth metal ions, is Al ₂ O ₃ CaO, Al ₂ O ₃ MgO, SrAl ₂ O ₄ , SrAl ₂ O ₄ (OH), Al ₂ O ₃ CaOSrOB ₂ O Thermoplastic polyurethane photoluminescent molding composition, characterized in that ₃ . The method of claim 1,
The composition of claim 1, wherein the composition further comprises an antioxidant, a wet dispersant, an antifoaming agent, an antisettling agent, a flame retardant, and an antimicrobial agent. a) diisocyanate compound; And continuously reacting at least one compound selected from linear polyester polyols and polyether polyols having a number average molecular weight of 1000 to 6500 in a reactor for 3 hours at 75 ° C. until the conversion rate is 95% or more. To prepare a thermoplastic polyurethane by adding a chain extender having a number average molecular weight of 60 to 600, the NCO: OH equivalent ratio of the prepared compound is 0.9: 1 to 1.1: 1, Shore A hardness of 60 to 75 and
b) The thermoplastic polyurethane is cured, pulverized and dried, and then injected by blending an inorganic photoluminescent pigment, which is an alkali earth metal aluminate composite activated with rare earth metal ions, wherein the photoluminescent pigment is 30 to 70% by weight of the polyurethane. ~ 70 weight percent
Method for producing a thermoplastic polyurethane photoluminescent molding composition comprising a. 6. The method of claim 5,
The diisocyanate compound is a method for producing a thermoplastic polyurethane photoluminescent molding composition, characterized in that at least one compound selected from a hydroxyl group-terminated linear polyester polyol and a polyether polyol. 6. The method of claim 5,
The inorganic photoluminescent pigment, which is an alkaline earth metal aluminate composite activated with rare earth metal ions, is Al ₂ O ₃ CaO, Al ₂ O ₃ MgO, SrAl ₂ O ₄ , SrAl ₂ O ₄ (OH), Al ₂ O ₃ CaOSrOB ₂ O _A method for producing a thermoplastic polyurethane photoluminescent molding composition, characterized in that ₃ . 6. The method of claim 5,
A method for producing a thermoplastic polyurethane photoluminescent molding composition further comprising an antioxidant, a wet dispersant, an antifoaming agent, an antisettling agent, a flame retardant and an antimicrobial agent in addition to the phosphorescent pigment.