KR101057615B1 - Resin composition and coating composition for laser etching - Google Patents

Abstract

The present invention is a resin obtained by solution polymerization of a carboxyl group, a hydroxyl group and a methacrylic acid ester monomer, having an acid value of 2 to 10 mgKOH / g, a hydroxyl value of 60 to 120 mgKOH / g, and an average molecular weight of 1000 to 20000 and a Tg of 20 to 60. The present invention relates to a resin composition for laser etching and a coating composition composed of isocyanate containing 0.9 to 1.5 equivalents to 1 equivalent of acrylic resin, which is high in saturation, high glossiness, and high smoothness while satisfying automotive interior materials as a coating material for automobile interior materials. It can be used for applications such as plastic coatings including industrial coatings, home appliances and the like is excellent.

High gloss, laser etching, automotive interior

Description

Resin composition and coating composition for laser etching {RESIN AND PAINT COMPOSITION FOR LASER ETHING}

TECHNICAL FIELD This invention relates to the composition of the coating material for laser etching. Specifically, It is related with the coating composition used when etching a character or a figure using a laser beam.

Looking at the laser etching apparatus and the laser etching method, when processing the workpiece of the inorganic material, it can be processed without generating deposits around the etching position, and also to fine processing of materials such as micromachines, ICs or diode devices It is common to use the high frequency of an excimer laser or a YAG laser for the microfabrication of the structure by laser processing by a suitable etching method.

By the way, a high-gloss coating film was formed on materials such as ABS, ABS / PC, PC, and the like, and conventionally, matt or semi-glow was used for etching using laser light, and a coating process has been performed by a bottom coat color + top coat clear coating process.

Therefore, according to the conventional method, there was a limit to the gloss, and also the process was complicated and cost-effective.

The present invention has been made to solve the above problems, it is an object of the present invention to provide a coating composition excellent in gloss and excellent physical properties, the coating process can be more simple.

The resin composition for laser etching which concerns on this invention is resin which carried out the solution polymerization of the carboxyl group, the hydroxyl group, and the methacrylic acid ester monomer, The acid value is 2-10 mgKOH / g, The hydroxyl value is 20-50 mgKOH / g, The average molecular weight is 1000 -15000, Tg is characterized by consisting of isocyanate containing 0.9-1.5 equivalents with respect to 1 equivalent of acrylic resin which is 20-50 degreeC.

Moreover, the coating composition for laser etching which concerns on this invention is 50-60 weight% of said resin compositions, 3-6 weight% of pigments, 10-20 weight% of hardening | curing agents, 0.5-5 weight% of additives, 0.1-10 weight% of a dispersing agent. And it characterized in that it comprises a solvent 26 to 36% by weight,

The pigment is characterized in that the Gas Black more specific.

Next, the resin composition for laser etching concerning this invention is resin which carried out solution polymerization of the carboxyl group, the hydroxyl group, and the methacrylic acid ester monomer, and has an acid value of 2-10 mgKOH / g, and a hydroxyl value of 60-120 mgKOH / g, and averages The molecular weight is 1000 ~ 20000, Tg is characterized by consisting of isocyanate containing 0.9 to 1.5 equivalents to 1 equivalent of acrylic resin of 20 to 60 ℃.

The resin composition for laser etching according to the present invention is a resin obtained by solution polymerization of the resin composition: carboxyl group, hydroxyl group, and methacrylic acid ester monomer, and has an acid value of 5 to 30 mgKOH / g and a hydroxyl value of 80 to 200 mgKOH /. The resin composition which consists of isocyanate containing 0.9-1.5 equivalent with respect to 1 equivalent of acrylic resin coating material whose average molecular weight is 1000-20000 and Tg is 40-80 degreeC is characterized by the above-mentioned.

According to the coating composition of the present invention, it is excellent in gloss and can be applied to parts requiring high quality and high appearance, such as automobile interior and exterior materials, household appliances (TV, refrigerator, etc.), general furniture, etc. You can approach it.

In addition, compared with the conventional coating composition for laser etching, physical properties are equal or more,

By performing the existing undercoat color + top coat cree coating process with 1 degree coating, there is an effect of reducing the process, cost reduction and workability.

The present invention is divided into two parts, a shielding paint for top coat and high gloss black for top coat, and after the top and bottom coat is completed, it is not a matte paint but a high gloss black that has not been implemented until now by using the principle of laser processing. A high gloss paint is applied, and the part regarding the paint composition is demonstrated in detail.

In the present invention, the undercoat has a shielding function and has excellent adhesion to the PC 100% material as a undercoat and expresses high glossiness for the shielding function and top coat high gloss black using a special black pigment.

The undercoat resin according to the present invention is a resin obtained by solution polymerization of a carboxyl group, a hydroxyl group, and a methacrylic acid ester monomer, having an acid value of 2 to 10 mgKOH / g, a hydroxyl value of 20 to 50 mgKOH / g, and an average molecular weight of 1000 to 15000, Tg It is an acrylic resin (Example 1, #B) manufactured with the isocyanate containing 0.9-1.5 equivalent with respect to 1 equivalent of acrylic resin which is 20-50 degreeC.

When the resin content is 50 to 60% by weight, the adhesion to the 100% PC material is the best, and it satisfies the specifications of its own automotive interior materials, and when the resin content is 30 to 50%, the 100% PC material is inferior in adhesion.

In the concealment test by pigment type (GAS BLACK, OIL FURANCE BLACK, NAPHTHALENE BLACK, ACETYLENE BLACK, SONGYON, FLEX BLACK, ANIMAL BLACK), the concealment is best when the pigment content is 3 ~ 6%.

In addition, in the weather resistance test, GAS BLACK (POLOR BLACK FW200, SPECIAL BLACK 6, SPECIAL BLACK 5, SPECIAL BLACK 4, COLOUR BLACK XPB FW 285, COLOR BLACK S 160, Pigment using PRINTEX U alone or mixed) is the best and the laser processability All pigments are good.

Therefore, the undercoat according to the present invention is the undercoat having the highest GAS BLACK 3-6% pigment content in the acrylic resin (#B), 0.1-1 wt% antifoaming agent, UV stabilizer, 1-3 wt% absorbent, leveling agent 0.1 It is prepared by adding ~ 3% by weight and 0.1 to 10% by weight dispersant.

The acrylic resin (#A) type described later in Comparative Example 1 has a poor holding force regardless of the resin content.

Next, the top coat is a resin obtained by solution polymerization of a carboxyl group, a hydroxyl group, and a methacrylic acid ester monomer, having an acid value of 2 to 10 mgKOH / g, a hydroxyl value of 60 to 120 mgKOH / g, and an average molecular weight of 1000 to 20000 and a Tg of 20. Acrylic resin (#C) alone or solution-polymerized with a carboxyl group, a hydroxyl group, and a methacrylic acid ester monomer prepared from isocyanate containing 0.9 to 1.5 equivalents to 1 equivalent of acrylic resin at -60 ° C. MgKOH / g, hydroxyl value of 80-200 mgKOH / g, average molecular weight of 1000-20000, Tg of acrylic resin made of isocyanate containing 0.9-1.5 equivalents to 1 equivalent of acrylic resin paint having 40-80 ° C (#D ) A thermosetting resin composition for paints having a ratio of 50:50 (weight ratio), wherein when the ratio of acrylic polyol resin (#C) and acrylic polyol resin (#D) is 50/50 (weight ratio), Glossiness, appearance etc All of them are satisfactory, and they satisfy the physical properties with respect to their own automotive test specifications, and when the ratio of acrylic polyol resin (#C) / acrylic polyol resin (#D) is 65/35%, adhesion to the channel is good, but the #C resin itself Since the gloss is low, the overall gloss is low, which is not suitable (gloss: 80 to 90%). When the ratio of acrylic polyol resin (#C) / acrylic polyol resin (#D) is 30/70%, the glossiness is excellent (gloss: 100-105%), but the adhesion to the bottom is somewhat poor, which is not suitable.

Examples of the paint coating of the present invention are as follows.

Example  One

Acrylic polyol resin (#A) is styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acryl Rate, t-butyl (meth) acrylate, 2-methyl hexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cellosolve (meth) acrylate alone or in combination It is used as a solution polymerized carboxyl group, hydroxyl group, methacrylic acid ester monomer, acid value 2 ~ 10 mgKOH / g, hydroxyl value 20 ~ 50mgKOH / g, average molecular weight 1000 ~ 15000, Tg is 20 ~ 50 ℃ It is an acrylic resin manufactured from isocyanate containing 0.9-1.5 equivalent with respect to 1 equivalent of phosphorus acrylic resin paint.

Example  2

Acrylic polyol resin (#B) is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyoxy Ethylene (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-methyl hexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cellosolve (meth) acrylate is used alone or in combination, one crosslinking agent selected from isocyanate compounds By mixing appropriately and curing with an accelerator, it has a fast curing property and excellent chemical and physical properties, and is a solution polymerized carboxyl group, hydroxyl group, and methacrylic acid ester monomer. As the acid value 5 ~ 15 mgKOH / g, hydroxyl value 20 ~ 30 mgKOH / g, the average molecular weight is 1000 ~ 20000, Tg is made of isocyanate containing 0.9 ~ 1.5 equivalents to 1 equivalent of acrylic resin paint 20 ~ 50 ℃ Acrylic resin.

And the coating composition which concerns on this invention can add a small amount of antioxidant, an ultraviolet stabilizer, an ultraviolet absorber, a leveling agent, an antifoamer, etc. as needed.

The amount is suitably 0.01 to 5 parts by weight of 100 parts by weight of the resin solid content, respectively, may adversely affect the adhesion and water resistance when using more.

The coating composition thus prepared is selected from ABS (acrylonitrile butadiene styrene), ABS (acrylonitrile butadiene styrene) / PC (polycarbonate), PC (polycarbonate), and then spray-coated the surface.

In addition, a comparative test is carried out for the adhesion of PC materials and the amount of black pigment and the degree of concealment, weather resistance and interlayer adhesion of acrylic polyol resins #A and acrylic resin #B. And the results of the laser workability and physical property test specifications of the top coat and the final coating of the top coat of high gloss.

Experimental Example  One

Reflect 10-10% of isocyanate compounds in 100% of the main weight ratio of acrylic polyol resin paint, and experiment after diluting with urethane thinner, and use the above-mentioned additives within 0.5-5%. The material adhesion strength and test specification test according to the acrylic resin content is carried out in the state after the hot air heat drying at 80 ℃, 30 minutes.

Table 1 shows the material adhesion and test spec test results for each resin.

Characteristics Resin #A Resin #A Resin #B Resin #B Material PC 100% PC 100% PC 100% PC 100% Acrylic resin content 30 to 40% (100 compounds) 50 to 60 (100 compounds) 30-50% (100 compounds) 50 to 60% (100 compounds) Material adhesion × △ △ ~ ○ ◎ Exterior after painting × ○ ○ ◎ Acid resistance test × ○ ○ ◎ Water resistance × ○ ○ ◎ Scratch resistance × ○ ○ ◎ Petty × ○ ○ ◎ Impact resistance × ○ ○ ◎ Salt water spray resistance × ○ ○ ○ Alkali resistance × × × ○ Heat resistance × × ○ ○ Moisture resistance × △ ○ ○ Heat cycle resistance × × ○ Weatherability △ △ ○ ◎ Final balance decision × × × ◎

Table 2 shows the detailed test items after the bottom test.

Test Items The details  Adhesion Adhesion test during cross cut for undercoat and top coat (Scotch tape peel test (100/100)) Top appearance No defects that can be identified after visual inspection Polish Measured at GLOSSMETER 60’C Acid resistance test
0.2 ml of 0.5% sulfuric acid and 0.1 N hydrochloric acid are dropped on the surface of the coating film, and left for 24 hours at room temperature.
Water resistance Examination of adhesion test after 1 hour at room temperature after 40'c * 240 hours Moisture resistance After 50'C * 168 hours, room temperature 1 hour Weatherability Black panel 89'C, chamber humidity 50%, setting condition 300 ~ 400NM based on xenon arc type and after 1 hour at room temperature Sunscreen Lay two sheets of white cotton cloth on the acrylic plate, apply sun cream 0.25g, leave 80'c * 1 hour, wash with neutral detergent and examine adhesion Scratch resistance Appearance evaluation by test according to JIS K6718 Petty Rub the lead-free gasoline 10 times with 5N force and let it stand for 1 hour, then leave it in a 80'C * 2 hour thermostat for 3 hours and examine the surface condition. Impact resistance Inspect coating state after testing to ISO 6272 standard Salt spray After spraying for 240 hours according to ISO 7253 or JIS K 5600-7, removing water and then standing for 1 hour at room temperature Alkali resistance After 0.2 ml of 0.1N sodium hydroxide dropping, temperature 20'c humidity 65% After 24 hours, rinse with water and stand for 1 hour at room temperature Heat resistance Perform adhesion test after leaving 110'c * 300 hours Heat cycle resistance After 80'c * 3h After room temperature 1h After -40'c * 3h After room temperature 1h After 50'c * 2h / humidity 95% * 7 ~ 15h After room temperature 1h Take a test Top and bottom laser processability Conduct on its own condition currently in progress Wear resistance Judge the appearance after 4.9N * 1000 round trip using the reciprocating tester.

The bottom test results for the present invention resulted in the best adhesion with the PC material when the acrylic resin #B type is 50 ~ 60% resin content.

Next, the laser etching property and the concealment and weather resistance test of carbon black by classification in the final undercoat acrylic resin #B are performed.

Experimental Example  2

Experiment by diluting 10-20% of isocyanate compounds with urethane thinner to 100% of the main weight ratio of acrylic resin paint, and using the above-mentioned additives within 0.5-5%. Drying conditions are carried out in the state after 80 ℃ hot air heating drying for 30 minutes.

The basic material is 100% PC, and the detailed results and conditions of the experiment are shown in Tables 3, 4, and 5.

Characteristics  Gas black Oil furnace black Naphthalene black  Acetylene Black Concealment rate by pigment content 1 ~ 2% 3-6% 1 ~ 2% 3-6% 1 ~ 2% 3-6% 1 ~ 2% 3-6% △ ○ △ ○ △ ○ △ ○ Material adhesion ○ ○ ○ O ○ ○ ○ ○ Weatherability ○ ◎ △ △ △ △ △ △ Laser etching ○ ○ ○ ○ ○ OO ○ ○ ○ Final black crystal × ◎ × × × × × ×

Characteristics      Songyeon, Yonyeon BLACK            ANIMAL Black Concealment rate by pigment content 1 ~ 2% 3-6% 1 ~ 2% 3-6% × ○ × ○ Material adhesion ○ ○ ○ ○ Weatherability △ △ △ △ Laser processability ○ ○ ○ ○ Final black crystal × × × ×

Test Items The details Adhesion with Undercoat Adhesion test during cross cut for undercoat and top coat (Scotch tape peel test (100/100)) Weatherability Black panel 89'C, chamber humidity 50%, setting condition 300 ~ 400NM based on xenon arc type and after 1 hour at room temperature Laser processability Current company mass production standard (detailed standard secret)

The paint coating composition test in the present invention, 3-6% of the pigment content of the GAS BLACK type in the acrylic polyol resin #B has the best concealment rate and material adhesion, the best in weather resistance and excellent laser processability.

100% of the acrylic polyol resin paint main weight ratio is mixed with 20-40% of one of the above-mentioned curing agents (mixing ratio: 3/1), and then diluted with urethane thinner (10-20% of the thinner main material). Use the additives mentioned above within 0.5 to 5%. Test the adhesion test with the base material according to the acrylic resin type and content. And drying conditions are experimented in 80 degreeC, the state after 30 minutes hot air heating drying.

Example  3

(Acrylic polyol resin #C) / (acrylic polyol resin #D) is (acrylic polyol resin C) is methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, N-butyl (meth) acrylic Rate, butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-methyl hexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, It is a curable resin composition obtained by mixing cellosolve (meth) acrylate alone or in a mixture, and by appropriately mixing one type of crosslinking agent selected from an isocyanate compound and curing with an accelerator, it has fast curing property and excellent chemical and physical properties. It is resin which carried out solution polymerization of the actual group and the methacrylic acid ester monomer, The acid value is 2-10 mgKOH / g, The hydroxyl value is 60-120 mgKOH / g, The average molecular weight is 1000-20000, Tg is 20-60 degreeC A resin obtained by solution polymerization of an acrylic resin prepared from an isocyanate containing 0.9 to 1.5 equivalents of an acrylic resin paint, and a carboxyl group, a hydroxyl group, and a methacrylic acid ester monomer, having an acid value of 5 to 30 mgKOH / g and a hydroxyl value of 80. It is a thermosetting resin for paints composed of 50:50 acrylic resin ratio made of isocyanate containing 0.9-1.5 equivalents to 1 equivalent of acrylic resin paint having an average molecular weight of 1000 to 20000 and Tg of 200 mgKOH / g. .

Physical property tests were carried out based on the lubricity, smoothness, laser workability, and existing test specifications based on the interlayer adhesion with the top coat and the top resin content of the top coat resin composition, and the test results are shown in Table 6.

#One #2 # 3 Resin Contents (# C / # D) 50/50 65/35 30/70 Adhesion with Undercoat Good Good Bad Top appearance Good Bad Good Polish 95-100% 80-90% 100-105% Acid resistance test Good Good Good Water resistance Good Bad Bad Moisture resistance Good Bad Bad Weatherability Good Bad Bad Sunscreen Good Bad Bad Scratch resistance Good Bad Good Laser processability Good Good Good Chemical resistance Good Good Bad Impact resistance Good Bad Bad Paint-resistant fouling Good Good Good Salt spray Good Good Bad Alkali resistance Good Good Good Heat resistance Good Good Bad Heat cycle resistance Good Bad Bad Wear resistance Good Bad Bad

Detailed test evaluation method for the present invention is shown in Table 7.

Test Items The details Adhesion with Undercoat Adhesion test during cross cut for undercoat and top coat (Scotch tape peel test (100/100)) Top appearance No defects that can be identified after visual inspection Polish Measured at GLOSSMETER 60’C Acid resistance test
0.2 ml of 0.5% sulfuric acid and 0.1 N hydrochloric acid are dropped on the surface of the coating film, and left for 24 hours at room temperature.
Water resistance Examination of adhesion test after 1 hour at room temperature after 40'c * 240 hours Moisture resistance After 50'C * 168 hours, room temperature 1 hour Weatherability Black panel 89'C, chamber humidity 50%, setting condition 300 ~ 400NM based on xenon arc type and after 1 hour at room temperature Sunscreen Lay two sheets of white cotton cloth on the acrylic plate, apply sun cream 0.25g, leave 80'c * 1 hour, wash with neutral detergent and examine adhesion Scratch resistance Appearance evaluation by test according to JIS K6718 Petty Rub the lead-free gasoline 10 times with 5N force and let it stand for 1 hour, then leave it in a 80'C * 2 hour thermostat for 3 hours and examine the surface condition. Impact resistance Inspect coating state after testing to ISO 6272 standard Salt spray After spraying for 240 hours according to ISO 7253 or JIS K 5600-7, removing water and then standing for 1 hour at room temperature Alkali resistance After 0.2 ml of 0.1N sodium hydroxide dropping, temperature 20'c humidity 65% After 24 hours, rinse with water and stand for 1 hour at room temperature Heat resistance Perform adhesion test after leaving 110'c * 300 hours Heat cycle resistance After 80'c * 3h After room temperature 1h After -40'c * 3h After room temperature 1h After 50'c * 2h / humidity 95% * 7 ~ 15h After room temperature 1h Take a test Top and bottom laser processability Conduct on its own condition currently in progress Wear resistance Judge the appearance after 4.9N * 1000 round trip using the reciprocating tester.

As described above, the detailed description of the present invention has been made by the embodiments with reference to the accompanying drawings. However, since the above-described embodiments have only been described with reference to preferred embodiments of the present invention, the present invention is limited to the above embodiments. It should not be understood that the scope of the present invention is to be understood by the claims and equivalent concepts described below.

Claims (5)

A resin obtained by solution polymerization of a carboxyl group, a hydroxyl group, and a methacrylic acid ester monomer, having an acid value of 2 to 10 mgKOH / g and a hydroxyl value of 20 to 50 mgKOH / g, with an average molecular weight of 1000 to 15000 and Tg of 20 to 50 ° C. Resin composition for laser etching consisting of isocyanate containing 0.9 to 1.5 equivalents per resin equivalent 50 to 60% by weight of the resin composition according to claim 1; Pigment 3-6 wt%; 10-20 weight% of hardeners; 0.5-5% by weight of additives and 0.1 to 10% by weight of dispersant; And Solvent 26-36 wt%; Coating composition for laser etching comprising a The method of claim 2, The pigment is a coating composition for laser etching, characterized in that Gas Black A resin obtained by solution polymerization of a carboxyl group, a hydroxyl group, and a methacrylic acid ester monomer, having an acid value of 2 to 10 mgKOH / g and a hydroxyl value of 60 to 120 mgKOH / g, and an average molecular weight of 1000 to 20000 and Tg of 20 to 60 ° C. Resin composition for laser etching consisting of isocyanate containing 0.9 to 1.5 equivalents per resin equivalent The resin composition according to claim 3: A resin obtained by solution polymerization of a carboxyl group, a hydroxyl group and a methacrylic acid ester monomer, having an acid value of 5 to 30 mgKOH / g, a hydroxyl value of 80 to 200 mgKOH / g, and an average molecular weight of 1000 to 20000, Tg is a resin composition for laser etching, characterized in that the resin composition composed of isocyanate containing 0.9 to 1.5 equivalents with respect to 1 equivalent of acrylic resin paint having a temperature of 40 to 80 ° C. is 1: 1.