KR100717215B1 - Acrylic resin and method of preparing the same - Google Patents

Abstract

Disclosed are an acrylic resin used in a binder of a transparent paint having a transparent appearance and excellent storage properties, and a method of manufacturing the same. The acryl resin is a mixed vinyl-based monomer 200 to 400 containing a first monomer containing a branched alkyl group having 2 or less branched carbon atoms and a second monomer including a branched alkyl group having a higher branched carbon number than the first monomer. After forming a mixture comprising 5 to 30 parts by weight of the vinyl monomer having a weight part and a hydroxyl group and 60 to 250 parts by weight of an organic solvent including a polymerization initiator, the mixture is added to the mixture and the total of 1 part of the first monomer included in the mixture. It is formed by first polymerization reaction by adding 20 to 65% of the first monomer and 0.5 to 2 parts by weight of the polymerization initiator, and has an alcohol value of 5 to 30 mgKOH / g, a weight average molecular weight of 50,000 to 100,000, and a glass transition temperature. Has a characteristic of 50 to 80 ℃.

Description

ACRYLIC RESIN AND METHOD OF PREPARING THEREOF {ACRYLIC RESIN AND METHOD OF PREPARING THE SAME}

The present invention relates to an acrylic resin and a method for producing the same, and more particularly, to an acrylic resin and a method for producing the same applied as a binder of a transparent coating paint.

High weather resistant Acrylic resin is used as a binder of Acrylic fluorine paint that is applied to panel or window frame, which is a building or industrial aluminum material, and can form a coating film with excellent effect on weather resistance, adhesion, scratch resistance and heat resistance. have. In addition, the high weather resistance acrylic resin is applied when the adhesion is required in the paint using a variety of acryl resin as the main binder has the property to increase the adhesion performance of the paint.

The high weathering acrylic resin having the above-mentioned characteristics and a method of manufacturing the same have been filed by DEIPAI Co., Ltd. on December 29, 2004 (Application No. 2004-114655).

However, the acrylic resin has excellent properties in terms of physical properties for forming the paint, but has a problem that it is difficult to apply to a one-component clear transparent paint in which the appearance of the coating film is opaque.

Accordingly, it is an object of the present invention to provide an acryl resin that is applied as a binder of a transparent coating material that can form a transparent coating film while having physical properties of an acryl resin having high weather resistance.

In addition, another object of the present invention is to provide a method for producing an acrylic resin applied as a binder of the transparent coating paint.

Acryl resin according to a preferred embodiment for achieving the object of the present invention is a second monomer comprising a side chain alkyl group having a side chain alkyl group having a side chain alkyl group of 2 or less carbon atoms of the side chain and higher than the first monomer After forming a mixture comprising 200 to 400 parts by weight of the mixed vinyl monomer containing monomers, 5 to 30 parts by weight of the vinyl monomer having a hydroxyl group and 60 to 250 parts by weight of an organic solvent, the agent contained in the mixture in the mixture It is formed by first polymerization reaction by adding 0.5 to 2 parts by weight of the first monomer and 20 to 65% of the total weight of 1 monomer by weight of the monomer, and an alcohol value of 5 to 30 mgKOH / g and a weight average molecular weight of 50,000 to 100,000. And a glass transition temperature of 50 to 80 ℃.

In the method for producing an acryl resin according to a preferred embodiment for achieving another object of the present invention, the first vinyl-based monomer having a side chain alkyl group of 2 or less carbon atoms in the side chain and the carbon number of the side chain higher than the first monomer To form a mixture comprising 200 to 400 parts by weight of a mixed vinyl monomer containing a second vinyl monomer containing a side chain alkyl group having 5 to 5 parts by weight of a vinyl monomer having a hydroxyl group and 60 to 250 parts by weight of an organic solvent. . Subsequently, 0.5 to 2 parts by weight of the first vinyl monomer corresponding to 20 to 65% of the total weight of the first vinyl monomers included in the mixture and 0.5 to 2 parts by weight of the polymerization initiator are added to the mixture to perform the first polymerization reaction. Subsequently, the unreacted material contained in the first polymerization reactant is subjected to the second polymerization reaction. As a result, a high weather resistance acryl resin applied as a binder of the coating material for forming a transparent coating film is formed.

Acrylic resin prepared by this method is not only excellent in high weather resistance, heat resistance, scratch resistance, saline resistance and adhesion, but also in transparency and excellent storage stability. Can be used.

Hereinafter, the acrylic resin and its preparation method according to the present invention will be described in detail.

Akric Resin

The acryl resin applied to the transparent coating paint of the present invention includes a vinyl containing a first monomer having a side chain alkyl group having 2 or less side carbon atoms and a second monomer having a side chain alkyl group having a higher side chain carbon number than the first monomer. A vinyl monomer having a monomer and a hydroxyl group is polymerized to form.

Specifically, the acryl resin is a vinyl-based mixture of a first monomer containing a branched alkyl group having 2 or less carbon atoms in the side chain and a second monomer including a branched alkyl group having a higher branch carbon number than the first monomer. 20 to 400 parts by weight of the monomer, 5 to 30 parts by weight of the vinyl monomer having a hydroxyl group and 60 to 250 parts by weight of the organic solvent is formed to form a mixture of 20 parts by weight of the first monomer included in the mixture It is formed by adding a first monomer corresponding to from 65% to 0.5% by weight of the polymerization initiator and subjecting the first polymerization reaction. In this case, in order to further increase the yield of the formed acrylic resin, it is preferable to further perform a second polymerization reaction of the unreacted material contained in the first polymerization reaction product.

The vinyl monomers applied to form the acryl resin are monomers containing a side chain alkyl group having an unsaturated hydrocarbon bond, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, Isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, isobutyl methacrylate, normal hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, etc. are mentioned. have. In addition, ethylene glycol dimethacrylate having 2 fluorocarbon bonds, 1,6 hexanediol diacrylate, diethylene glycol dimethacrylate, 1,4 butanediol dimethacrylate and 3 or more unsaturated hydrocarbon bonds Trimethylol propane triacrylate which has, trimethylol propane trimethacrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more.

Monomers having a hydroxyl group to be applied to prepare the acrylic resin of the present invention are, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxy A ring opening part compound of (epsilon) -caprolactone etc. can be mentioned in addition to general monomers, such as oxypropyl acrylate. The monomers having these hydroxyl groups may be used alone or in combination of two or more thereof.

The vinyl monomers described above may form an aric resin that may satisfy the physical properties to be obtained in the present invention when using vinyl monomers including side chain alkyl groups having terminal side chain carbon atoms of 3 or less.

In particular, it is preferable to use the 1st monomer containing the side chain alkyl group of 2 or less side carbon atoms, and the 2nd monomer containing 2 side monomers containing the side chain alkyl group which has a higher carbon side chain than the said 1st monomer.

For example, the vinyl monomer of the mixture is formed by mixing the first monomer and the second monomer in a ratio (%) of 60:40 to 90:10 and the second monomer when the first monomer is methyl acrylate is used. Ethyl acrylate is used.

When the proportion of the first monomer in the mixed vinyl-based monomer is more than 90%, it is difficult to control the viscosity due to the increase in the glass transition temperature, the hardness is strengthened, but rather scratch resistance is generated. On the other hand, when the ratio of the first monomer is 60% or less, the hardness decreases and the heat resistance is lowered, and thus the physical properties of the acrylic resin required to form the transparent paint cannot be satisfied.

In particular, the first monomer is used two times in order to prepare the acrylic resin, the amount of the first monomer used is not only influences the appearance and storage stability of the acrylic resin to be formed, but also the overall physical properties of the acrylic resin .

Thus, the first monomer applied to carry out the first polymerization reaction uses 20 to 65% of the total amount of the first monomer applied to form the mixture, and preferably 25 to 60%.

If the amount of the first monomer exceeds 65% in the first polymerization reaction to form the acryl resin, the present invention may be applied to a transparent paint having excellent appearance, such as an acrylic resin, which the applicant has filed a patent on December 29, 2004. Has difficult physical properties That is, an acrylic resin having an opaque appearance is formed. On the other hand, when the amount of the first monomer used in the first polymerization reaction is less than 25% it is difficult to have the physical properties of the acryl resin.

The organic solvent applied to form the acryl resin is an aromatic solvent for mixing and dissolving monomers to carry out the polymerization reaction.

The acrylic resin of the present invention formed by the above-mentioned composition ratio has an alcohol value of 5 to 30 mgKOH / g, a weight average molecular weight of 50,000 to 100,000, and a glass transition temperature of 50 to 80 ° C.

If the alcohol value of the acrylic resin is less than 5mgKOH / g, there is a problem that the adhesion of the coating film to be formed is weak, the salt resistance of the coating film is formed when it exceeds 30.

In addition, when the weight average molecular weight of the acrylic resin is less than 50,000, problems occur in all physical properties such as hardness, scratch resistance, and saline resistance, and when it exceeds 100,000, the coating film is easily broken and scratch resistance is not preferable. Therefore, it is important that the above weight average molecular weight is in the above range. In addition, when the glass transition temperature is less than 50 ℃ hardness and heat resistance is weak, if the hardness exceeds 80 ℃, while the impact resistance may be lowered, the glass transition temperature should be within the above range.

Method for producing acric resin

In order to form the acrylic resin of the present invention, first, a mixture comprising a first monomer having a side chain alkyl group having 2 or less side chain carbon atoms and a second monomer having a side chain alkyl group having a higher side chain carbon number than the first monomer. 200 to 400 parts by weight of the vinyl monomer of 5 to 30 parts by weight of the vinyl monomer having a hydroxyl group and 60 to 250 parts by weight of an organic solvent to form a mixture. The mixture is then warmed up to 110-115 ° C. at the time of Reflux.

The vinyl monomer of the mixture is formed by mixing the first monomer and the second monomer in a ratio of 60:40 to 90:10. In addition, a polymerization initiator may be further added when the mixture is formed. The polymerization initiator is preferably used as a radical polymerization initiator by dissolving in an aromatic solvent which is an organic solvent to facilitate its use. Here, the mixing ratio of the monomers and the kind of monomers constituting the monomers are omitted in order to avoid duplication because they have been described in detail in the aric resin.

Examples of the polymerization initiator include benzoyl peroxide, 2,2-azobisisobutyronitrile, 2,2-azobismethylbutyronitrile, t-butyl peroxyoctoate, t-butyl peroxybenzoate, t-butyl Peroxy acetate etc. are mentioned.

Subsequently, 0.5 to 2 parts by weight of the first monomer and the polymerization initiator corresponding to 20 to 65% by weight of the total weight of the first monomers included in the mixture are added to the obtained mixture to undergo a first polymerization reaction. As a result, an acrylic resin is formed. It is preferable to add the said 1st monomer and a polymerization initiator over about 1 to 4 hours at about 90 degreeC temperature rising time.

Since the usage-amount of the 1st monomer and the kind of polymerization initiator which were applied to the said 1st polymerization reaction were demonstrated in detail for the purpose of a description, it abbreviate | omits to avoid duplication.

Subsequently, an unreacted product contained in the first polymerization reactant is subjected to a second polymerization reaction to form an aric resin applied to form a transparent coating film. The second polymerization reaction is performed by further adding an organic solvent in which a polymerization initiator is dissolved, and corresponds to increasing the yield of the aric resin to be formed.

As a result, an acrylic resin having a weight average molecular weight of 50,000 to 100,000 and a glass transition temperature of 50 to 80 ° C, an alcohol of 5 to 30 mgKOH / g, a Gardner viscosity of V to Z3, and a volatile matter of 30 to 60% by weight is formed. do.

Hereinafter, the present invention will be described through the following examples, comparative examples and test examples. However, the technical scope of the present invention is not limited by these.

Example 1

245.8 parts by weight of methyl methacrylate (first monomer), 61.4 parts by weight of ethyl acrylate (second monomer) and hydroxyethyl methacrylate (vinyl monomer having hydroxyl group) in a reactor equipped with a thermometer, a stirrer and a reflux cooler ) 16 parts by weight was added, 120 parts by weight of xylene as a solvent was added and the reaction temperature was raised to 105 ° C. at the time of reflux. Next, 0.3 parts by weight of 2,2-azobismethylbutyronitrile is added together with 2 parts by weight of xylene at the time of heating at 90 ° C. To the obtained mixture, 76.8 parts by weight of methyl methacrylate and 0.8 parts by weight of 2,2-azobismethylbutyronitrile were added dropwise over 3 hours, such as 103.3 parts by weight of xylene. After 60 minutes of holding reaction, 1.1 parts by weight of 2,2-azobismethylbutyronitrile and 166.1 parts by weight of xylene 50 parts by weight of toluene were added dropwise over 3 hours. Thereafter, after maintaining the reaction for 60 minutes, toluene was added to 156.2 parts by weight to prepare an acrylic resin.

The acrylic resin produced in this way has a weight average molecular weight of 77,000, a hydroxyl value of 9 mgKOH / g, a glass transition temperature of 67 ° C, a nonvolatile content of 40% by weight, and a Gardner viscosity Z1-.

<Example 2>

Acrylic resin was prepared in the same manner as in Example 1, except that 184.3 parts by weight of methyl methacrylate, 122.9 parts by weight of ethyl acrylate and 16 parts by weight of hydroxyethyl methacrylate were used while maintaining the reaction temperature of 105 ° C.

The acrylic resin produced by this method has a weight average molecular weight of 54,000, a hydroxyl value of 9 mgKOH / g, a glass transition temperature of 54 ° C, a nonvolatile content of 40%, and a Gardner viscosity W.

<Example 3>

Acrylic resin was prepared in the same manner as in Example 1, except that 276.5 parts by weight of methyl methacrylate, 30.7 parts by weight of ethyl acrylate and 16 parts by weight of hydroxyethyl methacrylate were used while maintaining the reaction temperature of 105 ° C.

The acrylic resin produced in this way has a weight average molecular weight of 98,000, a hydroxyl value of 9 mgKOH / g, a glass transition temperature of 82 ° C., a nonvolatile content of 40%, and a Gardner viscosity Z3 +.

Comparative Example 1

Manufactured the highly weather-resistant Acrylic Resin NORUCRYLIC 1120, which was developed at the existing Dipiai. The kind of the monomer used for the production of NORUCRYLIC 1120 is the same as in Example 1, except that the amount of methyl methacrylate used in the second reaction during the polymerization reaction corresponds to about 69% of the amount of methyl methacrylate used in the formation of the mixture. .

The acrylic resin of the said comparative example has a weight average molecular weight of 69,000, the hydroxyl value of 9 mgKOH / g, the glass transition temperature of 70 degreeC, 40% of non volatile matters, and Gardner viscosity Z-.

Comparative Example 2

PARALOID B-44, a product of ROHM & HASS, which is widely used as a high weather resistance resin, was implemented. The synthetic resin had a weight average molecular weight of 74,500, a Gardner viscosity W +, a glass transition temperature of 53 ° C, and a nonvolatile content of 40%.

<Production Examples 1-3 and Comparative Production Examples 1-2>

In Table 1 below, transparent paints containing the acrylic resins of the Examples and Comparative Examples were prepared in the compositions shown in Table 1 below.

TABLE 1

Preparation Example 1 Preparation Example 2 Preparation Example 3 Comparative Production Example 1 Comparative Production Example 2 Resin of Example 1 25 Resin of Example 2 25 Resin of Example 3 25 Resin of Comparative Example 1 25 Resin of Comparative Example 2 25 Cellulose acetate 39.8 39.8 39.8 39.8 39.8 Butyl Cellosolve 27.1 27.1 27.1 27.1 27.1 xylene 3.8 3.8 3.8 3.8 3.8 toluene 4.1 4.1 4.1 4.1 4.1  additive* 0.2 0.2 0.2 0.2 0.2

Coating Film Characterization of Coating Paint Containing Acric Resin

After spray coating the coating materials of Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 2 and completely dried, the physical properties of the formed coating film were evaluated. The following physical property evaluation evaluated the physical properties of the coating material which can be applied commercially in addition to evaluation of the characteristic value of this invention. The results are shown in Table 2.

TABLE 2

 Inspection items  standard result Preparation Example 1 Preparation Example 2 Preparation Example 3 Comparative Production Example 1 Comparative Manufacturing Example 2 Exterior No defect ◎ ◎ ○ △ X Polish 62.2 58.2 55.2 41.4 39.2 Weatherability (Q U V) △ E (300hrs) △ E reference value measurement 0.22 0.68 0.42 1.54 0.99 △ E (3000hrs) 1.56 2.54 2.06 3.59 1.68 Weatherability (WOM) △ E (300hrs) △ E reference value measurement 0.35 0.58 0.80 1.69 0.87 △ E (3000hrs) 1.67 2.01 1.68 3.87 1.65 Pencil hardness No more than 3 scratches 3 H or more 4 H or more 3 H or more 2 H or more 3 H or more Cross cut 100/100 ◎ ◎ ◎ △ ◎ Solvent resistance Swelling, no discoloration ◎ ◎ ◎ △ ◎ Flexural test No cracks or peeling ◎ ◎ ○ ○ ◎ Impact test No cracks or peeling ◎ ◎ ○ △ ◎ Navigability test No cracks or peeling ◎ ◎ ◎ X ○ Detergent resistance No problem ◎ ○ ◎ X ○ Corrosion resistance 240 Hrs ◎ ◎ ◎ Less than 10% of white rust occurrence Less than 5% of white rust occurrence Invasion test 50 ° C. x R.H. 98% 240 Hrs ◎ ◎ ◎ X ◎ Zhejiang 60 ℃, 720hrs ◎ ◎ ◎ △ △

In Table 2, ◎ indicates a very good (no exception at all), ○ indicates a good (substantially no exception), △ indicates a normal (slightly poor) state, X is bad ( Very poor). The performance of the coating film was evaluated according to the general coating material evaluation method.

1. Appearance: Protective film. Evaluate nothingness and stamping, appearance condition.

2. Gloss: Evaluate glossiness at 60 ° C.

3. Weather resistance: QUV / WOM TEST, the reference value measured below △ E 1.0 or less (QUV: 300hrs) / 3000hrs and △ E3.0 or less

4. Pencil hardness: draw 5 pieces with Mitsubishi Uni pencil lead and check

5. Cross cut: Draw 10 squares each with a checkerboard mode and evaluate the peeling state with cellopan tape.

6 Solvent resistance: Toluene, Benzene 20 ℃, 48 hours after standing, the naked eye to evaluate the swelling, discoloration, and other abnormalities.

7. Bend Test: (180o T Bend)

8. Impact test: Check the crack and peeling of impact film when falling from 500g x50cm height.

9. Boiling water test: Checking blisters, swelling discoloration and shrinkage after standing in boiling water above 98 ℃ for 0.5 hour.

10. Detergent resistance: Swell and discoloration after 240 hours in a 40%, 2% synthetic detergent solution.

11. Corrosion resistance test: salt spray test ((1) plate part: no abnormality in appearance, (2) cutting part: red blue color less than 50%)

12. Moisture resistance test: ((1) Flat plate part: No abnormality in appearance, (2) Processing part: No abnormality after peeling test with cellophane tape, (3) Cross section: Peeling amount 1.0 or less after peeling test with cellophane tape , (4) Cutting part: Red blue redness rate should be 50% or less)

13. Storage: No change in viscosity when confirmed by 25 ℃ Gardner viscometer

As shown in Table 2, it was confirmed that the coating material containing the acryl resins of Examples 1 to 3 had excellent characteristic values in all physical properties such as weather resistance, high hardness, scratch resistance, and adhesion.

Acrylic resin prepared by the method as described above is used as a binder of the paint to form a transparent coating film has the characteristics of high weather resistance, heat resistance, saline resistance, scratch resistance and adhesion, and has a transparent appearance and storage safety. Therefore, the acryl resin may be widely used as a binder of a clear transparent coating material for which appearance is important.

 As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified without departing from the spirit and scope of the invention described in the claims below. And can be changed.

Claims (8)

delete delete The first acrylate monomer containing a branched alkyl group having 2 or less side chain alkyl groups and the second acrylate monomer including a branched alkyl group having a side chain carbon number higher than that of the first acrylate monomer may be 60:40 to 90:10. Forming a mixture comprising 200 to 400 parts by weight of the mixed vinyl monomers, 5 to 30 parts by weight of an acrylate monomer having a hydroxyl group, and 60 to 250 parts by weight of an organic solvent, which are included in a ratio; Adding a first monomer corresponding to 20 to 65% of the total weight of the first monomer included in the mixture with 0.5 to 2 parts by weight of the polymerization initiator to the mixture to perform a first polymerization reaction; And A method of producing an acrylic resin applied to the transparent coating material comprising the step of forming a resin resin applied to form a transparent coating film by the second polymerization reaction of the unreacted material contained in the first polymerization reactant. delete According to claim 3, wherein the acryl resin has an alcohol value of 5 to 30mgKOH / g, a weight average molecular weight of 50,000 to 100,000, the glass transition temperature is applied to the transparent coating paint, characterized in that it has a characteristic of 50 to 80 ℃ Process for the production of acryl resin. The method of claim 3, wherein the first monomer is methyl acrylate, methyl methacrylate or a mixture thereof, and the second monomer is ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, At least one selected from the group consisting of normal butyl acrylate, normal butyl methacrylate, isobutyl methacrylate, normal hexyl methacrylate, lauryl methacrylate, stearyl methacrylate and cyclohexyl methacrylate A method of producing an acrylic resin applied to a transparent coating paint, characterized in that. According to claim 3, wherein the vinyl monomer having a hydroxyl group is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxy propyl methacrylate, 4-hydroxybutyl acrylate, caprolactone derivatives A method for producing an acrylic resin applied to the transparent coating paint, characterized in that any one selected from the group consisting of. The method of claim 3, wherein the second polymerization reaction is performed by adding an organic solvent including 0.8 to 1.5 parts by weight of the photoinitiator.