KR101008232B1 - Liquid hydrocarbon resin - Google Patents

Abstract

PURPOSE: A liquid hydrocarbon resin is provided to act as a thickening agent when used for coating and painting with curable materials and to improve stability to ultraviolet rays, heat resistance, compatibility, water resistance and chemical resistance. CONSTITUTION: A liquid hydrocarbon resin, based on the content of solid portion comprises 5-20 weight% of 1,1,3-trimethyl-3-phenyl-indane, 1-15 weight% of 2,4-diphenyl-4-methyl-1-pentene, 1-15 weight% of,4-diphenyl-4-methyl-2-penetene, 5-40 weight% of 2,4,6-triphenyl-4,6-dimethylhept-1-ene, and 5-40 weight% of 2,4,6-triphenyl-4,6-dimethylhept-2-ene.

Description

Liquid hydrocarbon resin

The present invention relates to a liquid petroleum resin.

Petroleum resins are prepared by polymerizing various feeds of Friedel-Crafts, which may be purified streams containing pure monomers or mixtures of various unsaturated substances. Typical feeds may be olefins having 4 to 6 or 8 to 9 carbon atoms, diolefin feeds and mixtures thereof, and various pure olefinic monomers.

The resulting petroleum resin is a low molecular weight thermoplastic produced through thermal or catalytic polymerization and is used in adhesives, rubbers, hot melt coatings, printing inks, paints, floorings, road markings, polymers and other applications. In general, petroleum resins can be used to modify other materials.

In one embodiment of the present invention is used to modify other materials to improve the stability, heat resistance, water resistance and chemical resistance, etc., to provide a liquid petroleum resin excellent in compatibility, and can improve the adhesion.

In one embodiment of the present invention, based on solids content, 1,1,3-trimethyl-3-phenyl-indane (1,1,3-Trimethyl-3-phenyl-indane) 5 to 20% by weight, 2,4- 1-15% by weight of diphenyl-4-methyl-1-pentene (2,4-Diphenyl-4-methyl-1-penetene), 2,4-diphenyl-4-methyl-2-pentene (2,4- Diphenyl-4-methyl-2-penetene) 1-15% by weight, 2,4,6-triphenyl-4,6-dimethylhept-1-ene (2,4,6-Triphenyl-4,6-dimethylhept- 1-ene) 5 to 40% by weight and 2,4,6-triphenyl-4,6-dimethylhept-2-ene (2,4,6-Triphenyl-4,6-dimethylhept-2-ene) 5 to It provides a liquid petroleum resin comprising 40% by weight.

Liquid petroleum resin according to an embodiment of the present invention includes up to 25% by weight of p-cumylphenol (p-Cumylphenol), up to 25% by weight of o, p-Dicumylphenol (o, p-Dicumylphenol) It may be to include.

Liquid petroleum resin according to an embodiment of the present invention may be an OH group content of up to 10% by weight.

Liquid petroleum resin according to one embodiment of the present invention may have a viscosity of 10 to 5000 cps at 25 ℃.

Liquid petroleum resin according to one embodiment of the present invention may have a volatile content of 5% or less.

In one exemplary embodiment of the present invention provides an epoxy resin composition comprising a liquid petroleum resin according to the embodiments.

In addition, an exemplary embodiment of the present invention provides a coating method for a heavy-duty / ship including a liquid petroleum resin according to the embodiments.

Another exemplary embodiment of the present invention provides a flooring comprising a liquid petroleum resin according to the above embodiments.

Liquid petroleum resin according to an embodiment of the present invention is used in coating and paint applications with a curable material such as alkyd and epoxy, in addition to the properties of the petroleum resin that is thermoplastic, not only serves as an extender, but also has all the physical properties of the curable material itself, For example, it is possible to improve ultraviolet stability, heat resistance, compatibility, water resistance and chemical resistance, and improve adhesion.

Hereinafter, the present invention will be described in more detail.

Liquid petroleum resin of the present invention, based on solids content, 1,1,3-trimethyl-3-phenyl-indane (1,1,3-Trimethyl-3-phenyl-indane) 5 to 20% by weight, 2,4- 1-15% by weight of diphenyl-4-methyl-1-pentene (2,4-Diphenyl-4-methyl-1-penetene), 2,4-diphenyl-4-methyl-2-pentene (2,4- Diphenyl-4-methyl-2-penetene) 1-15% by weight, 2,4,6-triphenyl-4,6-dimethylhept-1-ene (2,4,6-Triphenyl-4,6-dimethylhept- 1-ene) 5 to 40% by weight and 2,4,6-triphenyl-4,6-dimethylhept-2-ene (2,4,6-Triphenyl-4,6-dimethylhept-2-ene) 5 to 40 weight percent.

Herein, 1,1,3-trimethyl-3-phenyl-indane is represented by the following Chemical Formula 1, and may serve to impart plasticity in the liquid petroleum resin. The content of 1,1,3-trimethyl-3-phenyl-indane can be adjusted in consideration of provision of plasticity, preferably 5 to 20% by weight of the total liquid petroleum resin.

Formula 1

2,4-diphenyl-4-methyl-1-pentene is represented by the following Chemical Formula 2, and may serve to enhance weather resistance in the liquid petroleum resin. The content of 2,4-diphenyl-4-methyl-1-pentene may be adjusted in consideration of weathering resistance enhancement, preferably 1 to 15% by weight of the total liquid petroleum resin.

Formula 2

2,4-diphenyl-4-methyl-2-pentene is represented by the following Chemical Formula 3, and may serve to enhance weather resistance in the liquid petroleum resin. The content of 2,4-diphenyl-4-methyl-2-pentene can be adjusted in consideration of weathering resistance, preferably 1 to 15% by weight of the total liquid petroleum resin.

Formula 3

Liquid petroleum resin according to an embodiment of the present invention includes up to 25% by weight of p-cumylphenol (p-Cumylphenol), up to 25% by weight of o, p-Dicumylphenol (o, p-Dicumylphenol) It may be to include.

The p-cumylphenol is represented by the following Chemical Formula 4, and may serve to adjust chemical resistance, curing time, and pot life in a liquid petroleum resin. The content of p-cumylphenol can be adjusted in consideration of the pot life, preferably 5 to 25% by weight of the total liquid petroleum resin.

If the content is less than 5% by weight of the total liquid petroleum resin, the pot life is too long when mixed with the epoxy can be reduced workability, if the content is more than 25% by weight may be too short.

Formula 4

o, p-dicumylphenol is represented by the following formula (5), it may play a role in controlling the chemical resistance, curing time and pot life in the liquid petroleum resin. The content of o, p-dicumylphenol can be adjusted in consideration of the pot life, preferably 5 to 25% by weight of the total liquid petroleum resin.

If the content is less than 5% by weight of the total liquid petroleum resin, the pot life is too long when mixed with the epoxy can be reduced workability, if the content is more than 25% by weight may be too short.

Formula 5

2,4,6-triphenyl-4,6-dimethylhept-1-ene is represented by the following Chemical Formula 6, and may serve to impart high viscosity in the liquid petroleum resin. The content of 2,4,6-triphenyl-4,6-dimethylhept-1-ene may be adjusted in consideration of the viscosity, preferably 5 to 40% by weight of the total liquid petroleum resin.

6

2,4,6-triphenyl-4,6-dimethylhept-2-ene is represented by the following formula (7), and may serve to impart high viscosity in the liquid petroleum resin. The content of 2,4,6-triphenyl-4,6-dimethylhept-2-ene can be adjusted in consideration of the viscosity, preferably 5 to 40% by weight of the total liquid petroleum resin.

Formula 7

The liquid petroleum resin according to one embodiment of the present invention including all of the compounds represented by Chemical Formulas 1 to 7 has an OH group content of 10 wt% or less, preferably 1 to 1, in consideration of chemical resistance, weather resistance, and pot life. It is 6 weight%. Here, the OH group content can be defined as the weight of OH relative to the total weight as phenolic OH groups.

In addition, considering the workability and mixing conditions with epoxy, the liquid petroleum resin according to one embodiment of the present invention has a viscosity at 25 ° C. of 10 to 5,000 cps, preferably 50 to 2500 cps.

In addition, the liquid petroleum resin according to one embodiment of the present invention in order to comply with VOC free it may be preferred that the volatile content of 5% or less.

Method for producing a liquid petroleum resin according to an embodiment of the present invention having the composition as described above is not particularly limited, for example, at least one selected from the group comprising a pure monomer, C5 monomer and C9 monomer in the presence of a catalyst It may be prepared including a polymerization step of obtaining a resin solution by reacting a compound containing a phenol with a phenol.

In this case, as the catalyst, a Friedel-Craft polymerization catalyst such as a Lewis acid such as boron trifluoride, a complex of boron trifluoride, aluminum trichloride or alkyl aluminum chloride may be used.

As examples of other catalysts, catalysts which are particularly environmentally friendly and which do not need to be neutralized during the production process can be used, such as acid treated clay, silica-alumina, bristed acid-treated silica-alumina, mesoporous silica- It may be one or more selected from the group consisting of alumina and Bronsted acid treated mesoporous silica-alumina. Hereinafter, these are abbreviated as acid treated catalysts. More specifically, the acid-treated catalyst may be advantageous in that a mixture of silica and alumina in a weight ratio of 1 to 15: 1 has a high acid point (action point at which the catalyst occurs as an acid catalyst). The higher the acid concentration, the greater the activity of the catalyst. Accordingly, the polymerization of the aromatic monomer may be activated, which may be advantageous to have a high softening point. On the other hand, the acid-treated catalyst may be a pretreatment before the polymerization step, the pretreatment may be a heat treatment, a reduced pressure treatment, an inert atmosphere or a treatment in dry air. Alternatively, the above treatment method may be combined to pretreat. Through this pretreatment it is possible to further enhance the acidity of the catalyst and the activity for the polymerization. For example, it may be a pre-treatment by drying for 3 to 8 hours at 150 ~ 250 ℃ under vacuum. The vacuum condition may be 2 to 5 torr. By pretreatment as described above, free associated water forming chemical / physical bonds can be removed to increase the acidity and polymerization activity of the catalyst. In addition, the acid-treated catalyst may be used in an amount of 0.1 to 30% by weight based on the monomer weight included in the reaction, considering that the specific surface area is a solid acid catalyst, unlike a gas or liquid catalyst. The catalyst is preferably added slowly over 2 to 30 minutes in consideration of exothermic control. Rapid dosing of catalysts makes it difficult to control excessive exotherm, resulting in low molecular weight of the resin. A general Lewis acid catalyst works most efficiently in the presence of a cocatalyst, which is an ion or an organic compound, which is easily ionized to help activate the catalyst. However, the catalyst is supported by an inorganic compound such as silica-alumina and free of water. At the heart of catalytic activity, no promoter is required. As a result, the acid-treated catalyst is easy to filter and has the characteristic of eliminating other subsequent processes such as a neutralization process.

By pure monomer, it is meant a synthetically produced or highly purified monomer, which may contain relatively pure styrene-based monomers such as styrene, α-methyl styrene, β-methyl styrene, 4-methyl styrene and vinyl toluene fractions. have. The monomer may be used as a pure monomer or a mixture of two or more monomers, and other alkylated styrenes such as t-butyl styrene or phenyl styrene may be used. The pure monomer composition may be in a dried state if necessary, or may contain less than 100 ppm of water.

C5 monomers include unsaturated C5 and / or C6 olefins and diolefins that boil at about 20-100 ° C. under atmospheric pressure. Specifically, olefins such as isobutylene, 2-methyl-2-butene, 1-pentene, 2-methyl-1-pentene, 2-methyl-2-pentene and 2-pentene; Cycloolefins such as cyclopentene and cyclohexene; Diolefins such as 1-3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene and 1,4-hexadiene; Cyclodiolefins such as cyclopentadiene, dicyclopentadiene and alkyl substituted derivatives, and the like.

In addition to the reactive component in feeding the C5 monomer, the non-polymerizable component in the feed may comprise saturated hydrocarbons which may be co-distilled with unsaturated components such as pentane, cyclopentane or 2-methylpentane. Such comonomer feeds may be copolymerized with C4 or C5 olefins or dimers as chain transfer agents. Chain transfer agents can be added to obtain a resin having a lower, narrower molecular weight distribution than that made using only monomer alone. The chain transfer agent stops the growth of growing polymer chains by terminating the chains in such a way as to regenerate the polymerization initiation site. Components that act as chain transfer agents in these reactions include isobutylene, 2-methyl-1-butene, 2-methyl-2-butene or dimers or oligomers of these species. Chain transfer agents can be included in the reaction in purified form or in diluted form in a solvent. Such a C5 monomer composition may be in a dried state if necessary, or may contain less than 300 ppm of water.

C9 monomers, on the other hand, include unsaturated aromatic C8, C9 and / or C10 monomers that boil at about 100-300 ° C under atmospheric pressure. Specifically, it may include styrene, vinyl toluene, indene, dicyclopentadiene and alkylated derivatives of these components. The C9 monomer may generally contain at least about 20% by weight, preferably about 30-75% by weight of polymerizable unsaturated monomer. The remainder may generally be alkyl substituted aromatics that can be incorporated into the resin by alkylation reactions. The C9 monomer composition may be in a dried state if necessary, or may contain less than 500 ppm of water.

Terpene components may be further used in addition to compounds comprising at least one selected from the group comprising pure monomers, C5 monomers and C9 monomers. Terpenes may be selected from d-limonene, alpha-pinene and beta-pinene and dipentene.

In addition, the compound comprising at least one selected from the group consisting of the pure monomer, C5 monomer and C9 monomer may be used in 20 to 80% by weight of the total reactants, in the case of C5 monomer up to about 40% by weight of the chain transfer agent It may contain.

In addition, solvents such as toluene, octane, high boiling aromatic solvents, aliphatic solvents or solvent blends may be used at 20 to 80% by weight. The solvent may preferably be an aromatic solvent, typically toluene, xylene or lower aromatic petroleum solvents.

The phenols used in addition to the above-mentioned compounds are compounds which can be defined as hydroxy group-containing aromatic compounds, and are not particularly limited as long as at least one hydroxy group is an aromatic compound directly bonded to an aromatic ring. Examples of the aromatic ring include a benzene ring and a condensed naphthalene ring. More specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, p- 1 such as sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, α naphthol, β-naphthol Phenols; 2, such as resorcin, catechol, hydroquinone, 2,2-bis (4'hydroxyphenyl) propane, bis (hydroxyphenyl) methane, bis (hydroxynaphthyl) methane, tetramethylbiphenol, biphenol Phenols; Trihydric phenols such as tris (hydroxyphenyl) methane, mixtures thereof, and the like, and the like.

In order to prepare a liquid petroleum resin according to an embodiment of the present invention having the above-described composition, a monomer comprising at least one selected from the group consisting of pure monomers, C5 monomers and C9 monomers, and phenols may have a weight ratio of 20 to 5: 1. It may be a combination.

The polymerization may be advantageously performed at -50 to 150 ° C in terms of yield and molecular weight control.

In the case of the phenol-containing liquid petroleum resin obtained by polymerizing a C9 monomer, the molecular weight decreases and the molecular distribution becomes wider as the reaction temperature increases.

The reaction sequence may be a case where the raw material monomer is added to the reactor while stirring the catalyst, and the raw material monomer may be added while stirring the catalyst, and the latter is advantageous to increase the amount of phenol introduced.

The catalyst can be removed by filtering the resin solution obtained after the polymerization reaction under normal temperature, 0 ~ 10torr pressure. In particular, in the case of using an acid-treated catalyst, it can be easily removed through a filtration process even though the process is not neutralized.

The filtered resin solution may be further subjected to a degassing step of heating and degassing under vacuum. The degassing step may be performed at 150 to 250 ° C. for 3 to 30 minutes under vacuum. The vacuum condition may be 2 to 5 torr.

The liquid petroleum resin according to one embodiment of the present invention may be blended with various resins to act as a modifier, an extender and a diluent, a pot-life controller, an organic filler, and in particular, by mixing with an epoxy resin. It can be used for heavy-duty / ship paints and flooring applications.

When used for such a purpose, the mixing ratio of the liquid petroleum resin may be appropriately adjusted according to the application purpose, but it is preferable to be blended in an amount of 30 parts by weight or less, preferably 5 to 20 parts by weight based on 100 parts by weight of the main resin. Can be.

Hereinafter, examples of the present invention will be described in more detail, but the scope of the present invention is not limited to these examples.

Example 1

α-methylstyrene (AMS) (2000 g, Kumho P & B) and phenol (600 g, Kumho P & B) were added to xylene (1000 ml) and dissolved well.

After the mixture was stabilized at 40 ° C., the mixture was heated to 60 ° C. to 70 ° C. while the BF ₃ -phenolate catalyst was divided into 3 to 4 times. After the addition was completed, the mixture was aged for 1 hour, and then water was added to remove the catalyst component through water washing. After washing with water, vacuum degassing was carried out to 180 ° C. to obtain a resin having a viscosity of 1000 cps (yield: 95%).

Example 2

Phenol (300 g, Kumho P & B) was added to xylene (1000 ml) and dissolved well. BF ₃ -methanol catalyst was added thereto and stabilized at 40 ° C. The exotherm was gradually adjusted while heating AMS (2000 g, Kumho P & B) in 100 g units, and the temperature was raised to 80 ° C.

After the addition was completed, the mixture was aged for 1 hour, and then water was added to remove the catalyst component through water washing. After washing with water, vacuum degassing was carried out to 180 ° C. to obtain a resin having a viscosity of 400 cps (yield: 94%).

Analysis of the components of the liquid petroleum resin obtained in Examples 1 and 2 was used for the GC and GC-Mass method, the results are shown in Table 1 below.

On the other hand, by controlling the reaction ratio of α-methylstyrene (AMS), styrene monomer (SM), xylene (xylene), phenol (phenol) to the liquid petroleum resin (Examples 3 to 8) as shown in Table 1 Prepared.

In the description of Table 1, the unit is weight percent based on the solid content.

ingredient Example 1
( PL-40) Example 2
( PL-50) Example 3
(P L-150) Example 5
( PL-300) Example 6
( PL-400) Example 7
( PL-1000S) Example 8
( L-2000) Formula 1 15 15 15 10 15 15 10 Formula 2 25 15 15 10 20 10 5 Formula 3 25 20 20 15 20 5 5 Formula 4 0 12 10 15 4 5 5 Formula 5 0 12 10 20 4 10 10 6 14 12 15 20 18 25 30 Formula 7 21 14 15 10 19 30 35

The yield, OH group content, volatile content, and viscosity of the prepared liquid petroleum resin were measured as follows, and the results are shown in Table 2 below.

(1) OH group content (% by weight)

① Methanol 4% THF mixed solution was prepared to make a standard reagent in a 50ml flask to a concentration between 10ppm and 100ppm.

② UV spectrophotometer (Agilant 8453) Fill the reference cell and sample cell with methanol 4% THF solution at 400-250nm wavelength, add 20μl of 10% TBAH solution, shake it, and measure the absorbance between wavelength 400-250nm. A calibration curve was prepared at the absorbance of.

③ Sample was made in the same way as ①. (About 0.01 ~ 0.03g / 100mL)

④ Put the sample solution into the sample cell, add 20% of 10% TBAH, shake well, and measure the absorbance at 310 nm.

⑤ From the calibration curve, the concentration of residual phenolic OH group was obtained.

(2) volatile content

2 g of the resin was quantified in an aluminum dish and placed in an oven at 105 ° C., after 1 hour, the weight of the nonvolatile material was measured, and the ratio to the initial weight was calculated.

(3) viscosity

It was measured at 25 ° C. using a # .2 Spindle with a Brook Field Viscometer (Brookfield DV-III + Programmable Rheometer).

Product Volatile Content (%) Viscosity
(25 ℃, cps) -OH group content
(wt%) PL-25A 25 max 20-30 0.5-0.7 PL-40 4 Max 30-50 0 PL-50 4 Max 40-60 0.7-1.1 PL-100A 25 max 60-90 1.5-1.8 PL-150 4 Max 100-200 1.5-1.9 PL-220 4 Max 210-280 3.1-3.5 PL-300 4 Max 250-400 4.4-4.8 PL-400 4 Max 400-550 1.9-2.3 PL-1000S 4 Max 900-1200 2.4-2.8 PL-2000 4 Max 1800-2200 2.5-2.9 CL-50 4 Max 40-60 0.7-1.1 CL-300 4 Max 250-350 4.2-4.6

Experimental Example

(1) Experiment 1

Specimens were prepared using a general purpose bisphenol-A epoxy and a curing agent (Jeffamine curing agent), but the physical properties of the resin obtained from the above examples (hereinafter referred to as PL resin) were added.

The mixing ratio was Epoxy (EEW = 187) / Jeffamine D-230 / PL resin = 100/40/20 weight ratio to prepare a specimen by curing the mold at room temperature for 24 hours and post cure at 80 ° C for 2 hours. .

In the following example, Neat resin will be understood as a case where no PL resin is added.

1) Quick UV Tested Specimen

The obtained specimen was exposed to Quick UV (QUV-SE, product of Q-panel) for 24 hours and then visually observed is shown in FIG. 1.

From the results of FIG. 1, it can be seen that UV resistance is improved compared to the neat state when the PL resin is added.

2) Thermal Exotherm test

The exothermic properties of the obtained specimens were evaluated in the following manner.

Epoxy resin and PL resin are mixed uniformly first, then the curing agent (Jeffamine D-230) is added and mixed for 2 minutes. The exothermic behavior of the mixed resin was measured using a digital thermal exotherm tester.

The results are shown in Figure 2, from which it can be seen that the maximum exothermic temperature is significantly reduced compared to Neat formulation, except for PL-300 bar, PL-300 has a hardening promoting action due to the high OH content Maximum peak time seems to be shortened

3) Hardness

The hardness characteristics of the specimens having the above formulations were evaluated in the following manner.

The prepared specimens were measured for hardness using a Shore-D hardness tester.

The results are shown in FIG. 3, whereby Hardness after Post Cure was not significantly affected by the presence or absence of the PL resin, but it can be seen that the initial hardness value was high in the formulation containing the PL resin.

4) Tg

The glass transition temperature was measured by the following method with respect to the specimen having the formulation as described above.

Tg was measured at a temperature increase rate of 10 ° C. per minute using a DSC 2910 Model manufactured by TA Instrument.

The results are shown in Figure 4, it can be seen that from this, when the PL resin is added, the overall heat resistance is improved.

5) Compatibility with Resin

The compatibility of the specimens with the above formulations was evaluated by scanning electron microscopy (SEM).

The results are shown in FIG. 5, which shows that the PL-resin shows very good compatibility without being entangled.

6) Adhesive force (UTM)

Evaluation of adhesion strength was carried out on the specimens having the above formulation in the following manner.

Uniformly apply the uncured resin mixture (Epoxy + PL + D-230) to two 5cm * 2.5cm steel plates, and then prepare the specimens by curing at room temperature for 24 hours / 80 ° C for 2 hours and using UTM of Loyyd. Adhesion was measured using the instrument.

The results are shown in Figure 6, it can be seen from this from the overall improvement of the adhesive strength of the PL resin.

From the results of Experiment 1, BPA Epoxy (EEW = 187) and Jefamine D-230 curing agent resulted in the improvement of the overall physical properties of the PL resin. It is expected to be.

(2-1) Experiment 2-1

General purpose bisphenol-A epoxy and polyamide curing agents were used to compare the physical properties of each PL resin. At this time, the compounding ratio Epoxy (EEW = 187) / Polyamide (AV = 340) / PL resin = 100/45/20 weight ratio. In the following example, Neat resin will be understood as a case where no PL resin is added.

The specimens used were obtained by uniformly coating the mixed resin to a sandpaper treated 1.0T iron plate in a thickness of 100 μm, drying at room temperature for 24 hours, and then performing postcure at 80 ° C. for 2 hours.

1) Thermal Exotherm test

The obtained specimens were evaluated for exothermic properties in the same manner as in Experiment 1 2), and the results are attached to FIG. 7. From the results of FIG. 7, Except for PL-300, the maximum exothermic temperature is significantly lower than that of Neat formulation. In the case of PL-300, the hardening action is caused by the high OH content. The peak time seems to be shortened.

2) Adhesion Test (Cross Cut)

For the obtained specimens, the adhesive force was evaluated using Cross Cut, and the results are shown in FIG. 8. From this result, it can be seen that the surface adhesion is improved in the overall PL.

(2-2) Experiment 2-2

General purpose bisphenol-A epoxy and polyamide curing agents were used to compare the physical properties of each PL resin. At this time, the compounding ratio Epoxy (EEW = 187) / Polyamide (AV = 300) / PL resin = 70/30/20 weight ratio. In the following example, Neat resin will be understood as a case where no PL resin is added.

The specimens used were obtained by uniformly coating the mixed resin to a sandpaper treated 1.0T iron plate in a thickness of 100 μm, drying at room temperature for 24 hours, and then performing postcure at 80 ° C. for 2 hours.

The obtained specimens were evaluated for chemical resistance (after 72 hours at room temperature) for the drugs shown in Table 3 below, and the results are shown in Table 3 below.

From the results in Table 3, due to the mixed PL resin, the chemical resistance was also significantly improved, and in particular, it can be seen that it shows a good improvement effect on acetic acid, which is strongly corrosive.

10%
H2SO4 10%
HCl 10%
Acetic acid 10%
NaOH EtOH Water Neat 0.85 1.47 2.57 0.40 2.97 0.93 PL-25A 0.51 0.54 1.34 0.30 3.30 0.36 PL-50 0.66 0.67 2.44 0.28 4.63 0.47 PL-100A 0.37 0.31 0.98 0.18 2.93 0.31 PL-300 0.30 0.30 1.01 0.13 3.29 0.25 PL-1000S 0.30 0.31 0.98 0.10 3.67 0.25

From the results of Experiments 2-1 and 2-2, it can be seen that the application of the PL-resin shows the effect of improving adhesion and chemical resistance even in the mixing experiment with the polyamide curing agent.

(3) Experiment 3

BPA Epoxy (EEW = 475) and a polyamide curing agent were used, and the physical properties of each PL resin were compared. At this time, the compounding ratio Epoxy (EEW = 475) / Polyamide (AV = 220) / PL-resin = 65/35/10 weight ratio. In the following example, Neat resin will be understood as a case where no PL resin is added.

1) Erichsen Test

Flexural adhesion was evaluated for the obtained specimens using Erichsen Tester.

The results are shown in Figure 9, the Erichsen test to measure the flexural adhesion was relatively low molecular weight, especially the PL-25A containing some of the BA showed a particularly good result, the overall performance of the PL resin compared to Neat.

2) Chemical resistance (after 72 Hr at RT)

The obtained specimens were evaluated for chemical resistance in the same manner as in Experiment 2-2, 2). As a result, PL-1000S, CL-50, and CL-300 showed relatively excellent acid resistance. -The resin formulation showed excellent chemical resistance.

The formulation of Experiment 3 is the combination of epoxy and hardener most commonly used for heavy coatings. Experimental results As shown in the previous results, it can be seen that the flexural adhesion and chemical resistance are improved.

(4) Experiment 4

Experiments on storage stability, compatibility, etc. of PL resin with various epoxy and curing agents were carried out as follows.

1) Storage stability

The storage stability of the epoxy resin (YD-128, EEW = 187 ) alone and the epoxy resin in which each PL-resin was added to the epoxy resin at 50% by weight was evaluated. The results are shown in FIG. 10. In addition, the storage stability (storage temperature 50 ℃) for the case of blending the PL-resin to 50% by weight in various curing agents (polyamide, aromatic amine, Jeffamine) was evaluated and the results are shown in FIG. As a result, it can be seen that the initial characteristics stably without mixing the viscosity when mixed with various Epoxy and hardeners, there is little change in viscosity even when stored for 30 days at 50 ℃ compared to Epoxy Neat.

2) Non-volatile content

According to the method described above, the volatile matter content of the PL-resin was measured for each condition of Table 4, and the results are shown in Table 4 below. As a result of the measurement of non-volatile content of each condition, the overall value is high at room temperature, but the solid content decreases rapidly with increasing temperature. PL-1000S shows high solids even at 105 ℃, which makes it suitable for high soild use.

PL-100A PL-1000S
Nonvolatile content
(%) RT * 6Hr * 2g 98.63 99.78 105 ℃ * 1Hr * 1g 72.63 97.30 135 ℃ * 1Hr * 1g 52.16 88.08 160 ℃ * 1Hr * 1g 46.47 69.55

3) Compatibility  & Pot life

For each PL-resin, the pot life in the epoxy resin and various curing agents was measured, and also the compatibility with the modified aliphatic amine curing agent was evaluated and the results are shown in Table 5 below. As a result, when the epoxy resin (EEW = 187) and the Aliphatice amine curing agent were mixed, the higher the OH content of the PL resin, the shorter the pot life was. This is because the OH group in the PL resin acts as a curing accelerator. The compatibility was maintained in the case of KH-500F, a modified aromatic amine curing agent, in the entire product, but the difference was severe in the case of TH-438, an aliphatice amine curing agent. The high OH content was good in PL-300 and PL-220, but very poor in PL-140 and 400. PL-100A containing BA showed excellent compatibility but had a disadvantage of lengthening pot life.

OH
con. (%) Pot Life (min) in each curing agent Compatibility
24hrs later
with TH-438 TH-438 (42 pbw) KH-500F (28 pbw) PL-300 5 18 9 Good PL-400 2.1 22 9 Bad PL-1000S 2.6 26 9 Good enough PL-2000 2.7 27 10 More less PL-150 1.7 32 12 Bad PL-100A 1.65 33 9 Excellent PL-25A 0.6 38 9 Bad PL-220 2.05 19 - Good

From the results of Experiment 4, the storage stability when mixed and stored PL resin, a curing agent or Epoxy seems to be not a problem. The compatibility with the curing agent is highly dependent on the OH content of the resin, and the pot life seems to be affected. Other products except 25A and 100A in the PL-resin do not contain any solvents and therefore can be used for high solid applications. It is expected to be able.

(5) Experiment 5

In order to compare the change of physical properties with the addition of PL resin in the bisphenol-A epoxy resin (EEW = 475) and the polyamide curing agent system, a basic paint was prepared and its application evaluation was performed.

1) Experimental conditions

Ingredient blend

Next, the main composition was prepared in the composition and blending ratio as shown in Table 6. In addition, a curing agent composition was prepared in the following composition and blending ratios. The main / curing agent having this composition was mixed in an 8/1 weight ratio.

ingredient Input ratio (% by weight) YD-011X75 (EEW 475) 46.67 Xlyene 5.83 n-BuOH 10 PLs 10  Dispersant 0.2 Antifoam 0.2 CaCO3 17.1 Paste (White Pigment) 10 system 100

ingredient G-0240
(AV 400) (wt%) Hardener 70 Xlyene 7 n-BuOH 15 K-54 8 system 100

-Coating conditions

① The 0.5T iron sheet was washed with MEK solvent after sand paper treatment (30 round trips).

② Primer coating: Coating thickness: 15㎛, 2 hours post-cure at room temperature and then 2 hours postcure at 60 ℃.

③ After coating the blended paint twice to have a thickness of 55㎛ (period curing 24Hr at each time)

④ Evaluate each property after conducting postcure at 60 ℃ for 2 hours

2) Experiment result

The adhesive force and the drying rate were evaluated for the cured product (Neat) of the above-mentioned compounding conditions and each cured product obtained by further blending the PL-resin therein, and the results are shown in Table 8 below.

Here, the Dolly test measured the force falling to the Elcometer 106 after attaching a dolly 2cm in diameter using an adhesive to the iron plate coated with EPOXY solution.

Drying time was measured using a .K Drying Recorder.

Erichsen and Cross Cut tests are the same as described above.

From the results in Table 8, PL-1000S and CL-300 showed relatively good adhesion in the G-0240 curing agent system, and showed the same aspect according to each measurement method. The drying rate was longer than that of Neat formulation, and the results showed that the drying delay was lower than other PL products when using PL-1000 with high OH content.

Neat PL-150 PL-400 PL-1000S Adhesion
Dolly 0.9 0.8 1.1 1.2 Erichsen 6.5 6.76 7.15 7.25 Cross cut Good Good Good Good Drying time 2:20 3:15 3:00 2:50

In addition, the chemical resistance evaluation results are shown in Table 9 below. Also about the chemical resistance, the physical properties of the paint were generally good.

Neat PL-150 PL-400 PL-1000S division MEK Not good Bad Good Excellent HCl Good Good Good Good NaOH Good Good Good Good

From the results of the experimental examples, the liquid petroleum resin according to one embodiment of the present invention is expected to be applied as an epoxy modifier (Epoxy modifier), extender and diluent, Pot-life Controller, Organic filler, mainly Epoxy and It is expected to be able to mix and use for medium / ship coating and flooring applications.

1 is a photograph showing the results of UV stability evaluation for the specimens obtained according to Experiment 1.

2 is a graph showing the results of evaluation of the exothermic properties of the specimens obtained on the basis of Experiment 1.

3 is a bar graph showing the results of evaluation of the hardness characteristics for the specimen obtained according to Experiment 1.

4 is a bar graph showing the glass transition temperature measurement results for the specimen obtained according to Experiment 1.

FIG. 5 is a SEM photograph (× 3000) showing the results of compatibility measurements with resins on specimens obtained on Experiment 1. FIG.

6 is a bar graph showing the results of measuring the adhesion to the specimen obtained according to Experiment 1.

7 is a graph showing the results of evaluating the exothermic characteristics of the specimens obtained on the basis of Experiment 2-1.

Figure 8 is a photograph showing the cross-cut evaluation results for the specimens obtained on the basis of Experiment 2-1.

9 is a graph showing the results of adhesion evaluation (flexural adhesion) for the specimens obtained based on Experiment 3. FIG.

FIG. 10 is a graph showing the results of evaluating storage stability of an epoxy resin incorporating an epoxy resin (YD-128) and a PL-resin based on Experiment 4. FIG.

FIG. 11 is a graph showing the storage stability evaluation results for the case of blending PL-resin with each curing agent (polyamide, aromatic amine, Jeffamine) based on Experiment 4. FIG.

Claims (8)

On a solids content basis, 1,1,3-trimethyl-3-phenyl-indane (1,1,3-Trimethyl-3-phenyl-indane) 5 to 20% by weight, 2,4-diphenyl-4-methyl-1-pentene (2 , 4-Diphenyl-4-methyl-1-penetene) 1 to 15% by weight, 2,4-diphenyl-4-methyl-2-pentene (2,4-Diphenyl-4-methyl-2-penetene) 1 to 15 wt%, 2,4,6-triphenyl-4,6-dimethylhept-1-ene (2,4,6-Triphenyl-4,6-dimethylhept-1-ene) 5 to 40 wt% and 2, 4,6-triphenyl-4,6-dimethylhept-2-ene (2,4,6-Triphenyl-4,6-dimethylhept-2-ene) A liquid petroleum resin comprising 5 to 40% by weight. The liquid petroleum resin of claim 1, wherein the petroleum resin includes p-Cumylphenol at a maximum of 25% by weight and o, p-Dicumylphenol at a maximum of 25% by weight. The method of claim 2, Liquid petroleum resins containing up to 10% by weight of OH groups. The method of claim 1, Liquid petroleum resin having a viscosity of 10 to 5000 cps at 25 ° C. The method of claim 1, Liquid petroleum resin with a volatile content of 5% or less. An epoxy resin composition comprising the liquid petroleum resin of claim 1. Marine and heavy coating composition comprising the liquid petroleum resin of claim 1. Flooring comprising the liquid petroleum resin of claim 1.

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