KR100914076B1 - Resin of tempered adhesion - Google Patents

Abstract

The present invention is provided by strengthening the adhesive property of the general-purpose polymer, and can be provided at a low price, and it is possible to strengthen the adhesion of the general-purpose polymer by physical treatment only, and preserve the good extrusion properties and injection characteristics inherent in the general-purpose polymer even if the adhesion is enhanced. The present invention provides an adhesive reinforcing polymer having low cost and good processability compared to a conventional adhesive polymer. This invention provides a resin in which the polymer is reinforced with corona discharge sparks to enhance the adhesiveness of the polymer.

Corona, Adhesive

Description

Adhesion Resin {RESIN OF TEMPERED ADHESION}

The present invention relates to a resin having enhanced adhesion. The present invention provides an adhesive reinforcing resin that exposes a polymer to corona discharge sparks to enhance adhesion through preservation of flame and preserves processability. The adhesive reinforcing resin provided in this invention is provided in a pellet, film, or powder state.

The use of adhesive resins varies. Adhesive resin is used as a compounding raw material, the Tai resin of a multilayer film, an iron plate coating material, an iron pipe coating material, an adhesive film, an adhesive powder resin, etc. The adhesive resin is also used as a film for thermal collimation for forming a film and laminating on paper. Adhesive resins are also used to make composite films by adhering to nonwovens while molding into films in an extruder. Existing adhesive resins include sulfine, EVA, EAA, EMA, polyester or rubber resins with melting point below 130 ° C, and adhesive resins compounded by mixing various materials. EVA, which is a copolymer of ethylene and vinyl acetate, is classified as a general-purpose polymer because it is inexpensive, has a high amount of use, has a large amount of production, and has good processability. Since the adhesive resins mix monomers having an expensive polarity during polymer polymerization, they have an expensive price structure, are not environmentally friendly, exhibit adhesive strength even at low temperatures, and are difficult to compound and have poor extrusion processes. Adhesive resins incorporating hot melt materials must be compounded. In addition, maleic anhydride may be graft polymerized in polypropylene (PP), but graft polymerization may not be well performed in polyethylene (PE).

In addition, the conventional adhesive resins are difficult to increase the production speed due to poor extrusion processability when processing the film or sheet by extrusion, and a lot of gels occur to reduce the productivity. In order to increase the adhesive strength only by the composition of the raw materials as described above, expensive raw materials must be used and extrusion processability is deteriorated.

The use of multilayer composite films or adhesive films in which nylon or EVOH layers are superimposed on polyolefin films is on the rise.

The adhesive properties are weak between the polyolefin film and the nylon or EVOH layer. Due to this problem, the conventional composite film arranges the tie resin layer as an adhesive imparting agent at the interface of the composite film including the nylon or EVOH film layer in order to impart the adhesion between the polyolefin film and the nylon or EVOH layer.

As an adhesive imparting agent, the tie resin is very thinly imparted between the polyolefin film and the nylon or EVOH layer. To be satisfied as the adhesive imparting agent, the gel must be free of gel, have good extrusion processability, and have a low price. However, since the tie resin is expensive, has a lot of gel generation and has the property of inhibiting productivity, it is accompanied by technical and economic obstacles as an adhesive imparting agent. Conventional tie resins and other tacky resins present a number of problems, including high cost, even when producing adhesive films for other applications.

The adhesive reinforcing resin provided by this invention is inexpensive and has very good extrusion processability as compared with the tie resin or other adhesive resins. This enables low cost, high quality film production.

As described above, the present invention has a great industrial use value in that an adhesive resin having good film formability is provided. Another feature of the adhesive reinforcing resin of this invention is that the pulverization processability is good.

The adhesive film should be blended with more than 60% by weight of polyolefin resin or EVA resin with good processability to facilitate the molding and manufacturing of the film or sheet in the extruder and to provide economical cost by providing a low cost film.

As described above, in the manufacture of the composite film, it is difficult to dispose the tie resin layer at the interface between layers, and it is preferable to modify the composite film polymer material to enhance adhesion.

In order to preserve the economy and to facilitate the manufacture of a film or sheet, the present invention aims to blend 60% by weight or more of polyolefin-based resin or EVA resin with good extrusion processability in mixing an adhesive resin with a good processability resin. It is desirable to. The present invention has high economical efficiency and practicality by blending a low-cost polymer material with good extrusion processability by 60% by weight or more, and enhancing these adhesive properties by corona modification and preserving the workability.

Corona discharge is a phenomenon in which a strongly excited space of an electric field emits light while conducting when a high voltage is applied between two electrodes. When corona discharge sparks are formed on the surface of the molded plastic film or the molded plastic sheet, small grooves or bends are formed on the surface of the molded product, the area of the molded product surface is enlarged, and chemically, the carboxyl group (C = 0) is introduced and the surface tension is increased. Gets bigger Corona discharge spark bearing on the molded printing plastic film increases the adhesive force between the film surface and the printing ink layer, thereby improving printing aptitude.

The present invention focused on the phenomenon that the polyethylene film having the corona discharge spark bearing on the surface of the plastic molding increased as described above, and the polyethylene film having the corona discharge spark bearing on the surface also improved the thermal adhesiveness with the paper.

The present invention is to provide an adhesive polymer having a low cost and good processability when manufacturing a film sheet, which is a substitute for existing adhesive resins, which is expensive and does not have good extrusion processability. The present invention seeks to provide an adhesive resin provided by enhancing the adhesion of a general purpose polymer. The present invention seeks to provide an adhesive reinforcement resin that can be provided at a low price. The present invention seeks to provide an adhesive reinforcement resin that enhances the adhesive strength of general purpose polymers only by physical treatment. The present invention seeks to provide an adhesive polymer in which good extrusion properties inherent in general-purpose polymers are preserved even when adhesion is enhanced. The present invention seeks to provide an adhesive resin having a lower cost and better extrudability compared to a conventional adhesive polymer. An object of the present invention is to provide an adhesive reinforcing resin characterized by preparing a corona spark-supporting polymer by corona discharge spark bearing polymer and adding an adhesion enhancing material to the corona discharge spark bearing polymer or corona discharge spark bearing polymer. The present invention also seeks to provide an adhesive powder resin that can be used as a direct adhesive material. In addition, the present invention aims to reduce the use of adhesive raw materials with poor or expensive extrusion processability and to improve the extrusion processability by providing a corona discharge flame, and to provide a low cost adhesive resin.

The adhesive reinforcing resin of the present invention is a low-cost polymer, and is a resin in which adhesiveness is enhanced by modifying a polymer of at least one of polyolefin resin, ethylene and vinyl acetate copolymer (EVA). The present invention is to form a polymer film to be treated for adhesion reinforcement treatment, the polymer film to be treated to corona discharge sparks to produce a polymer film with enhanced adhesion, the polymer film with enhanced adhesion in the form of raw materials It is molded in the form of either pellets or powder to be turned to enhance the adhesion of the low cost polymer while preserving the processability of the low cost polymer raw material. Table 1 summarizes the steps for producing the inventive adhesive reinforcing resin.

Table 1. Adhesive resin manufacturing steps

 step  process  One  Polymer for reforming, which is at least one of polyolefin resin or ethylene and vinyl acetate copolymer (EVA)  2  Manufacture of polymer films from modifying polymers  3  Modification of polymer film by modifying corona discharge flame  4  Modified polymer film is formed from raw polymers in the form of pellets or powders

Since the adhesive resin is optionally added to the polymer for modifying the invention, the adhesiveness can be further improved. Specifically, tackyfire, maleic anhydride, amorphous polypropylene (APP), and polybutylene are used as polymers for adhesion reinforcement to 100 parts by weight of the polymer to be treated, which is at least one of polyolefin resin or ethylene and vinyl acetate copolymer (EVA). , 67 parts by weight of one or more polymers of polyisobutene, an adhesive resin having a melting point of less than 130 ° C., and a rubber-based polymer are mixed to prepare a polymer to be mixed. A film is formed from the polymer to be mixed for adhesion treatment, and the polymer film to be mixed with the corona discharge spark is prepared to produce a modified adhesive. To prepare an adhesive reinforcement resin. Table 2 summarizes the adhesive resin that can be optionally added to the modifying polymer of Table 1.

Table 2. Summary of Any Additional Resins

 material  Composition ratio (weight%)  Contents  Modified Polymer  60-100  Polymer of either polyolefin resin or ethylene and vinyl acetate copolymer (EVA)  Adhesive strengthening polymer  0-40  One or more of tackifiers, maleic anhydride, amorphous polypropylene (APP), polybutylene, polyisobutene and adhesive resins having a melting point of less than 130 ° C. and rubber-based resins.

 The present invention can further modify the adhesiveness of the raw material polymer of any one of the pellet or the powder modified adhesiveness. Specifically, an adhesive reinforcement polymer is prepared by further modifying the adhesive by modifying the raw material in any one of the pellets and the powder in which the adhesion is modified. Table 3 summarizes the steps to further enhance adhesion.

Table 3. Adhesive Strengthening Steps

 step  Contents  One  Polymer pellets or powders with improved adhesion by modifying Table 1 and Table 2 resins  2  Fillet or powder modified in step 1 by filling the fillet or powder in the corona discharge flame

The present invention can grind the adhesive modified polymer pellets to provide a powdered polymer. Specifically, the present invention grinds the polymer-enhanced polymer pellets within a particle size of 150㎛ in the grinder to provide an adhesive reinforcing powder. Table 4 summarizes the composition range of the adhesive reinforcing polymer powder.

Table 4. Composition range of adhesive reinforcement powder

 step  Contents  One  Adhesive reinforcement pellets cited in Tables 1, 2 and 3  2  Adhesion reinforcement powder provided by grinding the pellets of step 1

This invention is demonstrated in more detail. Of the adhesive resins, ethylene and vinyl acetate copolymers (EVA) are relatively inexpensive but have weak adhesion compared to other adhesive resins. Adhesive polymers are the mainstay of adhesive polymers including EAA, EMA, sulfin (DuPont) or polyester-based adhesive resins with melting temperatures below 130 ° C, tyresins, and maleic anhydride graft polymers. It is expensive and the workability is not good. In contrast, polyolefin-based polymers such as polyethylene (PE) and polypropylene (PP), which are general-purpose polymers, are inexpensive and have very good processability, but have poor adhesion, compared to the adhesive polymer. In this invention, EVA is to be included in the category of general purpose polymer. The relationship between adhesiveness and price is summarized in Table 5.

Table 5. Classification by Polymer Adhesion and Price

 division  characteristic  Polymer  Low price adhesive resin  1. Weak adhesion  Ethylene, Vinyl Acetate Copolymer (EVA)  High price resin adhesive resin  1. Strong adhesion 2. Poor processability  EAA, EMA, Sullyne (DuPont) or polyester-based adhesive resins with melting temperatures below 130 ° C, tyresins, maleic anhydride graft polymers, rubber-based resins  General purpose polymer  1. Good workability 2. Weak adhesion  Polyolefin polymer such as polyethylene (PE), polypropylene (PP), etc.

One important problem of the present invention is to provide a gavel polymer with enhanced adhesion while preserving good processability of a general-purpose polymer or a low-cost adhesive resin.

Preparation of Adhesive Reinforced Polymer

Surface of film (including sheet) formed by using PE, EVA, copolymer of ethylene and propylene and PP of 60 to 100% by weight of general-purpose polyolefin-based polymer (I) and 0 to 40% by weight of adhesive resin The film was modified with a corona discharge spark to produce a film having enhanced adhesion, that is, a modified polymer (II). When the corona discharge spark is supported on the general-purpose polymer (I), a carbonyl group (-C = O) is added to the polymer (I) surface. Carbonyl groups added to general purpose polymers increase the polarity of the polymer and act as an adhesive matrix for the polymer. As described above, the present invention is to strengthen the adhesiveness while impregnating the corona discharge spark on the general-purpose polymer (I) while preserving good extrusion processability of the general-purpose polymer. To preserve good processability of general purpose polymers, the amount of adhesive resin or adhesive material confused with the film material should be limited to 40% by weight or less.

The modified polymer (II), which is strengthened by the corona discharge spark and has improved adhesion, may be corona discharge spark bearing PE, corona discharge spark bearing PP, or corona discharge spark bearing EVA according to the type of polymer.

In order to sufficiently strengthen the adhesive matrix of the general-purpose polymer (I), more carbonyl groups should be produced in the modifying polymer (I). In order to generate a large amount of carbonyl groups in the polymer by the corona discharge spark bearing, it is necessary to increase the number of corona spark bearings and increase the corona flame bearing strength. Adding the number of corona discharge sparks to a polymer increases the carbonyl content of the polymer and increasing the corona spark strength increases the amount of carbonyl groups produced.

The corona discharge spark bearing of the present invention can be applied to a polymer in a film, sheet, strand, pellet, or powder state. Corona discharge spark bearing is to expose the polymer to the corona spark field generated between the corona discharge electrodes, thereby giving the support to the surface of the polymer by the corona discharge spark. Corona discharge spark-preserving material is a thin polymer film. The thickness range of the film (or sheet) theoretically possible for corona bearing is 1-500 g / m <2>, and the thickness of the preferable film which considered work efficiency is about 10-25 g / m <2>.

Corona discharge electrodes are generally bar type electrodes. The corona discharge electrode needs only to form a homogeneous and high intensity corona flame field sufficient to expose the polymer to the corona flame field.

The device for exposing the polymer to the corona flame field may be installed in various forms depending on the state of the polymer.

Corona Discharge Spark Support If the polymer is in a continuous state on a film, sheet or strand, the continuous polymer is moved along the guide roll and the polymer in motion is exposed to the corona discharge spark.

Adhesion-enhanced corona modified polymer film or modified polymer sheet is prepared as pellets in an extruder or pellet maker, or as a powder in a grinder, as a pellet manufacturing process of conventional adhesive polymers, and is provided as an adhesive polymer raw material.

Corona discharge flame support is provided with a belt for transferring the dispersed polymer if the polymer is dispersed in the form of particles or powder, at least one corona discharger along the belt, and supplying the dispersed polymer at least once on the driven belt. By exposing the dispersed polymer particles supplied on the belt to the corona discharge flame yard to give a corona discharge flame support to the dispersed polymer to produce a corona discharge flame support dispersion polymer.

As described above, the modification cost of strengthening the adhesive substrate to the general-purpose polymer (I) due to the present invention corona discharge spark is low cost. The reason for the low cost is that the corona discharger is a low-cost facility, and the material cost for corona discharge is about the power cost, so the cost of strengthening the adhesive property of the general-purpose polymer by corona discharge sparking is resource-saving and very low.

This invention adds a hot melt material, a good adhesive polymer, and materials having hot melt properties to the corona flame bearing polymer (II) in order to further enhance the adhesiveness, thereby producing a further strengthening adhesive corona flame bearing polymer (III). . Hot melt materials include tackifiers, polybutenes, polyisobutenes, EVA (VA content of 20% by weight or more), polyester polymers having a melting temperature of less than 130 ° C, APP (amorphous polypropylene), and the like. In addition, rubber-based materials may be used to improve adhesion in the present invention.

As described above, the present invention provides an adhesive polymer as a substitute material of conventional adhesive resins, which is expensive and poor in processability, and provides an adhesive resin provided by strengthening the adhesiveness of a general-purpose polymer, and at a low price. Adhesion reinforcement resin that can be used, Adhesion reinforcement resin that strengthens the adhesive strength of general-purpose polymers by physical treatment only, Preserving the good extrusion properties and injection characteristics inherent in general-purpose polymers even if the adhesion strength is enhanced To provide an adhesive resin having a low cost and good processability compared to a conventional adhesive polymer, and to produce a corona discharge spark bearing polymer by producing a corona discharge spark bearing polymer and to a corona discharge spark bearing polymer or a corona discharge spark bearing. Providing an adhesive reinforcing resin in which an adhesive enhancement material is added to the polymer, Using recycled water also provides ease of environmentally friendly adhesive reinforced polymer.

Example 1

A corona flame support line with three 10 kW corona flame dischargers was placed between the cold roll of the film forming line for melting the polymer to form the film and the cold cured film and the winder for collecting the cured film. .

LDPE (low density polyethylene), a polymer raw material, was melted in an extruder of a film forming line and molded into a 15 g / m 2 LDPE film on a T-die. Both sides of the molded film were contacted three times so as to be lipid-coated with the corona flame to prepare a corona modified film containing a large amount of carbonyl groups. The line speed of the film was 30 m / min.

The corona-modified film was melted in a pellet maker to prepare polymer pellets having enhanced adhesion.

Example 2

Corona while preparing the film as in Example 1 with 70 parts by weight of LDPE, 20 parts by weight of EVA with 15% by weight of VA, 5 parts by weight of EVA with 30% by weight of VA, and 5 parts by weight of polyethylene masterbatch containing 50% by weight of APP. The flame was carried out to prepare a modified film with a nose, and to prepare a polymer fillet having enhanced adhesion by melting the corona modified film.

Example 3

A feed belt for conveying the dispersed polymer and a feed hopper for supplying the dispersed polymer at the beginning of the conveying belt were provided. Three sets of corona flame dischargers were installed along the belt.

Example 4

Dispersion polymer was supplied to the hopper of Example 3. The seismic dispersion polymer was collected by contacting the corona flame on the conveyance belt, and the dispersed polymer was repeatedly supplied to the hopper to produce the corona modified dispersion polymer.

Example 5

An adhesive reinforcing film (A) of 25 g / m 2 was prepared using the adhesive reinforcing pellets prepared in Examples 1 and 2 as a material. In order to compare the adhesiveness with this film, a corona untreated film (coarse) of 25 g / m 2 was prepared from LDPE without corona exposure.

Example 6

An adhesive reinforcing film (A) of 25 g / ㎡ prepared in Example 5 was coated on a copy paper of A4 standard in a thermal bonding coating machine for a visit to prepare a corona discharge flame modified coating paper (b). In Example 5, the corona untreated film (mostly) was coated on a copy paper of A4 standard in a thermally bonded coating machine for stationery to prepare a corona untreated coated paper (you).

Example 7

The peeling strengths of the films of the corona discharge-modified coated paper (B) and the corona untreated coated paper (N) prepared in Example 6 were compared. The corona discharge-modified coated paper (b) could not be separated by bending by hand. Corona untreated coated paper (you) was bent by hand while separating the bonding surface by hand.

Example 8

The adhesive-enhanced polymer pellets prepared in Example 2 were ground in a grinder to prepare an adhesive polymer powder having a particle size of about 100 μm. The prepared adhesive polymer powder was sprinkled onto two copies of the paper as an adhesive and heated and pressed at 120 ° C. in the coating machine of Example 6 to bond two copies of the paper. The bond surface could not be separated by hand while bending two A4 standard copy papers.

Example 9

The workability of the film forming process was investigated using the polymer reinforced polymer pellets prepared in Example 1 as raw materials. The film formability was good even though the adhesion was enhanced.

The workability of the film forming process was investigated using the polymer reinforced polymer pellets prepared in Example 2 as raw materials. The results showed that the film formability was preserved even though the adhesion was enhanced by modifying the LDPE with corona flame.

Claims (5)

In the case where the surface of the propylene resin containing ethylene is corona discharged to enhance adhesion, As the polymer to be treated to enhance adhesion, at least one polymer of polyolefin resin or ethylene and vinyl acetate copolymer (EVA) is molded into a polymer film for corona discharge treatment, The polymer film to be treated is corroded with a corona discharge spark to enhance the adhesion of the pol-mimer, A resin with enhanced adhesion produced by molding into a form of pellets or powder in order to return a film reinforced with corona discharge sparks to enhance the adhesion to a raw material form. In the case where the surface of the propylene resin containing ethylene is corona discharged to enhance adhesion, Tackifier, maleic anhydride, amorphous polypropylene (APP), polybutylene, poly as a polymer for adhesion reinforcement to 100 parts by weight of the polymer to be treated, which is at least one of polyolefin resin or ethylene and vinyl acetate copolymer (EVA). A polymer to be mixed, which is a material obtained by mixing 67 parts by weight of at least one of isobutene, an adhesive resin having a melting point of less than 130 ° C., and a rubber-based polymer, is molded into a poly- and film for corona discharge treatment. The formed polymer film to be treated with mixing is corroded with a corona discharge flame to enhance the adhesion of the pol-mimer, Adhesive-enhanced resin produced by molding into a form of pellets or powder in order to return a polymer film reinforced by corona discharge sparks to enhance the adhesion to a raw material form. The adhesiveness according to any one of claims 1 and 2, wherein the raw polymer of any of the pellets or powders having enhanced adhesion is further subjected to corona discharge sparks to further enhance the adhesiveness of the raw polymer. Reinforced resin. An adhesive film made of the resin provided in any one of claims 1 and 2, wherein the adhesive film has enhanced adhesion. A resin powder having enhanced adhesion prepared by pulverizing the resin pellet provided in any one of claims 1 and 2.