KR101909703B1 - Plasticizer-migration resistant acrylic resin useful to pcm coating composition and method for manufacturing the same - Google Patents

Abstract

More particularly, the present invention relates to an acrylic resin for PCM paints, which comprises 30 to 50 parts by weight of a first monomer containing an aromatic hydrocarbon, 5 to 15 parts by weight of a second monomer containing a hydroxyl group, And 0.1 to 5 parts by weight of a third monomer to be used as a polymerization initiator are added to and reacted with 30 to 60 parts by weight of an organic solvent and 0.5 to 2 parts by weight of a polymerization initiator to produce an acrylic resin for a PCM paint having excellent plasticizer inner- .

Description

TECHNICAL FIELD [0001] The present invention relates to a plasticizer-erosion-resistant acrylic resin suitable for PCM paints and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to an acrylic resin for PCM paints and a method for producing the acrylic resin, and more particularly to an acrylic resin for a PCM paint having an excellent plasticizer innerwear and a method for producing the same.

Typical metal coating methods include Post-coating method, which is applied after forming process, and Pre-coating method, which is applied before forming process. Pre-coated metal) or a color steel plate, and a paint used for producing the same is called a PCM paint. As a metal plate for producing PCM, a zinc-plated steel plate is often used. There are two types of metal plates: a sheet cut in a certain size and a coil in the form of a coil. In the industrial field, coil coating is adopted, in which metal coils are automatically and continuously applied. For this reason, the term coil coating is often used with PCM. PCM has advantages such as process rationalization, quality stability, quality improvement, resource saving, pollution reduction, energy saving, construction period reduction and cost reduction.

PCM is widely used for household appliances and building materials. Domestic and foreign home appliance manufacturers manufacture products by applying PCM as an external case for products such as refrigerator, air conditioner, TV, washing machine and air conditioner. Normally, household appliances are shipped in polyethylene bag or styrofoam (EPS or Styrofoam) cushioning material. If the appearance of household appliances after removing the packaging is looked at, there is a problem of staining. Specifically, a packaging material such as a polyethylene bag or a styrofoam (EPS or Styrofoam) cushioning material includes a plasticizer for imparting flexibility. Such a plasticizer has a property of being migrated, , The plasticizer may be transferred to the contact surface, resulting in unevenness. In the case of a high-gloss material such as a refrigerator, such a stain becomes more prominent and becomes a problem.

In general, polyester resin is mainly applied to impart excellent film properties such as chemical resistance, film hardness and gloss to PCM coatings. However, in spite of excellent properties of the coating film of the polyester resin, there is a limitation in reducing the trace due to the plasticizer migration property, and development of a paint capable of improving the occurrence of stain caused by erosion of the plasticizer is required.

KR 100342913 B1

An object of the present invention is to provide an acrylic resin for PCM paints having an excellent plasticizer innerwear.

According to one aspect of the present invention, there is provided a method for producing a polymer electrolyte membrane, which comprises mixing 30 to 50 parts by weight of a first monomer containing an aromatic hydrocarbon, 5 to 15 parts by weight of a second monomer containing a hydroxyl group and 0.1 to 5 parts by weight of a third monomer containing a carboxyl group And 30 to 60 parts by weight of an organic solvent and 0.5 to 2 parts by weight of a polymerization initiator are added to and reacted with the mixture to provide an acrylic resin for a PCM paint excellent in plasticizability.

The monomer mixture may further comprise 1 to 10 parts by weight of a fourth monomer containing a branched alkyl group.

Also, the first monomer may be selected from the group consisting of styrene, vinyl toluene, 4-acetoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 4-methoxystyrene, and phenyl methacrylate containing aromatic hydrocarbons And may include at least one selected.

Also, the second monomer is preferably a copolymer comprising a hydroxyl group-containing 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate And at least one selected from the group.

In addition, the third monomer may include at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and fumaric acid including a carboxyl group.

The fourth monomer may be at least one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, And at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and cyclomethacrylate.

In addition, the first monomer may be contained in an amount of 60 to 85% by weight based on 100% by weight of the total amount of the monomer mixture.

The organic solvent may include at least one selected from the group consisting of an aliphatic hydrocarbon-based solvent and an ester-based solvent.

Further, the glass transition temperature of the resin may be 80 to 100 占 폚.

The resin may have a weight average molecular weight of 20,000 to 50,000 and a hydroxyl value (OH value) of 30 to 120 mgKOH / g.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: charging 30 to 60 parts by weight of an organic solvent and raising the temperature to 110 to 140 ° C; And 30 to 50 parts by weight of a first monomer containing an aromatic hydrocarbon, 5 to 15 parts by weight of a second monomer containing a hydroxyl group and 0.1 to 5 parts by weight of a third monomer containing a carboxyl group are added to a monomer mixture containing 0.5 to 2 And adding the mixture to an organic solvent. The method for producing an acrylic resin for a PCM paint excellent in plasticizer inner ear performance is provided.

The monomer mixture may further comprise 1 to 10 parts by weight of a fourth monomer containing a branched alkyl group.

The acrylic resin for PCM paints according to one aspect of the present invention has a double bond in the side chain and has a high content of aromatic hydrocarbon-containing monomers, thereby having excellent plasticizer anti-icing property, To reduce the deterioration of the product quality due to the migration of the plasticizer contained in the packaging material.

The acrylic resin for PCM paints according to one aspect of the present invention can be cured with melamine formaldehyde resin and thus can have good processability. In addition, since the processability is not lowered in spite of a high glass transition temperature, it is suitable for application as a PCM paint for household use.

The acrylic resin for PCM paint according to one aspect of the present invention is excellent in chemical resistance, transparency and storage stability, and contains a monomer containing a hydroxyl group, so that it is suitable for application as a high quality PCM paint Do.

The acrylic resin for PCM paints according to one aspect of the present invention has excellent physical properties while using a low-cost polymer, and can reduce the manufacturing cost of the PCM paint to which the acrylic resin is applied.

More particularly, the present invention relates to an acrylic resin for PCM paints, which comprises 30 to 50 parts by weight of a first monomer containing an aromatic hydrocarbon, 5 to 15 parts by weight of a second monomer containing a hydroxyl group, And 0.1 to 5 parts by weight of a third monomer to be added to a monomer mixture comprising 30 to 60 parts by weight of an organic solvent and 0.5 to 2 parts by weight of a polymerization initiator. And a manufacturing method thereof.

Hereinafter, the present invention will be described in more detail.

According to one aspect of the present invention, there is provided an acrylic resin for a PCM paint.

An acrylic resin for PCM paints according to one aspect of the present invention is prepared by polymerizing a monomer mixture. The monomer mixture comprises a first monomer comprising an aromatic hydrocarbon, a second monomer comprising a hydroxyl group and a third monomer comprising a carboxyl group. If necessary, it may further comprise a fourth monomer containing a branched alkyl group.

The first monomer containing the aromatic hydrocarbon enables the acrylic resin produced to exhibit excellent plasticizer anti-icing property and chemical resistance. In addition, the post-processability of the paint to which the acrylic resin to be produced is applied can be improved. More specifically, it is possible to suppress a large deterioration in workability after forming a coating film with a coating material to which the acrylic resin of the present invention is applied. Wherein the first monomer comprising an aromatic hydrocarbon is selected from the group consisting of styrene, vinyl toluene, 4-acetoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 4-methoxystyrene, and phenyl methacrylate But it is not limited thereto.

The second monomer containing a hydroxyl group can make the acrylic resin to be crosslinked with the curing agent to be suitable for a thermosetting paint such as a PCM paint. Wherein the second monomer comprising hydroxyl groups is selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate But it is not limited thereto.

The third monomer containing the carboxyl group plays an auxiliary role in promoting the reaction during the radical reaction of the acrylic resin to be produced. The third monomer containing a carboxyl group may include at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and fumaric acid, but is not limited thereto. Preferably, acrylic acid or methacrylic acid is included.

Optionally, the acrylic resin for PCM paints according to one aspect of the present invention may further comprise a fourth monomer comprising a side chain alkyl group. The fourth monomer containing the side chain alkyl group can be improved by complementing the workability and adhesiveness of the produced acrylic resin, which is high in aromatic hydrocarbon content, compatibility with other resins such as a curing agent, and the like. The fourth monomer containing the branched alkyl group may be at least one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, But is not limited to, at least one selected from the group consisting of ethylhexyl acrylate, ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and cyclomethacrylate. Preferably, the fourth monomer containing the side chain alkyl group includes a compound having an unsaturated hydrocarbon bond.

An acrylic resin for a PCM coating according to one aspect of the present invention is prepared by reacting an organic solvent and a polymerization initiator together with the monomer mixture.

The organic solvent may be selected from those well known in the art, and may be selected so as to have excellent solubility and meet PCM manufacturing process conditions after coating. For example, the aromatic hydrocarbon-based organic solvent and the ester-based organic solvent may be used alone or in combination.

As the polymerization initiator, those known in the art can be used, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, lauryl peroxide, azobisisobutyronitrile, and 2 , And 2-azobis-2-methylbutyronitrile. However, the present invention is not limited thereto.

The monomer mixture comprising 30 to 50 parts by weight of the first monomer containing the aromatic hydrocarbon, 5 to 15 parts by weight of the second monomer containing the hydroxyl group and 0.1 to 5 parts by weight of the third monomer containing the carboxyl group, 30 to 60 parts by weight of the polymerization initiator and 0.5 to 2 parts by weight of the polymerization initiator are mixed and reacted to produce an acrylic resin for a PCM paint excellent in plasticizer inner ear performance according to one aspect of the present invention. If necessary, the monomer mixture may further contain 1 to 10 parts by weight of a fourth monomer containing a side-chain alkyl group in order to improve the physical properties of the acrylic resin to be produced.

The acrylic resin produced when each monomer is contained and polymerized in the above content range can exhibit excellent plasticizer anti-planarity and excellent processability. If the amount of the first monomer containing the aromatic hydrocarbon is less than 30 parts by weight, plasticizer inner resistance and chemical resistance may be deteriorated. If it exceeds 50 parts by weight, miscibility with other resins, solubility and post- Preferably, the first monomer is added to the reaction in an amount of 30 to 40 parts by weight. If the amount of the second monomer containing a hydroxyl group is less than 5 parts by weight, hardening may not sufficiently take place and the solvent resistance may be lowered. If the amount of the second monomer is more than 15 parts by weight, a large amount of the curing agent may be added to lower the plasticizer inner- . The third monomer containing the carboxyl group promotes the acrylic reaction of the present invention. If the amount is more than 5 parts by weight, the acid value of the acrylic resin may be increased to deteriorate long term properties such as viscosity increase during storage after preparation of the coating. Preferably, the third monomer is added to the reaction in an amount of 1 to 3 parts by weight. If the amount of the fourth monomer containing the side-chain alkyl group is less than 1 part by weight, post-workability and solubility may be deteriorated. If the amount is more than 10 parts by weight, plasticizer inner-layer resistance and chemical resistance may be deteriorated. More preferably, the fourth monomer is added to the reaction in an amount of 2 to 5 parts by weight.

In addition, it is important for the resin to have a high glass transition temperature in order to have an anti-plasticizing property with respect to the plasticizer. It is more preferable to use a monomer having an alkyl group at the side chain terminal and a high glass transition temperature on the homopolymer, It is possible to exhibit excellent plasticizer anti-icing properties and chemical resistance. Further, when the content of the monomer containing an aromatic hydrocarbon is high, a large decrease in workability after the coating film formation can be suppressed. Preferably, within the above-mentioned content range, the first monomer comprising the aromatic hydrocarbon in the acrylic resin for the PCM paint according to the present invention is present in an amount of 60 to 85 By weight, more preferably 70 to 80% by weight.

The acrylic resin for PCM paints according to one aspect of the present invention may have a glass transition temperature of 80 to 100 캜. The glass transition temperature is an important resin property related to plasticizer anti-icing property and chemical resistance. If the glass transition temperature is lower than 80 ° C, the effect of inhibiting the erosion of the plasticizer is hardly exhibited. More preferably, the glass transition temperature of the acrylic resin for the PCM paint to be produced is 85 to 95 占 폚.

The acrylic resin for PCM paints according to one aspect of the present invention may have a weight average molecular weight of 20,000 to 50,000 and OH value of 30 to 120 mgKOH / g, preferably 30 to 100 mgKOH / g. If the hydroxyl value of the acrylic resin for the PCM paint to be produced is less than 30 mgKOH / g, the curing degree is lowered and the reaction can not be sufficiently performed with the curing agent, thereby causing a problem that the MEK (methyl ethyl ketone) rubbing property and adhesiveness of the paint are deteriorated . If the hydroxyl value of the resin to be produced is more than 120 mgKOH / g, the content of the curing agent introduced into the paint increases, which may result in deterioration of the physical properties of the resin to be produced. More preferably, the hydroxyl value of the acrylic resin for the PCM paint to be produced is preferably 60 to 80 mgKOH / g.

The acrylic resin for PCM paints provided in the present invention improves the resistance against the erosion of the plasticizer and has an excellent plasticizer anti-icing property. Therefore, when applied to PCM paints used in PCM for home appliance use, the stain caused by the plasticizer contained in the packaging material It is possible to reduce the deterioration of the merchantability. In addition, since the aromatic hydrocarbon-containing monomer is contained in an amount of 60 to 85% by weight based on 100% by weight of the total monomers, the glass transition temperature can be increased to improve hardness and chemical resistance. It is possible to alleviate the deterioration of the workability of the substrate. The acrylic resin for PCM paints provided in the present invention can be used as a resin suitable for application to PCM electric household clear coatings.

According to another aspect of the present invention, a method for producing an acrylic resin for PCM paints is provided.

According to another aspect of the present invention, there is provided a method for preparing an acrylic resin for a PCM paint, wherein an organic solvent is first added to the reactor and the temperature is raised to 110 to 140 ° C.

Next, the monomer mixture and the polymerization initiator are added dropwise to the reactor to carry out a polymerization reaction. The monomer mixture includes 30 to 50 parts by weight of a first monomer containing an aromatic hydrocarbon, 5 to 15 parts by weight of a second monomer containing a hydroxyl group, and 0.1 to 5 parts by weight of a third monomer containing a carboxyl group. If necessary, it may further comprise 1 to 10 parts by weight of a fourth monomer containing a branched alkyl group. The polymerization initiator is added in an amount of 0.5 to 2 parts by weight.

A coating composition for PCM can be prepared by adding a curing agent, a curing catalyst, a defoaming agent and a leveling agent to the acrylic resin. From the viewpoint of improving the post-processability and solvent resistance, it is preferable that an amino formaldehyde resin is selected as the curing agent.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example

[Production Examples 1 to 15] Preparation of acrylic resin

The organic solvent was first added to the reactor and the temperature was raised to the temperature at which the reaction was desired. The mixture obtained by mixing the monomer and the polymerization initiator was added dropwise to the reactor for 2 hours while the dropwise addition was completed, followed by stirring for 1 hour. 10% by weight of a polymerization initiator added to the initiator added to the first reaction was further added dropwise and reacted with stirring for 3 hours to react the unreacted monomers secondarily to prepare an acrylic resin. The monomers, organic solvents, initiator, temperature elevating temperature and physical properties of the respective preparation examples used for the respective production examples are shown in Table 1 below.

division Manufacturing example
One Production Example 2 Manufacturing example
3 Production Example 4 Manufacturing example
5 Production Example 6 Production Example 7 Manufacturing example
8 menstruum
(Parts by weight) Solvent Naphtha 100 39.7 49.9 39.9 39.9 40.0 49.9 49.9 49.8 Di basic ester 10.0 - 10.0 10.0 9.9 - - - Monomer
(Parts by weight) Methacrylic acid 1.2 0.3 1.0 1.0 1.2 - 0.3 1.0 Methyl methacrylate - - - - - - 29.7 12.5 2-ethylhexyl acrylate - - - - - 14.7 4.2 - 2-hydroxyethyl methacryl
Relay 9.1 5.3 6.7 9.1 13.3 10.0 8.5 7.2 Styrene 36.5 41.6 33.0 38.8 34.5 - - 28.3 Isobutyl methacrylate 2.3 - 8.3 - - 24.9 - - N-butyl acrylate - 1.8 - - - - 6.8 - Polymerization initiator
(Parts by weight) 2,2-azobis 2-methylbutyronitrile - - - - - 0.5 0.6 - t-Butyl peroxybenzoate 1.2 1.1 1.1 1.2 1.1 - - 1.2 Reaction temperature (캜) 135 135 135 135 135 120 110 135 Properties Tg (占 폚) 90 86 85 92 87 3 43 94 NV (%) 50 50 50 50 50 50 50 50 OHv (mgKOH / g) 75 47 60 75 115 85 70 63 division Manufacturing example
9 Manufacturing example
10 Manufacturing example
11 Manufacturing example
12 Manufacturing example
13 Manufacturing example
14 Manufacturing example
15 menstruum
(Parts by weight) Solvent Naphtha 100 49.9 39.9 39.9 40.2 39.8 49.8 39.9 Di basic ester - 9.9 10.0 10.0 10.0 - 10.0 Monomer
(Parts by weight) Methacrylic acid 1.2 1.0 1.0 1.1 1.1 1.0 7.0 Methyl methacrylate 17.7 7.9 - - - - - 2-ethylhexyl acrylate - - - 9.4 8.5 - - 2-hydroxyethyl methacryl
Relay 9.5 7.0 - 2.9 4.0 17.6 6.9 Styrene 20.5 28.7 36.5 35.3 35.5 28.5 32.6 Isobutyl methacrylate - - 11.4 - - 2.0 - N-butyl acrylate - 4.5 - - - - 2.4 Polymerization initiator
(Parts by weight) 2,2-azobis 2-methylbutyronitrile - - - - - - - t-Butyl peroxybenzoate 1.2 1.1 1.2 1.1 1.1 1.1 1.2 Reaction temperature (캜) 135 135 135 135 135 135 135 Properties Tg (占 폚) 92 72 88 45 57 80 85 NV (%) 50 50 50 50 50 50 50 OHv (mgKOH / g) 84 61 0 25 35 150 60

The solid content of the synthesized acrylic resin was adjusted to the same 50% in order to minimize the experimental error of the paint and the paint prepared.

[Production Example 16] Production of polyester resin

Generally, in the PCM field, a polyester resin having excellent gloss and chemical resistance is used for a transparent coating material for household electric appliances. Therefore, a polyester resin is prepared as a production example for comparison of plasticizer dying resistance and physical and chemical properties. 30.6 parts by weight of isophthalic acid, 9.8 parts by weight of terephthalic acid, 13.1 parts by weight of adipic acid, 40.7 parts by weight of neopentyl glycol, and 5.7 parts by weight of trimethylolpropane and 0.1 part by weight of dibutyltin oxide were charged into a reactor, . The condensed water was spilled at 150 to 160 ° C. The remaining water was removed by reduced pressure or a reflux reaction using xylene, and a hydrocarbon solvent and cyclohexanone were added at a ratio of 1: 1 to obtain a polyester for a PCM paint having a solid content of 65%, an OHv of 100 mgKOH / g and a mass average molecular weight of 8,000 Resin. The synthesis of the polyester resin for the PCM transparent paint is compared with the acrylic resin of the above-mentioned Preparations 1 to 11 in terms of the basic physical and chemical properties and the plasticizer innerwear, and the degree of improvement of the effect of the present invention relative to the conventional home PCM paint Table 2 shows the preparation method of the paint, and Table 3 shows the comparison of the physical properties.

[Examples 1 to 5 and Comparative Examples 1 to 11] Preparation of coating compositions for PCM

In order to confirm the physical properties of the resins of Production Examples 1 to 16, a coating composition was prepared in the weight ratio composition shown in Table 2 below. At the time of preparation, all raw materials other than the acid-blocked acid-catalyzed B-CAT 0025 (Efti Korea, dodecylbenzenesulfonic acid type) blocked in the amine were added to the vessel, and the acid catalyst was finally added thereto in a fixed amount. CYMEL 303 was a hexamethoxymethyl melamine type curing agent manufactured by CYTEC.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Production Example 1 75.3 - - - - - - - Production Example 2 - 75.3 - - - - - Production Example 3 - - 75.3 - - - - - Production Example 4 - - - 75.3 - - - - Production Example 5 - - - - 73.0 - - - Production Example 6 - - - - - 75.3 - - Production Example 7 - - - - - - 75.3 - Production Example 8 - - - - - - - 75.3 CYMEL 303 6.5 6.5 6.5 6.5 9.3 6.5 6.5 6.5 B-CAT 0025 1.0 1.0 1.0 1.0 1.1 1.1 1.1 1.0 LA-45 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Cyclohexanone 5.4 5.4 5.4 5.4 5.2 5.4 5.4 5.4 SOLVESSO 100 5.4 5.4 5.4 5.4 5.2 5.4 5.4 5.4 DBE 5.4 5.4 5.4 5.4 5.2 5.4 5.4 5.4 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Production Example 9 75.3 - - - - - - - Production Example 10 - 75.3 - - - - - - Production Example 11 - - 75.3 - - - - - Production Example 12 - - - 75.3 - - - - Production Example 13 - - - - 75.3 - - - Production Example 14 - - - - - 64.0 - - Production Example 15 - - - - - - 75.3 - Production Example 16 - - - - - - - 70.0 CYMEL 303 6.5 6.5 6.5 6.5 6.5 18.3 6.5 15.0 B-CAT 0025 1.0 1.0 1.0 1.1 1.1 1.1 1.0 1.0 LA-45 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Cyclohexanone 5.4 5.4 5.4 5.4 5.4 5.2 5.4 4.0 SOLVESSO 100 5.4 5.4 5.4 5.4 5.4 5.2 5.4 4.0 DBE 5.4 5.4 5.4 5.4 5.4 5.2 5.4 5.0

<Test Example>

The physical properties of the coating compositions prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

1. Solvent resistance: The gauze was soaked with MEK and rubbed back and forth with a load of 1 kg to confirm the appearance change. In general, more than 50 round trips are judged to be enough curing in the industry.

2. Processability: Measured by NCCA-II-19 ("T" band test method specified by National Coil Coaters Association). The lower the value, the better the workability.

3. Pencil hardness: Measured with reference to NCCA-II-12, measured 5 lines by Mitsubishi's Uni-pencil, and judged to be good when there were not more than 3 marks.

4. Adhesion force: 100 cross cells were cut at intervals of 1 mm to fabricate 100 cells. The cell was processed by ERICHSEN tester and tapping was performed.

5. Acid resistance: The change in appearance was observed after immersion in 5% (w / v) acetic acid (CH3COOH) for 24 hours.

6. Alkali resistance: After 24 hours immersion in 5% (w / v) sodium hydroxide solution (NaOH), changes in appearance were observed and measured.

7. Plasticizer Inner Planet I: The gasket was placed on a specimen at a temperature of 90 ° C (95% humidity and 95% RH) for 4 hours. After removing the condition, the surface was wiped with alcohol and the appearance was confirmed. After removing the test conditions, it was judged to be excellent when there was no mark.

8. Plasticizer Inner Planet II: PE-bag (polyethylene bag) containing plasticizer in a thermo-hygrostat (humidity 95%, temperature 90 ℃) under the condition of load 4kg after 4 hours, remove the test condition and surface with alcohol After wiping, the appearance was confirmed. After removing the test conditions, it was judged to be excellent when there was no mark.

For reference, in Table 3, the results of the plasticizer inner ear I and II items are expressed as X (very severe), DELTA (severe), O (weakly localized), and O (no localized).

The correlation between the workability and the pencil hardness in the art is considered to indicate excellent physical properties with excellent workability and high hardness.

Test Items standard Example
One Example
2 Example
3 Example
4 Example
5 Comparative Example
One Comparative Example
2 Comparative Example
3 Solvent resistance MEK Double Rubbing 50 ↑ 50 ↑ 50 ↑ 50 ↑ 50 ↑ 50 ↑ 50 ↑ 50 ↑ Processability T-bending 3T 3T 2T 4T 3T 2T 6T 4T Pencil hardness - H F F H F 2B 2H H Adhesion ERICHSEN 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Acid resistance - More than
none More than
none More than
none More than
none More than
none Blister More than
none More than
none Alkali resistance - More than
none More than
none More than
none More than
none More than
none Blister More than
none More than
none Plasticizer
Inner Planet I - ◎ ◎ ◎ ◎ ◎ X △ △ Plasticizer
My Planet II - ◎ ○ ○ ◎ ○ X X △ Test Items standard Comparative Example
4 Comparative Example
5 Comparative Example
6 Comparative Example
7 Comparative Example
8 Comparative Example
9 Comparative Example
10 Comparative Example
11 Solvent resistance MEK Double Rubbing 50 ↑ 50 ↑ Uncured Uncured 50 ↑ 50 ↑ Saving
Viscosity increase 50 ↑ Processability T-bending 2T 4T 2T 4T 2T Pencil hardness - F H HB 2H F Adhesion ERICHSEN
100/100 100/100 100/100 100/100 100/100 100/100 Acid resistance - More than
none More than
none More than
none More than
none More than
none Alkali resistance - More than
none More than
none More than
none More than
none More than
none Plasticizer
Inner Planet I - △ ○ △ ○ △ Plasticizer
My Planet II - △ ○ △ ○ △

Table 3 shows a PCM coating composition prepared by reacting the acrylic resin of the present invention prepared by reacting a first monomer containing an aromatic hydrocarbon, a second monomer containing a hydroxyl group, and a third monomer containing a carboxyl group. It can be confirmed that Examples 1 to 5 exhibit excellent plasticizer anti-icing properties while maintaining excellent solvent resistance, processability, hardness, acid resistance and alkali resistance. Comparing Examples 1 to 5 containing an acrylic resin of the present invention with Comparative Example 11 containing a polyester resin which is conventionally used show that Examples 1 to 5 containing the acrylic resin of the present invention are significantly superior to the plasticizer anti- . &Lt; / RTI &gt;

Examples 1-3, further comprising a fourth monomer comprising a side chain alkyl group, showed improved physical properties over Examples 4 and 5 while maintaining good plasticizer innerwear. The physical properties of Example 1 including 2 to 5 parts by weight of a fourth monomer containing a branched alkyl group were the most excellent.

In Comparative Examples 3 to 5 and Comparative Example 9, when the content of the first monomer is less than 30 parts by weight, the lower the content of the first monomer is, the lower the excellent plasticizer inner-planet characteristic of the present invention is.

In Comparative Examples 1 and 2, it was confirmed that the plasticizer inner ear performance of the resin to be produced when the first monomer was not contained was significantly lowered. In Comparative Example 10, the content of the third monomer was more than 5 parts by weight It is confirmed that the viscosity increases during the storage due to the high acidity and the physical properties of the paint are lowered.

In Comparative Examples 6 to 8, when the second monomer is not contained or the content of the second monomer is less than 5 parts by weight, hardening does not occur or the glass transition temperature of the resin to be produced becomes excessively low, Can not be shown.

Claims (12)

30 to 50 parts by weight of a first monomer containing styrene; A second acrylic copolymer containing at least one selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate. 5 to 15 parts by weight of a monomer; And 0.1 to 5 parts by weight of a third monomer comprising acrylic acid or methacrylic acid; and 30 to 60 parts by weight of an organic solvent and 0.5 to 2 parts by weight of a polymerization initiator are added to and reacted with the acrylic resin for PCM paint In this case,
Wherein the content of the first monomer is 60 to 85% by weight based on 100% by weight of the total of the monomer mixture,
And a glass transition temperature of 80 to 100 DEG C. The acrylic resin for PCM paints is excellent in innerwear resistance.
The plasticizer according to claim 1, wherein the monomer mixture comprises 1 to 10 parts by weight of a fourth monomer containing a side-chain alkyl group.
The method of claim 1, wherein the first monomer is selected from the group consisting of vinyl toluene, aromatic hydrocarbons, 4-acetoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 4-methoxystyrene, and phenyl methacrylate The acrylic resin for PCM paint is excellent in plasticizer inner ear goodness.
The acrylic resin for a PCM paint according to claim 1, wherein the second monomer comprises 2-hydroxyethyl methacrylate containing a hydroxyl group.
The acrylic resin for PCM paints according to claim 1, wherein the third monomer comprises methacrylic acid containing a carboxyl group.
3. The composition of claim 2 wherein said fourth monomer is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate , At least one selected from the group consisting of ethylhexyl acrylate, ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate and cyclomethacrylate. Acrylic resin for.
delete The plasticizer according to claim 1, wherein the organic solvent comprises at least one selected from the group consisting of aliphatic hydrocarbon-based and ester-based plasticizers.
delete The acrylic resin for PCM paints according to claim 1, which has a weight average molecular weight of 20,000 to 50,000 and a hydroxyl value (OH value) of 30 to 120 mgKOH / g.
Adding 30 to 60 parts by weight of an organic solvent and raising the temperature to 110 to 140 캜; And
And 0.5 to 2 parts by weight of a polymerization initiator is added to the monomer mixture, and the mixture is added dropwise to the organic solvent. In the method for producing an acrylic resin for PCM paints,
Wherein the monomer mixture comprises 30 to 50 parts by weight of a first monomer comprising styrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl methacrylate and 5 to 15 parts by weight of a second monomer containing at least one selected from the group consisting of hydroxypropyl acrylate and 0.1 to 5 parts by weight of a third monomer containing acrylic acid or methacrylic acid,
Wherein the content of the first monomer is 60 to 85% by weight based on 100% by weight of the total of the monomer mixture.
12. The method of claim 11, wherein the monomer mixture comprises 1 to 10 parts by weight of a fourth monomer comprising a side-chain alkyl group.