KR20100078439A - Pccd polyester composition for solvent-based adhesive or coating agent, polyester resin polymerized therefrom, solvent-based adhesive and coating agent comprising the same, and preparation method thereof - Google Patents

Abstract

PURPOSE: A poly(cyclohexane-1,4-dimethylene cyclohexane-1,4-dicarboxylate) polyester composition, and a producing method thereof are provided to secure the luster and the weathering ability of the composition. CONSTITUTION: A poly(cyclohexane-1,4-dimethylene cyclohexane-1,4-dicarboxylate) polyester composition for a solvent type coating agent or a solvent adhesive contains cyclohexanedicarboxylic acid with 50~100mol% of a cis type, dimethylcyclohexanedicarboxylate with 50~100mol% of the cis type, or cyclohexanediol. A coating agent contains a poly(cyclohexane-1,4-dimethylene cyclohexane-1,4-dicarboxylate) resin and an organic solvent.

Description

PCC Polyester Composition for Solvent-Based Adhesive or Coating Agent, Polyester Resin Polymerized Therefrom, Solvent-Based Adhesive and Coating Agent Comprising the Same, and Preparation Method Thereof}

The present invention relates to a polyester composition for a solvent type coating or a solvent type adhesive, a polyester resin, a solvent type coating agent and an adhesive comprising the same, and a method for producing the same.

Representative polyester resins used in various applications such as fibers, molded articles and films refer to high molecular weight aromatic polyester resins prepared by polycondensation of terephthalic acid and ethylene glycol or terephthalic acid and 1,4-butanediol. When high molecular weight polyester refers to a polymer having a number average molecular weight of 10,000 or more. However, the aromatic polyester resin does not decompose in the natural ecosystem after disposal, causing a serious environmental pollution problem.

The high molecular weight aromatic polyester resin is also used as an adhesive of various materials, and can be classified into a solvent-free adhesive and a solvent-free hotmelt type adhesive by application, adhesive object, and device. Hot-melt type adhesives are increasing in R & D and application due to increasing interest in environmental problems, etc., but are still in demand due to the advantages of thin film coating and ease of operation, which are characteristic of solvent-type adhesives. Therefore, interest in solvent-type adhesives including polyester resins which can be produced in a solvent-type while being biodegradable with little harm to the environment is increasing day by day.

On the other hand, a high molecular weight polyester resin can be used as a coating agent by adding a curing agent for the coating agent in a solution dissolved in a certain concentration in an organic solvent, in order to be used as a coating, not only the surface gloss after coating, but also has good weather resistance.

It is already known that aliphatic polyesters are biodegradable (Journal of Macromol., A-23 (3), 1986, 393-409), and therefore, aliphatic polyesters have recently been used in medical materials, agricultural materials and packaging. The present invention is used for materials and the like, and in addition to the above fields, studies for practical use of biodegradable aliphatic polyesters are being actively conducted. Among them, biodegradable aliphatic polyester is processed in the form of a film or sheet (solvent-free hot melt type adhesive) and applied to bond with biodegradable polyester such as paper or starch container, or interest in using as a coating agent. Increasingly, the hot melt type adhesives in the form of films or sheets as described above do not have sufficient adhesive strength, and in the case of the coating agent, they do not have sufficient gloss or have poor weather resistance.

Therefore, the inventors of the present invention are easily dissolved in the coating agent and the organic solvent for the adhesive to facilitate the production of the solvent-type coating agent and the solvent-type adhesive, the production is simple, when used as a coating, not only gloss but also excellent weather resistance, In the case of being used as an adhesive, while repeating studies on an aliphatic polyester resin having excellent adhesive strength and an adhesive including the same, the present invention was completed.

In order to solve the above problems, the present invention is to provide a polyester composition, a polyester resin, a coating agent and an adhesive comprising the same, and a manufacturing method thereof, which can be manufactured with a solvent type coating agent and a solvent type adhesive.

In order to achieve the above object, poly (cyclohexane-1,4-dimethylene cyclohexane-1,4-dicarboxylate) that can be produced with a solvent type coating agent or a solvent adhesive [poly (cyclohexane-1,4-dimethylene cyclohexane-1,4-dicarboxylate), PCCD] polyester composition, polyester resins, coatings and adhesives comprising the same, and methods for preparing the same.

Hereinafter, a PCCD polyester composition for a solvent type coating agent or a solvent type adhesive according to a specific embodiment of the present invention will be described.

PCCD polyester composition for a solvent type coating or solvent adhesive according to an embodiment of the present invention is a dimethylcyclohexanedicarboxylate (Dimethyl 1,4-Cyclohexanedicarboxylate, the content of the cis type of 50 to 100 mol%, DMCD) or cyclohexanedicarboxylic acid (1,4-cyclohexanedicarboxylic acid, CHDA) having a content of cis form of 50 to 100 mol%; And cyclohexanedimethanol (1,4-cyclohexanedimethanol, CHDM).

At this time, the PCCD polyester composition includes dimethylcyclohexanedicarboxylate (DMCD) or cyclohexanedicarboxylic acid (CHDA) as an acid component in order to produce a PCCD polyester resin condensation-polymerized through an esterification reaction. It may be, and may include cyclohexane dimethanol (CHDM) as an alcohol component, the dimethyl cyclohexane dicarboxylate (DMCD) and cyclohexanedicarboxylic acid (CHDA) which is the acid component It is preferable that the content of the cis type is 50 to 100 mol%.

As described above, the content of the cis-type of dimethylcyclohexanedicarboxylate (DMCD) and cyclohexanedicarboxylic acid (CHDA) included as an acid component should be in the above range, and it is esterified and condensation-polymerized PCCD. The polyester resin is easily dissolved in the organic solvent used in the preparation of the solvent type coating agent and the solvent type adhesive.

In addition, the coating agent containing the PCCD polyester resin as described above not only has excellent gloss, but also has excellent weather resistance, and the adhesive including the PCCD polyester resin as described above has excellent heat resistance and hydrolysis resistance in addition to general adhesive force.

PCCD polyester resin according to another embodiment of the present invention is a dimethyl cyclohexanedicarboxylate (DMCD) or a cis (cis) content of 50 to 100 mol% of the cis type (cis) content Cyclohexanedicarboxylic acid (CHDA) which is%; And cyclohexanedimethanol (CHDM) is esterified and condensed. At this time, when the cis type content of dimethylcyclohexanedicarboxylate (DMCD) and cyclohexanedicarboxylic acid (CHDA) which are acid components used in the esterification condensation polymerization reaction is 50 to 100 mol%. It can be easily dissolved in the organic solvent used in the preparation of the coating agent and the solvent-type adhesive as described above.

As will be described in more detail below, the PCCD polyester resin according to the embodiment of the present invention can be easily dissolved in a general organic solvent used in the solvent-type coating agent and solvent-type adhesive can be easily produced as a solvent-type coating agent or a solvent-type adhesive When produced with a coating agent, not only the initial gloss but also excellent weather resistance, and when used as a solvent-type adhesive, in addition to the general adhesive force, excellent hydrolysis resistance.

The present invention provides a coating agent comprising the polyester resin according to another embodiment. The coating agent may be produced in a form containing a PCCD polyester resin and an organic solvent according to the above-described embodiment. At this time, if the organic solvent is an organic solvent compatible with the coating agent, it can be used without limitation of the composition, preferably acetone, acetonitrile, butyl acetate, butyl alcohol, chloroform, cresol, ethyl acetate, methyl ethyl ketone, Ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, hexane, isopropyl alcohol, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, cyclohexa One or more selected from the group consisting of non-, isophorone, aromatic solvent naphtha and dibasic ethers can be used.

One of those widely used as the aromatic solvent naphtha is Kocosol produced by SK Chemicals. Cocosol of SK Chemicals Co., Ltd. is a trade name that refers to aromatic solvent naphtha, and is composed mostly of aromatic hydrocarbon compounds having 9 to 11 carbon atoms, and is mainly used as a material for organic solvents, pesticides, paints, and the like of solvent-based adhesives. The types of coco sol produced by SK Chemical Co., Ltd. are coco sol-100 and coco sol-150. Cocozol-100 is a light aromatic solvent naphtha, 1,2,4-trimethylbenzene, cumene, xylenes, 1,2,3-trimethylbenzene (1, A mixture of 2,3-Trimethylbenzene, 1-ethyl-2methylbenzene and Propylbenzene, the specific gravity at 15.6 ° C is in the range of 0.860 to 0.880, The breaking point range is 158.9 to 175.6 ° C. On the other hand, Cocozol-150 is a heavy aromatic solvent naphtha, 1,2,3-trimethylbenzene (1,2,3-Trimethylbenzene), 1,2,3,5-tetramethylbenzene (1,2,3,5 -Tertramethylbenzene), a mixture of 1,4-diethylbenzene (Specific Gravity) is 0.888 at 15.6 ℃, the breaking point range is 178 to 214 ℃. On the other hand, examples of the dibasic ethers include dimethyl glutarate, dimethyl susinate, dimethyl adipate and the like.

On the other hand, the adhesive according to the embodiment may additionally include a curing agent, if the curing agent that can be used in a conventional coating agent, may be used without limitation of the configuration, preferably one or more selected from the group consisting of isocyanate and melamine It may include a curing agent.

The present invention provides a solvent adhesive according to another embodiment. Solvent adhesive according to another embodiment of the present invention comprises a PCCD polyester resin and an organic solvent according to the above-described embodiments. At this time, if the organic solvent used is an organic solvent compatible with the solvent-type adhesive, it can be used without limitation in the constitution, but preferably acetone, acetonitrile, butyl acetate, butyl alcohol, chloroform, cresol, ethyl acetate, Methyl ethyl ketone, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, hexane, isopropyl alcohol, methyl isobutyl ketone, tetrahydrofuran, toluene, xyl One or more selected from the group consisting of lene, cyclohexanone, isophorone, aromatic solvent naphtha and dibasic ethers can be used. Preferred forms of the aromatic solvent naphtha and dibasic ethers are the same as those for the coating agent described above.

On the other hand, the adhesive according to the embodiment may additionally include a curing agent, if the curing agent that can be used in a conventional solvent-type adhesive, can be used without limitation of the composition, preferably isocyanate, melamine, carbodiimide, and epoxy Any one or more curing agents selected from the group consisting of can be used.

The present invention provides a method of preparing a solvent-borne coating or adhesive according to another embodiment. The method for producing a solvent-based coating or adhesive according to the embodiment is 50 to 100 mol% cis (cis) content of dimethylcyclohexanedicarboxylate (DMCD) or cis (cis) content of 50 to 100 Cyclohexanedicarboxylic acid (CHDA) in mole%; And stirring cyclohexanedimethanol (CHDM);

Carrying out the esterification reaction by raising the reactor temperature with the addition of the catalyst;

Reacting the oligomer which is the product of the esterification reaction for 0.1 to 24 hours at 0.01 to 10 torr and 150 to 300 ℃ conditions to obtain a polyester resin; And

And dissolving the polyester resin in an organic solvent.

At this time, if the catalyst used in the esterification reaction is usually used in the esterification reaction of the polyester resin, can be selected and used without limitation of the composition, preferably zinc-based, titanium-based and calcium-based, One or more selected from antimony, manganese and germanium may be used.

More preferably zinc acetate and tetrabutyl titanate can be used.

In addition, the organic solvent as described above in the embodiment of the solvent-type coating agent and solvent-type adhesive, there is no limitation in the configuration, preferably acetone, acetonitrile, butyl acetate, butyl alcohol, chloroform, cresol, ethyl Acetate, methyl ethyl ketone, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, hexane, isopropyl alcohol, methyl isobutyl ketone, tetrahydrofuran, toluene And xylene, cyclohexanone, isophorone, aromatic solvent naphtha, and dibasic ethers.

On the other hand, examples of the dibasic ethers as described above in the embodiment of the solvent-type coating agent and solvent-type adhesive of the present invention include dimethyl glutarate, dimethylsucinate, dimethyl adipate and the like.

Such PCCD polyester resin of the present invention can be easily dissolved in a general organic solvent used in solvent-based coatings and adhesives can be easily produced as a solvent-type coating agent and a solvent-type adhesive, when used as a coating agent, the alicyclic raw material of the resin Due to its properties, it has excellent gloss and weather resistance, and when used as an adhesive, has excellent heat resistance and hydrolysis resistance, and can be widely used as a solvent coating agent and a solvent adhesive.

As described above, the PCCD polyester resin of the present invention can be easily dissolved in a general organic solvent used in a solvent coating agent and an adhesive, and can be easily manufactured with a solvent coating agent and an adhesive, and when used as a coating agent, an alicyclic material of the resin Due to its properties, it is excellent in gloss and weather resistance, and when used as an adhesive, has excellent heat resistance and hydrolysis resistance, and can be widely used as a solvent coating agent and a solvent adhesive.

Hereinafter, preferred examples and comparative examples are presented to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

EXAMPLE

Example 1; Preparation of PCCD Polyester Resin and Coatings Comprising the Same

Into the reactor equipped with a column and a condenser with a temperature control, dimethylcyclohexanedicarboxylate (353g) and cyclohexanedimethanol (257g) containing 80% cis were added and stirred, and the reactor was heated at 150 ° C. It heated up slowly until. And zinc acetate (0.2g) and tetrabutyl titanate (0.1g) were added as a catalyst, it heated up to 250 degreeC, stirring again, and esterification was continued at this temperature. When methanol began to flow out as a reaction by-product during the reaction, the temperature of the column was maintained at 80 ° C. to prevent dicarboxylic acid or dihydric alcohol components from subliming or evaporating. When the reaction was continued for about 5 hours, methanol no longer flowed out, and the reaction product was white opaque to produce a pale yellow transparent oligomer, indicating that the esterification reaction was terminated.

A vacuum was gradually applied and the temperature was raised while being careful not to scatter the reactants to maintain a pressure in the reactor to 1 torr, and the reaction was allowed to reach a temperature of 260 ° C. for 1 hour to prepare a PCCD polyester resin. The PCCD polyester resin thus obtained had an intrinsic viscosity of 0.30 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 38 ° C. measured using a differential scanning calorimeter.

The resin (30 g) obtained above was placed in a mixed solvent of toluene, xylene, and cyclohexanone (70 g), and stirred at 80 ° C. for 3 hours to prepare a PCCD polyester resin solution.

The solution was cooled to 25 ° C., and 6 g of Cymel303 (Cytec) curing agent was added and mixed to prepare a coating agent, and then coated on a primer-treated steel plate to measure initial gloss and gloss after exposure to 1000 hr of QUV-A (340 nm).

Example 2; Preparation of PCCD Polyester Resin and Adhesive Containing the Same

The reaction was carried out by adding a vacuum to the reaction time of 3 hours, the other raw material input amount and the preparation was made of PCCD polyester resin by the same method as in Example 1. The PCCD polyester resin thus obtained had an intrinsic viscosity of 0.65 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 42 ° C. measured using a differential scanning calorimeter.

The resin (30 g) obtained above was placed in a mixed solvent of toluene, xylene, and cyclohexanone (70 g), and stirred at 80 ° C. for 3 hours to prepare a PCCD polyester resin solution.

The solution was cooled to 25 ° C., and 3 g of a block isocyanate BL3175 (Bayer) curing agent was added and mixed to prepare an adhesive, followed by coating and drying on a PVC film, adhering to a PET film, and measuring T-peel strength. After the adhesive film was immersed in water at 100 ° C. for 1 hour, the adhesive force was changed (heat resistance and hydrolysis resistance).

[Comparative Example]

Comparative Example 1; Preparation of PCCD Polyester Resin and Coatings Comprising the Same

In Example 1, a cis content of dimethylcyclohexanedicarboxylate was used at 20%, and other raw materials were added and prepared in the same manner as in Example 1 to prepare a PCCD polyester resin. The PCCD polyester resin thus obtained had an intrinsic viscosity of 0.30 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 45 ° C. measured using a differential scanning calorimeter.

The resin (30 g) obtained above was added to a mixed solvent of toluene, xylene, and cyclohexanone (70 g), and stirred at 80 ° C. for 3 hours to prepare a PCCD polyester resin solution, but dissolution was impossible.

Comparative Example 2; Preparation of PCCD Polyester Resin and Adhesive Containing the Same

In Example 2, a cis content of dimethylcyclohexanedicarboxylate was used at 20%, and other raw material input and preparation were made of PCCD polyester resin by the same method as in Example 2. The PCCD polyester resin thus obtained had an intrinsic viscosity of 0.65 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 47 ° C. measured using a differential scanning calorimeter.

The resin (30 g) obtained above was added to a mixed solvent of toluene, xylene, and cyclohexanone (70 g), and stirred at 80 ° C. for 3 hours to prepare a PCCD polyester resin solution, but dissolution was impossible.

The resin (30 g) obtained above was added to a mixed solvent of toluene, xylene, and cyclohexanone (70 g), and stirred at 80 ° C. for 3 hours to prepare a PCCD polyester resin solution, but dissolution was impossible.

Comparative Example 3; Preparation of polyester resin and coating agent comprising same

Terephthalic acid (100 g), isophthalic acid (100 g), ethylene glycol (70 g) and hexanediol (70 g) were added to a reactor equipped with a temperature-controlled column and a condenser. Prepared. The polyester resin thus obtained had an intrinsic viscosity of 0.30 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 28 ° C. measured using a differential scanning calorimeter.

This resin was prepared in the same manner as in Example 1 to prepare a coating material, and the physical properties were evaluated.

Comparative Example 4; Preparation of polyester resin and adhesive containing same

Terephthalic acid (100 g), isophthalic acid (50 g), sebacic acid (60 g), ethylene glycol (100 g) and neopentyl glycol (70 g) were added to a reactor equipped with a temperature-controlled column and a condenser. Resin was prepared by the same method as 2. The polyester resin thus obtained had an intrinsic viscosity of 0.73 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 17 ° C. measured using a differential scanning calorimeter.

An adhesive was produced in the same manner as in Example 2, and the resin was evaluated for physical properties.

The acid and alcohol components of the polyester composition used as a reaction raw material for the preparation of the polyester resins of the examples and comparative examples are summarized in Table 1 below.

Component Comparison of Polyester Composition
Polyester composition mountain
Alcohol
Example 1 Dimethylcyclohexanedicarboxylate (DMCD) with cis-type content of 80 mol%
Cyclohexanedimethanol (CHDM) Example 2 DMCD with cis-type content of 80 mol%
CHDM Comparative Example 1 DMCD with cis-type content of 20 mol%
CHDM Comparative Example 2 DMCD with cis-type content of 20 mol%
CHDM Comparative Example 3 Terephthalic acid, isophthalic acid
Ethylene glycol, hexanediol Comparative Example 4 Terephthalic acid, isophthalic acid, sebacic acid Ethylene Glycol, Neopentyl Glycol

Experimental Example Measurement of physical properties of polyester resins of Examples and Comparative Examples and coatings and adhesives including the same

Solubility, organic intrinsic viscosity (Intrinsic Viscosity, IV), glass transition temperature (Tg), and poly of the comparative examples and examples of the polyester resin prepared by the examples and comparative examples submitted by the above-described method Measurement of initial gloss of coating agent including ester resin and gloss after 1000 hours of QUV-A (340 nm) exposure, T-peel strength of adhesive, T-peel strength (g / 20mm) after 1hr treatment at 100 ℃ water As shown in Tables 2 to 4 below.

1. Solubility evaluation of resin in organic solvent

30 g of the polyester resin prepared according to the above Examples and Comparative Examples was placed in 70 g of an organic solvent such as toluene shown in Table 2 or 70 g of a mixed organic solvent such as toluene / cyclohexanone = 25/75 (mass ratio), at 80 ° C. Solubility after stirring for 3 hours was evaluated. The results are shown in Table 2.

2. Measurement of Intrinsic Viscosity (IV) of Resin

The intrinsic viscosity of the resins of Examples and Comparative Examples was measured according to ASTM D4603-86 method at 30 ° C. using an Ostwald viscometer (SKVIS5000). The measured intrinsic viscosity is shown in Table 2.

3. Measurement of glass transition temperature (Tg) of resin

The glass transition temperatures of the resins of Examples and Comparative Examples were measured using a differential scanning calorimetry (DSC 2910 Modulated DSC; TA Instruments) according to ASTM D3418 method. The measured glass transition temperature is shown in Table 2.

4. Initial Gloss Measurement of Coatings Containing Polyester Resins

Coatings prepared in the same manner as the resins prepared in Example 1 and Comparative Example 3 were coated on a primer-treated steel sheet, and the initial gloss was measured using a Glossmeter (BYK). The results are shown in Table 3.

5. Gloss measurement after 1000hr exposure of QUV-A (340nm) of coating material containing polyester resin

After coating the coating prepared from the resin prepared according to Example 1 and Comparative Example 3 to the primer-treated steel sheet, and irradiated with an ultraviolet light lamp (QUV-A) for 1000 hours so that the coating surface is irradiated with ultraviolet light of 340nm, Measurement was made using a glossmeter. The results are shown in Table 3.

6. Measurement of T-peel strength of adhesives including polyester resins

The solvent-type adhesive prepared from the resin prepared according to Example 2 and Comparative Example 4 was coated and dried on a polyvinyl chloride (PVC) film, and then adhered to a polyethylene terephthalate (PET) film, followed by T-peel. strength was measured. T-peel strength was measured according to ASTM D5179-98 method. The measured T-peel strength is shown in Table 4.

7. Measurement of heat resistance and hydrolysis resistance of adhesive [Measure T-peel strength (g / 20mm) after 1hr treatment in 100 ℃ water]

In order to measure the hydrolysis resistance of the solvent-type adhesive prepared from the resin prepared according to Example 2 and Comparative Example 4, each adhesive was coated and dried on a PVC film, adhered to the PET film, and then the bonded film was 100 After soaking in water at 1 ° C. for 1 hour, it was taken out and T-peel strength was measured according to the ASTM D5179-98 method as described above. The measured results are shown in Table 4.

Evaluation of the physical properties of the resin and its dissolution in solvent Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Intrinsic Viscosity (IV) 0.3 0.65 0.3 0.65 0.3 0.73 Glass transition temperature (Tg), (℃) 38 42 45 47 28 17
for
year
female
part


Toluene 100% O O X X X X Xylene 100% O O X X X X 100% cyclohexanone X X X X O O Toluene / cyclohexanone = 25/75 * O O X X O O Toluene / cyclohexanone = 50/50 * O O X X O O Xylene / cyclohexanone = 75/25 * O O X X O O Xylene / cyclohexanone = 25/75 * O O X X O O Xylene / cyclohexanone = 50/50 * O O X X O O Xylene / cyclohexanone = 75/25 * O O X X O O

(week); The ratio indicated by * indicates mass ratio.

As shown in Table 2, Examples 1 and 2 in which the cis type content of dimethylcyclohexanedicarboxylate (DMCD) added as an acid of the PCCD polyester composition is 80 mol%. It was confirmed that the resin was easily dissolved in various organic solvents shown in Table 2. However, even if it is a PCCD polyester produced by esterification condensation polymerization of an acid and an alcohol of the same kind, as in Comparative Examples 1 and 2, cis type of dimethylcyclohexanedicarboxylate (DMCD), which is an added acid, is used. When the content of 20 mol% did not dissolve in a general organic solvent, it was found that it is not suitable for use as an adhesive or coating agent.

On the other hand, in the case of the resins of Comparative Examples 1 and 2, it is not dissolved in an organic solvent and can not be produced with a coating agent containing the same, in order to compare the physical properties of the coating agent and the adhesive according to Examples 1 and 2, respectively, The physical properties of the coating agent and the adhesive prepared according to Comparative Examples 3 and 4 were compared and shown in Tables 3 and 4, respectively.

Evaluation of Physical Properties of Coatings Example 1 Comparative Example 3 Initial Gloss (60 °) 110 105 QUV-A gloss after 1000hr (60 °) 85 53

As shown in Table 3, in the coating agent of Example 1, not only the initial gloss was excellent, but even after exposure to ultraviolet light at 340 nm for a long time (1000 hours), the decrease rate of gloss was 13.6%, Comparative Example 3 The gloss reduction rate of 49.5% was much better than that.

Therefore, in the case of the coating agent comprising the PCCD polyester resin according to the present invention, not only the initial gloss was excellent, but also the weather resistance was confirmed that it can be widely used as a varnish of various substrates.

Evaluation of Adhesive Properties Example 2 Comparative Example 4 Initial T-peel strength (kg / cm ² ) 1630 1890 T-peel strength (g / 20mm) measured after 1hr treatment at 100 ℃ water 1150 352

As shown in Table 4, in the case of the adhesive of Comparative Example 4, which is a commercially available adhesive, it can be seen that the initial adhesive strength is similar to that of commonly used, and in particular, T-peel strength measured after 1hr treatment in water at 100 ° C (g / 20 mm) was 3.3 times that of Comparative Example 4, and in particular, compared with the initial adhesive strength, the rate of decrease in adhesion rate was 41.7%. Therefore, it was confirmed that the present invention can be particularly useful for adhesion of molded articles exposed to moisture.

Comparing the experimental results of the above Examples and Comparative Examples, the PCCD polyester resin of the present invention has a high solubility in organic solvents for the production of commonly used solvent-type coating agent and adhesive, the production of solvent-type coating agent and adhesive This is easy. In addition, when used as a coating agent is not only excellent in the initial gloss, but also excellent in weather resistance, when used as an adhesive, as well as the initial adhesion, as well as excellent heat resistance and hydrolysis resistance, It can be widely used in the industrial field.

Claims (11)

Dimethylcyclohexanedicarboxylate having a content of cis form of 50 to 100 mol% or cyclohexanedicarboxylic acid having a content of cis form of 50 to 100 mol%; And poly (cyclohexane-1,4-dimethylene cyclohexane-1,4-dicarboxylate) (PCCD) polyester resin composition for a solvent type coating agent or solvent type adhesive including cyclohexanedimethanol. Dimethylcyclohexanedicarboxylate having a content of cis form of 50 to 100 mol% or cyclohexanedicarboxylic acid having a content of cis form of 50 to 100 mol%; And PCCD polyester resins which are condensation-polymerized by cyclohexanedimethanol. A coating agent comprising the PCCD resin according to claim 2 and an organic solvent. The method of claim 3, wherein the organic solvent is acetone, acetonitrile, butyl acetate, butyl alcohol, chloroform, cresol, ethyl acetate, methyl ethyl ketone, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene Glycol monobutyl ether, ethylene glycol monoethyl ether, hexane, isopropyl alcohol, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, cyclohexanone, isophorone, aromatic solvent naphtha and dibasic ethers At least one coating selected. The coating agent according to claim 3, further comprising any one or more curing agents selected from the group consisting of isocyanates and melamine. Solvent-type adhesive containing PCCD resin and organic solvent of Claim 2. The method of claim 6, wherein the organic solvent is acetone, acetonitrile, butyl acetate, butyl alcohol, chloroform, cresol, ethyl acetate, methyl ethyl ketone, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene Glycol monobutyl ether, ethylene glycol monoethyl ether, hexane, isopropyl alcohol, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, cyclohexanone, isophorone, aromatic solvent naphtha and dibasic ethers Solvent type adhesive, which is one or more selected. The solvent type adhesive according to claim 6, further comprising any one or more curing agents selected from the group consisting of isocyanate, melamine, carbodiimide, and epoxy. Dimethylcyclohexanedicarboxylate having a content of cis form of 50 to 100 mol% or cyclohexanedicarboxylic acid having a content of cis form of 50 to 100 mol%; And stirring cyclohexanedimethanol; Carrying out the esterification reaction by raising the reactor temperature with the addition of the catalyst; Reacting the oligomer which is the product of the esterification reaction for 0.1 to 24 hours at the conditions of 0.01 to 10 torr and 150 to 300 ℃ to obtain a polyester resin; And Method for producing a solvent-type coating agent or a solvent-type adhesive comprising a PCCD polyester resin comprising the step of dissolving the polyester resin in an organic solvent. The method of claim 9, wherein the catalyst is at least one selected from zinc-based, titanium-based and calcium-based, antimony-based, manganese-based, and germanium-based. The method of claim 9, wherein the organic solvent is acetone, acetonitrile, butyl acetate, butyl alcohol, chloroform, cresol, ethyl acetate, methyl ethyl ketone, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene Glycol monobutyl ether, ethylene glycol monoethyl ether, hexane, isopropyl alcohol, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, cyclohexanone, isophorone, aromatic solvent naphtha and dibasic ethers At least one manufacturing method selected.