KR101149741B1 - Adhesive composition for polyolefine thermoplastic elastomer - Google Patents

Abstract

The present invention uses a polymer mixture of an epoxy resin, a chlorinated polyolefin resin, a chloroprene rubber and a thermoplastic polyurethane resin. The present invention relates to an adhesive composition for a polyolefin-based thermoplastic elastomer, wherein a complicated pretreatment process such as buffing, cleaning agent, primer, and plasma treatment is omitted during adhesion of a polyolefin-based thermoplastic elastomer having a non-polar and hard-adhesive property, thereby simplifying the work process. It is improved, maintains excellent adhesive properties, and does not use any toxic organic solvents such as toluene or xylene, so no toxic gas is generated, so it is an eco-friendly environment with no harm to the worker's body by a comfortable working environment. .

Polyolefins, thermoplastic elastomers, adhesives, epoxy resins, chlorinated polyolefin resins, chloroprene rubbers and thermoplastic polyurethane resins

Description

Adhesive composition for polyolefin thermoplastic elastomers

The present invention uses a polymer mixture of an epoxy resin, a chlorinated polyolefin resin, a chloroprene rubber and a thermoplastic polyurethane resin. The present invention relates to an adhesive composition, in which a pretreatment step is omitted when adhering a polyolefin-based thermoplastic elastomer, which is a material having non-polarity and poor adhesion properties, to simplify the process, maintain excellent adhesion, and use no toxic organic solvent such as toluene or xylene at all. The present invention relates to an adhesive composition for a polyolefin-based thermoplastic elastomer, which is environmentally friendly.

Polyvinyl chloride (PVC) resins have been widely used due to their excellent moldability and mechanical properties and scratch resistance compared to their prices, but the odor caused by the plasticizer contained in polyvinyl chloride (PVC) resin is irritating. It is a synthetic resin that has been recently limited in use in terms of strengthening environmental regulations because there is a problem such as causing a dioxin, a carcinogen when incinerated.

Recently, polyolefin-based thermoplastic elastomers have been in the spotlight as alternative materials for polyvinyl chloride (PVC) resin elastomers. The polyolefin-based thermoplastic elastomer is flexible at high temperature and can be molded. At room temperature, it is a polymer material that exhibits the properties of rubber elastomer. The moldability is excellent, and the material is reusable, so it is economical, and there is no need for the use of a plasticizer. The ratio is low and the product production can be diversified.

However, polyolefin-based thermoplastic elastomers are polyolefin resins such as polypropylene and polyethylene, and hard segments are non-polar polymer compounds in which olefin rubbers, including ethylene-propylene rubber (EPDM), are the mainstream. As a raw material having a poor adhesion property, there is a problem in that the property of the adhesive force is poor when the polyolefin-based thermoplastic elastomer is bonded using a conventional adhesive composition.

Therefore, in order to bond the polyolefin-based thermoplastic elastomer, which is a material having a poor adhesion property as described above, it has to undergo a complicated pretreatment process such as a buffing, a cleaning agent, a primer and a plasma, and also by using a toxic organic solvent such as toluene or xylene. Although conventional methods have been used to prepare primers or adhesives to improve adhesion, the above-described conventional methods are economically complicated due to the complicated work process and the need for pretreatment as described above, and are caused by the use of toxic organic solvents. There was a problem that is harmful to the human body due to pollution of the working environment by the toxic gas.

On the other hand, looking at the patent of the adhesive composition for bonding the polyolefin-based thermoplastic elastomer, which is a material having a poor adhesion properties as described above, in Korea Patent Publication No. 2006-0129326 proposes an adhesive composition for bonding the thermoplastic elastomer and the glass article However, such an adhesive composition uses toxic organic solvents such as xylene and toluene, so there is a problem that is harmful to the human body due to contamination of the working environment, and Korean Patent Publication No. 2009-0058469 has excellent adhesiveness to polyolefins. Although the adhesive composition is disclosed, such a hot melt adhesive composition requires an applicator when applied and applied at a high temperature of 100 to 200 ° C., and has to be adhered to the adhesive within a short time before the adhesive is cooled and solidified. Handling problems and work tricky There was a difficult problem with new process conditions.

Accordingly, the present invention is an adhesive composition using a polymer mixture of an epoxy resin, a chlorinated polyolefin resin, a chloroprene rubber, and a thermoplastic polyurethane resin as a solution to solve the problems as described above, and is a polyolefin-based material having nonpolar and poor adhesion properties. The adhesive composition for a polyolefin-based thermoplastic elastomer is characterized in that the work process is simplified and the productivity is improved because the complicated pretreatment processes such as buffing treatment, cleaning agent, primer and plasma treatment are omitted during adhesion of the thermoplastic elastomer. The task is to provide.

In addition, the present invention is a solvent for dissolving the mixed polymer, does not use any toxic organic solvents such as toluene or xylene, so no toxic gas is generated, the environment is not harmful to the worker's body by a pleasant working environment Another object of the present invention is to provide an adhesive composition for a polyolefin-based thermoplastic elastomer.

The present invention for achieving the above object in the adhesive composition for a polyolefin-based thermoplastic elastomer comprising a polymer mixture,

The mixed polymer mixture is composed of 20 to 35 parts by weight of epoxy resin, 15 to 45 parts by weight of chlorinated polyolefin resin, 20 to 30 parts by weight of chloroprene rubber and 10 to 15 parts by weight of thermoplastic polyurethane resin,

An adhesive composition for a polyolefin-based thermoplastic elastomer comprising 5 to 15 parts by weight of a tackifier, 5 to 15 parts by weight of an additive, and 250 to 740 parts by weight of 3 to 5 kinds of mixed solvents, based on 100 parts by weight of the polymer mixture. It is a problem solving means.

In addition, the chlorinated polyolefin resin is characterized in that the chlorine degree occupied by replacing a portion of hydrogen in the chlorinated polyolefin molecules with chlorine in the ethylene chloride resin or propylene chloride, 10 to 40% by weight, used alone or in combination,

The chloroprene rubber is used alone or in combination in chloroprene rubber using acetylene as starting material or chloroprene rubber using butadiene as starting material,

It is preferable to adjust and use the adhesive composition for polyolefin thermoplastic elastomers so that solid content of an adhesive composition may be 15-30 weight%.

According to the present invention by the above-mentioned means for solving the problem, by using the adhesive composition for a polyolefin thermoplastic elastomer, a complicated pretreatment step is omitted when bonding a polyolefin thermoplastic elastomer of a non-polar and non-adhesive material, the work process is simplified to improve productivity, It maintains excellent adhesive properties and also does not use any toxic organic solvents such as toluene or xylene, so no toxic gas is generated.

The present invention for achieving the above effect relates to an adhesive composition for a polyolefin-based thermoplastic elastomer, and only parts necessary for understanding the technical configuration of the present invention are described, and descriptions of other parts are omitted so as not to distract from the gist of the present invention. It should be noted that

Hereinafter, the adhesive composition for a polyolefin-based thermoplastic elastomer according to the present invention will be described in detail.

The present invention is based on 100 parts by weight of the polymer mixture consisting of epoxy resin, chlorinated polyolefin resin, chloroprene rubber and thermoplastic polyurethane resin, 5 to 15 parts by weight of tackifier, 5 to 15 parts by weight of additive and 3 to 5 kinds of mixed solvent It relates to an adhesive composition for a polyolefin-based thermoplastic elastomer composed of 250 to 740 parts by weight.

The polymer used as the polymer mixture in the present invention is composed of 20 to 35 parts by weight of epoxy resin, 15 to 45 parts by weight of chlorinated polyolefin resin, 20 to 30 parts by weight of chloroprene rubber and 10 to 15 parts by weight of thermoplastic polyurethane resin. The amount of the polymer mixture is based on 100 parts by weight.

As the epoxy resin used in the present invention used as the polymer mixture, it is preferable to use a bisphenol A type having excellent properties such as adhesion, mechanical properties, acid resistance, alkali resistance, water resistance, etc. as a conventional epoxy resin.

And it is preferable to use the usage-amount of the said epoxy resin within 20-35 weight part. If it is less than 20 parts by weight, there is a fear that the adhesive strength is reduced, if it exceeds 35 parts by weight, the cohesive force of the adhesive is lowered and the compatibility with other polymers is lowered.

In addition, the chlorinated polyolefin resin used in the present invention is a resin used for reinforcing adhesion and impact properties, the amount of the chlorinated polyolefin resin is preferably used within the range of 15 to 45 parts by weight. When the amount of the chloride polyolefin resin is less than 15 parts by weight, the effect of improving the adhesive strength is insignificant, and when it exceeds 45 parts by weight, the solubility is inferior.

In addition, the chlorinated polyolefin resin has a chloride degree of 10 to 40% by weight representing the weight of chlorine relative to the total weight of the polychlorinated polyolefin resin by containing chlorine in a part of hydrogen in the molecule of ethylene chloride or propylene chloride. It is preferable to use these individually or in combination, and it is more preferable to use the thing of 20-30 weight% of chloride specifically, in the point which can express the adhesive strength which is more excellent in a polyolefin thermoplastic elastomer within the said range.

In the present invention, the chloroprene rubber used as the mixed polymer may be used alone or in combination in chloroprene rubber using acetylene as starting material or chloroprene rubber using butadiene as starting material.

The chloroprene rubber is preferably used in an amount of 20 to 30 parts by weight. When the amount of the chloroprene rubber is less than 20 parts by weight, the workability is good, but the cohesive force may decrease and the adhesive force may decrease. When the amount of the rubber used exceeds 30 parts by weight, the molecular weight of the adhesive increases to increase the mechanical properties such as tensile strength and rebound elasticity, while the compatibility and solubility with other polymers may decrease.

In addition, the thermoplastic polyurethane resin used as the polymer mixture in the present invention is a resin that is excellent in mechanical strength, durability, heat resistance, wear resistance, elasticity, elasticity, flexibility, low temperature characteristics, and exhibits high adhesive strength, and is easy to handle and other resins. Mixing with is easy. For example, it is preferable to select and use individually or more from the thermoplastic polyurethane resin which has a polyether, polyester, and polycaprolactone as a main component, respectively.

The thermoplastic polyurethane resin is preferably used in an amount of 10 to 15 parts by weight. When the amount of the thermoplastic polyurethane resin is less than 10 parts by weight, the effect of improving the elasticity and mechanical strength of the adhesive is reduced, and the thermoplastic polyurethane resin is used. When the amount of is used exceeds 15 parts by weight, the flexibility increases more than necessary, so that the cohesive force is lowered, there is a fear that the adhesive force is reduced.

In addition, the tackifier used in the present invention is a compound used for imparting tackiness to the adhesive composition, and specific examples of the petroleum resin include aliphatic (C ₅ ) tackifiers, aromatic (C ₉ ) tackifiers, C ₅ / C ₉ copolymer tackifier, can cheomji is preferably used singly or in combination from hwanjok-based tackifier.

And it is preferable to use the usage-amount of the said tackifier within the range of 5-15 weight part. When the amount of the tackifier is less than 5 parts by weight, the effect of adhesion reinforcement is reduced, and the initial adhesive strength is remarkably decreased. When the amount of the tackifier is more than 15 parts by weight, the cohesive force of the adhesive is lowered to reduce the initial adhesive strength and the state adhesive strength. It is not suitable as an adhesive.

In addition, the additive used in the present invention may be used alone or in combination of silicas and metal oxides such as titanium diceramic side, aluminum ceramic side, magnesium ceramic side, zinc oxide, iron oxide.

In particular, the silicas are preferably Zeosyl-155, Zeosyl-175 (manufacturer: Rhodia silica), Aerosil-200, Aerosil-300 (manufacturer: Degussa).

The amount of the additive is preferably 5 to 15 parts by weight. When the amount of the additive is less than 5 parts by weight, the properties such as workability, elongation, hardness, tensile property, heat resistance, etc. may be lowered. When it exceeds weight part, it will not melt | dissolve in a solvent well, and there exists a possibility that especially solid content may become difficult to control.

In addition, the solvents usable in the present invention include, for example, methyl cyclohexane, methyl ethyl ketone, cyclohexane, acetone, ethyl acetate, cyclohexanol, isopropanol, n-propanol, and ethanol, which can be dissolved in a combination or mixed ratio. It is preferable to use together 3 to 5 types. If the solvent is used alone, the storage stability and solubility are inferior.

The solvent used in the present invention is preferably used to adjust the concentration of the solid content so that the total solid content is 15 to 30% by weight in terms of workability or stability of the polymer itself.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not necessarily limited only to the following Examples.

1. Preparation of adhesive composition for polyolefin thermoplastic elastomer

Examples 1-4 and Comparative Examples 1-4 were manufactured by the following manufacturing methods, respectively, and the composition table is shown in [Table 1].

(Example 1)

Add 20 parts by weight of chloroprene rubber (A-100, DENKA) to the kneading equipment that can control temperature and speed, and add 5 parts by weight of silica (A-200, Degussa) for 5 to 20 minutes at a temperature of 60 ~ 110 ℃. After kneading, the mixture was mixed into a reactor capable of mixing, 35 parts by weight of epoxy resin (YD-128, Kukdo Chemical), 30 parts by weight of chlorinated polyolefin resin (Superchlon 822S, Nippon Paper), and 15 parts by weight of thermoplastic polyurethane (NEOTIE 3202, Hosung Chemex). To 36 parts by weight of cyclohexane, 108 parts by weight of methylcyclohexane, 108 parts by weight of methyl ethyl ketone, 72 parts by weight of ethyl acetate and 36 parts by weight of isopropanol were added and stirred at 200 rpm to dissolve. Next, 15 parts by weight of a tackifier (ESCOREZ 1404, Exxon) was added thereto, and the mixture was sufficiently stirred and dissolved at 200 rpm to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer.

(Example 2)

Chloroprene rubber (A-100, DENKA) 20 parts by weight, silica (A-200, Degussa) 10 parts by weight, epoxy resin (YD-128, Kukdo Chemical) 25 parts by weight, chloride polyolefin resin (Superchlon 822S, Nippon Paper) 45 Parts by weight, 10 parts by weight of thermoplastic polyurethane (NEOTIE 3202, Hosung Kemex), 36 parts by weight of cyclohexane, 108 parts by weight of methylcyclohexane, 108 parts by weight of methyl ethyl ketone, 72 parts by weight of ethyl acetate, 36 parts by weight of isopropanol, and tackifying Using 10 parts by weight of the agent (ESCOREZ 1404, Exxon) in the same manner as in Example 1 to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer having a 25% solids.

(Example 3)

Chloroprene rubber (A-100, DENKA) 25 parts by weight, silica (A-200, Degussa) 10 parts by weight, epoxy resin (YD-128, Kukdo Chemical) 25 parts by weight, chloride polyolefin resin (Superchlon 822S, Nippon Paper) 40 Parts by weight, 10 parts by weight of thermoplastic polyurethane (NEOTIE 3202, Hosung Kemex) and 35 parts by weight of cyclohexane, 106 parts by weight of methylcyclohexane, 106 parts by weight of methyl ethyl ketone, 71 parts by weight of ethyl acetate, 36 parts by weight of isopropanol, and tackifying Using 8 parts by weight of the agent (ESCOREZ 1404, Exxon) in the same manner as in Example 1 to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer having a 25% solids.

(Example 4)

Chloroprene rubber (A-100, DENKA) 30 parts by weight, silica (A-200, Degussa) 5 parts by weight, epoxy resin (YD-128, Kukdo Chemical) 30 parts by weight, chloride polyolefin resin (Superchlon 822S, Nippon Paper) 30 Parts by weight, 10 parts by weight of thermoplastic polyurethane (NEOTIE 3202, Hosung Kemex), 33 parts by weight of cyclohexane, 99 parts by weight of methylcyclohexane, 99 parts by weight of methyl ethyl ketone, 66 parts by weight of ethyl acetate, 33 parts by weight of isopropanol, tackifying Using 5 parts by weight of (ESCOREZ 1404, Exxon) was prepared in the same manner as in Example 1 to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer having a 25% solids.

(Comparative Example 1)

Chloroprene rubber (A-100, DENKA) 10 parts by weight, silica (A-200, Degussa) 10 parts by weight, epoxy resin (YD-128, Kukdo Chemical) 15 parts by weight, chloride polyolefin resin (Superchlon 822S, Nippon Paper) 10 Parts by weight, 65 parts by weight of thermoplastic polyurethane (NEOTIE 3202, Hosung Kemex) and 34 parts by weight of cyclohexane, 101 parts by weight of methylcyclohexane, 101 parts by weight of methyl ethyl ketone, 67 parts by weight of ethyl acetate, 33 parts by weight of isopropanol, tackifying Using 2 parts by weight of (ESCOREZ 1404, Exxon) to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer having a solid content of 25% in the same manner as in Example 1.

(Comparative Example 2)

Chloroprene rubber (A-100, DENKA) 10 parts by weight, silica (A-200, Degussa) 2 parts by weight, epoxy resin (YD-128, Kukdo Chemical) 35 parts by weight, chloride polyolefin resin (Superchlon 822S, Nippon Paper) 15 Parts by weight, 40 parts by weight of thermoplastic polyurethane (NEOTIE 3202, Hosung Kemex), 34 parts by weight of cyclohexane, 101 parts by weight of methylcyclohexane, 101 parts by weight of methyl ethyl ketone, 67 parts by weight of ethyl acetate, 33 parts by weight of isopropanol, tackifying Using 10 parts by weight of the agent (ESCOREZ 1404, Exxon) in the same manner as in Example 1 to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer having a 25% solids.

                                                          (Unit: parts by weight) Ingredient Example Comparative example One 2 3 4 One 2 Epoxy resin ¹⁾ 35 25 25 30 15 35 Chlorinated Polyolefin Resin ²⁾ 30 45 40 30 10 15 Chloroprene rubber ³⁾ 20 20 25 30 10 10 Thermoplastic polyurethane ⁴⁾ 15 10 10 10 65 40 Tackifier ⁵⁾ 15 10 8 5 2 10 Silica ⁶⁾ 5 10 10 5 10 2 Cyclohexane 36 36 35 33 34 34 Methylcyclohexane 108 108 106 99 101 101 Methyl ethyl ketone 108 108 106 99 101 101 Ethyl acetate 72 72 71 66 67 67 Isopropanol 36 36 36 33 33 33

Note 1) YD-128: Kukdo Chemical

   2) Superchlon 822S: Nippon Paper (Salt: 20 ~ 30 wt%)

   3) A-100: DENKA

   4) NEOTIE 3202: Hosung Chemex

   5) ESCOREZ 1401: Exxon

   6) A-200: Degussa

2. Evaluation of Peel Strength of Polyolefin-Based Thermoplastic Elastomer

Each composition prepared through the Examples and Comparative Examples was evaluated for the peel strength of the polyolefin-based thermoplastic elastomer according to the following test method, the results are shown in Table 2 below.

1) Preparation of Adhesion Specimen of Polyolefin Thermoplastic Elastomer

The adherend made of polyolefin-based thermoplastic elastomer is cut to a size of 10 × 120 mm and prepared so that they can be bonded to each other. After applying the adhesive to the adherend without a pretreatment step, it is dried for 60 to 5 minutes, and then the adherents are bonded to each other about 5 kg. _It was pressed by the load of _f and bonded.

2) peeling strength

After each obtained adhesive specimen was allowed to stand at room temperature for 24 hours, the peel strength (kg _f / cm) was measured at room temperature using a universal tensile tester with a moving speed of 150 ± 20 mm / min. Adhesion specimens were measured by measuring the average value of five gks results are as shown in Table 2 below.

Evaluation item Example Comparative example One 2 3 4 One 2 Peel Strength (kg _f / cm) 8.5 ¹⁾ 8.2 ¹⁾ 7.9 ¹⁾ 7.4 ¹⁾ 1.8 2.4

Note 1) Destruction of adherend

As shown in Table 2, Examples 1 to 4 in the present invention, respectively, using the composition within the weight range to prepare an adhesive composition for a polyolefin-based thermoplastic elastomer, to the adhesive specimen of the polyolefin-based thermoplastic elastomer adherend prepared Although the peel strength was excellent in all, Comparative Example 1 added the amount of epoxy resin and chlorinated polyolefin in the polymer mixture below the range, and the amount of the thermoplastic polyurethane resin exceeded the range and the amount of the tackifier was added below the range, thereby causing cohesion. Its weakness and insufficient adhesion reinforcement effect resulted in a decrease in peel strength due to poor adhesion to the adherend. In Comparative Example 2, the amount of the thermoplastic polyurethane resin used in the polymer mixture exceeded the range and the amount of the additive used ranged. Less than four Cohesion resulted in the fall of cohesion force, and the peeling strength fell markedly.

Accordingly, the present invention relates to an adhesive composition for a polyolefin-based thermoplastic elastomer, as described above, excellent in peel strength and no toxic organic solvent when bonding a non-polar and non-adhesive polyolefin-based thermoplastic elastomer without complicated pretreatment. Therefore, the excellence was confirmed through the above examples as an environment-friendly composition.

As described above, the adhesive for the polyolefin-based thermoplastic elastomer according to the present invention has been described through the above-described preferred embodiments, and the superiority thereof has been confirmed, but those skilled in the art will recognize the spirit and scope of the present invention described in the following claims. It will be understood that various modifications and variations can be made in the present invention without departing from the scope thereof.

Claims (5)

In the adhesive composition for a polyolefin-based thermoplastic elastomer comprising a polymer mixture, The polymer mixture is composed of 20 to 35 parts by weight of epoxy resin, 15 to 45 parts by weight of chlorinated polyolefin resin, 20 to 30 parts by weight of chloroprene rubber and 10 to 15 parts by weight of thermoplastic polyurethane resin, With respect to 100 parts by weight of the polymer mixture, 5 to 15 parts by weight of tackifier, 5 to 15 parts by weight of additives and 3 to 5 kinds of mixed solvents of 250 to 740 parts by weight, The chlorinated polyolefin resin is used alone or in combination with a chlorine degree of 10 to 40% by weight of a part of hydrogen in the chlorinated polyolefin molecules substituted by chlorine in the ethylene chloride resin or propylene chloride resin, The chloroprene rubber An adhesive composition for polyolefin thermoplastic elastomers, which is used alone or in combination in chloroprene rubber using acetylene as starting material or chloroprene rubber using butadiene as starting material. delete delete The method of claim 1, Adhesive composition for a polyolefin-based thermoplastic elastomer, the adhesive composition for a polyolefin-based thermoplastic elastomer, characterized in that the solid content of the adhesive composition is adjusted to 15 to 30% by weight. The method of claim 1, For the polyolefin-based thermoplastic elastomer, the solvent is selected from 3 to 5 selected from methylcyclohexane, methyl ethyl ketone, cyclohexane, acetone, ethyl acetate, cyclohexanol, isopropanol, n-propanol, or ethanol. Adhesive composition.