KR102754512B1 - Environmental-friendly plasticizer composition, and selant/adhesive compositions comprising the same - Google Patents

Abstract

The present invention relates to a plasticizer composition which is environmentally friendly and exhibits excellent cold resistance, viscosity control effect, and migration resistance, and a sealant/adhesive composition comprising the same.

Description

{Environmental-friendly plasticizer composition, and selant/adhesive compositions comprising the same}

The present invention relates to an environmentally friendly plasticizer composition that does not contain a phthalate plasticizer and includes a recycled raw material.

As polymer additives, plasticizers are used to adjust hardness or ductility, impart contamination resistance, and modify tensile properties (e.g., strength, elongation, or elasticity) and processability.

Adhesive or sealant compositions generally used in the construction and civil engineering fields contain plasticizers as main components along with resins such as polyurethane, polyurea, and polyacrylate. Plasticizers used in adhesive or sealant compositions have the functions of reducing the hardness of polymers, compatibilizing polymer and filler mixtures, increasing low-temperature elasticity, and increasing the extensibility of manufactured films.

Meanwhile, phthalate plasticizers such as dibutyl phthalate (DBP), which can easily control viscosity and thus improve processability, and can improve cold resistance by lowering the glass transition temperature, have been mainly used as plasticizers used in existing adhesive or sealant compositions. However, phthalate plasticizers are suspected of being endocrine disruptors that interfere with or disrupt human hormonal function, and thus there is a movement to regulate them.

In addition, for environmental protection and resource recycling, research is actively being conducted to recover useful resources from waste synthetic resins or by-products generated during the synthetic resin manufacturing process, and to reduce carbon emissions generated during the production of synthetic resin products. For example, a method of recovering raw materials by depolymerizing waste polyester in the presence of a catalyst is known, and the recycled raw materials can be converted into terephthalate-based plasticizer components through esterification reaction or transesterification reaction. However, the plasticizer components recovered through such a regeneration process have a problem in that their quality deteriorates due to impurities during the regeneration process.

Therefore, there is a need to develop a plasticizer composition that replaces phthalate plasticizers to ensure stability, reduce carbon emissions in resource recycling and manufacturing processes, and exhibit superior quality.

The present invention aims to provide a plasticizer composition that can replace a phthalate-based plasticizer and is environmentally friendly while having equivalent or better physical properties compared to existing phthalate-based plasticizers, a sealant or adhesive composition comprising the same, and an environmentally friendly method for producing the plasticizer composition.

The present invention provides a plasticizer composition comprising i) di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate derived from a recycled phthalate compound; ii) dibutylcyclohexane-1,2-dicarboxylate; and iii) a compound represented by the following chemical formula 1:

[Chemical Formula 1]

In the above chemical formula 1,

R ₁ is hydrogen or acetyl,

R ₂ to R ₄ are each independently C _1-10 alkyl.

The present invention also provides a composition comprising a polyol compound, an isocyanate compound, and the plasticizer composition of the present invention.

Additionally, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly indicates otherwise.

In this specification, the terms “comprise,” “include,” or “have” are intended to describe a feature, number, step, component, or combination thereof implemented, but do not exclude the possibility of one or more other features, numbers, steps, components, combinations, or additions thereof.

The present invention may have various modifications and may take various forms, and specific embodiments are exemplified and described in detail below. However, this does not limit the present invention to a specific disclosed form, but should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

In this specification, “DEHCH” refers to di(ethylhexyl)cyclohexane-1,4-dicarboxylate. Additionally, “recycled-DEHCH”, or “R-DEHCH” refers to DEHCH prepared from recycled phthalate compounds.

Hereinafter, the present invention will be described in detail.

The present invention provides a plasticizer composition comprising i) di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate derived from a recycled phthalate compound; ii) dibutylcyclohexane-1,2-dicarboxylate; and iii) a compound represented by the following chemical formula 1:

[Chemical Formula 1]

In the above chemical formula 1,

R ₁ is hydrogen or acetyl,

R ₂ to R ₄ are each independently C _1-10 alkyl.

C _1-10 alkyl can be straight-chain, branched-chain or cyclic alkyl. Specifically, C _1-10 alkyl can be C _1-10 straight-chain alkyl; C _1-8 straight-chain alkyl; C _2-8 straight-chain alkyl; C _3-10 branched-chain or cyclic alkyl; C _3-8 branched-chain or cyclic alkyl; or C _3-5 branched-chain or cyclic alkyl. More specifically, C _1-10 alkyl having carbon atoms can be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, n-hexyl, or a cyclohexyl group.

The plasticizer composition according to the present invention may include di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) represented by the following chemical formula 2.

[Chemical formula 2]

In the present invention, the DEHCH can be obtained from a regenerated phthalate compound. Generally, DEHCH can be obtained through the hydrogenation reaction of a phthalate compound, for example, dioctylterephthalate (DOTP). However, in this case, since an additional process is performed on DOTP, there is a problem that carbon emissions increase somewhat compared to DOTP due to the electricity, gas, steam, etc. used in the additional process. To overcome this, the present invention uses DEHCH (R-DEHCH) manufactured from a “regenerated phthalate compound” rather than general DTOP.

The above-mentioned regenerated phthalate compound can be obtained from waste using a known method. For example, the regenerated phthalate compound can be obtained by depolymerizing waste polyester to obtain an aromatic dicarboxylic acid or an ester thereof, and reacting it with an appropriate alcohol. Alternatively, phthalic acid can be extracted from waste materials such as wastewater discharged during alkaline weight loss processing of polyester fibers, wastewater generated in a process for manufacturing a pure terephthalate compound, and residues after filtration, and the regenerated phthalate compound can be obtained by reacting it with alcohol.

The properties of the recycled phthalate compound used in the present invention are not particularly limited, but it may be more preferable to use a recycled phthalate compound having a low acid value in order to obtain a higher quality plasticizer.

Specifically, the acid value of the recycled phthalate compound for improving the quality of the plasticizer is preferably 0.20 KOH mg/g or less, 0.15 KOH mg/g or less, or 0.10 KOH mg/g or less. The lower the acid value, the better the quality, but there is no restriction on the lower limit, and theoretically, it can be 0 KOH mg/g. In particular, when the acid value of the recycled phthalate compound, which is the raw material of DEHCH represented by the chemical formula 2, is high, the color of the composition may change from colorless and transparent to yellow or brown, or the composition may have a strong odor. In addition, when the acid value of the raw material is high, the migration resistance of the finished product using the plasticizer may be poor, and therefore it is preferable to use a recycled phthalate compound having the acid value range described above.

At this time, the acid value is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1 g of the sample, and can be obtained by titrating the sample solution with a 0.1 N alcoholic KOH solution.

According to one embodiment of the present invention, the recycled phthalate compound, which is a raw material of R-DEHCH in the plasticizer composition, may be recycled dioctyl terephthalate. Preferably, it may be recycled di(2-ethylhexyl) terephthalate.

In general, DEHCH has low viscosity at room temperature and low temperature, so it can implement excellent coating properties, has a fast gelling speed, low plasticizer migration, and excellent hardness properties. However, when DEHCH is used alone, it has a disadvantage in that the viscosity improvement effect is insufficient compared to existing general-purpose plasticizers, and the viscosity changes greatly during long-term storage. Therefore, in order to supplement the shortcomings of the DEHCH, the present invention further includes dibutylcyclohexane-1,2-dicarboxylate (DBCH) represented by the following chemical formula 3 and a citrate compound represented by the above chemical formula 1 together with R-DEHCH.

[Chemical Formula 3]

The above DBCH, like DEHCH, is one of the cyclohexane dicarboxylate compounds. DBCH has high volatility at high temperatures, making it unsuitable for use alone as a plasticizer composition, but it has excellent viscosity control effects and cold resistance, so it can compensate for the shortcomings of DEHCH.

In addition, the citrate compound represented by Chemical Formula 1 is included to further complement the thickening effect of the plasticizer composition and to lower the viscosity change rate over time during long-term storage. The compound represented by Chemical Formula 1 can be manufactured through an esterification reaction of citric acid and a C _2-8 alcohol.

Representative examples of the compound represented by the above chemical formula 1 are tributylcitrate, tri(butyloctyl)citrate, trioctylcitrate, or acetyltributylcitrate. Here, tri(butyloctyl)citrate is a general term for compounds in which some of R ₂ to R ₄ of the above chemical formula 1 are butyl and some are octyl. In a preferred embodiment, the compound represented by the above chemical formula 1 may be tributylcitrate.

Meanwhile, the plasticizer composition of the present invention contains 10 to 85 parts by weight of the R-DEHCH based on 100 parts by weight of the plasticizer composition. If the content of R-DEHCH is less than 10 parts by weight based on 100 parts by weight of the plasticizer composition, the volatilization loss and migration of the plasticizer may increase, and there may be a problem of loss of the plasticizer during processing due to increased volatilization of the plasticizer. On the other hand, if the content of R-DEHCH is too large, exceeding 85 parts by weight based on 100 parts by weight of the plasticizer composition, the contents of DBCH and the compound of chemical formula 1 in the plasticizer composition relatively decrease, so the viscosity of the plasticizer composition decreases, the viscosity may increase significantly during long-term storage, and there may be a problem of decreased cold resistance.

In a preferred embodiment, the R-DEHCH may be included in an amount of 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, but 80 parts by weight or less, or 70 parts by weight or less, per 100 parts by weight of the plasticizer composition.

In addition, the plasticizer composition of the present invention may contain DBCH in an amount of 9 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, and 50 parts by weight or less, or 40 parts by weight or less, per 100 parts by weight of the plasticizer composition.

If the content of DBCH is less than 9 parts by weight per 100 parts by weight of the plasticizer composition, the compound of chemical formula 1 must be used in an excessive amount to secure a sufficient thickening effect, and thus, there may be a problem of a characteristic citric acid odor. In addition, if the content of DBCH exceeds 50 parts by weight per 100 parts by weight of the plasticizer composition, the amount of volatility of the plasticizer may increase, and thus, the physical properties of the plasticizer may change during storage, and there is a problem of a lot of migration of the plasticizer, which is not desirable.

Meanwhile, the compound represented by chemical formula 1 may be included in an amount of 1 part by weight or more, 5 parts by weight or more, or 10 parts by weight or more, but 30 parts by weight or less, or 20 parts by weight or less, per 100 parts by weight of the plasticizer composition.

If the compound represented by chemical formula 1 is less than 1 part by weight per 100 parts by weight of the plasticizer composition, DBCH must be used in excess to adjust the viscosity and lower the glass transition temperature. In this case, there is a high possibility that the loss of the plasticizer will occur during high-temperature processing, thereby deteriorating the overall physical properties of the product. In addition, the compound represented by chemical formula 1 has a disadvantage of having a strong odor, and if the content is too high, the amount of plasticizer volatilization will increase, and there is a possibility that the mechanical strength will deteriorate due to the loss of the plasticizer. Therefore, it is preferable that the amount does not exceed 30 parts by weight per 100 parts by weight of the plasticizer composition.

In a preferred embodiment, the plasticizer composition of the present invention may contain 10 to 85 parts by weight of DEHCH, 9 to 50 parts by weight of DBCH, and 1 to 30 parts by weight of the compound of formula 1, per 100 parts by weight. In this case, the compound of formula 1 may be tributyl citrate.

In another preferred embodiment, the plasticizer composition of the present invention may contain 40 to 70 parts by weight of DEHCH, 20 to 50 parts by weight of DBCH, and 10 to 30 parts by weight of the compound of formula 1, per 100 parts by weight. In this case, the compound of formula 1 may be tributyl citrate.

Meanwhile, the content ratio of the R-DEHCH and DBCH is not particularly limited as long as they are used in the content ranges described above, but for example, the weight ratio of R-DEHCH:DBCH may be 3:1 to 1:1, 2:1 to 1:2, or 1.5:1 to 1:1. When the content of R-DEHCH is the same as or greater than that of DBCH, it is preferable because loss due to migration and volatilization of the plasticizer can be reduced.

Meanwhile, the plasticizer composition of the present invention may further include a compound represented by the following chemical formula 4.

[Chemical Formula 4]

In the above chemical formula 4,

Q ₁ and Q _-2 are the same or different, and each independently represents a single bond, or -COO-,

R ₅ and R ₆ are the same or different and each independently is C _1-10 alkyl.

The compound represented by the above chemical formula 4 is a compound that can be produced in the process of manufacturing R-DEHCH from a regenerated phthalate compound, and specifically, may be at least one selected from the group consisting of the following compounds.

In addition, the plasticizer composition of the present invention may contain 0 to 3 parts by weight of the compound represented by the chemical formula 4 based on 100 parts by weight of the plasticizer composition. Preferably, the plasticizer composition may contain 0 to 2.5 parts by weight, 0 to 2 parts by weight, or 0 to 1 part by weight of the compound represented by the chemical formula 4 based on 100 parts by weight of the plasticizer composition.

As described above, the plasticizer composition according to the present invention can reduce carbon emissions by including R-DEHCH manufactured from recycled raw materials, compared to the case where it includes DEHCH manufactured from pure raw materials.

Carbon emissions are a measure of the amount of carbon generated during the production process of various products, and are calculated based on the annual usage of various fuels such as gas, electricity, and steam used in the production of products, as well as the emission coefficient and calorific value of each fuel. Since the phthalate compound is obtained from a renewable raw material, the energy consumption and greenhouse gas emissions consumed in producing terephthalic acid, a raw material for general phthalate compounds, are reduced, and therefore the plasticizer composition of the present invention can reduce carbon emissions.

The above carbon emissions are generated by using recycled terephthalic acid. Assuming that the esterification process for manufacturing plasticizers is the same as before, it is reasonable to set the energy consumption and greenhouse gas emissions consumed for manufacturing terephthalic acid, the raw material for phthalate compounds, as 0, and calculate only the fuel consumption consumed in the remaining esterification process and hydrogenation process as carbon emissions.

In this specification, the carbon emissions of the plasticizer composition correspond to the sum of carbon emissions (tCO ₂ eq/MT) according to the composition ratio of each component included in the plasticizer composition. Here, the unit of carbon emissions is expressed as the weight equivalent (eq) of total CO ₂ emissions per metric ton.

For example, the carbon emissions of a plasticizer composition containing R-DEHCH:DBCH:TBC in a ratio of 50:30:20 are calculated as the sum of the carbon emissions of each component according to the composition ratio, i.e., carbon emissions of R-DEHCH * 0.5 + carbon emissions of DBCH * 0.3 + carbon emissions of TBC * 0.2, which is 0.592 _tCO2 eq/MT.

At this time, the carbon emissions of each component used in the plasticizer composition are as follows.

- Regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH): 0.565 tCO ₂ eq/MT

- Pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, or Pure-DEHCH): 0.651 tCO ₂ eq/MT

- Dibutylcyclohexane-1,2-dicarboxylate (DBCH): 0.651 tCO ₂ eq/MT

- Tributyl citrate (TBC): 0.571 tCO ₂ eq/MT

- Dibutyl phthalate (DBP): 0.571 tCO ₂ eq/MT

The carbon emissions of each component used in the above plasticizer composition can be calculated by referring to the value provided by the manufacturer or by calculating based on the manufacturing process and chemical reaction of each component.

The plasticizer composition of the present invention described above reduces carbon emissions by using R-DEHCH obtained from a renewable raw material, is environmentally friendly, and simultaneously contains DBCH and a compound represented by the chemical formula 1 together with R-DEHCH, so that it exhibits excellent viscosity improvement effects, cold resistance, and migration resistance even though it does not contain a phthalate plasticizer.

In addition, the present invention provides a composition comprising a polyol compound, an isocyanate compound, and a plasticizer composition according to the present invention. The composition is more specifically a composition used as a sealant or adhesive.

The above polyol compound is not particularly limited as long as it is known in the art as a raw material for polyurethane. Specifically, it may be, but is not limited to, a polyether-type polyol such as polypropylene glycol or a modified form thereof, polytetramethylene glycol, or polyethylene glycol; a polyester-type polyol such as poly(hexamethylene adipate), poly(caprolactone); a polycarbonate polyol; a polybutadiene polyol; or a combination thereof.

The above isocyanate compound may be at least one selected from the group consisting of, for example, diphenylmethane-4,4'-diisocyanate, toluene diisocyanate, methylenediphenyl diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, pyridine diisocyanate, and methylcyclohexane diisocyanate.

The above polyol compound and isocyanate compound may be included so that the equivalent ratio of the isocyanate group to the hydroxyl group (NCO/OH) is in the range of 1:1 to 1:5. If the isocyanate ratio is too high or too low, the mechanical properties required as an elastic adhesive cannot be secured.

The above plasticizer composition may be included in an amount of 1 to 50 parts by weight, or 5 to 30 parts by weight, per 100 parts by weight of the sealant or adhesive composition. If the content of the plasticizer composition in the adhesive composition is too small, the hardness of the coating film after curing of the adhesive composition may increase, which may cause problems such as difficulty in processing, and if the content of the plasticizer composition is too large, the adhesiveness and mechanical properties may deteriorate, so it is preferable that the above range is satisfied.

The above sealant or adhesive composition may further include a chain extender, a crosslinking agent, a diluent, a catalyst, a filler, a foaming agent, a pigment, etc., as needed.

The above chain extender is added to change the strength and hardness of the adhesive composition, and for example, diols such as ethylene glycol, propylene glycol, and 1,4-butanediol; diamines such as hexamethylenediamine and m-phenylenediamine, and the like can be used.

The above cross-linking agent is a multifunctional compound used to improve cross-linking between chains and thereby increase mechanical strength, and examples of cross-linking agents include, but are not limited to, glycerin, trimethylolpropane, pentaerythritol, oxypropylated ethylenediamine, and triethanolamine.

As the above diluent, one or more of trimellitic acid ester, benzoic acid ester, ethylcyclohexane, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and dimethyl carbonate (DMC) can be used.

As the above catalyst, a tertiary amine such as dimethylcyclohexylamine, tetramethylenediamine, pentamethylenediethylenediamine, or tetraethylenediamine; or a catalyst of the imidazole organometallic compound series can be used.

The filler may be a filler known in the art and is not particularly limited. For example, it may be calcium carbonate, carbon black, titanium oxide, kaolin, aluminum oxide, silica, PVC powder or hollow beads, or a mixture thereof. At this time,

The amount of the above additive may be appropriately adjusted as needed and is not particularly limited, but may be included in an amount of 1 to 10 parts by weight, or 0.5 to 30 parts by weight, for example, per 100 parts by weight of the sealant or adhesive composition, respectively.

Meanwhile, in the sealant or adhesive composition, the polyol compound and the isocyanate compound may be included in the form of a prepolymer. In this case, the prepolymer may further include the additives described above depending on the intended use.

According to one embodiment of the present invention, a composition having a glass transition temperature of -20° C. or lower as measured using DSC (Differential Scanning Calorimetry) is provided. Since a lower limit of the glass transition temperature is preferable, the lower limit is theoretically not limited, but may be, for example, -30° C. or higher, or -25° C. or higher.

The above sealant or adhesive composition has excellent processability as its viscosity at 25° C. is 40,000 to 50,000 cps, or 45,000 to 49,000 cps, and can be suitably used as an adhesive/sealant for construction, building materials, or industrial purposes. The viscosity can be measured using a viscometer (for example, a Brookfield viscometer) as in the examples described below.

The sealant or adhesive composition of the present invention described above includes a plasticizer composition comprising DEHCH, DBCH, and a compound of chemical formula 1, and thus has excellent viscosity characteristics and a low glass transition temperature, thereby having excellent cold resistance and excellent volatility and plasticizer migration resistance.

As such, the sealant or adhesive composition of the present invention is environmentally friendly and has excellent physical properties such as processability, long-term storage stability, and cold resistance compared to existing sealant or adhesive compositions, and thus can be suitably used as an adhesive or sealant in the fields of architecture, civil engineering, automobiles, and ship structures.

The plasticizer composition according to the present invention does not contain phthalate and is therefore not harmful to the human body, and is environmentally friendly as it reduces carbon emissions by being manufactured using a regenerated compound. In addition, it has an excellent viscosity control effect, little change in viscosity over time, and excellent cold resistance, volatility, and migration resistance, so it can be suitably used as environmentally friendly adhesives, sealants, etc.

In addition, the polyurethane adhesive composition containing the plasticizer composition of the present invention is environmentally friendly and has excellent physical properties, so it can be usefully used as an adhesive or sealant in the fields of construction, civil engineering, automobiles, ship structures, etc.

Hereinafter, the operation and effect of the invention will be described in more detail through specific examples of the invention. However, these examples are merely presented as examples of the invention, and the scope of the invention is not determined by them. In addition, "%" and "part" indicating the content in the following examples and comparative examples are based on weight unless specifically stated otherwise.

<Example>

Example 1

Preparation of plasticizer composition

Regenerated dioctyl terephthalate (R-DOTP, Runzenenguyuan, acid value 0.175 KOH mg/g) was hydrogenated to produce regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH).

The manufactured R-DEHCH was mixed with dibutylcyclohexane-1,4-dicarboxylate (DBCH), tributyl citrate (TBC) so that R-DEHCH:DBCH:TBC had a weight ratio of 50:30:20 to manufacture a plasticizer composition.

Preparation of adhesive composition

12 parts by weight of the prepared plasticizer composition was added to 100 parts by weight of a mixture containing methylene diphenyl isocyanate (MDI, Lupranate MS available from BASF) and polypropylene glycol (PPG, PPG2025 available from Bayer) in an equivalent ratio of 1:2, and the mixture was mixed at a speed of 1000 rpm for 1 hour at room temperature (25°C), thereby preparing a polyurethane adhesive composition.

Comparative Example 1

An adhesive composition was prepared in the same manner as in Example 1, except that DEHCH was used instead of R-DEHCH.

Comparative Example 2

In Comparative Example 1, an adhesive composition was prepared in the same manner as in Comparative Example 1, except that the weight ratio of DEHCH:DBCH:TBC was set to 90:5:5.

Comparative Example 3

An adhesive composition was prepared in the same manner as in Comparative Example 1, except that the weight ratio of DEHCH:DBCH:TBC was set to 5:60:35.

Comparative Example 4

In the above Comparative Example 1, an adhesive composition was prepared in the same manner as in Comparative Example 1, except that the weight ratio of DEHCH:DBCH:TBC was set to 50:50:0 (excluding TBC).

Comparative Example 5

An adhesive composition was prepared in the same manner as in Comparative Example 1, except that dibutyl phthalate (DBP) was used instead of the DEHCH:DBCH:TBC mixture in Example 1.

The composition of the plasticizer composition manufactured as described above is summarized in Table 1 below.

The composition below is expressed in weight ratios of major components in the plasticizer composition. R-DEHCH DEHCH DBCH TBC DBP Example 1 50 - 30 20 - Comparative Example 1 - 50 30 20 - Comparative Example 2 90 - 5 5 - Comparative Example 3 5 - 60 35 - Comparative Example 4 50 - 50 - - Comparative Example 5 - - - - 100

<Experimental example>

For each adhesive composition of the above examples and comparative examples, the glass transition temperature, viscosity, volatility, plasticizer migration resistance, and odor were evaluated as follows, and the results are summarized in Table 2 below.

(1) Viscosity

The viscosity of each adhesive composition of the above examples and comparative examples was measured after stabilizing it at 25°C for 1 day and after leaving it at 25°C for 14 days.

Specifically, the viscosity was measured using a Brookfield viscometer (#6 spindle, 10 rpm).

(2) Glass transition temperature (Tg)

The glass transition temperature of each adhesive composition of the above examples and comparative examples was measured using DSC (Differential Scanning Calorimetry).

(3) Loss on volatility

Each plasticizer composition was placed in a 200°C gear oven for 4 hours, and the weight loss was measured and compared.

(Good) ◎ > O > △ > X (Unfavorable)

(4) Plasticizer migration resistance

The migration of plasticizer was performed with reference to the ISO 177:1988 (Plastics - Determination of migration of plasticizer) method. Molding sheet specimens cut into circles with a diameter of 50 mm were prepared, and oil-based paper (PP porous film) and a glass plate were sequentially placed on the top and bottom of the specimen so that the plasticizer migrated from the specimen was absorbed into the oil-based paper. A load of 5 kg was applied on the specimen, and the weight change rate (%) of the specimen after leaving it in an oven at 60 ℃ for 7 days was measured to analyze the degree of plasticizer migration.

The weight change rate of the specimen was calculated as [(weight change of specimen/weight of specimen before test) * 100], and the weight change rate of the oil-blotting paper was calculated as [(weight change of oil-blotting paper/weight of oil-blotting paper before test) * 100]. Since the weight decrease of the specimen is the same as the weight increase of the oil-blotting paper, in this experiment, the plasticizer migration was evaluated only by the weight change rate of the specimen.

(Good) ◎ > O > △ > X (Unfavorable)

(5) Smell

The odors were compared in the following order through a sensory test.

(Good) ◎ > O > △ > X (Unfavorable)

(6) Carbon emissions increase/decrease rate (%) and environmental friendliness

For the plasticizer compositions of the above examples and comparative examples, the carbon emission reduction rate (%) was calculated according to the following equation 1.

[Formula 1]

Carbon Emission Reduction Rate (%) = 100 - [(A1/A2)*100]

In the above equation 1,

A1 is the carbon emissions (tCO ₂ eq/MT) of the examples and comparative examples,

A2 is the carbon emissions (tCO ₂ eq/MT) of Comparative Example 5.

Specifically, A1 corresponds to the sum of carbon emissions (tCO ₂ eq/MT) according to the composition ratio of each component included in the plasticizer composition, and A2 is the carbon emissions (tCO ₂ eq/MT) of the plasticizer composition of Comparative Example 5. Here, the unit of carbon emissions is expressed as weight equivalent (eq) of total CO ₂ emissions per metric ton.

For example, the plasticizer composition of Example 1 contains R-DEHCH:DBCH:TBC in a ratio of 50:30:20, and the sum of the carbon emissions of each component according to this composition ratio (A1, i.e., carbon emissions of R-DEHCH * 0.5 + carbon emissions of DBCH * 0.3 + carbon emissions of TBC * 0.2) is 0.592 tCO ₂ eq/MT.

Here, the carbon emissions of each component used in the plasticizer compositions of the examples and comparative examples are as follows.

- Regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH): 0.565 tCO ₂ eq/MT

- Pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, or Pure-DEHCH): 0.651 tCO ₂ eq/MT

- Dibutylcyclohexane-1,2-dicarboxylate (DBCH): 0.651 tCO ₂ eq/MT

- Tributyl citrate (TBC): 0.571 tCO ₂ eq/MT

- Dibutyl phthalate (DBP): 0.571 tCO ₂ eq/MT

The carbon emissions of each component used in the above plasticizer composition were calculated by referring to the value provided by the manufacturer or by estimating based on the manufacturing process and chemical reaction of each component. That is, the carbon emissions of DBCH, which is produced by a chemical reaction similar to DEHCH, were assumed to be the same as DEHCH, and TBC and DBP were assumed to be the same as DOTP. The carbon emissions of DOTP were referred to the value provided by the manufacturer (0.571 tCO ₂ eq/MT).

Based on the increase/decrease rate of carbon emissions calculated through the above equation 1, the eco-friendliness of the plasticizer composition was evaluated as follows.

Within ± 5%; Equal, Over 5%; Slightly inferior, Over 10%; Inferior

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Tg(℃) -20.2 -20.2 -17.5 -18.0 -19.5 -19.5 Viscosity at 25℃ (cps, after 1 day) 47300 47300 27500 47000 38000 63000 Viscosity at 25℃ (cps, after 14 days) 48400 48400 35400 30400 56000 32000 Volatility O 0 0 X △ X Plasticizer-resistant O O O X △ △ smell O O O X ◎ O Carbon emissions of plasticizer compositions
(tCO ₂ eq/MT) 0.592 0.635 0.570 0.619 0.608 0.571 Carbon emissions increase/decrease rate (%) +3.7 +11.2 -0.2 +8.4 +6.5 standard Eco-friendliness equality Thirteen equality somewhat inferior somewhat inferior standard

Referring to Table 2 above, Example 1 including the plasticizer composition of the present invention has excellent cold resistance due to a low glass transition temperature by mixing appropriate amounts of R-DEHCH, DBCH, and TBC, and exhibits a viscosity suitable for an adhesive and a low change in viscosity over time. In addition, it is environmentally friendly as it reduces carbon emissions compared to Comparative Example 1.

Claims (15)

For 100 parts by weight of the plasticizer composition,
i) Containing 10 to 85 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate derived from a recycled phthalate compound;
ii) containing 9 to 50 parts by weight of dibutylcyclohexane-1,2-dicarboxylate;
iii) Containing 1 to 30 parts by weight of tributyl citrate,
The weight ratio of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and dibutylcyclohexane-1,2-dicarboxylate is 3:1 to 1:1,
Plasticizer composition.
In the first paragraph,
The above-mentioned regenerated phthalate compound has an acid value of 0.2 KOH mg/g or less.
Plasticizer composition.
delete delete delete delete delete delete In the first paragraph,
Further comprising a compound represented by the following chemical formula 4,
Plasticizer composition:
[Chemical Formula 4]

In the above chemical formula 4,
Q ₁ and Q _-2 are the same or different, and each independently represents a single bond, or -COO-,
R ₅ and R ₆ are the same or different and each independently is C _1-10 alkyl.
A composition comprising a polyol compound; an isocyanate compound; and a plasticizer composition of claim 1.
In Article 10,
A composition comprising 1 to 50 parts by weight of a plasticizer composition per 100 parts by weight of the composition.
In Article 10,
A composition further comprising at least one additive selected from chain extenders, cross-linkers, diluents, catalysts, and fillers.
In Article 12,
A composition comprising 1 to 10 parts by weight of an additive per 100 parts by weight of the composition.
In Article 10,
A composition having a glass transition temperature of -20°C or lower as measured using DSC (Differential Scanning Calorimetry).
In Article 10,
A composition used as a sealant or adhesive.