KR101928148B1 - Paint composition - Google Patents

Abstract

The present invention provides a coating composition comprising a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and an additive.
According to the coating composition of the present invention, it is possible to provide a coating composition which is excellent in scratch resistance and appearance of a coating film while providing physical properties such as hardness, water resistance, weather resistance, and the like, .

Description

 [0001] Paint composition [0002]

The present invention relates to a coating composition.

Generally, automobile interior and exterior materials have a three-dimensional three-dimensional shape in many cases. Therefore, a water pressure transfer method is widely used for transferring pattern patterns to the surface of the internal and external materials.

Here, in the case of a paint for water pressure transfer protection used in automobiles, a print film of a specific pattern such as a wood pattern is transferred to ABS / PC-ABS based materials as an automobile interior part, and then the surface is coated with a paint. Accordingly, there is an increasing tendency to apply a hydraulic transfer method applied to interior materials according to a high-level design strategy in automobile exterior materials. In the case of exterior materials for automobiles, it is inevitable to provide paints with improved physical properties so that the pattern transferred under water pressure can be protected even in a harsh environment than the interior. Particularly, when the coating material for hydraulic transfer protection is applied to the exterior material, the water resistance and weather resistance must be excellent. In order to realize the water transfer film pattern without distortion, the appearance should be excellent.

On the other hand, Patent Document 1 discloses a top coating paint for protecting a printed pattern layer or a decorative layer formed by a hydraulic transfer method on the surface of a plastic molded article, and Patent Document 2 discloses a coating composition for protecting a water pressure transfer pattern layer Discloses a technique of including a polyolefin-based resin in a composition.

Japanese Patent Application Laid-Open No. 2000-007946 International Patent Publication No. WO2006-035708

The present invention provides a coating composition which can be used for water pressure transfer protection of an automobile exterior material, and a method for producing a paint kit using the same.

The present invention provides a coating composition comprising a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and an additive.

The present invention also provides a paint kit comprising a curing agent composition comprising a curing agent and a diluent in a coating composition comprising a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and an additive do.

The present invention also relates to a curing agent composition comprising a coating composition comprising a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and additives, a curing agent composition containing a curing agent and a diluent, To 6: 1 to 7: 1, wherein the coating composition comprises 30 to 40 parts by weight of the first acrylic polyol resin, 5 to 15 parts by weight of the second acrylic polyol resin, Wherein the curing agent comprises 15 to 25 parts by weight of a resin, 20 to 50 parts by weight of a solvent, and 1 to 15 parts by weight of an additive, wherein the weight ratio of the curing agent to the diluent is 3: 2 to 4: .

According to the coating composition of the present invention, it is possible to provide a coating material kit which is excellent in scratch resistance and appearance of a coating film while providing physical properties such as hardness, water resistance, weather resistance and the like, which are applied to automotive exterior parts for water pressure transfer protection .

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.

It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by terms. Terms are used only for the purpose of distinguishing one component from another.

In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Therefore, the constitution shown in the embodiments described herein is merely a preferred embodiment of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and substitutes There may be variations.

As used herein, the term "parts by weight " means the weight ratio between the raw material components.

The resin composition for paints according to one aspect of the present invention may comprise a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and an additive.

Hereinafter, each component of the composition will be described in detail.

[Acrylic polyol resin]

The acrylic polyol resin according to the present invention may comprise at least two kinds of resins having different properties. Specifically, for the physical properties of the coating film surface, a first acrylic polyol resin having a relatively low hydroxyl group, And a second acrylic polyol resin having a relatively high hydroxyl group for ascending and physical properties.

The monomers used in the acrylic polyol resin are preferably selected from the group consisting of 2-hydroxy (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di Acrylic monomers having at least one hydroxy group such as acrylic acid, and mixtures thereof.

The acrylic monomer having at least one hydroxyl group may be at least one selected from the group consisting of styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, isobutyl ≪ / RTI >

The first acrylic polyol resin may have a solid content of 50 to 60 wt%, a hydroxyl value of 50 to 60 mgKOH / g and a Tg of 40 to 50 DEG C, and the second acrylic polyol resin has a solid content of 40 to 50 wt% , A hydroxyl group of 130 to 145 mg KOH / g, and a Tg of 30 to 40 ° C.

The weight ratio of the first acrylic resin to the second acrylic resin composition is preferably 3: 1 to 2: 1. If the ratio is out of the above range, there arises a problem in the appearance of the coating film.

 [Polyester polyol resin]

The composition according to the present invention may comprise a polyester polyol resin in order to enhance the appearance of the coating film of the coating material and ensure the surface physical properties.

The polyester polyol resin may have a solid content of 65 to 75% by weight, a hydroxyl value of 130 to 145 mgKOH / g, and a Tg of 30 to 40 ° C.

The polyester polyol used in the present invention is usually obtained by reacting a polybasic acid component with a polyol component. Examples of the polybasic acid component include at least one of orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetrahydrophthalic acid Aromatic dicarboxylic acids such as benzoic acid; There may be mentioned oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, fumaric acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, Aliphatic dicarboxylic acids such as linoleic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid; Alicyclic dicarboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; And reactive derivatives thereof such as acid anhydrides, alkyl esters, and acid halides. These may be used alone or in combination.

Examples of the polyol component are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 1,6- Methylene-1,3-butylene glycol, 1-methyl-1,4-pentylene glycol, 2- Methyl-1,4-pentylene glycol, 1,2-dimethyl-neopentyl glycol, 2,3-dimethyl- neopentyl glycol, Butylene glycol, 1,2-dimethylbutylene glycol, 1,3-dimethylbutylene glycol, 2,3-dimethylbutylene glycol, 1,4-dimethylbutylene Diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol F, hydrogenated bisphenol A, Bisphenol F < / RTI > These may be used alone or in combination.

 [solvent]

The coating composition of the present invention may be selected from the group consisting of an aromatic hydrocarbon solvent, an ether solvent and a ketone solvent in order to ensure the physical properties of the coating material. Or a mixture thereof.

Specifically, examples of the aromatic hydrocarbon solvent include toluene, xylene, and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl isoacyl ketone, and 2-heptanone.

Examples of the ether solvent include monomethyl ether such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, Monophenyl ether, and the like.

 [additive]

The coating composition of the present invention may contain further additives such as adjusting the surface tension of the coating material or accelerating the curing. Here, the additive may include at least one selected from the group consisting of a surface modifier, an ultraviolet absorber, and a curing accelerator, and may further include materials known in the art.

(1) Surface conditioner

The surface modifier may be a compound commonly used in the coating composition for controlling the surface tension, and may be a mixture of at least one of a polysiloxane-based surface modifier and a non-silicon-based surface modifier.

Examples of the polysiloxane-based surface conditioning agent include silicone oil, silicone surfactant and silicone-based synthetic lubricating oil. Non-silicone surface conditioning agents substantially free of silicon (Si) include low-alcohol, mineral oil, oleic acid, polypropylene glycol, Esters, fluorine-containing surfactants, and the like.

(2) Curing accelerator

The curing accelerator may be included in order to accelerate the curing of the coating material. An example of the curing accelerator is dibutyl tin dilaulate (DBTDL).

(3) Ultraviolet absorbers

Ultraviolet absorbing agent is stronger than ultraviolet absorbing ability of chromophore of acrylic resin and suppresses the generation of radicals of acrylic resin, and is effective in preventing discoloration, swelling, delamination and gloss loss of acrylic resin. An example of the ultraviolet absorber is hydroxyphenyl benzotriazole.

[content]

The coating composition according to one embodiment of the present invention comprises 30 to 40 parts by weight of the first acrylic polyol resin, 5 to 15 parts by weight of the second acrylic polyol resin, 15 to 25 parts by weight of the polyester polyol resin, 20 to 50 parts by weight of the solvent And 1 to 15 parts by weight of an additive.

If the total amount of the first acrylic polyol resin and the second acrylic polyol resin exceeds 55 parts by weight based on the paint composition, there may be a problem that the appearance of the coating film is lowered. If the total amount is less than 30 parts by weight, .

When the content of the polyester polyol resin is less than 10 parts by weight, the appearance of the coating film may be deteriorated. When the content of the polyester polyol resin exceeds 35 parts by weight, the hardness of the coating film may be decreased.

If the amount of the solvent exceeds the above range, the solid content of the coating is lowered, and the viscosity of the coating may be lowered, thereby lowering the yield of the coating. When the amount of the solvent is less than the above range, the cost of the raw material A problem may arise. When the solvent is a mixture of an aromatic hydrocarbon solvent, an ether solvent and a ketone solvent, the first acrylic polyol resin is mixed with 30 to 40 parts by weight of an aromatic hydrocarbon solvent in an amount of 10 to 20 parts by weight, 10 to 20 parts by weight of a solvent, and 1 to 10 parts by weight of a ketone solvent.

When the mixture is used as the surface modifier, the additive may include 0.1 to 1 part by weight of the polysiloxane-based surface control agent and 0.1 to 1 part by weight of the non-silicon surface-regulating agent, based on 30 to 40 parts by weight of the first acrylic polyol resin. May be contained in an amount of 1 to 10 parts by weight, and the curing accelerator may be included in an amount of 0.01 to 1 part by weight, and may further include conventional additives in this field such as antifoaming agents or retarding agents.

In addition, the coating composition is provided in the form of a coating kit. Specifically, the coating kit is a two-component coating composition comprising a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and an additive , A curing agent composition containing a curing agent and a diluent, and the like.

The curing agent in the curing agent composition cures the coating composition. In the present invention, the curing agent may be a polyisocyanate curing agent.

The isocyanate functional group of the polyisocyanate-based curing agent reacts with the hydroxyl group of the acrylic polyol resin to form a urethane bond. The polyisocyanate curing agent may have a solids content of, for example, 80 to 100% and an NCO value of 17 to 23%. One example of the polyisocyanate-based curing agent is hexamethylene diisocyanate having excellent yellowing resistance and light resistance.

The polyisocyanate-based curing agent may be diluted with an appropriate diluent to form a curing agent composition and stored in a separate container, followed by sufficient stirring immediately before use. The dilution ratio of the polyisocyanate diluent is such that when the main mixture is mixed with the polyisocyanate diluent, the isocyanate functional groups of the resin and the curing agent are combined so that the urethane reaction is equivalent to the equivalent equivalent , And the mixing is preferably 1: 0.9 to 1: 1.2 on the basis of the equivalence ratio. If the ratio is more than 1: 1.2, there is a problem that excess isocyanate is generated, and when the ratio is less than 1: 0.9, there is a problem that the degree of curing is deteriorated.

The weight ratio of the curing agent to the diluent may be 3: 2 to 4: 1, and the ratio of the total weight of the coating composition to the total weight of the curing agent composition when formed with the coating kit may be from 6: 1 to 7: 1, and if it exceeds the above-mentioned ratio range, physical properties of the coating film may be deteriorated due to poor crosslinking.

According to another aspect of the present invention, there is provided a method of manufacturing the above-described coating material kit. Specifically, a curing agent composition containing a coating composition comprising a first acrylic polyol resin, a second acrylic polyol resin, a polyester polyol resin, a solvent and an additive, a curing agent and a diluent is mixed with the total weight of the coating composition and the total weight of the curing agent composition Wherein the coating composition comprises 30 to 40 parts by weight of the first acrylic polyol resin, 5 to 15 parts by weight of the second acrylic polyol resin, 15 to 15 parts by weight of the polyester polyol resin, 20 to 50 parts by weight of a solvent, and 1 to 15 parts by weight of an additive, wherein the weight ratio of the curing agent to the diluting agent in the curing agent composition is 3: 2 to 4: 1.

Example  And Comparative Example

The coating compositions and coating kits of the present invention were prepared in the same proportions as in Table 1.

 (Unit: parts by weight) ingredient Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The first acrylic polyol resin 35 29 5 51 24 14 The second acrylic polyol resin 12 15 51 5 5 15 Polyester polyol 18 21 9 9 36 36 Ultraviolet absorber 2.9 2.9 2.9 2.9 2.9 2.9 Silicon surface conditioner 0.5 0.5 0.5 0.5 0.5 0.5 Non-silicon surface control agent 0.1 0.1 0.1 0.1 0.1 0.1 Hardening accelerator 0.01 0.01 0.01 0.01 0.01 0.01 solvent 31.49 31.49 31.49 31.49 31.49 31.49 Total 100 100 100 100 100 100

First acrylic polyol resin: (solid content 55% by weight, 57 mg KOH / g, Tg 45 ° C (KCC))

Second acrylic polyol resin: (solid content 47% by weight, 135 mgKOH / g, Tg 35 ° C (KCC))

Polyester polyol: (solid content 68% by weight, 139 mgKOH / g, Tg 37 DEG C (KCC))

Ultraviolet absorber: (Tinuvin 5151 (product of BASF))

Silicon Surface Conditioning Agent: (Tego glide b-1484 (EVNONIK DEGUSSA GMBH))

Non-silicone surface modifier: Polyacrylate Copolymer

Curing accelerator: CATALYST PVC stabilizer (DBTDL) (Songwon Industrial Co., Ltd.)

Solvent: An aromatic hydrocarbon compound, an ether compound, and a ketone compound are mixed at a weight ratio of 20: 8: 5.

A curing agent composition was prepared by mixing polyisocyanate (HDI TRIMER) and diluted thinner at a ratio of 2.5: 1, and the coating composition prepared in the above Examples and Comparative Examples and the curing agent composition were mixed at a weight ratio of 6.5: 1.

Experimental Example

The kits of Examples and Comparative Examples were painted under the conditions of viscosity (Fordcup # 4) of 15 to 17 sec, and the properties of the coating film were evaluated as follows.

A separate silver collar base (dry film thickness: 15 to 20 microns) was coated on the substrate of ABS (exterior parts such as an outside mirror), dried at 70 ° C for 1 hour, pressure- After drying, the paint was applied on the top and cured by hot air for 3 hours at 70 ° C.

Painting workability The appearance and physical properties of the final coating were measured as follows, and the results are shown in Table 2 below.

1) Painting workability

IWATA was applied to a 30x40 cm tin plate twice for 61 reciprocating cycles to compare the degree of atomization and degree of smoothness of the coating and the degree of scratching.

2) Appearance

After coating the paint on the coated plastic substrate, it was dried at 80 ° C for 6 minutes, and the clearcoat was applied thereon to compare the surface bubbles, foreign matter, spots, grooves and smoothness.

3) Adhesiveness

Based on the ASTM D3359 tape adhesion test method, the degree of the peeled portion after the tape adhesion test among 100 pieces of 1 mm x 1 mm scale was observed.

4) Water resistance

After the coating film was immersed for 10 days in a 40 ° C thermostat, adhesion test and appearance evaluation were carried out.

5) Weatherability

The appearance, color difference, and adhesion of the film were compared after exposure to 2500 kJ energy in a Xenon weatherometer environment.

6) Chemical resistance

A weight of 4.9 N load (4 cm in diameter) was wrapped in gauze, and the surface of the film was rubbed back and forth ten times by visual inspection of the outer appearance with gasoline, polishing wax, glass cleaner, ethyl alcohol and acetone.

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Painting workability ◎ ○ △ △ ◎ X Exterior ◎ ○ △ ○ ◎ △ Attachment ◎ ◎ ◎ ◎ ◎ ◎ Water resistance ◎ ◎ ○ ◎ △ △ Weatherability ◎ ◎ ○ ○ ○ △ Chemical resistance ◎ ◎ ◎ ○ ◎ ◎ Evaluation: ◎ - Excellent, ○ - Good, △ - Normal, X-poor

As shown in Table 2, it was confirmed that the coating composition of the present invention is excellent in workability of the coating film (lubrication property) and provides excellent physical properties such as adhesion water resistance, weather resistance, chemical resistance, and further excellent appearance .

Claims (11)

A first acrylic polyol resin having a hydroxyl value of 50 to 60 mg KOH / g,
A second acrylic polyol resin having a hydroxyl value of 130 to 145 mg KOH / g,
Polyester polyol resin,
Solvent and
An additive,
Wherein the first acrylic polyol resin is contained in an amount of 30 to 40 parts by weight and the second acrylic polyol resin is contained in an amount of 5 to 15 parts by weight. The method according to claim 1,
Wherein the first acrylic polyol resin has a solids content of 50 to 60 wt%. The method according to claim 1,
And the second acrylic polyol resin has a solid content of 40 to 50 wt%. The method according to claim 1,
Wherein the solvent comprises at least one selected from the group consisting of an aromatic hydrocarbon solvent, an ether solvent, and a ketone solvent. The method according to claim 1,
Wherein the additive comprises at least one selected from the group consisting of a surface modifier, an ultraviolet absorber, and a curing accelerator. The method of claim 5,
Wherein the surface modifier comprises at least one of a polysiloxane-based surface modifier and a non-silicon-based surface modifier. The method according to claim 1,
Wherein the composition comprises 15 to 25 parts by weight of a polyester polyol resin, 20 to 50 parts by weight of a solvent, and 1 to 15 parts by weight of an additive. A paint kit further comprising a curing agent composition comprising a curing agent and a diluent in the composition of claim 1. The method of claim 8,
Wherein the ratio of the total weight of the coating composition to the total weight of the curing agent composition is from 6: 1 to 7: 1. The method of claim 8,
Wherein the weight ratio of the curing agent to the diluent is 3: 2 to 4: 1. A coating composition comprising a first acrylic polyol resin having a hydroxyl value of 50 to 60 mg KOH / g, a second acrylic polyol resin having a hydroxyl value of 130 to 145 mg KOH / g, a polyester polyol resin, a solvent and an additive, and a curing agent composition containing a curing agent and a diluent , Mixing the ratio of the total weight of the coating composition to the total weight of the curing agent composition in a ratio of 6: 1 to 7: 1,
Wherein the coating composition comprises 30 to 40 parts by weight of a first acrylic polyol resin, 5 to 15 parts by weight of a second acrylic polyol resin, 15 to 25 parts by weight of a polyester polyol resin, 20 to 50 parts by weight of a solvent and 1 to 15 parts by weight of an additive Including,
Wherein the weight ratio of the curing agent to the diluent in the curing agent composition is from 3: 2 to 4: 1.