KR20100052255A - Polyurethane composition for three-d patterning - Google Patents

Abstract

PURPOSE: A polyurethane composition containing a magnetic pigment for three-d patterning are provided to apply the composition for producing interior materials of a vehicle, and to improve the marketability of an article. CONSTITUTION: A polyurethane composition containing a magnetic pigment for three-d patterning contains 10~45wt% of polyester polyol with an amine-based or glycol-based branched chain, 6~30wt% of polyester polyol with an acrylonitrile branch chain, 40~75wt% of hardener, 6~30wt% of magnetic pigment, 0.01~1.2wt% of UV stabilizer, 0.05~1.7wt% of light-proof stabilizer, and 0.01~0.5wt% of chain stabilizer.

Description

Polyurethane composition for three-D patterning

The present invention relates to a polyurethane composition for realizing a three-dimensional pattern, by simultaneously injecting a polyol containing a magnetic pigment and a curing agent into a mold, applying an external magnetic field having a specific pattern, and applying a magnetic pigment to the magnetic pigment during the urethane reaction. The present invention relates to a polyurethane composition for realizing a three-dimensional three-dimensional pattern by curing simultaneously with the arrangement.

As is commonly known, in order to improve the degree of freedom of design in products having complex three-dimensional shapes and various sizes, a lot of efforts have been made to implement various patterns and colors in the surface layer while maintaining excellent physical properties. In particular, various methods have been applied to maximize the aesthetic effect in automobile interior materials, home appliances, etc. In recent years, various shapes, such as painting, plating, hydraulic transfer, insert molding, etc. are used to satisfy consumer needs. I give color, a pattern.

Existing painting process is possible to implement a variety of colors, but it is difficult to implement a specific pattern, even if the implementation of the masking process is required, due to the difficulty of implementing a variety of patterns it was difficult to mass production by manual.

In the case of the hydraulic transfer, various patterns and colors can be implemented, but there are disadvantages in that the process is complicated and the production cost is high. In the case of the insert molding, the process is simple, but the price of the film for insert molding is expensive, and the preforming is performed. There was a hassle to go through the process.

In addition, the existing processes have a disadvantage that the clear layer or the uppermost layer is thin and the sense of quality is poor. Accordingly, the present invention is to implement a method of improving the degree of freedom of design by implementing a coating layer having a high sensational thick film feeling by using polyurethane reaction injection, and implementing a specific pattern by reacting the ferromagnetic pigment to an external magnetic field.

Therefore, the inventors of the present invention, in view of the above point, as a result of research, polyester polyol having a branched chain of glycol or amine, polyester polyol having an acrylonitrile branched chain, curing agent, magnetic pigment, UV stabilizer, light resistance The present invention has been completed by developing a polyurethane composition in which a three-dimensional pattern is implemented using a specific amount of stabilizer and chain extender.

Accordingly, an object of the present invention is to provide an optimum resin composition for preventing the particle size and content of magnetic pigments and oxidation of magnetic pigments.

Polyurethane composition for implementing a three-dimensional pattern according to the present invention is excellent in the effect of improving the merchandise by implementing a specific pattern of a three-dimensional shape using a magnetic pigment, such as automotive interior and exterior parts, home appliances, or decorative products. In addition, it is expected that the process may be simple and excellent in aesthetic effect because the polyurethane composition may implement a sense of depth and a specific pattern in a product in the process of implementing the pattern.

Referring to the polyurethane composition for implementing a three-dimensional pattern according to the present invention in more detail.

The present invention

(1) 10 to 45% by weight of a polyester polyol having a branched chain of glycol or amine;

(2) 6 to 30% by weight of polyester polyol having acrylonitrile as branch chain;

(3) 40 to 75 weight percent of hardener;

(4) 6 to 30 weight percent of magnetic pigment;

(5) 0.01-1.2 wt% of ultraviolet stabilizer;

(6) a light resistance stabilizer of 0.05 to 1.7 wt%; and

(7) 0.01-0.5 wt% chain extender;

It features a polyurethane composition for implementing a three-dimensional pattern comprising.

Hereinafter, the present invention will be described in detail.

(1) The polyester polyol having a branched chain of glycol or amine is 10 to 45% by weight based on 100% by weight of the total polyurethane composition, and the content of polyester polyol having a branched chain of glycol or amine is If it is less than 10% by weight, a problem that the coating film properties such as impact resistance is lowered, and if it is more than 45% by weight, a problem that mechanical properties such as wear resistance is lowered, the above range is appropriate. The polyester polyol having a branched chain of glycol or amine is preferably a polyester polyol having a branched chain selected from triethylene glycol, tetraethylene glycol triethanolamine and aniline. Moreover, it has 2-3 OH hydroxyl groups. The number average molecular weight of the polyester polyol having a branched chain of the glycol- or amine-based is 1,500 to 5,000% by weight, preferably 1,500 to 2000% by weight, the hydroxyl value is 10 to 150 mgKOH / g, preferably 20 to 70 mgKOH / g is suitable. When the molecular weight of the polyester polyol having a branched chain of glycol or amine is less than 1,500% by weight, the hardness of the coating film of the clear coating layer is lowered, and when it is more than 5000% by weight, the viscosity is increased during injection, thereby increasing the pressure during low pressure injection. There is this. In addition, when the hydroxyl value is less than 10 mgKOH / g is less reacted with the isocyanate, the formation of the coating film is incomplete, if more than 150 mgKOH / g cross-linking reaction occurs a lot of problems that the coating film is too hard.

(2) Polyester polyol having acrylonitrile as the branched chain is based on 100% by weight of the total polyurethane composition If it is 6 to 30% by weight, less than 6% by weight, the surface hardness of the coating film is lowered, causing surface problems such as scratchability, and if it exceeds 30% by weight, the coating film is broken after heat resistance evaluation. The polyester polyol having the acrylonitrile as a branched chain improves the coating film properties of the resin, such as wear resistance and scratch resistance, by using a high molecular weight. The number average molecular weight is 500 to 1,300% by weight, and the hydroxyl value is 20 to 100 mgKOH / g, but preferably 30 to 100 mgKOH / g. When the molecular weight of the polyester polyol having an acrylonitrile as a branch chain is less than 500% by weight, the hardness of the desired coating film cannot be obtained, and when it is more than 1,300% by weight, the coating film becomes hard and may be broken in heat resistance evaluation or the like.

(3) The curing agent is 40 to 75% by weight based on 100% by weight of the total polyurethane composition, when less than 40% by weight does not complete the curing reaction, it is difficult to form a complete coating film, when more than 75% by weight unreacted curing agent This causes a problem that the chemical properties of the coating film are lowered. The curing agent uses at least one selected from isophorone diisocyanate (ISPI), toluene anate (TDI), methylene diphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI). . The number average molecular weight is 100 to 2,000% by weight, preferably 150 to 1,000% by weight. At this time, the content of the cyanide group (NCO) of the curing agent used is 0.5 to 5% by weight is appropriate, preferably 0.5 to 2.0% by weight is appropriate. When the content of cyanide (NCO) is less than 0.2% by weight, it is difficult to form a reaction, and when the content of more than 5% by weight occurs, a problem of deterioration of coating properties due to excess cyanide (NCO) after the reaction occurs.

(4) The magnetic pigment is 6 to 30% by weight with respect to 100% by weight of the total polyurethane composition, when less than 6% by weight is difficult to form a pattern, when more than 30% by weight problems such as discoloration after evaluation of light resistance and heat resistance. The magnetic pigment may be one or more selected from nickel, cobalt, iron, ferrite, silicon coated ferrite, silicon coated iron oxide, and ferrite coated mica. Considering the viscosity of the polyurethane resin, it is preferable to use ferromagnetic iron oxide and silicon coated iron oxide, and it is most preferable to use silicon coated iron oxide to prevent the pigment from being oxidized by external heat and light. Do. In this case, the magnetic pigment used has an average particle diameter of 5 to 30 µm and a thickness of 1 to 5 µm. If the particle diameter of the pigment is more than 30 ㎛, it is difficult to rotate the external magnetic field having a specific pattern, and if it is less than 5 ㎛ the area that can reflect light is small, three-dimensional pattern is not visible.

(5) In order to prevent oxidation of iron oxide and to prevent discoloration caused by heat resistance and light resistance, it is preferable to add an ultraviolet stabilizer (UAV). The ultraviolet stabilizer is a benzotriazole and benzophenone, preferably 2- (2-hydroxymethylphenyl) benzotriazole, 2- (2-hydroxy-3-5- Dibutylphenyl) benzotriazole or 2- (2-hydroxy-3-tetrabutyl-5-methylphenyl) -5-chlorobenzoltriazole and the like are preferred. In addition, with respect to 100% by weight of the total polyurethane composition, 0.01 to 1.2% by weight, when less than 0.01% by weight does not exhibit a sufficient effect on the heat resistance, when more than 1.2% by weight occurs a problem that the adhesion with the plastic base layer.

(6) HALS which is a light resistance stabilizer as an amine stabilizer is bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770), bis- [N-methyl-2,2 , 6,6-pentamethyl-4-piperidinyl] sebacate or tetrakis (2,2,6-tetramethyl-4-piperidinyl-1,2,3,4-butanetetracarboxylate is preferred The content of the light resistance stabilizer is about 0.05 to 1.7% by weight, and preferably about 0.1 to 1.0% by weight based on 100% by weight of the total polyurethane composition. The above range is appropriate because it does not solve the problem of discoloration, and may cause a problem of deterioration of the plastic body and adhesion when it exceeds 1.7% by weight.

(7) The chain extender is 0.01 to 0.5% by weight relative to 100% by weight of the total polyurethane composition, when less than 0.01% by weight does not occur a sufficient bonding reaction occurs a problem that the hardness of the coating film is reduced, 0.5% by weight When the hardness of the coating film is too high when the problem occurs such that the mechanical properties such as impact resistance is lowered, the above range is preferable. As the chain extender, dibutyltin dilaurate (DBTDL), which is a tin reaction catalyst, is preferably used.

The composition having the features of (1) to (7) is molded through the following process. Low-temperature low-pressure injection of the polyol containing a magnetic pigment and the curing agent on a plastic part using a polyurethane reaction injection used in the past, and impart a magnetic force having a specific shape pattern at the same time, the magnetic pigments in the paint By arranging in the same shape as, to realize a specific three-dimensional pattern. In order to have a specific pattern to the magnetic pigment, the magnetic field strength is preferably 1,000 to 15,000 Gauss, and more preferably 5,000 to 12,000 Gauss. In the case of the resin composition for polyurethane reaction injection, the Melt Index is 30 to 200 g / min, and the viscosity of the resin requires a strong magnetic field to form the magnetic pigment included in the resin in a desired pattern. . Therefore, when the strength of the magnetic field is less than 1,000 Gauss, it is difficult to form a pattern because the strength of the magnetic field is small. When the strength of the magnetic field is more than 15,000 Gauss, the magnetic pigment is oriented to one side of the magnetic field, making it difficult to accurately form the pattern. Simultaneously with the formation of such a pattern, the polyol and the curing agent react with the urethane, thereby obtaining a coating film having good sensibility and realizing various patterns.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

EXAMPLE

Examples 1-6

(1) Polyester polyol having a branched chain of glycol or amine type, (2) Polyester polyol having an acrylonitrile branched chain, and (3) isophorone diisocyanate in Table 1 were put into a stirrer, at 45 rpm. Mix for 15 minutes so that the magnetic pigment of (4), (5) UV stabilizer, (6) light resistance stabilizer and (7) chain extender are dispersed well and the temperature is controlled to 40 ~ 60 ℃ by using a temperature control heater. Maintained. At this time, it stirred for 15 minutes, heating up at the temperature of 60-70 degreeC with (1) and (2) polyester polyol which mixed isophorone diisocyanate stored at 50-60 degreeC.

The mixed polyol resin and isocyanate were injected into a mold and a magnetic field was formed by high pulse (500 Μf, 700 to 900 V) for 10 to 30 seconds to create a magnetic field of a desired pattern. At this time, the strength of the magnetic field was maintained at 8,000 Gauss. The thickness of the polyurethane composition coating layer formed by the reaction injection method is 0.8 mm, the shape of the pattern formed by this method is shown in FIG.

[Test Example]

[Property Measurement Evaluation]

1) Chemical resistance evaluation

6 chemicals of gasoline, engine oil, wax, grease, glass cleaner, and ethyl alcohol were soaked in a soft cloth, and subjected to 10 round trip rub tests with a load of 0.5 kg, and then observed for 3 hours in an oven at 80 ℃. Then, the external surface was observed.

2) Light resistance evaluation

Under XENON ARC, the total cumulative light intensity is 700 KJ / m ² under the conditions of black panel temperature 89 ± 3 ℃, ambient humidity 50 ± 5% RH, irradiation illuminance 0.55 ± 0.02 W / m ² nm (at 340 nm) After irradiation, the coated specimens were washed with an aqueous neutral detergent solution, dried with air, and evaluated for appearance and adhesion.

3) Wear resistance evaluation

Using a reciprocating abrasion tester, the exposure and the damage of the coating film were compared between 10,000 kg reciprocation using a double-sided cloth friction material under the conditions of 1 kgf test load, 30 reciprocation / minute test speed, and 100 mm friction stroke. At this time, the wear resistance evaluation is carried out dry and wet wear test, the wet wear test was sprayed on the surface artificial sweat per 500 times.

4) Heat resistance evaluation

The coated specimens were left at 90 ° C. for 300 hours, then taken out and left at room temperature for 1 hour, and immediately evaluated for the adhesion test and the degree of discoloration.

5) Pattern Formation Evaluation

As shown in Table 2, it can be seen that the polyurethane composition in which the three-dimensional pattern of the present invention is implemented is excellent in chemical resistance, light resistance, wear resistance, and heat resistance, and is also excellent in pattern formation.

Figure 1 shows a three-dimensional pattern formed of the polyurethane composition of Example 1.

Claims (8)

1) 10 to 45% by weight of a polyester polyol having a branched chain of glycol or amine; 2) 6 to 30% by weight of polyester polyols having branched chains of acrylonitrile; 3) 40 to 75 weight percent of hardener; 4) 6-30 weight percent of magnetic pigment; 5) 0.01-1.2 wt% UV stabilizer; 6) 0.05-1.7 wt% light resistance stabilizer; And 7) chain stabilizer 0.01 ~ 0.5% by weight; Polyurethane composition for implementing a three-dimensional pattern comprising a. The method of claim 1, The glycol-based is triethylene glycol or tetraethylene glycol, the amine-based polyurethane composition for the three-dimensional pattern is characterized in that the triethanolamine or aniline. The method of claim 1, The polyester polyol having a branched chain of glycol or amine type has two to three OH hydroxyl groups, has a number average molecular weight of 1,500 to 5,000 wt%, and has a steric value of 10 to 150 mgKOH / g hydroxyl value Embodiment polyurethane composition. The method of claim 1, The polyester polyol having the acrylonitrile as a branched chain has 2 to 3 OH groups, has a number average molecular weight of 500 to 1,300% by weight, and a hydroxyl group implementation of a three-dimensional pattern, wherein the hydroxyl group is 20 to 100 mgKOH / g. Composition. The method of claim 1, The curing agent is at least one selected from isophorone diisocyanate (ISPI), toluene anate (TDI), methylenediphenyl diisocyanate (MDI), and hexamethylene diisocyanate (HDI), the number average molecular weight is 100 to 2,000 Polyurethane composition for implementing a three-dimensional pattern, characterized in that%. The method of claim 1, The magnetic pigment is at least one selected from nickel, cobalt, iron, ferrite, silicon coated ferrite, silicon coated iron oxide, and ferrite coated mica, an average particle diameter of 5 to 30 μm, and a thickness of 1 to 5 μm. Polyurethane composition for implementing a three-dimensional pattern, characterized in that. The method of claim 1, The ultraviolet stabilizer is 2- (2-hydroxymethylphenyl) benzotriazole, 2- (2-hydroxy-3-5-dibutylphenyl) benzotriazole or 2- (2-hydroxy-3-tetrabutyl- 5-methylphenyl) -5-chlorobenzoltriazole is a polyurethane composition for implementing a three-dimensional pattern. The method of claim 1, The light resistance stabilizer is bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- [N-methyl-2,2,6,6-pentamethyl-4-piperidinyl ] Sebacate or tetrakis (2,2,6-tetramethyl-4-piperadinyl-1,2,3,4-butanetetracarboxylate) Polyurethane composition for implementing a three-dimensional pattern, characterized in that.

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