KR101144865B1 - Polyester resin composition and paint composition for golf ball prepared by using the same - Google Patents

Abstract

Disclosed is a polyester resin composition and a coating composition for golf ball coating prepared using the same. The polyester resin composition applied for the production of the coating composition for golf ball coating is prepared by reacting an acid including a polyhydric alcohol and aliphatic monocarboxylic acid having 9 carbon atoms. The hydroxyl value is in the range of 130-170 mgKOH / g, the acid value is in the range of 15-18 mgKOH / g, and the weight average molecular weight is in the range of 15,000-25,000. Coating the surface of a golf ball using a coating composition prepared using such a polyester resin composition shows excellent yellowing resistance, impact resistance, scratch resistance, and the like.

Description

Polyester resin composition and coating composition for golf ball coating manufactured using same {POLYESTER RESIN COMPOSITION AND PAINT COMPOSITION FOR GOLF BALL PREPARED BY USING THE SAME}

The present invention relates to a polyester resin composition and a coating composition for golf ball coating prepared using the same, and more particularly, to a polyester resin composition and a coating composition for golf ball coating prepared using the same and having excellent yellowing resistance and impact resistance. It is about.

In general, the coating composition for the golf ball surface coating is an important physical property to be equipped with adhesion, yellowing resistance, scratch resistance and the like with the golf ball surface. The polyester resin composition used to prepare the coating composition for golf ball surface coating is prepared by using polyhydric alcohols such as tetrafunctional and trifunctional groups, and alicyclic acid of non-yellowing as a main raw material.

However, when the polyester resin composition is prepared using polyhydric alcohols such as the above-described tetrafunctional group and trifunctional group, and the coating composition prepared using the resin composition is applied to the surface of a golf ball, the adhesion and scratch resistance are good. There is a problem that the viscosity of the resin becomes high. In addition, since the coating composition is required to have a certain level of impact resistance, the molecular weight of the resin should be maintained above a certain level. In order to satisfy these conditions, when a polyester resin prepared by synthesizing a linear polymer having a long chain and using it as a raw material is used to prepare a coating composition, there is a problem that the coating surface has good impact resistance but poor scratch resistance and toughness. .

Accordingly, an object of the present invention is to solve the above problems and to provide a polyester resin composition having desired physical properties.

Another object of the present invention is to provide a coating composition comprising the polyester resin composition and excellent in physical properties such as yellowing resistance, scratch resistance, impact resistance when applied to the base material.

In order to realize the above object of the present invention, the present invention is prepared by reacting an acid including a polyhydric alcohol and an aliphatic monocarboxylic acid having 9 carbon atoms, and the hydroxyl value is in the range of 130 to 170 mgKOH / g. It provides a polyester resin composition in the range of 15-18 mgKOH / g and having a weight average molecular weight in the range of 15,000 to 25,000.

According to one embodiment, the polyhydric alcohol is 20 to 40% by weight of a tetrafunctional polyhydric alcohol, 60 to 70% by weight of trifunctional polyhydric alcohol and 10 to 20% by weight of difunctional alcohol based on the total amount of polyhydric alcohol It is made, including.

According to one embodiment, the acid is 60 to 80 equivalents of diacid, 10 to 30 equivalents of carbon-containing double bonds and 10 to 25 equivalents of aliphatic based on the total number of equivalents of acid. Monocarboxylic acid.

According to another embodiment, the acid is an aliphatic monocarboxylic acid having 10 to 40 equivalents of 9 carbon atoms based on the total number of equivalents of acid and 60 to 100 equivalents of phthalic anhydride and tetrahydro phthalic anhydride. It may also include at least one divalent acid selected from the group consisting of hydride and hexahydro phthalic hydride.

According to one embodiment, the aliphatic monocarboxylic acid having 9 carbon atoms is represented by the following formula (1) and is a compound having an equivalent weight of about 158.

C ₉ H ₁₈ O ₂ ------------ (1)

In an embodiment, the tetrafunctional polyhydric alcohol is pentaerythritol, the trifunctional polyhydric alcohol is at least one of trimethylolpropane and glycerin, and the bifunctional polyhydric alcohol is 1,3-butylene glycol, 1, At least one selected from the group consisting of 4-butylene glycol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, methylpropanediol and 1,4-cyclohexanedimethanol.

According to one embodiment, the diacid is at least one selected from the group consisting of phthalic anhydride, tetrahydro phthalic hydride and hexahydro phthalic hydride, the acid containing an inter-carbon double bond is maleic anhydride and puma At least one of the lyxanes.

In order to achieve another object of the present invention, a polyhydric alcohol and an acid including an aliphatic monocarboxylic acid having 9 carbon atoms are prepared by reacting with a hydroxyl value in the range of 130 to 170 mgKOH / g and an acid value of 15 to 18 mgKOH /. There is provided a coating composition for golf ball coating, which is prepared using a polyester resin composition having a g range and a weight average molecular weight in the range of 15,000 to 25,000 and a block isocyanate curing agent in a weight ratio of 3 to 5: 1 to 1.5.

Applying the polyester resin composition as a coating composition for golf ball surface coating can produce a coating film excellent in physical properties such as yellowing resistance, impact resistance, scratch resistance, adhesion.

Hereinafter, the present invention will be described in more detail. As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In this application, the terms "comprises" or "having" are intended to indicate that there is a feature, ingredient, step, process, composition, or combination thereof described on the specification, one or more other features or ingredients, It is to be understood that it does not preclude the presence or possibility of addition of steps, processes, compositions or combinations thereof.

Also, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art, and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, the present invention will be described in detail.

In the present invention is prepared by reacting an acid comprising a polyhydric alcohol and aliphatic monocarboxylic acid having 9 carbon atoms, the hydroxyl value is in the range of 130 ~ 170 mgKOH / g, the acid value is in the range of 15 ~ 18 mgKOH / g, the weight average It provides a polyester resin composition having a molecular weight in the range of 15,000 to 25,000.

Examples of the aliphatic monocarboxylic acid having 9 carbon atoms used in the preparation of the polyester resin composition according to the present invention include a compound represented by the following general formula (1).

C ₉ H ₁₈ O ₂ ------------ (1)

The compound of formula (1) is a carboxylic acid compound having 9 carbon atoms and includes both linear and branched chains. That is, straight chain nonanoic acid, branched isononanoic acid, isomers thereof and mixtures thereof. Branched isononanoic acids may include, for example, 3,5,5-trimethylhexanoic acid. The carboxylic acid compound having 9 carbon atoms has an equivalent weight of about 158, and serves to impart excellent yellowing resistance to the coating composition prepared by applying the polyester resin composition prepared using the same.

Polyester resin composition according to one embodiment has a hydroxyl value of 130 ~ 170 mgKOH / g range. If the hydroxyl value of the polyester resin composition to be prepared is less than 130 mgKOH / g, the viscosity of the resin is high, it is difficult to manage the reaction. If the hydroxyl value is higher than 170 mgKOH / g, the amount of the curing agent is used because the -OH value is too large As it increases, it is not desirable when considering economic aspects. Therefore, the hydroxyl value of a polyester resin composition shall be in the said range.

Polyester resin composition according to one embodiment has an acid value of 15-18 mgKOH / g range. If the acid value of the produced resin is less than 15 mgKOH / g, the viscosity of the resin is high, the reaction management is difficult, and if it exceeds 18 mgKOH / g, because the resin having a sufficient molecular weight is not formed, the durability of the product is poor There is. Therefore, the acid value of the polyester resin composition is to be in the above range.

Polyester resin composition according to one embodiment has a weight average molecular weight of 15,000 ~ 25,000 range. If the weight average molecular weight of the resin composition is less than 15,000, the molecular weight is low, there is a problem that the impact resistance and abrasion resistance remarkably lower when applied to the paint, and if it exceeds 25,000, the viscosity is high, the appearance such as leveling, sagging (sagging) Characteristics related to the deterioration. Therefore, the weight average molecular weight of a polyester resin composition shall be in the said range.

The polyhydric alcohol used for the preparation of the polyester resin composition is not particularly limited, but a tetrafunctional, trifunctional, bifunctional polyhydric alcohol is used in an appropriate ratio. In this case, it is preferable to include 20 to 40% by weight of tetrafunctional polyhydric alcohol, 60 to 70% by weight of trifunctional polyhydric alcohol, and 10 to 20% by weight of bifunctional polyhydric alcohol based on the total amount of polyhydric alcohol. do. By adjusting and selecting in appropriate ratio according to the number of functional groups, resin which satisfy | fills both scratch resistance and impact resistance can be manufactured easily.

Pentaerythritol is mentioned as a tetrafunctional polyhydric alcohol. The tetrafunctional polyhydric alcohol is added for the purpose of improving the scratch resistance when the prepared resin composition is applied to the paint. Its amount is to be in the range of about 20 to 40% by weight based on the total amount of polyhydric alcohols. If the amount thereof is less than 20% by weight, the impact resistance is good when the prepared polyester resin composition is applied to the paint, but the scratch resistance is poor. If the addition amount thereof is more than 40% by weight, the scratch resistance is good when the prepared polyester resin composition is applied to the paint, but the impact resistance is poor. Therefore, it is recommended that the addition amount of the tetrafunctional alcohol be in the above range.

Trimethylolpropane, glycerin, and the like may be used as the trifunctional polyhydric alcohol, and its amount may be in the range of about 60 to 70 wt% based on the total amount of polyhydric alcohol. If the addition amount thereof is less than 60% by weight, the viscosity of the resin is too high, which is not preferable. If the addition amount thereof is more than 70% by weight, it is not preferable because the wear resistance may be weak. Therefore, it is recommended that the amount of trifunctional alcohol added be within the above range.

As the bifunctional polyhydric alcohol, 1,3-butylene glycol, 1,4-butylene glycol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, methyl propanediol and 1,4-cyclohexanedi At least one selected from the group consisting of methanol is available. Such a bifunctional polyhydric alcohol is added for the purpose of improving the impact resistance when the resin composition is applied to the paint. Its addition amount should be in the range of about 10 to 20% by weight, based on the total amount of polyhydric alcohols. If the addition amount thereof is less than 10% by weight, when the polyester resin composition prepared is applied to the paint, there is a problem that the scratch resistance is good but the impact resistance is poor. If the amount thereof exceeds 20% by weight, the impact resistance is good when the prepared polyester resin composition is applied to the paint, but there is a problem that the scratch resistance is poor. Therefore, it is good to make the addition amount of the said bifunctional polyhydric alcohol into the said range.

Acids usable with the polyhydric alcohols for the production of polyester resin compositions include diacids, acids containing double carbon to carbon bonds, in addition to aliphatic monocarboxylic acids having 9 carbon atoms.

When all three acid components mentioned above are used, their addition amounts are based on the total number of equivalents of acid, 60 to 80 equivalents of divalent acid, 10 to 30 equivalents of carbon-containing double bond and 10 to 10 equivalents. It is preferable to contain 25 equivalent% of aliphatic monocarboxylic acid.

As the diacid, at least one of phthalic anhydride, tetrahydro phthalic hydride and hexahydro phthalic hydride may be used. This diacid is mainly an alicyclic acid, which serves to provide yellowing resistance. Its addition amount is used in the range of about 60-80 equivalent% based on the total equivalent of acid. If the addition amount of di-acid is less than 60 equivalent%, it is difficult to prepare a resin composition with a sufficiently high molecular weight. If it is more than 80 equivalent%, the hardness is excellent, but the impact resistance is lowered and the leveling property is low, resulting in poor appearance. There is this. Therefore, it is good to make the addition amount of a diacid fall in the said range.

As the acid containing the carbon-to-carbon double bond, at least one of maleic anhydride and fumaric acid may be used. Its addition amount should be in the range of about 10-30 equivalent% based on the total equivalent of acid. If the addition amount thereof is lower than 10 equivalent%, the toughness (toughness) is lowered, and if it exceeds 30 equivalent%, there is a problem that the process control is difficult because the viscosity increases sharply at the end of the reaction. Therefore, it is recommended that the amount of the acid containing the carbon-to-carbon double bond be in the above range.

The amount of aliphatic monocarboxylic acid having 9 carbon atoms is in the range of about 10-25 equivalent% based on the total equivalent of acid. If the addition amount thereof is less than 10 equivalent%, the wear resistance is lowered. If the addition amount thereof exceeds 25 equivalent%, the addition amount of the monofunctional acid is too high, making it difficult to increase the molecular weight of the resin. Therefore, it is recommended that the amount of aliphatic monocarboxylic acid having 9 carbon atoms is in the above range.

According to one embodiment, examples of the acid usable with the polyhydric alcohol for preparing a polyester resin composition include an aliphatic monocarboxylic acid having 9 carbon atoms and an acid including the diacid.

In this case, the said acid comprises 10-40 equivalent% of said aliphatic monocarboxylic acid with 9 carbon atoms, and 60-90 equivalent% of divalent acid. Examples of the diacid include at least one selected from the group consisting of phthalic anhydride, tetrahydro phthalic hydride and hexahydro phthalic hydride.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

≪ Example 1 >

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer and condenser and attached to a temperature raising device. It contains 62.4 g of pentaerythritol, 133 g of trimethol propane, 35.1 g of propylene glycol, 220.3 g of hexahydro phthalic anhydride, 47.1 g of maleic anhydride and an aliphatic monocarboxylic acid having 9 carbon atoms (Kyowa Hakko). 125.7g) was added, and it heated up at 220 degreeC, stirring gradually. Condensation reaction was carried out for about 3 to 4 hours to prepare a condensation reaction product. A thermosetting polyester resin composition having an acid value of 16 to 17 and a Gardner viscosity of Y was prepared.

<Example 2>

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer and condenser and attached to a temperature raising device. Herein, 62.4 g of pentaerythritol, 163 g of trimethol propane, 35.1 g of propylene glycol, 220.3 g of hexahydro phthalic anhydride, 47.1 g of maleic anhydride, and an aliphatic monocarboxylic acid having 9 carbon atoms (Kyowa Hakko) 125.7g) was added, and it heated up at 220 degreeC, stirring gradually. Condensation reaction was carried out for about 3 to 4 hours to prepare a condensation reaction product. A thermosetting polyester resin composition having an acid value of 16 to 17 and a Gardner viscosity of Y was prepared.

Comparative Example 1

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer and condenser and attached to a temperature raising device. 62.4 g of pentaerythritol, 133 g of trimethol propane, 35.1 g of propylene glycol, 210.3 g of phthalic anhydride, 47.1 g of maleic anhydride and 60.7 g of adipic acid were added thereto, and the temperature was raised to 220 ° C. while gradually stirring. Condensation reaction was carried out for about 3 to 4 hours to prepare a condensation reaction product. A thermosetting polyester resin composition having an acid value of 17 to 18 and a Gardner viscosity of W was prepared.

Comparative Example 2

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer and condenser and attached to a temperature raising device. To this was added 62.4 g of pentaerythritol, 133 g of trimethol propane, 35.1 g of propylene glycol, 220.3 g of hexahydro phthalic anhydride, 47.1 g of maleic anhydride and 60.7 g of adipic acid, and the mixture was gradually heated to 220 ° C. It was. Condensation reaction was carried out for about 3 to 4 hours to prepare a condensation reaction product. A thermosetting polyester resin composition having an acid value of 16 to 17 and a Gardner viscosity of X was prepared.

Using the polyester resin composition prepared in Examples 1 and 2 and Comparative Examples 1 and 2 to prepare a coating composition for golf ball coating. The coating compositions according to Examples 3 and 4 and Comparative Examples 3 and 4 were prepared using the components as shown in Table 1 below. The compounding quantity of each component shows a weight ratio. In addition, the coating composition according to Comparative Example 5 was prepared using a linear polyester resin having a weight average molecular weight of 8,000 to 12,000 as the polyester resin composition used in the past.

[Table 1]

 Table 2 shows the results of testing the properties of the coating film to determine the properties of the coating compositions according to Examples 3 and 4 and Comparative Examples 3 to 5. Each characteristic of the coating film was measured in the following manner.

First, gloss (60 microseconds) was measured by ASTM-D-523, MEK rubbing property NCAA-11-19, pencil hardness NCAA-11-12, adhesiveness NCAA-11-20.

To measure the yellowing resistance, half of the coated film was wrapped with aluminum foil, and the specimen was exposed to a QUV meter for 1000 hours. Then, the change of the coating state of the part wrapped with aluminum foil and the exposed part was visually discriminated and judged as good or bad.

In order to measure the impact resistance, when a weight of 100 g was dropped on a substrate formed with a coating film at a height of 50 cm, it was visually judged as good or bad by visually discriminating an abnormality of the site of the impact caused by the impact on the surface of the substrate.

The scratch resistance was judged as good or bad by visually discriminating the change of the surface of the body for a certain number of times when the surface of the body was reciprocated using the reciprocating pulley. Even if the pulley reciprocated 500 times or more, if there was no change in the surface of a base, it was good.

TABLE 2

Looking at the results shown in Table 2, it can be seen that the coating composition according to the embodiment of the present invention exhibits much superior properties compared to the coating composition according to the comparative example. Although the scratch resistance was shown to be slightly poor in Example 1, it can be confirmed that the yellowing resistance, the impact resistance, and the adhesion are excellent, thereby providing excellent physical properties than the coating composition according to the comparative example. On the contrary, it can be confirmed that the paint compositions according to the comparative examples are not generally good physical properties.

As described above, the coating composition prepared by applying the polyester resin composition prepared according to the present invention is particularly suitable for golf ball coating because it has excellent yellowing resistance, impact resistance, and scratch resistance.

Although described above with reference to the embodiments, those skilled in the art can be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below. I can understand.

Claims (8)

Polyhydric alcohols including 20-40% by weight of tetrafunctional polyhydric alcohols, 60-70% by weight of trifunctional polyhydric alcohols and 10-20% by weight of difunctional polyhydric alcohols, based on the total amount of polyhydric alcohols and 9 carbon atoms A polyester resin prepared by reacting an acid containing aliphatic monocarboxylic acid, having a hydroxyl value in the range of 130 to 170 mgKOH / g, an acid value in the range of 15 to 18 mgKOH / g, and a weight average molecular weight in the range of 15,000 to 25,000. Composition. delete The acid according to claim 1, wherein the acid is 60 to 80 equivalents of diacid, 10 to 30 equivalents of carbon-containing double bond and 10 to 25 equivalents of aliphatic based on the total number of equivalents of acid. A polyester resin composition comprising a monocarboxylic acid. According to claim 1, wherein the acid is 10 to 40 equivalent% aliphatic monocarboxylic acid having 9 to 10 equivalents of carbon and 60 to 100 equivalent% of phthalic anhydride, tetrahydro phthalic acid based on the total equivalent number of acid. Polyester resin composition comprising at least one divalent acid selected from the group consisting of hydride and hexahydro phthalic hydride. The polyester resin composition according to claim 1, wherein the aliphatic monocarboxylic acid having 9 carbon atoms is a compound represented by the formula (1). C ₉ H ₁₈ O ₂ ------------ (1) The method according to claim 1, wherein the tetrafunctional polyhydric alcohol is pentaerythritol, the trifunctional polyhydric alcohol is at least one of trimethylolpropane and glycerin, and the bifunctional polyhydric alcohol is 1,3-butylene glycol, 1, Polyester, characterized in that at least one selected from the group consisting of 4-butylene glycol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, methylpropanediol and 1,4-cyclohexanedimethanol Resin composition. According to claim 3, wherein the diacid is at least one selected from the group consisting of phthalic anhydride, tetrahydro phthalic hydride and hexahydro phthalic hydride, wherein the acid containing the inter-carbon double bond is maleic anhydride and puma Polyester resin composition, characterized in that at least one of the lyric acid. Polyhydric alcohols including 20-40% by weight of tetrafunctional polyhydric alcohols, 60-70% by weight of trifunctional polyhydric alcohols and 10-20% by weight of difunctional polyhydric alcohols, based on the total amount of polyhydric alcohols and 9 carbon atoms A polyester resin prepared by reacting an acid containing aliphatic monocarboxylic acid, having a hydroxyl value in the range of 130 to 170 mgKOH / g, an acid value in the range of 15 to 18 mgKOH / g, and a weight average molecular weight in the range of 15,000 to 25,000. The coating composition for golf ball coating manufactured using a composition and a block isocyanate hardening | curing agent so that it may become a range of 3-5: 1-11.5 by weight ratio.