KR102199841B1 - Adhesive composition and method of fabricating the same - Google Patents

Abstract

Examples disclose an adhesive composition and a method of manufacturing the same. The adhesive composition according to the embodiment is polyolefin; oil; And wax.

Description

Adhesive composition and its manufacturing method {ADHESIVE COMPOSITION AND METHOD OF FABRICATING THE SAME}

The examples relate to an adhesive composition and a method of manufacturing the same.

Conventionally, polypropylene has been widely used as a thermoplastic molding material having excellent rigidity, heat resistance, transparency, and the like. Since dipolypropylene is inferior in flexibility, when used as an adhesive, a soft rubber component is usually blended with polypropylene. When a soft rubber component is mixed with polypropylene in this way, a polypropylene-based adhesive with improved adhesion can be obtained (for example, Patent Literature 1 and Patent Literature 2). There was a problem that it became. For this reason, the appearance of a polypropylene-based adhesive having excellent initial adhesiveness and excellent adhesiveness after heat history has been desired.

Patent document 1: Japanese Patent Laid-Open Publication No. 9-111069

Patent document 2: Japanese Patent Laid-Open Publication No. Hei 4-300933

The embodiment is to provide an adhesive having improved adhesive performance and a method of manufacturing the same.

The adhesive composition according to the embodiment is a polyolefin having a weight average molecular weight of 4000 to 20000; oil; And wax.

The adhesive composition according to an embodiment is maleic anhydride, 1,2,3-triazole-4,5-dicarboxylic acid, propane-1,2,3-tricarboxylic acid, diethylene glycol, and 2,5 -It may further contain furandicarboxylic acid.

A method of preparing an adhesive composition according to an embodiment includes the steps of preparing a resin composition by mixing a polyolefin having a weight average molecular weight of 4000 to 20000, an oil and a wax; And raising the temperature of the resin composition.

In one embodiment, in the step of preparing the resin composition, maleic anhydride, 1,2,3-triazole-4,5-dicarboxylic acid, and propane-1,2,3-tricar are added to the resin composition. Acid, diethylene glycol and 2,5-furandicarboxylic acid may be further added.

The adhesive composition according to the embodiment has improved adhesion. In addition, the adhesive composition according to the embodiment may be used as a hot melt stick for a glue gun, a post-it adhesive, an adhesive for interior finishing of a vehicle, an adhesive for insulation of wires and cables, and an adhesive for modifying color asphalt. In addition, the adhesive composition according to the embodiment is non-toxic and eco-friendly because it contains almost no toxic substances than the existing polyurethane-based raw materials.

1 is a view showing a method of manufacturing an adhesive composition according to an embodiment.

The adhesive composition according to the embodiment includes polyolefin, oil and wax.

The polyolefin may be at least one or more selected from the group consisting of polypropylene, polyethylene, polyalphaolefin, polypropylene-based copolymer, polyethylene-based copolymer, and combinations thereof.

The polyolefin may be selected from the polypropylene or the polypropylene-based copolymer.

The polyolefin may be a polypropylene homopolymer. The polyolefin may be a polyolefin modified with a carboxylic acid such as maleic anhydride.

The polyolefin may be a polypropylene-based copolymer. For example, the polyolefin may be selected from the group consisting of propylene/α-olefin copolymer, propylene/ethylene random copolymer, and ethylene/propylene random copolymer.

In the above propylene/α-olefin copolymer, the α-olefin is not limited, but preferably ethylene and/or an α-olefin having 4 to 20 carbon atoms are exemplified, and these α-olefins are 1 type alone or 2 types. You may use more than one. As a more preferable α-olefin in the present invention, ethylene or an α-olefin having 4 to 10 carbon atoms is used, and among them, ethylene or an α-olefin having 4 to 8 carbon atoms is particularly preferable.

Here, in the propylene/α-olefin copolymer, it is preferable that the content of the structural unit obtained from propylene is at least 90 mol% or more.

The MFR is not particularly limited, but it may be preferably 0.1 to 100 g/10 minutes, more preferably 0.5 to 50 g/10 minutes. In addition, the MFR of this specification was measured under 230 degreeC and 2.16 kg load.

The method for producing the propylene-?-olefin copolymer is not particularly limited, and can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst and a metallocene catalyst. Further, a crystalline polymer can be preferably used, and in the case of a copolymer, a random copolymer or a block copolymer may be used. In addition, the propylene/α-olefin copolymer may be grafted with a small amount of maleic anhydride, or the like, and after grafting a small amount of maleic anhydride, etc., the grafted monomer is further modified with diamine, carbodiimide, etc. (修飾; modified) may be used.

The propylene-ethylene random copolymer (B) is defined by the following (i) to (iii). (i) 60 to 90 mol% of the unit obtained from propylene and 10 to 40 mol% of the unit obtained from ethylene, and (ii) the melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120°C And (iii) the molecular weight distribution (Mw/Mn) required by gel permeation chromatography (GPC) is in the range of 1.0 to 3.0. For (i), propylene: 65 to 90 mol%, ethylene: preferably in the range of 10 to 35 mol%, propylene: 70 to 90 mol%, ethylene: more preferably in the range of 10 to 30 mol% . For (ii), the melting point (Tm) is preferably in the range of 40 to 110°C, and more preferably in the range of 40 to 100°C. For (iii), Mw/Mn is preferably in the range of 1.0 to 2.8, and more preferably in the range of 1.0 to 2.5.

The MFR is not particularly limited, but it may be preferably 0.1 to 100 g/10 minutes, more preferably 0.5 to 50 g/10 minutes.

The method for producing the propylene-ethylene random copolymer (B) is not particularly limited, and can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst and a metallocene catalyst. In the present invention, as long as the above conditions are satisfied, a small amount of maleic anhydride or the like may be grafted. Further, as long as the above conditions are satisfied, a small amount of maleic anhydride or the like may be grafted, and then the grafted monomer may be further modified with diamine, carbodiimide, or the like.

The ethylene/propylene random copolymer (C) contains 60 to 90 mol% of units obtained from ethylene and 10 to 40 mol% of units obtained from propylene, ethylene: 65 to 90 mol%, propylene: 10 to If it is in the range of 35 mol%, it is preferable, and if it is in the range of ethylene: 70-90 mol% and propylene: 10-30 mol%, it is more preferable. MFR may range from 0.1 to 100 g/10 minutes, and may range from 0.5 to 50 g/10 minutes. Mw/Mn is preferably in the range of 1.0 to 5.0, and more preferably in the range of 1.0 to 3.0.

The method for producing the ethylene-propylene random copolymer (C) is not particularly limited, and can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst and a metallocene catalyst. As long as the above conditions are satisfied, the ethylene/propylene random copolymer may be grafted with a small amount of maleic anhydride or the like. Further, as long as the above conditions are satisfied, a small amount of maleic anhydride or the like may be grafted, and then the grafted monomer may be further modified with diamine, carbodiimide, or the like.

The weight average molecular weight of the polyolefin may be about 4000 to about 20000. In more detail, the weight average molecular weight of the polyolefin may be about 5000 to about 15000. The weight average molecular weight of the polyolefin may be about 5000 to about 12000. The weight average molecular weight of the polyolefin may be measured by high-temperature gel permeation chromatography.

The polyolefin may have a melting point of about 70°C to about 160°C. The polyolefin may have a melting point of about 90°C to about 150°C. The melting point of the polyolefin can be measured by a differential scanning calorimeter.

The melt viscosity of the polyolefin may be about 50 mPa·s to about 6000 mPa·s. The melt viscosity may be measured at a temperature of about 160°C.

The acid value of the polyolefin may be about 2 mgKOH/g to about 15 mgKOH/g. The acid value can be measured according to JIS K0070 standards.

The oil may be included in the adhesive composition according to the embodiment in about 10 parts by weight to about 70 parts by weight based on 100 parts by weight of the polyolefin.

Examples of the oil include paraffinic oil, naphthenic oil, and aromatic oil. Commercially available products can be used as the oil. His example is Idemitsu Kosan Co., Ltd. Manufactured by Diana Fresia S32 (trade name), Diana Process Oil PW-90 (trade name) and Process Oil NS-100 (trade name); PHAZOL35 (trade name) manufactured by SK LUBRICANTS; KN4010 (trade name) manufactured by PetroChina Company; Kukdong Oil & Chemical Co. Ltd. Manufacturing White Oil Broom350 (brand name) and DN oil KP-68 (brand name); BP Chemicals Ltd. Manufactured by Enerper M1930 (trade name); Kaydol (trade name) manufactured by Crompton Corporation; And Esso Corp. Manufacturing Primol 352 (trade name) is included. These oils may be used alone or in combination.

In addition, the weight average molecular weight of the oil may be 5000 to 50000.

In addition, the adhesive composition according to the embodiment may further include polyethylene glycol. The molecular weight of the polyethylene glycol may be 5000 to 50000. The polyethylene glycol may be included in the adhesive composition according to the embodiment in about 10 parts by weight to about 70 parts by weight based on 100 parts by weight of the polyolefin.

In addition, the adhesive composition according to the embodiment may further include the wax. The wax is about 5 parts by weight to about 50 parts by weight based on 100 parts by weight of the polyolefin, and may be included in the adhesive composition according to the embodiment. As used herein, "wax" refers to an organic substance having a weight average molecular weight of less than 10,000, which is solid at room temperature and becomes liquid when heated, and is commonly regarded as "wax".

As long as it has wax-like properties, there is no particular limitation on the wax as long as the adhesive composition according to the present embodiment is obtained.

The wax may include an olefin wax modified with carboxylic acid or carboxylic anhydride.

In this embodiment, the term "carboxylic acid or carboxylic anhydride modified olefin wax" refers to an olefin wax chemically or physically processed with carboxylic acid or carboxylic anhydride, and the adhesive composition according to this embodiment It is not particularly limited as long as it can be obtained. Examples of chemical or physical processing include oxidation, polymerization, compounding, synthesis, and the like.

Examples of the wax include a wax obtainable by graft polymerization of a carboxylic acid or carboxylic anhydride and an olefin wax; And a wax obtainable by copolymerization of a carboxylic acid or a carboxylic anhydride when synthesizing the olefin wax by polymerization.

Accordingly, the wax may be an olefin wax that is modified by introducing carboxylic acid or carboxylic anhydride using various reactions into the "olefin wax".

"Carboxylic acid" and/or "carboxylic anhydride" used to modify the olefin wax is not particularly limited as long as the desired adhesive composition of this example can be obtained.

Specific examples of carboxylic acid or carboxylic anhydride include maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, itaconic acid, acrylic acid, methacrylic acid, and the like. These carboxylic acids and/or carboxylic anhydrides may be used alone or in combination. Maleic acid and maleic anhydride are preferred, and maleic anhydride is particularly preferred.

"Carboxylic acid" and/or "carboxylic anhydride" used to modify an olefin wax refers to a wax that can be obtained by copolymerization of two or more olefins, as long as the desired wax according to the present invention can be obtained. It is not particularly limited. Thus, the wax obtained by homopolymerization of one olefin may not be included in the olefin wax.

Specific examples of the olefin wax include polyethylene wax, polypropylene wax, polyethylene/polypropylene wax, polyethylene/polybutylene wax, polyethylene/polybutene wax, and the like.

Therefore, the wax in this embodiment may be a polyolefin wax modified with maleic anhydride.

“Wax” may include, in addition to wax, base wax, examples of which include:

Synthetic waxes such as Fischer-Tropsch wax and polyolefin wax (eg, polyethylene wax, polypropylene wax, polyethylene/polypropylene wax);

Petroleum waxes such as paraffin wax and microcrystalline wax;

Natural waxes such as caster wax.

The base wax can be modified. As a material for modifying the base wax, various carboxylic acid derivatives may be used as long as a polar group can be introduced. Examples of "carboxylic acid derivatives" include:

Carboxylic acid esters such as ethyl acetate and vinyl acetate;

Acid halides such as benzoyl bromide;

Amides such as benzamide, N-methylacetamide and N,N-dimethylformamide;

Imides such as succinimide;

Acyl azide such as acetyl azide;

Hydrazides such as propanoyl hydrazide;

Hydroxamic acids such as chloroacetylhydroxamic acid;

lactones such as γ-butyrolactone; And

lactams such as δ-caprolactam.

The modified base wax does not include olefin waxes modified with carboxylic acids or carboxylic anhydrides.

In this embodiment, the melting point of the wax may be 70 to 130 ℃. The melting point of the base wax may be 60 to 90 ℃.

The acid value of the wax is preferably 5 to 200 mgKOH/g, more preferably 20 to 160 mgKOH/g.

The acid number can be measured according to ASTM D1308 or BWM 3.01A.

The adhesive composition according to the embodiment may further include an additive.

The adhesive composition according to the embodiment may further include about 0.5 parts by weight to about 10 parts by weight of maleic anhydride based on 100 parts by weight of the polyolefin.

In addition, the adhesive composition according to the embodiment may further include about 0.5 parts by weight to about 10 parts by weight of 1,2,3-triazole-4,5-dicarboxylic acid based on 100 parts by weight of the polyolefin.

In addition, the adhesive composition according to the embodiment may further include about 0.5 parts by weight to about 10 parts by weight of propane-1,2,3-tricarboxylic acid based on 100 parts by weight of the polyolefin.

In addition, the adhesive composition according to the embodiment may further include about 0.5 parts by weight to about 10 parts by weight of diethylene glycol based on 100 parts by weight of the polyolefin.

In addition, the adhesive composition according to the embodiment may further include about 0.5 parts by weight to about 10 parts by weight of 2,5-furandicarboxylic acid based on 100 parts by weight of the polyolefin.

The additive may modify at least one type of material selected from the group consisting of the polyolefin, the oil, and the wax. Accordingly, the additive may improve physical properties such as adhesion and melt viscosity of the adhesive composition according to the present embodiment.

Referring to Figure 1, the adhesive composition according to the embodiment may be prepared by the following process.

First, the polyolefin is heated to a temperature above the melting point and melted.

Thereafter, the oil and the wax are added to the molten polyolefin and mixed to form a resin composition.

Thereafter, the additive may be further added to the resin composition. In the molten polyolefin, the maleic anhydride, the 1,2,3-triazole-4,5-dicarboxylic acid, the propane-1,2,3-tricarboxylic acid, the diethylene glycol and the 2 At least one or more may be added from the group consisting of ,5-furandicarboxylic acid. In the molten polyolefin, the maleic anhydride, the 1,2,3-triazole-4,5-dicarboxylic acid, the propane-1,2,3-tricarboxylic acid, the diethylene glycol and the 2 ,5-furandicarboxylic acid may all be added.

Thereafter, the resin composition is heated, and the temperature may be further increased. The temperature of the resin composition may be about 130 ℃ to 180 ℃. The resin composition may be maintained at the above temperature for about 5 minutes to about 4 hours.

In this way, impurities or unreacted residues in the prepared resin composition are removed, and an adhesive composition according to the embodiment may be prepared.

The adhesive composition according to the embodiment has improved adhesion. In addition, the adhesive composition according to the embodiment may be used as a hot melt stick for a glue gun, a post-it adhesive, an adhesive for interior finishing of a vehicle, an adhesive for insulation of wires and cables, and an adhesive for modifying color asphalt. In addition, the adhesive composition according to the embodiment is non-toxic and eco-friendly because it contains almost no toxic substances than the existing polyurethane-based raw materials.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not subject to any restrictions on these Examples unless departing from the gist of the present invention.

Manufacturing Example 1

100 parts by weight of polyolefin resin (UMEX 100TS from Sanyo Chemical Industries) was added to a 1 liter autoclave. Then, the polyolefin resin was heated and melted to a temperature of about 140°C. Thereafter, about 30 parts by weight of oil (Diana Fresia S32 manufactured by Idemitsu Kosan Co., Ltd.) and about 10 parts by weight of wax (IndraAlpha 2024 manufactured by Industrial Raw Materials LLC) were added to the molten polyolefin resin. Thereafter, the mixed resin composition was stirred at a temperature of about 150° C. for about 20 minutes. Thereafter, the stirred resin composition was cooled.

Manufacturing Example 2

In the molten resin composition of Preparation Example 1, 5 parts by weight of maleic anhydride, 1,2,3-triazole-4,5-dicarboxylic acid (1,2,3-Triazole-4,5-dicarboxylic acid, Sigma-Aldrich Corporation) 2 parts by weight, propane-1,2,3-tricarboxylic acid (Propane-1,2,3-tricarboxylic acid) 2 parts by weight, diethylene glycol 1 part by weight and 2, 1 part by weight of 5-furandicarboxylic acid was added. Then, the resin composition was heated to about 150 ℃. Thereafter, 4 parts by weight of di-tert-butyl peroxide was added to the resin composition, and the resin composition was heated to about 160° C. and then stirred for 3 hours. Thereafter, the obtained reaction solution was cooled and poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. Thereafter, the liquid containing the resin was centrifuged to separate the adhesive composition and the low molecular weight substance into solid and liquid, followed by purification. Thereafter, the adhesive composition was prepared by drying at 70 for 5 hours under reduced pressure.

Manufacturing Examples 3 to 5

In addition to the composition changes shown in Table 1 below, modified polypropylene was prepared in the same manner as in Preparation Example 1.

Examples 1-5

The modified polypropylene prepared in Preparation Examples 1 to 5 was melt-extruded to produce a hot melt film.

Fabrication of the laminate

For the polar material, an aluminum plate (manufactured by Nippon Test Panel, A1050P, thickness×width×length=1.6×25×100 mm) was used, and a polypropylene plate (manufactured by Nippon Test Panel, PP, thickness×width× Length=1.6×25×100 mm) was used.

The hot melt adhesives obtained in Examples 1 to 5 were adjusted by thermocompression so as to have a thickness of 50 µm, and laminated on a polar material. Subsequently, a polyolefin resin substrate was superimposed on the surface of the adhesive layer, and the laminated body (polar material/adhesive layer/polypropylene resin substrate) by thermocompression bonding for 2 minutes at a cylinder temperature of 140 and 0.1 MPa of a heat seal tester manufactured by Tester Sangyo Co., Ltd. Got it. The adhesive strength of the laminate was measured by a tensile shear test.

Tensile shear test (PP/AL tensile shear strength)

According to JIS K 6850 (1999) tensile shear adhesion strength test method of adhesive, using Tensilon (registered trademark) RTM-100 manufactured by Orientec Corporation, under 25 atmosphere, shear strength at 5 mm/min. Was measured. The tensile shear strength (MPa) between the polar material/polyolefin resin substrate was taken as the average value of three test values. Table 1 shows the results.

<Evaluation criteria>

○ (Excellent in practical use): 7 MPa or more

△ (Practical): 5 MPa or more

× (not practical): less than 5 MPa

Manufacturing example Polyolefin oligomer Diethylene glycol Maleic anhydride Triazole dicarboxylic acid Propane tricarboxylic acid Furandicarboxylic acid One 100 2 100 One 3 3 3 One 3 100 One 7 One One One 4 100 One 6 One 2 One 5 100 One 4 3 2 One

Example Adhesive strength One ○ 2 ○ 3 ○ 4 ○ 5 ○

As shown in the experimental results of Table 2, it was confirmed that the adhesive composition according to the Example has improved adhesive strength.

Claims (4)

Polyolefins having a weight average molecular weight of 4000 to 20000;
oil; And
Containing wax,
Maleic anhydride, 1,2,3-triazole-4,5-dicarboxylic acid, propane-1,2,3-tricarboxylic acid, diethylene glycol and 2,5-furandicarboxylic acid Adhesive composition comprising.
delete Preparing a resin composition by mixing a polyolefin having a weight average molecular weight of 4000 to 20000, an oil and a wax; And
Including the step of raising the temperature of the resin composition,
In the step of preparing the resin composition, maleic anhydride, 1,2,3-triazole-4,5-dicarboxylic acid, propane-1,2,3-tricarboxylic acid, diethylene in the resin composition A method for producing an adhesive composition further adding glycol and 2,5-furandicarboxylic acid.
delete

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