JP2001240620A - Raw material composition for high solid acrylic resin composition, high solid acrylic resin composition, coating material including high solid acrylic resin composition and method for producing high solid acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a raw material composition for high solid acrylic resin composition excellent in scratch resistance, clearness and smoothness. SOLUTION: This raw material composition is obtained by including 50-80 pts.wt. methacrylic monomer having an aliphatic group, 10-40 pts.wt. methacrylic monomer having a hydroxy group, 5-50 pts.wt. acrylic or methacrylic functional monomer having a higher alkyl group, 1-20 pts.wt. methacrylic monomer containing a metal component, 2-8 pts.wt. chain transfer agent containing a hydroxy group, 3-9 pts.wt. initiator and 1-20 pts.wt. silicone monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a raw material composition of a high solid acrylic resin composition, a high solid acrylic resin composition, a paint containing the high solid acrylic resin composition, and a method for producing the high solid acrylic resin composition. More specifically, a raw material composition of a high solid acrylic resin composition having excellent scratch resistance, sharpness and smoothness, and a high solid acrylic having excellent scratch resistance, sharpness and smoothness. The present invention relates to a resin composition, a paint containing such a high solid acrylic resin composition, and a method for producing such a high solid acrylic resin composition.

[0002]

2. Description of the Related Art Recently, volatile organic compounds (VO) have developed among developed countries including the United States in connection with the problem of air pollution.
The emission allowance for latile organic compounds (hereinafter referred to as “VOC”) has been strictly strengthened.
Environmental regulations on VOCs have begun in 1999.

As an appropriate countermeasure against the above, V
A method using a non-staining paint capable of relatively lowering the content of OC has already been proposed.

[0004] Such conventional non-staining paints include:
Silicone resin paints, acrylic resin paints, fluororesin paints and emulsion resin paints are well known.

However, the above-mentioned silicone resin paint and acrylic resin paint have strict curing conditions, and fluorine resin paint has solvent solubility because a higher alkyl group is introduced into its structure. Due to the low polarity, not only is the contaminant easily adsorbed to the coating film, but it is difficult to remove traces of the contamination, and there is a problem that it is impossible to maintain the aesthetic appearance over a long period of time.

[0006] Emulsion resin paints are water-based paints prepared by using an emulsion resin containing an acrylic monomer as a binder, and blending a pigment, a filler and an additive. In reality, it is closer to a stain-removing paint than a non-stainable paint, and because of the poor weather resistance described above, it is necessary to perform repair painting. There is a problem that it is difficult to apply as a material for an exterior finish in a difficult place.

Therefore, in order to fundamentally improve the stain resistance of the paint, the surface of the paint film is replaced with a hydrophilic component,
The main cause of pollution is exhaust gas, weakening the binding with lipophilic substances such as soot, increasing the cross-linking density of the coating film not only makes it difficult for the contaminants to penetrate, but also once contaminated, Research and development of high-solid non-polluting paints that have a function to remove attached pollutants that can be easily removed by rainwater are absolutely necessary.

[0008] In particular, high solid resin coatings are excellent in workability, can use existing manufacturing and coating equipment as they are, and can reduce the VOC content. And in the paint industry.

As for the above-mentioned high solid resin paint, for example, Korean Patent No.
As a vivid high solid resin composition and a method for producing the same, a vinyl monomer having an organic acid group is used in an amount of 1 part by weight or more.
Not more than 15 parts by weight of a vinyl monomer having a hydroxyl group and not more than 50 parts by weight, and not more than 15 parts by weight and not more than 35 parts by weight of a vinyl monomer having an aromatic group and having an aliphatic group. The vinyl monomer is composed of 15 parts by weight or more and 65 parts by weight or less, and has an acid value of 5 mgKOH / g or more.
mgKOH / g or less, the hydroxyl group content is 2% or more and 6% or less, and the glass transition temperature (glass transition temperatu
re, Tg) is −15 ° C. or more and 30 ° C. or less, and the kinematic viscosity at 25 ° C. is 17.6 stokes or more and 22.7.
The acrylic resin composition for high-definition high-solid resin paint having Stokes or less, an average molecular weight of 3,000 or more and 8000 or less, and a molecular weight distribution of 3 or less, and 99.2% of the acrylic resin composition described above. In the aromatic hydrocarbon-based solvent containing the above, while dropping the initiator solution over 3 hours to 6 hours, in the temperature range of 130 ° C to 170 ° C, 4 hours to 6 hours A method for producing an acrylic resin for a high definition high solid resin coating composition which is polymerized over a long period of time is disclosed.

The acrylic resin for a high definition high solid resin coating composition obtained by this production method is characterized in that the low molecular weight acrylic resin used in the above high solid resin coating composition is characterized by a decrease in physical properties of the coating film such as weather resistance. Causes a decrease in coating film appearance performance such as fluidity and smoothness, and has a wide molecular weight distribution.
It is difficult to form a uniform crosslink density because the distribution of hydroxyl groups that undergo a crosslink reaction is different for each resin molecule, and some acrylic resin molecules that are not involved in crosslinkage are present. However, there arises a problem that coating film performance such as resistance, scratch resistance and chemical resistance becomes poor.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and is intended to solve the above problems.
Ink) exhibits high elasticity and high durability, while expanding the elastic region of the coating film and expressing a large breaking energy. While improving the surface hardness and the like, and maintaining the hydrophilicity of the coating film, the raw material composition of the high solid acrylic resin composition having excellent water resistance, weather resistance and sharpness, and also having non-staining properties, such as Provided are a high-solid acrylic resin composition having excellent properties, a paint containing the high-solid acrylic resin composition having such excellent properties, and a method for producing a high-solid acrylic resin composition having such excellent properties. It is intended to be.

[0012]

Means for Solving the Problems The present invention has been made to achieve the above object, and the raw material composition for a high solid acrylic resin composition according to claim 1 is a methacrylic monomer, In the high solid acrylic resin composition containing a chain transfer agent and an initiator, as a methacrylic monomer, a methacrylic monomer having an aliphatic group is 50 to 80 parts by weight, and a methacrylic monomer having a hydroxyl group is used. 10 to 40 parts by weight of a monomer, 5 to 50 parts by weight of an acrylic or methacrylic functional monomer having a higher alkyl group, and a methacrylic monomer containing a metal component , 1 to 20 parts by weight, and as a chain transfer agent, 2 to 8 parts by weight of a hydroxyl group-containing chain transfer agent, and 3 to 9 parts by weight of an initiator. Wherein, and, silicone monomer (si
licone monomer) in an amount of 1 to 20 parts by weight. The high solid acrylic resin composition raw material composition according to claim 2 is the high solid acrylic resin composition according to claim 1, wherein the acrylic or methacryl functional monomer having a higher alkyl group is acetoacetyl. Acetoxyethyl methacrylate having a group and / or ε-caprolactone acrylate monomer having a hydroxyl group.

[0013] In the present specification, when a compound name in English is shown by adding () to the compound name in Japanese notation, the compound name in English notation is used.
It takes precedence over the compound name shown in Japanese notation. Also,()
The compound name in katakana notation shown after the semicolon (;) after the compound name shown in English notation is the transliteration of the compound name shown in English notation. It is attached. The high solid acrylic resin composition raw material composition according to claim 3 is the high solid acrylic resin composition according to claim 1, wherein the methacrylic monomer containing a metal component is tetraisopropyl titanat.
e) or tetranormal butyl titanate (tetra-nb)
to alkylalkoxy titanates such as utyl titanate and tetrakis (2-ethylhexyl) titanate;
After reacting fatty acids having 8 to 12 carbon atoms,
It is characterized in that it is titanium methacrylate (titanium methacrylate) synthesized by modifying methacrylic acid.

[0014] The high solid acrylic resin composition according to claim 4 is a silicone monomer of the high solid acrylic resin composition according to claim 1.
Is ethyl silicate, tetrakis-2-ethylorthosilicate
silicate analogues having alkoxy groups or hydroxy groups, such as osilicate, and / or alkylalkoxy silane compo, such as methylmethoxysilane.
unds). Further, the method for producing a high solid acrylic resin composition according to the present invention provides a method for producing a high solid acrylic resin composition for producing the high solid acrylic resin composition according to the present invention more effectively. The method for producing a high solid acrylic resin composition according to claim 5, wherein the methacrylic monomer having an aliphatic group is 50 to 80 parts by weight, and the methacrylic monomer having a hydroxyl group is 10 parts by weight. More than 40
Parts by weight, an acrylic or methacrylic functional monomer in an amount of 3 to 50 parts by weight, a methacrylic monomer containing a metal component in an amount of 1 to 20 parts by weight, and a silicone monomer. 1 to 20 parts by weight of a monomer, 2 to 8 parts by weight of a chain transfer agent containing a hydroxyl group, and 3 to 9 parts by weight of an initiator in a medium boiling solvent for 6 hours or more. The method is characterized in that polymerization is carried out in a temperature range of 110 ° C. or more and 150 ° C. or less over 8 hours to 11 hours while dripping over 8 hours or less. The high solid acrylic resin composition according to claim 5 is obtained by polymerizing the high solid acrylic resin composition raw material composition raw material composition according to any one of claims 1 to 4. In the paint containing the high solid acrylic resin composition according to claim 6, the high solid acrylic resin composition according to claim 5 was dissolved in a solvent. The paint containing the high-solid acrylic resin composition according to claim 7 is a paint according to claim 5.
60 parts by weight or more and 90 parts by weight or less of the high-solid acrylic resin composition described in the above, and 10 parts by weight or more and 40 parts by weight or less of the low-viscosity non-yellowing aliphatic polyisocyanate resin composition to obtain a solid content. It is characterized in that the concentration is 60% and the viscosity is 16 seconds or more and 20 seconds or less (Zahn cup # 2).

[0015] The method for producing a high solid acrylic resin composition according to claim 8 is the same as the method for producing a high solid acrylic resin composition according to claim 5, wherein the acrylic or methacrylic functional monomer is a higher-functional monomer. An acetoacetoxyethyl methacrylate monomer having an alkyl group and an acetoacetoxy group (acetoacetoxyethyl methacr)
ylate monomer and / or ε-caprolactone acrylate monomer having a hydroxyl group (ε-caprolactoneacryl)
ate monomer).

The method for producing a high solid acrylic resin composition according to claim 9 is a method for producing a high solid acrylic resin composition according to claim 8, wherein the methacrylic monomer containing a metal component is: Tetraisopropyl titanate or tetra-n-butyl titanate and tetrakis-2-ethylhexyl titanate (tetrakis)
After reacting an alkyl titanate such as (2-ethylhexyl) titanate) with a fatty acid having 8 to 12 carbon atoms, methacrylic acid is denatured, and titanium methacrylate (titaiummethacrylic) is synthesized.
ate; titanium methacrylate). The method for producing a high-solid acrylic resin composition according to claim 10 is the method for producing a high-solid acrylic resin composition according to claim 8, wherein ethyl silicate (ethy) is used as the silicone monomer.
l silicate), alkoxy groups (alkoxy groups) or hydroxy groups (hydroxy group) such as tetrakis-2-ethylorthosilicate.
silicate analogues (groups)
s) and / or methylmethoxysilane
It is characterized in that alkylalkoxy silane compounds such as xy silane are used.

[0017] The method for producing a high solid acrylic resin composition according to claim 11 is a method for producing a high solid acrylic resin composition according to any one of claims 8 to 10, wherein
In order to modify and polymerize a hydrophilic silicone substance to an acrylic resin containing a hydroxyl group, as a methacrylic monomer containing a metal component, an organic titanate such as an alkyl titanate, any one of an organic tin compound and an alkali catalyst is used. With respect to 100 parts by weight of the reactant of the polymer,
It is characterized in that 0.01 to 0.1 parts by weight is added.

The raw material composition of the high solid acrylic resin composition, the high solid acrylic resin composition, the paint containing the high solid acrylic resin composition and the method for producing the high solid acrylic resin composition according to the present invention will be described in detail below. I do.

First, the high solid acrylic resin composition according to the present invention is prepared by subjecting various types of monomers having vinyl-type double bonds of acrylate or methacrylate to a solution using a thermal decomposition initiator. Manufactured by radical polymerization inside.

The monomer having a vinyl-type double bond includes 50 to 80 parts by weight of a methacrylic monomer having an aliphatic group and 10 parts by weight of a methacrylic monomer having a hydroxyl group. To 40 parts by weight, 5 to 50 parts by weight of an acrylic monomer or a methacrylic monomer, and 1 to 20 parts by weight of a methacrylic monomer containing a metal component. And one silicone monomer
Not less than 20 parts by weight, not more than 20 parts by weight, 2 to 8 parts by weight of a chain transfer agent containing a hydroxyl group, and not less than 3 parts by weight of an initiator.

At this time, the methacrylic monomer having an aliphatic group includes butyl methacrylate (butyl m-methacrylate).
ethacrylate), ethyl methac
rylate-2-ethylmethacr
ylate), lauryl methacryla
te), isobornyl methacrylate (isobornyl metha)
crylate) or the like can be selected and used at least.

The above-mentioned methacrylic monomer having a hydroxyl group is used in consideration of a co-condensation reaction with an inorganic silicone substance and a crosslinking bond with an isocyanate.
It may be added in an amount of not less than 40 parts by weight and more preferably not less than 35 parts by weight.

If the amount of the methacrylic monomer having a hydroxyl group is less than 10 parts by weight, the position where the inorganic silicone material is formed becomes narrow, and the influence on the crosslink density with the isocyanate is reduced. This gives rise to a problem that the physical properties of the coating film deteriorate. If the amount of the methacrylic monomer is more than 40 parts by weight, the coating density is excessively increased to harden the coating film, storage stability, compatibility with a crosslinking agent and a non-polar solvent. However, there arises a problem that the device becomes defective. Examples of the methacrylic monomer having a hydroxyl group include 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.
rylate) can be used. Further, the acrylic or methacrylic functional monomer having a higher alkyl group used in the present invention enhances the elasticity of the coating film and causes a crosslinking reaction with a polyisocyanate.
It is added to increase the crosslink density in the king reaction and form a dense coating to give flexibility to the coating and to improve the scratch resistance. If considered, it is added in an amount of 5 to 50 parts by weight. The acrylic or methacrylic functional monomer having a higher alkyl group used in the present invention is preferably added in an amount of 5 to 20 parts by weight. If the addition amount of the acrylic or methacrylic functional monomer having a higher alkyl group is less than 5 parts by weight, a crosslinking reaction (crosslinking reaction) is performed.
In the case of n), there arises a problem that the crosslinking density is reduced, and the scratch resistance and the stain resistance are reduced. Further, when the addition amount of the acrylic or methacrylic functional monomer having a higher alkyl group exceeds 50 parts by weight, there is a problem that the strength of the coating film is reduced. Examples of the acrylic or methacrylic functional monomer having a higher alkyl group include acetoacetoxyethyl methacrylate (acetacetoxyethyl) having an acetoacetyl group.
methacrylate) and ε-caprolactone acrylate monomer having a hydroxyl group (ε-caprolactoneacrylate mono)
maer).

As described above, by introducing a functional group of a soft component into the acrylic structure, the cross-linking expands the elastic region of the coating film while exhibiting high elasticity and high durability, and causes large destruction. By expressing energy, an acrylic resin composition having excellent scratch resistance can be obtained.

The methacrylic monomer containing a metal component is added in an amount of 1 part by weight or more and 20 parts by weight or less in order to increase the hardness of the coating film and the adhesion to the coating object. The methacrylic monomer containing a metal component is preferably added in an amount of 1 part by weight or more and 10 parts by weight or less.

If the addition amount of the methacrylic monomer containing a metal component is less than 1 part by weight, problems such as a decrease in hardness of the coating film and a decrease in adhesiveness occur, and the addition of 20 parts by weight. If added in excess of, the viscosity rises sharply, causing a problem that it is difficult to form a high solid. In the present invention, zinc methacrylate (zincmethacrylate) or titanium methacrylate (titanium methacrylate) was used as the methacrylic monomer containing a metal component, but the titanium methacrylate (titanium methacrylate) was used as the methacrylic monomer. Is tetraisopropyl titanate
sopropyltitanate) or tetra-n-butyl titanate and tetrakis-
2-ethylhexyl titanate (tetrakis (2-ethylhexy
l) titanate) and other alkyltitanates
Itanate is reacted with a fatty acid having 8 to 12 carbon atoms, and then reacted with methacrylic acid (methacrylic acid).
The reaction product of d) was used.

Further, in the present invention, the surface of the coating film is replaced with a hydrophilic component to reduce the binding force with the lipophilic substances such as exhaust gas and soot, which are the main causes of contamination, and to increase the crosslink density of the coating film. Not only is it difficult for contaminants to penetrate, but once it is contaminated, it can be easily removed by rainwater.
er) was added.

At this time, a silicone monomer (silicone mon
When the amount of omer) is less than 1 part by weight, there is a problem that the stain resistance is reduced. When the amount exceeds 20 parts by weight, an excessive increase in viscosity and a decrease in hydroxyl group concentration are caused. Therefore, it is desirable that the amount of the silicone monomer added be 1 part by weight or more and 20 parts by weight or less. It is particularly desirable to add the silicone monomer in an amount of 1 part by weight or more and 10 parts by weight or less. This silicone monomer
Examples include ethyl silicate and tetrakis-2-ethyl orthosilicate (tetrakis-2-e).
Alkoxyg (alkoxyg) like thylorthosilicate
alkoxide silane compounds such as silicate analogues having a roups or hydroxy groups, and alkylalkoxy silane compounds such as methylmethoxy silane.
ds) etc. can be used.

The chain transfer agent containing a hydroxyl group not only plays an important role in reducing the molecular weight of the resin during the polymerization reaction, but also finally binds to the terminal of the synthetic polymer to form a coating film. At this time, it is added in order to increase the density of the hydroxyl group serving as a cross-linking point with the cross-linking agent and to form a polymer chain while being cured.

At this time, if the amount of the chain transfer agent containing a hydroxyl group is less than 2 parts by weight, there is a problem that the viscosity cannot be easily adjusted. The amount of the chain transfer agent containing a hydroxyl group does not need to be added in excess of 8 parts by weight.
It is desirable to add from not less than 8 parts by weight to not more than 3 parts by weight, especially not more than 3 parts by weight and not more than 6 parts by weight. Compounds that can be added as a hydroxyl group-containing chain transfer agent include hydroxyl group-containing 2-mercaptoethanol, 2-hydroxyethyl-3-
Mercaptopropionate (2-hydroxyethyl-3-mercapt
It is desirable to use o-propionate).

Further, a polymerization initiator of a radical initiator is added to adjust the molecular weight of the high solid acrylic resin composition, and the amount of the initiator added is more than that of a general acrylic resin. It is about 3 times more than 3 parts by weight to 10 parts by weight, and a particularly desirable amount is 3 parts by weight or more and 8 parts by weight or less.

At this time, the amount of the radical initiator added is 3
If the amount is less than 10 parts by weight, the degree and molecular weight of the acrylic resin composition will increase, and the spray workability will deteriorate. If the amount exceeds 10 parts by weight, the molecular weight will decrease. A problem arises in that the physical properties of the coating film are deteriorated due to the excessive coating. Compounds that can be added as the radical initiator include benzoic peroxide,
Tertiary butyl peroxybenzoate (ter-buty
l-peroxy-benzoate, tertiary butyl-peroxy-2-ethyl hexanate
ylhexanoate), tertiary amyl-peroxy-2
-Ethyl hexanate (ter-amyl-peroxy-2-ethylhexan
oate) can be used, and such an organic peroxide radical polymerization initiator can be used alone or
A mixture of more than one species can be used.

A methacrylic monomer having an aliphatic group, a methacrylic monomer having a hydroxyl group, an acrylic or methacrylic functional monomer, and a methacrylic monomer containing a metal component having the above composition ratio. The monomer, the silicone monomer, the chain transfer agent containing a hydroxyl group and the initiator are added dropwise to the medium boiling point solvent over a period of 6 hours to 8 hours, and the temperature of 110 ° C. to 150 ° C. In the temperature range, the polymerization is carried out over a period of 8 hours to 11 hours.

Here, usable solvents include aromatic hydrocarbons such as toluene and xylene, normal butyl acetate, ethylene glycol ethyl ether acetate, and the like.
There are esters such as racetate and ketones such as methyl-isobutyl ketone and methyl-n-amylketone. Considering the effect of the reaction temperature on the molecular weight and final viscosity as needed. It is possible to use a high-boiling or medium-boiling solvent singly or as a mixture.
Most preferably, the synthesis is performed within a temperature range of 110 ° C. or more and 150 ° C. or less using a solvent of not more than 110 ° C.

As described above, a mixed solution containing a monomer, an initiator and a chain transfer agent is dropped at a uniform rate over a period of 6 to 8 hours into a medium boiling point solution at 110 ° C.
The polymerization is carried out in a temperature range of not less than 150 ° C. and not less than 8 hours and not more than 11 hours.

At this time, the reason why the dripping time is lengthened as described above is to prevent in advance the reflux of the medium boiling point solvent which can generally occur during the dripping of the monomer mixture in the conventional acrylic resin synthesis. is there.

As described above, by stably inducing the reaction conditions, the monomer formation ratio and the functional group distribution are made uniform,
And when a chain transfer agent with a functional group sticks to the end of the molecular structure and a coating film is formed through cross-linking with the resin, the molecular weight of the resin is polymerized in a linear direction, ultimately resulting in excellent gloss and hardness In addition, it is possible to obtain a high solid acrylic resin composition that provides excellent performance in chemical properties. In the course of this reaction, a reaction catalyst can be used to modify and polymerize the hydrophilic silicone substance to the hydroxyl group-containing acrylic resin. Usable reaction catalysts include organic titanates such as alkyl titanates, organic tin compounds, and alkali catalysts, and the amount added is 0.01 to 0.1 parts by weight based on 100 parts by weight of the total reactants. Of the reaction catalyst is preferably used in an amount of 0.01 part by weight or less, more preferably 0.05 part by weight or less.

When a high solid acrylic resin composition is produced by the above-described method, the resin composition has a water average molecular weight (Mn) of 2,000 to 5,000, and a glass transition temperature (Tg) of 30 to 7 ° C.
0 ° C., viscosity (viscosity at 23 ° C.) of 1200 cP or more and 2000 cP or less, and acid value of 5 mgKOH / g or more and 30 m
An acrylic resin composition having a non-volatile content of 75% or more can be produced in a range of gKOH / g or less and a hydroxyl group content of 2% or more and 6% or less.

Further, according to the present invention, the high solid acrylic resin composition formed as described above can be used for producing a general coating composition. In particular, the present invention, the high solid acrylic resin composition formed as described above and 60 parts by weight or more and 90 parts by weight or less,
Low-viscosity non-yellowing aliphatic polyisocyanate (non-yellow
a high solid acrylic resin composition containing 10 to 40 parts by weight of a resin composition. The paint within the above range has a solid content of 60% and a viscosity of 16 seconds or more and 20% or more.
Seconds or less (Zahn cup♯2).
Generally, conventional paints have a viscosity of 20 seconds (Zahnc
Up♯2), a large amount of volatile solvent had to be added to adjust the solid content to 50%. However, according to the present invention, a small amount of volatile solvent was used to increase the solid content to 60%. % Even if adjusted to 16% or more and 20 seconds or less (Zah
ncupｕ2), which is an advantage of the present invention. "Zahn cup" is a viscosity defined by a viscosity measurement method (ASTM D-4212).

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the present invention is not limited to only the following examples.

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Example 1> In a 4-neck flask equipped with a stirrer, normal butyl acetate (n-butyl acetate) was used as a solvent.
After the addition of 9.9 g, the inside of the four-ball flask is replaced with nitrogen gas, and the temperature is raised to 130 ° C. and maintained while stirring. In the above-mentioned solvent, normal butyl methacrylate (n-bu
tylmethacrylate), 173.0 g of methyl methacrylate, and 2-hydroxyethylmethacrylate as a methacrylic monomer having a hydroxyl group.
And acetoacetoxyethyl methacrylate (acetoacetoxyethylmethacrylat) as an acrylic or methacrylic functional monomer having a higher alkyl group.
e) was added while changing the weight shown in Table 1 below,
6.0 g of titanium methacrylate (titanium methacrylate) as a methacrylic monomer containing a metal component and 2-mercaptoethanol as a chain transfer agent containing a hydroxyl group
Of tertiary amyl peroxy-2-ethylhesnate as an initiator.
exanoate) over a period of 4 hours.
After dropping at a uniform rate, the reaction temperature is raised to 1
After raising to 40 ° C. and aging for about 2 hours, tertiary amyl peroxy-2-ethylhexanate (te
r-amyl-peroxy-2-ethylhexanoate) 4 g, and
The unreacted monomer is allowed to react with stirring for 2 hours, and then 0.3 g of tetraisopropyltitanate as an esterification catalyst and ethyl silicate as a silicone monomer are reacted. Was added, and the reaction was completed at the same temperature for about 3 hours to produce a high solid acrylic resin composition.

Next, after mixing 109 g of the high solid acrylic resin composition produced as described above and 36 g of an aliphatic polyisocyanate (NCO = 23%), the mixture is composed of butyl acetate, xylin and the like. Add 35 g of diluted solvent to be able to air spray.
At 25 ° C., the viscosity was adjusted to 20 seconds (Zahncup # 2) to produce a coating containing the high solid acrylic resin composition. Example 2 As an acrylic or methacrylic functional monomer having a higher alkyl group, acetacetoxyethyl methacrylat was used.
e) as methacrylic monomer containing 40.0 g of metal component and titanium methacrylate (titaniummeth
acrylate (titanium methacrylate) was changed to the weight shown in Table 1 below, except for the addition of the additives.
Experiments were conducted in the same manner as in Example 1 to produce a high-solid acrylic resin composition and a paint containing the composition. Example 3 As an acrylic or methacrylic functional monomer having a higher alkyl group, acetaacetoxyethyl methacrylat was used.
e) and add 40.0 g of a silicone monomer (silicone
Ethyl silicate (ethyl silicat)
While changing e) to the weight shown in Table 1 below, a high solid acrylic resin composition and a paint containing the composition were produced in the same manner as in Example 1 except for the additives. <Comparative Example 1> An acrylic or methacrylic monomer, a methacrylic monomer containing a metal component and a silicone monomer (silicone monomer) were added, except that
Experiments were conducted in the same manner as in Example 1 to produce a coating containing the high solid acrylic resin composition. <Experimental Example> In order to evaluate the coating film properties of the paint containing the high solid acrylic resin composition produced as described above, first, the surface of a thin plate was polished with a polishing paper # 220, and then the paint was dried. Spray-coated to a thickness of 50 μm and dried, then polished with abrasive paper # 600, sprayed and dried with a base coat white paint to a coating thickness of 25 μm, and then dried with high solids produced according to Example 1 above. A paint containing the acrylic resin composition was spray-coated to a dry film thickness of 50 μm, and this was naturally dried for 7 days, and the physical properties of the paint film were evaluated by the following methods. The results are shown in Table 1. −60 ° Specular Gloss − The 60 ° specular gloss is a KSM5000-3312 paint 60 ° specular gloss test method (JISK5400.7.6), and the incidence angle and the horizontal angle are each measured by a gloss meter. The reflectance at 60 ° was measured, and the reflectance was expressed as a percentage with respect to the case where the inclined surface gloss of the glass surface of the standard plate was set to 100, and the average value of five measurements was taken. -Adhesion test-The adhesion test is performed in accordance with ISO2409 paint adhesion surface test method so that the distance between the specimens is 1 mm.
Draw eleven lines vertically and horizontally, affix the cellophane adhesive tape on top of it, peel off, and in 100 separate coated surfaces on the coating, the number of remaining fragments The adhesive strength was evaluated. -Pencil hardness- Pencil hardness is determined according to the pencil hardness method of JIS K-5400 using a pencil hardness tester by applying a pencil to a dried coating film according to the type of brush (B, HB, F, H, 2H, 3H, 4H
), The angle was set to 45 degrees, and the degree of pulling was determined with the naked eye. -Accelerated staining property-Accelerated staining property is measured by spraying carbon black dispersed in water and a solvent onto a test piece at 60 ° C for 1 hour, followed by aging (agin).
g) After performing a water washing experiment after evaluation, evaluation was made based on a difference in lightness index. Here, the larger the brightness index difference, the higher the pollution,
The smaller the particle size, the lower the contamination. -Scratch resistance-Scratch resistance was measured by mixing sand having a size of 90 µm or more and 150 µm with a glue solution, dropping 2 or 3 drops on a test piece, and rubbing the sample 20 times with a 200 g vibrating rod. Thereafter, evaluation was made based on the gloss preservation value. -Accelerated weathering resistance-Accelerated weathering resistance is evaluated according to the accelerated weathering resistance test method of paint of KS M 5000-3241 by using a gloss preservation value after 1000 hours using a sunshine-weather-Ometer. did. -Sharpness-Sharpness measured the value of a vertical and a horizontal plane using portable gloss distinctiveness (PGD).

[0042]

[Table 1] As can be seen in Table 1, in Example 1 carried out while changing the amount of acetoacetoxyethyl methacrylate having a higher alkyl group, the amount of acetoacetoxyethyl methacrylate having a higher alkyl group was adjusted so as to fall outside the scope of the present invention. Is less than 5 parts by weight, it can be confirmed that the scratch resistance is greatly reduced. In addition, acetoacetoxyethyl methacrylate having a higher alkyl group (acetacetate) falls within the scope of the present invention.
acetoxyethylmethacrylate) in an amount of 40 g, 200 g, 40 parts by weight so as to be 5 to 50 parts by weight.
When 0 g is added, gloss, adhesiveness, pencil hardness,
It was confirmed that all were excellent in accelerated stain resistance, scratch resistance, accelerated weather resistance and sharpness.

Further, the amount of acetoacetoxyethyl methacrylate having a higher alkyl group is set to 5 so as to fall outside the range of the present invention.
When 500 g was added so as to exceed 0 parts by weight, it can be confirmed that the pencil hardness was greatly reduced.

As a methacrylic monomer containing a metal component, titanium methacrylate (titanium methacryla) is used.
te; Titanium methacrylate) In Example 2, which was carried out while changing the amount of addition, so that the methacrylic monomer containing a metal component was less than 1 part by weight so as to fall outside the scope of the present invention. When 2 g is added, it can be confirmed that the adhesiveness and the pencil hardness are low. On the other hand, a methacrylic monomer containing a metal component is added so that the amount of the methacrylic monomer containing the metal component is 1 part by weight or more and 20 parts by weight or less so as to be within the scope of the present invention. 12g, 50g,
When 100 g is added, it can be confirmed that the gloss, the adhesiveness, the pencil hardness, the accelerated stain resistance, the scratch resistance, the accelerated weather resistance, and the sharpness are all excellent, and are outside the scope of the present invention. When 150 g of the methacrylic monomer containing the metal component was added so as to exceed 20 parts by weight, it was confirmed that the glossiness and the adhesiveness were reduced.

In Example 3 in which the addition amount of ethyl silicate as the silicone monomer was changed, the amount of the silicone monomer was less than 1 part by weight so as to fall outside the scope of the present invention. So that
When g was added, it was found that the contamination was high. On the other hand, within the scope of the present invention, a silicone monomer (in this example, ethyl silicat
e) is 1 part by weight or more and 20 parts by weight or less.
When 2 g, 50 g, and 100 g were added, it was confirmed that the gloss, the adhesion, the pencil hardness, the accelerated stain resistance, the scratch resistance, the accelerated weather resistance, and the sharpness were all excellent. So that the silicone monomer (silico
When 150 g of nemonomer (in this example, ethyl silicate) was added so as to exceed 20 parts by weight, it was confirmed that the sharpness was reduced.

In all of the above Examples 1 or 3 which were added so as to be within the scope of the present invention, acetoacetoxyethyl methacrylate having a higher alkyl group was used.
e) Adhesiveness, pencil hardness, accelerated stain resistance, scratch resistance, accelerated weatherability and more than the comparative example in which a methacrylic monomer containing a metal component and a silicone monomer (acetoacetoxyethylmethacrylate) were not added. It can be confirmed from Table 1 above that the image has excellent sharpness.

[0047]

As described above, the present invention is excellent in scratch resistance because the elastic region of the coating film is expanded and large breaking energy is developed while exhibiting high elasticity and high durability. Not only high-solid acrylic resin that improves stain resistance, adhesiveness, surface hardness, etc., and maintains the hydrophilicity of the coating film while providing excellent water resistance, weather resistance and sharpness, and imparts non-staining properties. It is a useful invention to provide a composition and a paint containing the composition. In particular, the high-solid acrylic resin composition according to the present invention is a high-solid acrylic resin having a low VOC content as compared with the existing hydroxyl-containing acrylic resin, and has a special molecular structure despite its low molecular weight. Because of the cross-linking reaction with isocyanate, it has excellent mechanical properties such as impact resistance, flex resistance, etc., and chemical properties such as water resistance and solvent resistance. It is a useful invention capable of reducing pollution in the aspect of protecting the human body of a coating worker and in the aspect of the atmospheric environment when applied as a transparent coating for repairing automobiles because it forms a coating film having excellent hardness.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C09D 183/02 C09D 183/02 183/04 183/04 (72) Inventor Park Hong Sue Daikan Minkoku Seoul Tokubetsu Shi Seo Chak Bang Po Dong Karayou Apartment 2- 806 (72) Inventor Kim Baek Jin Daikanmin Kok Gyeonggi Dowswon Shi Jiang Ang Jong Jadong 857 -1 Uban Apartment 320-405 F-term (Reference) 4J038 CG141 CL001 DG262 DL022 DL032 GA02 GA03 GA06 GA15 GA16 JA33 JC38 JC39 KA04 MA07 MA10 MA14 NA01 NA03 NA05 NA11 PA18 4J100 AL03P AL04P AL05P AL08R AL08S AL09Q AP00S BA10R BA82H BA95S BC65R CA06 HA61 JA01

Claims (12)

[Claims] 1. A high solid acrylic resin composition containing a methacrylic monomer, a chain transfer agent and an initiator, wherein the methacrylic monomer comprises at least 50 parts by weight of an aliphatic group-containing methacrylic monomer. 80 parts by weight or less, and 10 parts by weight or more of a methacrylic monomer having a hydroxyl group
0 parts by weight or less; 5 to 50 parts by weight of an acrylic or methacrylic functional monomer having a higher alkyl group; and 1 to 20 parts by weight of a methacrylic monomer containing a metal component. The chain transfer agent contains 2 to 8 parts by weight of a chain transfer agent having a hydroxyl group, the initiator contains 3 to 9 parts by weight of a silicone transfer agent, and A raw material composition for a high-solid acrylic resin composition, comprising 1 to 20 parts by weight of a monomer. 2. The method according to claim 1, wherein the acrylic or methacrylic functional monomer having a higher alkyl group is acetoacetoxyethyl methacrylate having an acetoacetyl group, and / or
The raw material composition for a high-solid acrylic resin composition according to claim 1, which is an ε-caprolactone acrylate monomer having a hydroxyl group. 3. The methacrylic monomer containing a metal component is obtained by adding tetraisopropyl titanate or an alkali titanate such as tetranormal butyl titanate and tetrakis-2-ethylhexyl titanate to a compound having 8 to 12 carbon atoms. The raw material composition for a high-solid acrylic resin composition according to claim 1, wherein the raw material composition is titanium methacrylate synthesized by reacting not more than two fatty acids and then modifying methacrylic acid. 4. The silicone monomer is a silicate having an alkoxy group or a hydroxy group such as ethyl silicate or tetrakis-2-ethyl orthosilicate, and / or an alkylalkoxysilane compound such as methylmethoxysilane. The raw material composition for a high-solid acrylic resin composition according to claim 1, wherein: 5. A high solid acrylic resin composition obtained by polymerizing the high solid acrylic resin composition raw material composition according to any one of claims 1 to 4. 6. A paint containing the high solid acrylic resin composition, wherein the high solid acrylic resin composition according to claim 5 is dissolved in a solvent. 7. A high solid acrylic resin composition according to claim 5 in an amount of 60 to 90 parts by weight, and a low viscosity non-yellowing aliphatic polyisocyanate resin composition in an amount of 10 to 40 parts by weight. And the solid content concentration is 6
0%, viscosity of 16 seconds or more and 20 seconds or less (Zahn cup
# 2) A paint containing a high solid acrylic resin composition, characterized in that: 8. A methacrylic monomer having an aliphatic group,
0 to 80 parts by weight, a methacrylic monomer having a hydroxyl group of 10 to 40 parts by weight, and an acrylic or methacrylic functional monomer of 3 to 50 parts by weight, 1 to 20 parts by weight of a methacrylic monomer containing a metal component, 1 to 20 parts by weight of a silicone monomer, and 2 to 8 parts by weight of a chain transfer agent containing a hydroxyl group. Part by weight and 3 to 9 parts by weight of an initiator are dropped into a medium-boiling solvent over a period of 6 to 8 hours while the temperature is kept at 110 to 15 ° C.
A method for producing a high solid acrylic resin composition, characterized in that polymerization is carried out in a temperature range of 0 ° C. or less over 8 hours to 11 hours. 9. The acryl- or methacryl-functional monomer includes an acetoacetoxyethyl methacrylate monomer having a higher alkyl group and an acetoacetyl group and / or ε-caprolactone acrylate monomer having a hydroxyl group. The method for producing a high solid acrylic resin composition according to claim 8, wherein a monomer is used. 10. A methacrylic monomer containing said metal component, wherein the alkyl titanate such as tetraisopropyl titanate or tetranormal butyl titanate and tetrakis-2-ethylhexyl titanate has 8 to 12 carbon atoms. 9. A titanium methacrylate synthesized by reacting a fatty acid of formula (1) with methacrylic acid after the reaction.
3. The method for producing a high solid acrylic resin composition according to item 1. 11. The silicone monomer includes a silicate having an alkoxy group or a hydroxy group such as ethyl silicate or tetrakis-2-ethyl orthosilicate, and / or an alkylalkoxysilane compound such as methylmethoxysilane. The method for producing a high solid acrylic resin composition according to claim 8, wherein the composition is used. 12. A methacrylic monomer containing a metal component such as an organic titanate such as an alkyl titanate, an organic tin compound, and a methacrylic monomer containing a metal component in order to modify and polymerize a hydrophilic silicone substance on the hydroxyl group-containing acrylic resin. 12. The method according to claim 8, wherein one of the alkali catalysts is added in an amount of 0.01 to 0.1 part by weight based on 100 parts by weight of the reaction product of the polymer. A method for producing the high solid acrylic resin composition according to the above.