KR20150016689A - Modified asphalt composition, and Waterproof sheet for roofing - Google Patents

Abstract

The present invention relates to a modified asphalt composition and a waterproof sheet used for waterproof roofs and, more specifically, an asphalt modifying agent with improved physical properties of asphalt at high temperatures, which includes a specific modified conjugated diene based polymer and accordingly has a high softening point when asphalt is modified, and decreases flowability when sheets made from the asphalt stay at high temperatures, thereby providing heat stability for climate or weather change.

Description

Modified asphalt composition and waterproof sheet for roofing [

The present invention relates to a modified asphalt composition for roof waterproofing and a waterproof sheet, and more particularly, to an asphalt modifier which improves the high temperature properties of modified asphalt, comprising a specific modified conjugated diene polymer and having a high softening point when modifying asphalt, The present invention relates to a modified waterproofing sheet and a waterproofing sheet for roof waterproofing which is resistant to aging due to weather or climate change by lowering the flowability when a sheet is allowed to stand at a high temperature.

Unmodified asphalt is limited in its use due to the problem of sintering at high temperature and cracking at low temperature. In order to solve such a problem, research has been conducted to improve physical properties by adding various polymers.

The vinyl aromatic hydrocarbon-conjugated diene block copolymer such as styrene-butadiene-styrene block copolymer exhibits an effect of improving the high-temperature and low-temperature properties of the asphalt composition and imparting elasticity. Therefore, the vinyl aromatic hydrocarbon- It is most widely used in the industrial field.

The waterproof sheet such as roof waterproofing is expected to prolong the life of the structure due to its resistance to weather or climate change as well as its waterproof function and adhesion with the structure. Especially, it is exposed to the outside of the structure, And it is necessary to develop an asphalt modifier that compensates for the slope of the roof and the flowability due to solar heat in the daytime.

In order to solve this problem, a technique of increasing the content of the asphalt modifier or blending it with an additive such as a tackifier or a heat-resistant antioxidant has been proposed, but it is not effective.

Therefore, there is a demand for a roof waterproofing asphalt modifier excellent in thermal stability which is resistant to aging and flow increase due to weather or climate change when producing a waterproof sheet.

In order to solve the problems of the prior art as described above, the present invention relates to a modified waterproofing asphalt composition for roof waterproofing which comprises a modified conjugated diene polymer having solubility similar to that of a conventional vinyl aromatic hydrocarbon-conjugated diene block copolymer, And to provide a waterproof sheet using the same.

In order to achieve the above objects, the present invention relates to a modified conjugated diene polymer; And an asphalt; and a roof waterproofing modified asphalt composition.

In addition, the present invention provides a waterproof sheet obtained from the above roof waterproof modified asphalt composition.

According to the present invention, there is an effect of providing a modified waterproofing sheet and a modified waterproofing sheet for roof waterproofing which has a modified conjugated diene polymer exhibiting solubility similar to that of a conventional vinyl aromatic hydrocarbon-conjugated diene block copolymer and has excellent thermal stability.

Hereinafter, the roof waterproofing modified asphalt composition of the present invention, the waterproof sheet and the like will be described in detail.

Modified asphalt composition for roof waterproofing

The modified asphalt composition for roof waterproofing according to the present invention comprises a modified conjugated diene polymer; And asphalt.

In the composition, the weight mixing ratio of the modified conjugated diene polymer to the asphalt may be in the range of 1:99 to 50:50, or 5:95 to 30:70.

The modified conjugated diene polymer includes, for example,

[Chemical Formula 1]

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3, 1 and k are an integer of 0 to 2, m Is an integer of 1 to 3, 1 + k + m is 3, p is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain, and b is an integer of 1 to 3. When k is 2 or more, Two or more R _{1 's} may be the same or different from each other, and when l and m are 2 or more in the same manner, corresponding groups may be the same or different from each other) .

The R ₁ is, for example, an alkyl group having 1 to 12 carbon atoms or an alkylsilyl group.

The R ₂ is, for example, an alkyl group or an alkylene group having 1 to 12 carbon atoms.

R ₃ and R ₄ are, for example, alkyl groups having 1 to 12 carbon atoms.

The l may be 0 or 1, for example.

M may be 1 or 2, and may be 2 or 3, for example.

remind p may have a total number of 1 to 9, 1 to 5, or 1 to 3, and when applied to asphalt within this range, the softening point during stay at a high temperature is increased and the heat flow is lowered, Lt; / RTI >

In formula (1), k is 1, l is 0, and m is 2, for example.

In another example, k is 1, l is 1, and m is 1 in the formula (1).

In another example, the formula 1 may be a mixture of a modified conjugated diene polymer having k of 1, l of 0 and m of 2, and a modified conjugated diene polymer of which k is 1, 1 is 1, and m is 1 have.

The vinyl aromatic hydrocarbon-conjugated diene copolymer chain may be, for example, a random or block copolymer chain.

In another example, the vinyl aromatic hydrocarbon-conjugated diene copolymer chain may be a vinyl aromatic hydrocarbon-conjugated diene block copolymer chain.

As another example, the vinyl aromatic hydrocarbon-conjugated diene copolymer chain may contain 1 to 50% by weight, 10 to 40% by weight, or 20 to 35% by weight of a vinyl aromatic monomer based on 100% by weight of the total of the conjugated diene monomer and the vinyl aromatic monomer By weight of the block copolymer chain.

Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and the like.

Examples of the vinyl aromatic monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- Vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene.

The modified conjugated diene polymer may have a weight average molecular weight of 50,000 to 500,000 g / mol, 50,000 to 350,000 g / mol, or 80,000 to 350,000 g / mol, for example.

The modified conjugated diene polymer may have a vinyl content of 5 to 60%, 10 to 40%, or 10 to 30%, for example.

Here, the vinyl content means the content of the vinyl group-containing monomer or the content of the 1,2-added conjugated diene monomer, not 1,4-addition to 100% by weight of the conjugated diene-based monomer.

The method for producing a modified conjugated diene polymer according to the present invention comprises the steps of: (a) polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in the presence of a solvent in the presence of an organometallic compound to form an active polymer having a metal terminal; And (b) adding to said active polymer a compound of formula

(2)

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3 and n is an integer of 0 to 2. In addition, Two R ₁ groups bonded to nitrogen may be the same as or different from each other, and in the same manner, when 3-n is 2 or more, the corresponding groups may be the same or different from each other) And a step of introducing the compound to denature it.

The n may be 0 or 1, for example.

R ₁ to R ₄ are the same as described above.

Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and the like.

Examples of the vinyl aromatic monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- Vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene.

The vinyl aromatic monomer may be 1-50% by weight, 10-40% by weight or 20-35% by weight based on 100% by weight of the total of the conjugated diene monomer and the vinyl aromatic monomer.

The solvent may be at least one selected from the group consisting of hydrocarbons or n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.

The organic metal compound may be at least one selected from the group consisting of an organic alkali metal compound, an organic lithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound and an organic cesium compound.

As another example, the organometallic compound may be at least one selected from the group consisting of methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, Naphthyl lithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium Or more.

 In another example, the organometallic compound is n-butyllithium, sec-butyllithium, or a mixture thereof.

In another example, the organometallic compound is selected from the group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide And may be used in combination with other organometallic compounds.

The organometallic compound is used in an amount of 0.01 to 10 mmol, 0.05 to 7 mmol, or 0.1 to 5 mmol based on 100 g of the total amount of the monomers.

The molar ratio of the organometallic compound to the compound represented by Formula 2 is, for example, 1: 0.1 to 1:10, or 1: 0.5 to 1: 2.

The active polymer having the metal terminal of the present invention means a polymer to which a polymer anion and a metal cation are bonded.

As a method for producing the modified conjugated diene-based polymer of the present invention, for example, the polar additive may be further added during the polymerization of (a) to effect polymerization.

The polar additive may be, for example, a base, and in another example, an ether, an amine, or a mixture thereof, or a mixed solvent of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cyclo- (Dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine Ethylenediamine, and another example is diethtrahydropropyl propane, triethylamine or tetramethylethylenediamine.

The polymerization of (a) may be anionic polymerization, for example.

As another example, the polymerization of (a) may be a living anionic polymerization in which an active terminal is obtained by a growth reaction with an anion.

The polymerization temperature of (a) is, for example, -20 to 200 占 폚, 0 占 폚 to 150 占 폚, or 10 to 120 占 폚.

The denaturation step (b) may be carried out, for example, by adding one or more, preferably two or three, compounds represented by the general formula (2).

The denaturation step (b) may be carried out at 0 to 150 ° C for 1 minute to 5 hours, for example.

The modified conjugated diene polymer of the present invention is, for example, characterized in that the modified conjugated diene polymer is produced by the above-described method for producing a modified conjugated diene polymer.

The asphalt can be a residue obtained when refining crude oil, and is mainly composed of hydrogen and carbon, and can be made of hydrocarbon compounds having a small amount of nitrogen, sulfur, or oxygen bonded thereto.

As the asphalt, straight asphalt, cut-back asphalt, goose asphalt, blown asphalt, emulsified asphalt or sebum (PG) grade asphalt may be used.

Among them, the straight asphalt can be used as a raw material for various petroleum-based asphalt containing a large amount of bituminous material which is not decomposed as a final residue obtained by distillation of the crude oil at the atmospheric distillation column and distillation of the residual atmospheric residue. Commercialized straight asphalt includes AP-3 or AP-5 supplied by SK Energy or GS Caltex.

The roof waterproofing modified asphalt composition may comprise an oil.

The oil may be, for example, mineral oil or an aromatic oil such as Treated Distillate aromatic extract (TDAE) oil.

The oil may be used in an amount of, for example, 1 to 60% by weight, 5 to 50% by weight or 7 to 40% by weight based on 100% by weight of the modified asphalt composition, , And the rubber composition is softened appropriately, so that the processability is excellent.

The roof waterproofing modified asphalt composition may include a filler.

The filler may be calcium carbonate, talc, or the like.

Waterproof sheet

The waterproof sheet of the present invention is characterized by being obtained from the roof waterproof modified asphalt composition.

The waterproof sheet may be an adhesive or self-adhesive waterproof sheet.

The waterproof sheet may be, for example, a waterproof sheet coated with the modified asphalt composition at a thickness of 1 to 5 mm on a release paper or a nonwoven fabric.

The degree of improvement of the physical properties of the waterproof sheet can be evaluated by, for example, a softening point or a heat flow. If the softening point is high or the heat flow is low, The degree of softening is small and it can be evaluated that the high-temperature properties are improved.

The softening point herein refers to the high temperature properties of the modified asphalt according to the American Society for Testing and Materials (ASTM) D36, which upon heating of water or glycerin at 5 [deg.] C per minute begins to soften the specimen It can be defined as the temperature when a ball of 9.525 mm in diameter and 3.5 g in weight located on the specimen is struck by 1 inch.

The heat flow of the present invention is included in the quality standard of the modified asphalt waterproof sheet of KS F 4917 as a method of representing the heat resistance and weather resistance of the modified asphalt waterproof sheet and is waterproofed on a plate inclined at 45 ° or 90 ° It can be defined as the length from the initial position when the sheet is heated after it is attached.

The cold bending temperature of the present invention represents the low temperature properties and weatherability of the modified asphalt waterproof sheet and is included in the quality standard of the modified asphalt waterproof sheet of KS F 4917, It can be defined as a temperature at which a crack due to bending does not occur when bent.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. And modifications that fall within the scope of the appended claims.

[ Example ]

Example 1

≪ Preparation of Modified Styrene-Butadiene Block Copolymer >

1470 g of purified cyclohexane and 93 g of styrene were charged into a 3 L reactor purged with nitrogen, and the temperature was raised to 70 캜 while stirring. The styrene block was polymerized by adding 0.32 g of n-butyllithium to the mixed solution of cyclohexane and styrene at 70 DEG C, 207 g of butadiene was added thereto, and the polymerization was continued until the butadiene completely consumed. After the butadiene is completely consumed, 0.84 g of bis (3-methyldimethoxysilylpropyl) -N-methylamine of the following formula 3 is added. After completion of the reaction, 0.1 g of water was added to the reactor to remove the activity of the active polymer. Then, 1.74 g of an antioxidant Irganox 1076 (BASF) and 0.9 g of TNPP (Weston Chemical Co.) Solution to prepare a modified styrene-butadiene block copolymer solution having a weight average molecular weight of 109,000 g / mol.

(3)

≪ Polymer recovery from polymer solution & Crumb ( crumb ) Manufacturing>

In order to recover only the polymer from the polymer solution, a stripping process is generally performed. Namely, 2.5 g of Tamol (TAMOL) and 0.5 g of CaCl ₂ were added to 3 L of water and boiled. Subsequently, when the polymer solution is slowly dropped into boiling water, the solvent in the solution is evaporated, and the polymer is agglomerated in water and dispersed in water to a size of 1 to 20 mm. The polymer produced in the above process was recovered and dried in an oven at 60 ° C. for 16 hours to prepare a crumb polymer.

≪ Preparation of modified asphalt composition and waterproof sheet >

AP-3 product having physical properties as shown in Table 1 was purchased from SK Innovation Co., Ltd. as an asphalt.

Intrusion (dmm) Softening point (℃) SK AP-3 80 45.7

In Table 1, the penetration was measured at 25 DEG C according to ASTM D946, and the softening point was measured according to ASTM D36.

500 g of AP-3 and 62.5 g of TDAE oil (treated distillate aromatic extract oil) were placed in a mixing container, and the crumb of the modified styrene-butadiene block copolymer was maintained at 160 ° C. and a stirring speed of 1,500 rpm. , The mixture was heated to 190 DEG C and stirred at 3,000 rpm for 2 hours. The stirring speed was lowered to 500 rpm and further stirred for 30 minutes to prepare modified asphalt, which was sampled to measure the physical properties of the dissolved modified asphalt. In order to measure the heat flow and the cold bending temperature, a 3 mm thick waterproof sheet was prepared from the modified asphalt.

Comparative Example 1

(3-methyldimethoxysilylpropyl) -N- (3-methyldimethoxysilylpropyl) -N-methylmethoxysilylpropyl) -bis (3-methyldimethoxysilylpropyl) -N- -Methylamine in Example 1 was replaced with 0.37 g of dichloromethylsilane in place of methylamine, to thereby prepare an unmodified styrene-butadiene block copolymer solution having a weight average molecular weight of 104,000 g / mol. In the same manner as in Example 1 A polymer crumb and a modified asphalt composition were prepared. The dissolved asphalt and waterproof sheet were sampled for physical properties.

[Test Example]

The properties of the asphalt compositions prepared in Example 1 and Comparative Example 1 were measured by the following methods, and the results are shown in Tables 2 and 3 below.

Weight average molecular weight: Each sample was dissolved in tetrahydrofuran (THF) for 30 minutes and then loaded on GPC (Gel Permeation Chromatography, manufacturer: Waters) and flowed. Then, the standard of PS (Polystyrene) The molecular weight was measured in comparison with the molecular weight.

* Softening point: measured according to ASTM D36.

Viscosity (160 占 폚, 180 占 폚): Measured according to ASTM D4402 under the condition of spindle 27 using Brookfield DV-II + Pro Model.

Heat-flow (72 ° C., 90 ° C., 100 ° C.): A modified asphalt waterproof sheet 5 cm in width, 5 cm in length, and 3 mm in thickness was applied to a steel use stainless plate slanted at 90 ° After attaching the specimen, allow the specimen to stand in the oven at a specified temperature for 1 hour and measure the length of the specimen from the initial position.

* Cold bending temperature (-15 ° C, -20 ° C): The specimen with the modified asphalt waterproof sheet of 5cm width, 10cm length and 3mm thickness was allowed to stand for 1 hour in a low temperature thermostat. After the specimen has been bent in the U-shape, check whether any residue or cracks have occurred.

Example 1 Comparative Example 1 Softening point (° C) 107.2 102.4 Viscosity (160 ° C) (cPs) 1250 1310 Viscosity (180 ° C) (cPs) 1080 1055 Heat flow (72 ° C) (mm) 2 3 Heat flow (90 ° C) (mm) 10 12 Heat flow (100 ° C) (mm) 40 58 Low temperature bending performance (-15 ℃) Good Good Low temperature bending performance (-20 ℃) balance balance

As shown in Table 2, Example 1 of the present invention corresponds to Comparative Example 1 as a waterproof sheet containing a modified conjugated diene polymer.

Specifically, it can be confirmed that the softening point of Example 1 is about 5 ° C higher than that of Comparative Example 1 in the production of the waterproof sheet in Table 2 above.

The viscosity at 160 ° C of Example 1 was slightly lower than that of Comparative Example 1, but the difference was small at about 4%, and the viscosity at 180 ° C was higher than that of Comparative Example 1, so that the flowability was similar to that of Comparative Example 1. The waterproof sheet of Example 1 retains a tendency that the length of the waterproof sheet flowing from the initial position at each temperature is smaller than that of Comparative Example 1 and the waterproof sheet of Example 1 at a high temperature of 100 캜 It was confirmed that the sheet was 18 mm smaller than that of the waterproof sheet of Comparative Example 1 and excellent in heat resistance.

Further, when the low temperature bending performance indicating the weather resistance at low temperature was compared, it was confirmed that both of Example 1 and Comparative Example 1 had residual properties at -20 캜 and had similar low-temperature properties.

Claims (12)

A modified conjugated diene polymer; And asphalt. ≪ RTI ID = 0.0 > A < / RTI > The method according to claim 1,
Wherein the weight ratio of the modified conjugated diene polymer to the asphalt is 1:99 to 50:50. The method according to claim 1,
The modified conjugated diene polymer preferably has the following general formula
[Chemical Formula 1]

(Wherein R ₁ is an alkyl group or an alkylsilyl group, R ₂ is an alkyl group or an alkylene group, R ₃ and R ₄ are an alkyl group, a is an integer of 1 to 3, 1 and k are an integer of 0 to 2, m Is an integer of 1 to 3, l + k + m satisfies 3, P is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain, and b is an integer of 1 to 3. When k is 2, The two R ₁ groups to be bonded may be the same or different from each other and when l and m are 2 or more in the same manner, the corresponding groups may be the same or different from each other) Modified asphalt composition for roof waterproofing. The method of claim 3,
Wherein the vinyl aromatic hydrocarbon-conjugated diene copolymer chain is a random or block copolymer chain comprising a conjugated diene monomer and a vinyl aromatic monomer. The method of claim 3,
Wherein the modified conjugated diene polymer has a weight average molecular weight of 50,000 to 500,000 g / mol. The method of claim 3,
Wherein the modified conjugated diene-based polymer has a vinyl content of 5 to 60%. The method of claim 3,
Wherein the modified conjugated diene polymer comprises 1 to 50% by weight of a vinyl aromatic monomer based on 100% by weight of the total of a conjugated diene monomer and a vinyl aromatic monomer. The method of claim 3,
Wherein P in the formula (1) is a styrene-butadiene block copolymer chain. The method according to claim 1,
Wherein the composition comprises an oil. ≪ RTI ID = 0.0 > 18. < / RTI > 10. The method of claim 9,
Wherein the oil is an aromatic oil or a mineral oil. 10. The method of claim 9,
Wherein the oil is 1 to 60% by weight based on 100% by weight of the modified asphalt composition. A waterproof sheet obtained from the waterproof modified asphalt composition of claim 1.