KR102359758B1 - Reactively thermal extrusion-molded article of flocking fabric, flocking fabric containing the same, and Manufacturing method thereof - Google Patents

Abstract

The present invention, which is developed as a method to solve a problem such as low-density implant and an environmentally harmful process due to the decrease in electrical conductivity of a conventional hair implant process using an organic solvent-type adhesive resin, relates to a floating fabric manufactured by inducing direct laminating adhesions and implanting fibers using a reactive thermo-extrusion molded article as a substrate, the reactive thermo-extrusion molded article used for the same, and a manufacturing method thereof.

Description

Reactive thermal extrusion-molded article for flocking fabric base material, flocking fabric including same, and manufacturing method thereof

The present invention was developed as a method to solve the problems of low-density hair transplantation and environmentally harmful process due to the decrease in electrical conductivity of the conventional hair transplantation process using an organic solvent-type adhesive resin. It relates to a flocking fabric manufactured by bonding rating and fiber implantation, a reactive thermo-extrusion molded article used therein, and a manufacturing method thereof.

[etc]

[National R&D project supporting this invention]

[Project unique number] D202069

[Buddhist name] Gyeonggi-do

[Research and Management Specialized Institution] Gyeonggi-do Economic Science Promotion Agency

[Research project name] Gyeonggi-do technology development project

[Research project name] Eco-friendly NVH, high-functionality and lightweight automobile Flocked Laminating Seal component material development

[Contribution rate] 20/100

[Organizer] Yuhan Intertek

[Research period] 2020.03.01~2021.05.31

Materials for sealing parts, which are essential modules for automobiles, are evolving. In particular, vehicle weight reduction, NVH (noise/vibration) blocking function, and application of eco-friendly construction methods are the key to technology development. In particular, the application field of TPE (Thermo Plastic Elastomer), an eco-friendly material that maintains rubber-like elasticity while simultaneously possessing thermoplastic functions like plastic, is increasing day by day. The market demand is increasing, and there are problems of low adhesion to materials, deterioration of material durability, and deterioration of functionality.

Traditionally, the rubber and elastic material industry has been conducted by emphasizing performance aspects such as elasticity and abrasion resistance, etc., and more than 80% of the market is used for automotive parts and tires such as automotive sealing parts, hoses, and various interior materials. have.

In the past, EPDM (ethylene propylene diene monomer), which had emotional qualities such as noise, vibration, and touch, and characteristics such as heat resistance, weather resistance, ozone resistance, electrical insulation, and acid resistance, was the centerpiece of the parts material. As a recyclable eco-friendly material that can be recycled as a high-functional hybrid elastomer with rubber-like elasticity and processability of thermoplastic resin, which is currently being expanded due to the expansion of the eco-friendly market such as Glass Run, Channel, Tailgate Sealing, Hood Sealing, Body Sealing, Door Sealing, Sunroof Sealing, etc. Substitute application is expanding as a basic material for parts.

As a sealing part material, TPE is an olefin material with a non-adhesive property despite its many strengths. Field application of adhesive resin in the fusion process with flocking materials for complex functions such as NVH is separate for surface modification of polymers on the adhesive side. Pre-treatment was unavoidable and a complex multi-step hazardous process required for the use of special adhesive resin was required. The production of these flocking sealing parts is carried out in a continuous production process such as the Roll Foaming method of the sealing base material. Plasma treatment, applying an adhesive resin with a brush method with a liquid flow of medium viscosity, flocking in a flocking unit, and curing it with a thermal setting was the method of production. This is a method of laminating a heat-activated flocked film, which is a high-density flocked pile in an upright shape, on the sealing material in the injection process. A method of using polycondensation polymer for laminating is being applied to some.

By using a multilayer film of Thermoplastic Polycondensation Polymer in the direct lamination process in the injection process with the development of technology to replace the harmful process of the existing sealing parts material processing, low adhesion is solved or the heat and tension of the multilayer film is reduced. Efforts have been made to solve the above problem by using a heterogeneous polymer on both sides of the fiber as a medium for weak strength. The method to solve the above problem by composing a multilayer film with a release polymer depends on the difficulty of the injection process, and there are problems such as defective hair transplantation process, durability due to thin film polymer and manufacturing process conditions due to thermal deformation.

Korean Patent Publication No. 2003-0076258 (published on September 26, 2003)

Existing flocking fabrics use water-soluble or organic solvent-type polyurethane resins as binder materials, so a high-temperature curing process of thermal setting that separates moisture and solvents is essential in the process of reacting the adhesive resin for hair transplantation, and in this process, the thermoplastic film There is a problem in workability due to the deformation of the resin, and it is difficult to meet the required physical properties by using a low-solids resin, so the heat-reactive material and the durable material must be configured in a multi-layer structure. It was difficult to secure the composition of physical properties and work stability.

Accordingly, the present invention is a flocking fabric in which a thermoplastic film has a single-layer structure and a high solids non-solvent-type urethane-type binder resin is introduced as a binder layer thereon. An object of the present invention is to provide a base material for flocking fabric that can provide a flocking fabric, a flocking fabric including the same, and a manufacturing method thereof.

The reactive thermo-extrusion molded article for a flocking fabric base material of the present invention for solving the above problems is prepared by performing a maleation reaction on a mixed resin including polypropylene, maleic anhydride, a reaction initiator and an additive, and the maleic acid reaction It is performed by a reactive thermal extrusion process that does not use a silver solvent, and the molded article may include a reactive thermal extrusion product of a polypropylene-based polymer grafted with maleic anhydride as a single layer.

In addition, another object of the present invention relates to a method for manufacturing the reactive thermo-extrusion molded article, the first step of preparing a mixed resin; and a second step of extruding the melt of the mixed resin on the release paper in a T-die method by performing a reactive thermal extrusion process on the mixed resin to form an extrudate in the form of a sheet or film; The mixed resin may include a polypropylene-based polymer, maleic anhydride, a reaction initiator, and an additive.

The flocking fabric utilized in the present invention includes a base layer including the reactive thermo-extrusion molded article; a binder layer formed of a solvent-free urethane-type binder resin on the substrate; and a pile layer including fibers implanted in the binder layer.

In addition, the present invention relates to a method of manufacturing a flocking fabric, and for preventing thermal deformation and mechanical strength of the substrate, (a) preparing a urethane prepolymer containing a hydroxyl group at the terminal having a melt viscosity of 2,000 to 20,000 cps at 60° C. or less to do; (b) melting the urethane prepolymer at 58 to 62°C; (c) preparing a solvent-free urethane-type binder resin by injecting a mixture containing a molten urethane prepolymer, an isocyanate-based compound, a crosslinking curing catalyst, and a surfactant into a high-speed reaction molding machine and mixing at high speed; (d) discharging the reaction solution on the upper surface of the reactive hot-extrusion molded article, and then performing knife coating or comma coating to form a binder layer; (E) planting a fiber pile in the binder layer, crosslinking and primary curing under 60 ~ 90 ℃; And (f) aging and secondary curing at 40 ~ 60 ℃; may perform a process comprising a.

The flocking fabric manufactured by applying the reactive thermo-extrusion molded article of the present invention as a base material can be manufactured using a solvent-free high-solid content urethane binder resin without a pre-treatment process such as primer, corona discharge, and plasma surface treatment, and is water-soluble However, it is eco-friendly because it uses a non-solvent type high-solids urethane binder resin rather than a solvent type resin. In addition, for a thermally reactive flocking sheet, curing and aging at a temperature of 40 ~ 50 ℃ to prevent thermal deformation, and not a water-soluble or solvent-type resin, but a 100% high-solids urethane adhesive resin It is an adhesive resin with a high-density structure without pores from which moisture and solvents have fallen off. It has excellent adhesion with a non-adhesive sealing, so that excellent durability and work stability can be secured in preparation for the post-coating of the heat-reactive sheet. The reactive hot-extrusion molded article has excellent thermal stability and excellent adhesion to a solvent-free urethane binder resin, and the flocking fabric of the present invention has excellent abrasion resistance and durability. The flocking fabric of the present invention is a vehicle headliner, weather strip, tailgate sealing, body sealing, door sealing, hood sealing) Alternatively, it can be used in the absence of a sunroof sealing.

1 is an SEM measurement image of a cross section of a flickering fabric (sealing molding material) prepared in Preparation Example 1. Referring to FIG.
Each of A and B of FIG. 2 is a photograph of the device used for the sliding resistance test measured in Experimental Example 3.
Each of A and B of Figure 3 is a photograph of the device used for the semi-dry sliding resistance test measured in Experimental Example 3.
4 is an SEM image of a cross section of the flocking fabric of Preparation Example 6-2.
5A to 5C are photographs taken of the wear resistance, sliding resistance, and sliding resistance test apparatus performed in Experimental Example 5, respectively.

Existing heat-reactive film manufacturing process requires pre-surface modification with primer pretreatment, corona discharge treatment, plasma surface treatment, etc. Complex processes such as constraints and space movement were required. However, in the process of the present invention, the heat-reactive resin layer was commercially reformed with a modified polypropylene copolymer of mPP (polypropylene)/elastomer compound through reaction extrusion to solve the surface difficulty adhesion, so durability without prior surface modification It maximizes the adhesive strength with the high-solids solvent-free hair-transplantation adhesive resin with a A high-durability, complex functional implantation-type sealing material is manufactured by performing a hair transplantation process using a solvent-free type implantation resin in the reaction resin layer, peeling it, and bonding the prepared film with a molding sealing material of the injection process by thermal lamination.

In order to achieve the above object of the invention, in order to provide adhesion to the sealing molding material, which is currently being converted to modified EPDM (ethylene propylene diene monomer) of TPE (thermo plastic elastomer) component, first of all, the existing water-soluble and solvent type It was necessary to form a base resin layer with excellent thermal bonding performance of a sealing material of a new method that improves the manufacturing method of forming a hair transplantation layer using a liquid adhesive resin and a TPE adhesive sheet structure that is adhered to a heat sealing method.

In the past, multiple co-extruded materials such as ethylene propylene copolymer, polyethylene homopolymer, and polypropylene homopolymer to secure thermal adhesiveness while solving the difficult-to-adhesive properties of the sealing material It was necessary to prepare a heat-reactive film in which a single layer or a multi-layer of the two layers were combined in advance, and to use a polyurethane adhesive resin again for the implantation process on the upper part. However, since the hair transplantation process also has difficulty in adhesion of the surface of the heat-reactive film, plasma processing, corona discharge, or a coating process with a solvent-type primer is performed on the reaction-type film, and water-soluble or organic solvent-type adhesive resin for hair transplantation is performed. Plasma processing, which performs surface modification on the upper part of the polymer to improve adhesion, and corona discharge process, which is performed by using a polyurethane adhesive resin The polar groups (C=O, COH, COOH created by surface oxidation) are generated by ionizing the air to generate charged particles and inducing oxidation of the polymer surface while these particles come into contact with the surface located between the electrode and the top of the thermally reactive polymer. , COOR, COR, etc.) increase the surface energy of the polymer to improve reactivity and affinity.

In addition, solvent-type primer application is applied on top of a thermally reactive polymer in order to generate a cross-linked structure between polar groups and non-polar polymer molecules, or the solvent is volatilized, which is harmful to the human body and its effect is limited.

Therefore, the thermally-reactive film composed in this way does not meet the performance requirements for durability of the sealing, is cut off by the high injection temperature in the thermal bonding process with the molding material of the injection process, or the film surface is thermally deformed. there was. In order to solve this problem, attempts have been made to increase heat resistance and tensile strength by structurally forming several layers of copolymers and homopolymers in the manufacture of thermally reactive films to solve this problem, but fundamentally, the thin film structure layer is formed as an aggregate of release components, so that each property is different. Because they are different, there are limitations in the adhesive resin and adhesiveness of the hair transplantation process, as well as the curing and aging conditions of the resin, making it difficult to design an appropriate process and there were many defects. In order to improve this, it was attempted to solve the problem by inserting and reinforcing the fiber material between the layers, but it is not used in reality due to the problem of increased thickness and the problem of phase separation due to the difficult adhesion between the fiber material and the co-polymer. Tensile strength in polymer layers to solve the current problem. An attempt is made to improve the multi-layered structure by forming a polypropylene homopolymer layer that enhances mechanical properties such as elongation and heat resistance, but this is only a slight improvement, and the coextrusion of the thin film layer is also technically limited and economically problematic. etc.

In the present invention, it was attempted to solve by a method of composing a modified PP heat-reactive resin layer of a single layer of mPP/Elastomer compound with good adhesion by carrying out compatibilizing hydrophilic modification by introducing a reactive group to the PP (polypropylene) polymer. In order to bond with a non-polar polymer, a specific substance having a polar group must be introduced into the polymer chain. To date, many possible polar monomers have been tried for PP. Among them, PP (PP-g-MAH) grafted with maleic anhydride (MAH) showed the best modification effect. There is a solution method as this reforming method, but it was decided to prepare a reaction extrusion method grafted PP in consideration of the possibility of residual substances harmful to the environment and fairness. For the reaction extrusion, it is possible to combine with other polar groups due to the radicals generated in the process of breaking the polymer chain due to the thermal energy transferred from the outside, the shear stress inside the screw, and the initiator. In order to efficiently introduce MAH in the PP chain through melt processing, acid anhydride and reaction initiators DCP (di-cumyl peroxide), BPO (benzoyl peroxide) and/or BP (Benzophenone) are added together with MAH as an initiator. Thermal decomposition and molecular weight reduction were minimized by extruding at a lowered melting temperature by lowering the viscosity of

Reaction extrusion uses co-PP, MAH, and an initiator of polymer PP, first mixes PP and MAH so that the initiator BPO is well dispersed in PP, and then styrene is mixed to induce an initiation reaction at 40°C. For grafting efficiency, the most useful grafting rate was obtained when 2% MAH was added and the content of BNP initiator was 2%. In order to enhance the efficiency and mechanical properties of the grafted PP, if styrene is simultaneously added during maleic acid modification of PP, chain scission due to radical formation can be prevented, and MAH and styrene are alternately polymerized. Grafted to the PP chain, it was possible to manufacture PP with a large MAH graft amount, and mechanical properties were increased.

For grafting efficiency and micropores on the upper surface of the film, BPO, a thermal initiator, is melted during maleic acid modification of PP, heated to a temperature higher than the temperature at which BPO is thermally initiated, and reacted with styrene (St, Since it is dispersed in styrene), a reaction in which grafting occurs mainly on the film surface was used.

Therefore, this method has high heat resistance and high tensile strength compared to the conventional method, and has thermal bonding performance and resin adhesion on both sides of the injection molding material and the implanted adhesive resin, while maintaining the strength of the film. Therefore, it is applied to the manufacture of products requiring high rigidity.

A melt of modified mPP/Elastomer compound can be formed by this manufacturing method, and the modified PP, which is the melt, is reacted and extruded to melt in a T-die method, coated with a doctor blade, and solidified to a certain thickness to produce a heat-reactive resin film will do If the modified PP of the mPP/Elastomer compound is manufactured as a single layer, and a polyurethane adhesive resin with 100% solids is applied to the upper part of the mPP/Elastomer compound and the implantation process is performed, curing and aging conditions are improved under temperature conditions with little thermal change. It had excellent thermal durability, strong thermal adhesion, and mechanical durability properties. By thermally bonding this to the sealing material of the injection process, an eco-friendly process with process stability and a simple process was developed.

Hereinafter, the present invention will be described in more detail. The reactive thermo-extrusion article for flocking fabric base material of the present invention is in the form of a sheet or film, and is a polymer obtained by grafting maleic anhydride (MAH) to polypropylene by maleic acid reaction. It is formed, and the graft rate of MAH may be 1 to 10%, preferably 1.5 to 4.0%, more preferably 2 to 3.5%. By grafting MAH to polypropylene in this way, the viscosity of polypropylene is lowered, and by lowering the melting temperature and extruding, thermal decomposition and molecular weight reduction can be minimized.

Such, the reactive thermo-extrusion molded article of the present invention is a first step of preparing a mixed resin; and a second step of extruding the melt of the mixed resin on the release paper in a T-die method by performing a reactive thermal extrusion process on the mixed resin to form an extrudate in the form of a sheet or film; It can be prepared by performing

The mixed resin of step 1 includes a semi-crystalline polypropylene polymer, maleic anhydride, and a reaction initiator.

The semi-crystalline polypropylene polymer is a semi-crystalline co-PP copolymer obtained by copolymerizing 90 to 95% by weight of a polypropylene monomer and 5 to 10% by weight of a polyethylene monomer, preferably 93.5 to 95% by weight of a polypropylene monomer and 5% by weight of a polyethylene monomer A semi-crystalline co-PP copolymer copolymerized with ~ 6.5% by weight may be used. At this time, if the amount of polyethylene monomer used in the copolymer exceeds 10% by weight, the viscosity of the mixed resin in reactive extrusion is too high, so there may be a problem in that extrusion through the reactive thermal extrusion process is not good, and the graft rate of MAH is It is very high, but it is formed inside the polymer, so it is difficult to secure the surface hydrophilicity for commercialization, the thermal crystallinity is low, and there is a deformation in the molecular structure.

Next, the maleic anhydride of the mixed resin component is preferably used in an amount of 1.5 to 5.0 wt%, preferably 1.5 to 3.5 wt%, based on the total weight of the mixed resin, and when the maleic anhydride content is less than 1.5 wt%, MAH The graft rate is too low, less than 1%, so there may be a problem that the viscosity of the polymer synthesized by the maleic acid reaction is too high. Since there may be a lowering problem, it is recommended to use it within the above range.

Next, as the reaction initiator among the mixed resin components, a general reaction initiator used in the art may be used, and preferably at least one selected from di-cumyl peroxide (DCP), benzophenone (BP) and benzoyl peroxide (BPO). can be used, and more preferably BPO is used. And, the content of the reaction initiator may include 1.0 to 10.0% by weight, preferably 1.0 to 4.0% by weight, more preferably 1.2 to 2.5% by weight of the total weight% of the mixed resin. At this time, if the content of the reaction initiator is less than 1.0% by weight of the total weight of the mixed resin, there may be a problem that the MAH graft rate is low, and if the content of the reaction initiator exceeds 10.0% by weight, there may be a problem that the MAH graft rate is rather lowered. It is recommended to use within the above range.

Next, the mixed resin of step 1 may further include a graft increasing agent in order to increase the MAH graft rate and improve physical properties. The graft increasing agent may use styrene.

If St(styrene) is added at the same time, chain scission due to radical formation can be prevented, and MAH and St are alternately polymerized, grafting onto the polypropylene chain to increase the graft amount, and volatilization in the solvent-free reaction extrusion process while performing the complementary function of the solvent. In addition, the mechanical properties of the composite material are also increased due to the high molecular weight and high graft rate.

When using styrene as a graft increasing agent, the content of styrene is preferably 1 to 5 wt%, preferably 1 to 2.5 wt%, more preferably 1.2 to 2.0 wt%, based on the total weight of the mixed resin, and the amount of styrene used is If it is less than 1% by weight, the amount used is small, so the effect of increasing the MAH graft rate may be insufficient, and if it is used in excess of 5% by weight, there may be a problem that the melting temperature of the polymer synthesized through the maleic acid reaction increases. it's good

The process of manufacturing the mixed resin described above can be performed as follows.

Using a 12-axis rotating screw extruder, high-speed rotation mixing (10,000 ~ 15,000 rpm/min) applies a strong shearing stress to crystalline maleic anhydride (MHH) with a particle size of 5 to 25 mm to form large crystalline particles. It was powdered to 1 mm or less so that the MAH was more uniformly dispersed on the surface of the semi-crystalline polypropylene polymer (co-PP) in the form of pellets. As a preferred embodiment, co-PP and MAH are added to the extruder for each content above and mixed for 2 minutes at 10,000 to 15,000 rpm/min. After that, add DCP (di-cumyl peroxide ) and mix for 2 minutes. If the dispersion of MAH is not sufficient in co-PP, 1 to 5 parts by weight of styrene, a graft increaser, based on 100 parts by weight of co-PP Parts by weight may be mixed.

When manufacturing the mixed resin, co-PP can be used in powder form so that it stays in the process for a long time because styrene is vaporized at the same time as it is added as a volatile liquid. In addition, the use of the 12-axis rotating screw extruder of Germany's Extricom RE7XP M/C so that the reactive thermal extrudate is smooth and well-dispersed so that it can be mixed well even at low temperatures is conventionally based on a single screw or screw installed in the extruder. Due to the small number of twin shafts, the stirring/shearing force is weak. In order to react-extrude and melt the co-PP injected into the extruder, the L/D (length/diameter) ratio of the extruder has to be increased, and the L/D ratio of the extruder is high. For this reason, the residence time of co-PP in the extruder is prolonged, and as a result, it is thermally deformed due to severe thermal exposure and thus loses individual properties, and the limitation of the weak stirring shear force of the extruder can be improved.

Next, in step 2, the mixed resin prepared in step 1 is subjected to a reactive thermal extrusion process to extrude the melt of the mixed resin on the release paper in a T-die method to form an extrudate in the form of a sheet or film It is a process that makes

To perform the reaction extrusion process of co-PP/MAH/DCP/St mixed using the above high-speed rotary mixer, a screw rotation speed of 50 rpm using a modular meshing co-rotating twin-screw compressor (L/D is 30 to 42) , the extrusion temperature was 190/190/180/160/130.

Through the reactive thermal extrusion process, the polypropylene polymer grafted with MAH is formed through the maleation reaction of the mixed resin, and at the same time, a melt in which the polymer is melted is formed. The reactive thermal extrusion process may be performed using a general extruder, but preferably, the reactive thermal extrusion process is performed to cause maleic acid reaction at 40 to 50°C.

And, it is preferable to use a paper release paper without a pattern for the release paper of step 2, which is to prevent deformation of the release paper due to the heat of extrusion.

The flocking fabric of the present invention is a solidified polymer formed by reaction extrusion in a co-extruding method, and a hair transplantation process can be performed without prior surface modification of the upper surface of the application. The subsequent process is an eco-friendly process by curing and aging at an appropriate temperature of 40 to 50℃ to prevent thermal deformation of the completed thermally reactive flocking fabric. It is a high-density adhesive resin with no pores from which moisture and solvents have been removed, and has excellent adhesion with a difficult-to-adhesive sealing material. It does not contain harmful substances and manufacturing processes.

Polypropylene-based polymer (modified mPP/elastomer) grafted with maleic anhydride by reaction extrusion for commercialization is basically weak in mechanical durability and strength due to thermal deformation and tensile force problems. The hair transplantation process is performed on the upper surface with high-strength, solvent-free 100% solid urethane adhesive resin, and the heat-reactive hair-transplantation film for lamination, which is peeled off from the release paper, is formed by bonding with a strong high-solids hair-transplantation resin layer, so structurally it has strong cohesive force and is durable. The structure has excellent peel strength, tensile strength, heat resistance, elasticity, and hydrolysis resistance.

Compared to the existing low-solids resin for hair transplantation, the high solid content not only improves hair transplantation density, abrasion resistance, weather resistance, and mechanical properties, but also mPP/elastomer itself has weak physical properties such as thermal deformation and tensile strength problems, resulting in mechanical durability and strength It is weak, but solvent-free urethane binder exhibits appropriate melting temperature and viscosity at relatively low temperatures, and under processing conditions without thermal deformation, crosslinking and curing properties are easily secured. At the same time, the hair-transplantation resin and the adhesive resin layer are changed into a high-strength film with excellent mechanical properties, which is a uniform mPP/elastomer base layer (reactive thermo-extrusion molded article) on the release paper. It is applied to the surface of the sealing material in a high-density upright structure by electrically fixing the fiber pile cut to a certain length on it using a constant voltage, thereby providing complex functionality and durability.

The conventional flocking process uses a method of coating and applying a polymer resin blending solution containing an organic solvent and a water-soluble polymer blending solution with a binder on a substrate to implant a fiber pile, and curing and aging at a high temperature. However, volatilized organic solvents such as DMF and MEK are highly toxic and harmful to the human body. Water-based resin-based materials that are not organic solvents require thermal curing at high temperatures. A stronger temperature condition was required for application, so there were limitations such as thermal deformation and thermal crystallization. Therefore, in the present invention, a solvent-free urethane-type hair-transplanted resin having no thermal deformation and dense structural properties of the resin layer structure was used to exclude solvent and moisture in curing and aging the resin.

There is also a method of using reactive hot-melt urethane as a hair-transplantation resin as a manufacturing method for an eco-friendly resin that excludes water-soluble and organic solvents. It has "hot melt property", in which cohesive force is again expressed by Even with a structure with strong cohesive force, it was difficult to apply because the gelation time was short and the solidification rate was too fast, so that the crosslinking and curing were not sufficiently performed. In general, polymers can be classified into amorphous polymers in which the constituent molecular structures are irregularly and disorderly arranged, and crystalline polymers in a regular three-dimensional arrangement. A stereoregular polymer has a high degree of crystallinity, and the degree of crystallinity (crystallization rate) is closely related to a melting temperature and a solidification temperature in a polymer processing process.

The heat-reactive film resin layer used in the present invention is formed by performing a reactive thermal extrusion process of the mixed resin of the present invention described above to form an extrudate formed in a sheet or film form on a release paper, and high durability and low temperature process on the upper part By forming a binder layer as an adhesive layer for hair transplantation with a solvent-free urethane-type binder resin with characteristics, weak physical properties were reinforced and fairness was secured.

Solvent-free urethane binder resin of high solid content melts the target polymer at a certain temperature to secure proper flowability, then applies it to a substrate and solidifies curing and aging to have a stable resin layer of a certain shape. In addition, urethane with a high degree of crystallinity has a fast solidification rate, good work efficiency, and strong cohesive force, resulting in excellent product properties. Polyurethane is composed of two phases in the polymer, that is, a hard segment (HS) and a soft segment (SS), and HS, which serves as a crystalline structure by physical bonding, is dispersed in the SS domain. exists in the form The physical properties and solidification rate of polyurethane depend not only on the crystallinity of HS but also on the type of SS. The viscosity, basic physical properties, thermal properties and solidification rate also vary depending on the type of polyol used as SS. If the crystallinity is too high, the melting temperature There are problems in that it takes a long time to melt and the gelation time is short due to the high

Therefore, the heat-reactive resin layer for thermal bonding in the invention process of performing thermal lamination using the mPP/elastomer described above in the automotive sealing injection process is subject to high temperature thermal exposure conditions during the pre-manufacturing process fatally causing the hair transplantation adhesive resin. It can be melted at a relatively low temperature (below 60°C) and has a high-strength high solid content with appropriate crystallinity, rigidity and cohesive force adjusted in order to improve crosslinking hardening and solidification speed while maintaining an appropriate viscosity at a constant temperature. A solvent-free urethane-type binder resin is used as an adhesive resin (or binder layer).

The solid content of the existing flocking binder resin is 30 ~ 45% by weight, and after mixing with an additive auxiliary and a crosslinking agent, it has weak physical properties using water and a solvent as a medium. Since the present bar name requires mechanical durability, the solvent-free urethane-type binder resin containing 100 wt% solids as a binder layer material was applied as an adhesive.

EPDM, which has been partially modified with TPE components, has poor adhesion to polymer resins due to its surface having a non-adhesive property. Also, the TPE component bleeds out to the surface of the injection-processed product, which further deteriorates the adhesive effect. do. In addition, the current curing and aging process of the low-solids hair-transplanted adhesive resin is not preferable from the viewpoint of environmental pollution, etc. because exposure to high temperature and volatilization of harmful gases are easy to occur and the compound itself is toxic.

The base layer composed of the reactive hot-extrusion molded article (sheet or film) of the present invention and the binder layer formed of the solvent-free urethane binder resin have excellent adhesion due to cohesive force and an adhesion reaction of a dense structure.

In this process, the viscosity is maintained at an appropriate temperature, and the urethane raw material is stirred and mixed at high speed through the mixing head in a liquid ratio determined according to the use of the product by a precision pump, and then immediately discharged, and is constantly discharged in the T-die method of reaction extrusion as Modify PP as mPP. / By applying a 100% solvent-free binder on the upper surface of the heat-reactive resin layer of the elastomer compound to form a heat-reactive resin layer implanted in a hair transplantation process, a heat-reactive hair transplant film for laminating is manufactured. The film implanted on the upper surface of the modified PP of this mPP/Elastomer compound is thermally combined with the surface of the molding sealing material in the injection process.

In addition, 100% solvent-free binder uses a processing process of high-density implantation with 100% solids non-solvent binder, so there is no change in solid content even after curing. As an invention that overcomes the adhesiveness of TPE material with difficult adhesion, the lower layer of the modified PP of the injection sealing material and mPP/Elastomer compound is a durable combination of the laminating process, and the upper layer of the modified PP of the mPP/Elastomer compound uses a high solids solvent-free adhesive resin. Since one implantation process has already been carried out, the manufacturing of high-durability, eco-friendly implantation-type sealing is completed in a batch process.

The solvent-free urethane-type binder resin will be described in more detail in the flocking fabric manufacturing method of the present invention.

The fibers constituting the pile layer may include at least one selected from short polyester fibers or recycled polyester composite short fibers. In addition, the polyester may include polyethylene terephthalate (PET).

The material of the adhesive resin in the flocking process of the present invention described above is the composition and ratio of a soft segment such as polyol and a hard segment such as diisocyanate/chain extender And the molecular structure, molecular weight, hardness, rebound elasticity, heat resistance, mechanical properties, etc. are determined according to the arrangement state, particularly the form of the polyol. In consideration of the high mechanical requirements of automotive interior sealing materials, polyester-type polyols and polycarbonate polyols are used together as main raw materials to improve light resistance, heat resistance, hydrolysis resistance and cold resistance. The focus was synthesized and selected to secure water decomposition and heat resistance, and aliphatic isocyanate type was used as the crosslinking agent in consideration of light resistance, and the appropriate viscosity was composed of 4,000 ~ 5000cps/60℃ depending on the type.

The solvent-free urethane-type binder resin is a urethane prepolymer (component A) including a hydroxyl group at the terminal; isocyanate-based compound (component B); and a mixture (component C) comprising a crosslinking curing catalyst and a surfactant;

[Component A - Urethane Prepolymer Containing a Hydroxyl Group at the End]

A urethane prepolymer containing a hydroxyl group at the terminal (hereinafter referred to as a prepolymer) is prepared by reacting an aromatic or aliphatic isocyanate with a mixed polyol containing a polyol and a chain extender, and preferably has at least two hydroxyl groups at both ends, preferably Preferably, it is a high molecular compound containing 2 to 4, and is in a semi-solid or solid state at room temperature.

In addition, the prepolymer has an appropriate melt viscosity of 2,000 to 20,000 cps, preferably 2,000 to 10,000 cps at 60° C., and the polyol used for synthesis is a polyester-based polyol, a polyether-based polyol, a lactone-based polyol, and a polycarbonate. A heterogeneous polyol may be used alone or in a mixture of two or more in an appropriate ratio.

The prepolymer has excellent work stability due to a long gelation time, and when heated above a certain temperature, crosslinking and hardening reactions easily occur, and when cooled, solidification speed is fast, and rigidity and strong cohesive force can be expressed.

[Component B-isocyanate-based compound]

As the isocyanate compound acting as a crosslinking agent of the prepolymer, carbodiimide-modified MDI having an isocyanate functional group capable of reacting with a hydroxyl group in the molecular structure, biuret-type HDI, isocyanurate-type HDI, modified IPDI, or isocyanate group-terminated prepolymer alone Or two or more may be mixed and used.

The isocyanate-based compound may be used in an amount of 1.00 to 3.0 equivalents based on 1 equivalent of the prepolymer.

[C component-mixture]

As the crosslinking curing catalyst, an amine-based catalyst may be used, and a thermally activated catalyst and a blowing catalyst may be used in combination with an effective temperature for a heating/curing system.

Examples of the amine-based catalyst include triethylenediamine (trade name: Dabco 33LV), bis(dimethyl amino ether) (Bis(dimethyl amino ether, trade name: Dabco BL-11), N,N-dimethylcyclohexylamine (N,N- dimethyl cyclohexyl amine, Polycat-8), and tris (dimethyl amino propyl amine, Polycat-9).

The amount of the crosslinking curing catalyst used is 0.01 to 5 parts by weight based on 100 parts by weight of the prepolymer. When using less than 0.01 parts by weight, the crosslinking and curing reaction is too slow to form a film, and when using more than 5 parts by weight, the crosslinking and curing reaction is fast and gelation is instantaneous, so work productivity may be difficult.

It is also possible to use a surfactant as a component of the mixture. The surfactant serves to lower the surface tension of the binder layer formed of the solvent-free urethane-type binder resin, minimize the occurrence of pinholes, and make the pore size distribution uniform.

In general, the surfactant is a silicone-based surfactant (Surfactant; surfactant), but these have a limit in compatibility with the catalyst, it is suitable to use a non-silicone-based surfactant as the surfactant in the present invention.

The amount of the surfactant used is 0.5 to 3 parts by weight based on 100 parts by weight of the prepolymer, and when the amount of the surfactant exceeds 3 parts by weight, too many pores are formed in the binder layer, and the adhesiveness with the sealing molding material decreases due to the excessive pores. there may be

A method of manufacturing a flocking fabric using the solvent-free adhesive resin will be described as follows.

The prepolymer (component A) is heated and melted in a temperature range of 60° C. or less, and then maintained at an appropriate temperature (58 to 62° C., preferably about 60° C.) in a thermal insulation container. Then, the isocyanate-based compound (component B) and the mixture (component C) are maintained at 30° C. in each thermal tank to prepare them, respectively.

Next, after quantitatively inputting each component in a certain amount in a high-speed reaction molding machine, high-speed stirring at 4,000 to 5,000 rpm for 3 to 5 seconds to prepare a solvent-free urethane-type binder resin. When performing the curing reaction in a high-speed stirring molding machine, the temperature range of the hydroxyl-terminated urethane-free polymer or isocyanate-based compound component should be managed within a temperature range that does not interfere with circulation of the molding machine.

Next, the solvent-free urethane-type binder resin is applied on the substrate, which is the reactive thermo-extrusion molded article (sheet or film) of the present invention described above, to form a binder layer. In this case, the binder layer may be formed by a general coating method such as knife coating or comma coating.

Next, a hair transplantation process of vertically stacking fiber piles in a high density on the binder layer is performed. Then, by heating to a temperature of 60 ~ 90 ℃ crosslinking and primary curing of the adhesive resin of the hair transplantation layer to complete the sheet, then performing aging and secondary curing at 40 ~ 60 ℃ for 10 ~ 14 hours.

Next, the flocking fabric can be manufactured by removing the remaining hair of the hair transplantation process.

The flocking fabric of the present invention manufactured by the above method may be formed by implanting the fibers implanted in the binder layer in the pile layer at 50 to 120 g/m2, preferably at 60 to 100 g/m2. If the amount of fibers implanted is less than 50 g/m2, the functionality is lowered, and if it exceeds 100 g/m2, it is uneconomical and technically difficult, and there is no excess benefit in function.

The flocking fabric of the present invention described above is a vehicle headliner, weather strip, tailgate sealing, body sealing, door sealing, hood sealing ) or as a sunroof sealing.

Hereinafter, the present invention will be described in detail based on the following examples. However, it should not be construed as limiting the scope of the present invention by the following examples, and the following examples are provided to aid understanding of the present invention.

[Example]

Example 1: Preparation of a sheet-type reactive thermo-extrusion molded article

2.0 wt% of maleic anhydride (MAH), 2.1 wt% of BPO (benzoyl peroxide) as a reaction initiator, 2.0 wt% of styrene as a graft increaser, and the remaining balance of semi-crystalline co-PP (co-propylene) copolymer are mixed and mixed A resin was prepared. At this time, the semi-crystalline co-PP copolymer is a copolymer prepared by copolymerizing 95% by weight of polypropylene and 5% by weight of polyethylene.

Next, after introducing the mixed resin into a 12-screw extruder, using this, the MAH-grafted polypropylene polymer (PP-g) was mixed at 40° C. for 2 minutes for 2 minutes to perform a maleic acid reaction for a mixing process for thermal extrusion. -MA-St) is polymerized. At this time, in the mixing process of the reactive thermal extrusion, maleic acid reaction was performed under 40° C., and a 12-screw rotating screw extruder manufactured by Extricom RE7XP M/C Germany was used as the 12-screw extruder.

The application of the 12-screw extruder has a short mixing and heat treatment time within the screw, so there is little thermal deformation of the material, maintaining the intrinsic properties of the raw material as it is, a strong mixing force of the raw materials, and the kneading zone and mixing zone (MIXING ZONE) is widely and evenly distributed. And, by using the 12-screw extruder, the reaction compact was smooth and well dispersed due to the mechanical function structure, so it was mixed well at a relatively low temperature.

In order to carry out the reaction extrusion process of the mixed polymer, a 30 mm diameter and LD 32 modular meshing type co-rotating twin-screw compressor was used, the screw rotation speed was 50 rpm, the residence time was 180 to 200 s, and the barrel temperature of the extruder was 190 to 150 A sheet-type reactive thermo-extrusion molded article having a thickness of 150 μm was prepared by discharging and coating the synthetically extruded melt at ℃ on the upper surface of a release paper.

The step-by-step temperature of the barrel of the extruder is shown in Table 1 below.

Barrel temperature(℃) Cy1 (cycle1) Cy2 Cy3 Cy4 Cy5 Cy6 Cy7 Die 140 150 160 160 190 160 160 150

Since the screws installed in the existing extruder have few single or twin screws, the stirring/shearing force is weak, so in order to react and extrude and mix the polymer resin injected into the extruder, the extruder L/D (length/diameter) ratio has to be increased. Because the /D ratio is high, the residence time of the polymer in the extruder is prolonged, and thus the problem of losing each intrinsic property due to thermal deformation due to severe thermal exposure, and to improve the limit of weak extruder stirring shear force, the 12-axis An extruder was used.

Although DCP (di-cumyl peroxide) can be applied as an initiator, a benzoyl peroxide (BPO) reaction initiator was used because it was considered easy to analyze the results of the maleic acid reaction.

For reaction extrusion synthesis of PP-g-MAH-St, BPO, a thermal initiator, and MAH, a monomer, are dissolved in styrene, and in a state in which PPs are dispersed therein, the temperature is raised above the temperature at which BPO is thermally initiated to react with polypropylene. The active sites of free radicals move to the polymer chain, and grafting proceeds from there. At this time, in MAH, electron-rich groups exist on both sides of the double-bonded carbon, and the difference between the energy levels at which these electrons are filled and the reaction can occur is too large, so homopolymers between MAHs are simply not made. . That is, as MAH reacts with PP, it reacts in the form of a monomer, and MAH is not grafted into the form of a polymer. Therefore, after the reaction was completed, the polymer produced by polymerization of MAH in the system did not exist, and unreacted MAH was removed.

Examples 2 to 5 and Comparative Examples 1 to 2

A mixed resin was prepared in the same manner as in Example 1, and using this, a polypropylene polymer grafted with MAH (PP-g-MA-St) was synthesized and a sheet-type reactive thermo-extrusion molded article was prepared, as shown in Table 2 below. Examples 2 to 4 were carried out by preparing a mixed resin by varying the maleic anhydride (MAH) and BPO contents in the mixed resin, respectively, and preparing a reactive thermo-extrusion molded article.

And, Example 5 is a co-PP polymer prepared without using styrene, which is a graft enhancer in the mixed resin.

Comparative Example 1 is an unmodified co-PP polymer without using MAH in the mixed resin.

Experimental Example 1: Measurement of melt flow index and MAH graft rate of reactive thermo-extrusion molding resin (PP-g-MA-st)

When preparing the polymer (PP-g-MA-St) forming the reactive hot-extrusion molded article of Examples 1 to 4, the MAH graft ratio of PP-g-MAH-st prepared by varying the concentration of the reaction initiator BPO ( %) was measured, and the results are shown in Table 2 below.

At this time, the graft ratio was obtained from the weight increase ratio increased with respect to the weight of the co-PP copolymer before the MAH graft reaction. This is because a carboxyl group exists in the co-PP copolymer, whereas a functional group capable of direct neutralization titration does not exist in MAH. exist without

In addition, in order to examine the processability and molecular weight change of PP-g-MA-St, that is, the rheological properties, the melt flow index (MFI) was measured for each sample.

composition in mixed resin
Maleic anhydride (MAH), BPO,
Styrene (St) content (wt%) MAH of PP-g-MA-St
Graft rate (%) melt flow index
(MFI(g/10min) Comparative Example 1 - 0.0 2 Example 1 MAH 2.0/BPO 1.5/St1.0 2.1 11 Example 2 MAH 2.0/BPO 2.0/St1.0 2.7 12 Example 3 MAH 2.0/BPO 4.0/St1.0 2.9 16 Example 4 MAH 2.0/BPO 10.0/St1.0 3.1 21 Example 5 MAH 2.0/BPO 1.5 1.9 42

Looking at Table 2, it seems that the increase in MFI as the amount of BPO added during manufacture increases is due to a decrease in molecular weight due to the cleavage of the PP main chain due to the action of a radical initiator. It can be confirmed that St acts with a radical initiator to induce a decrease in the molecular weight of coPP. Therefore, the input of St prevents mechanical property loss due to the decrease in molecular weight of coPP due to grafting.

Looking at the graft rate measurement results in Table 2, the melt flow index also increased as the MAH content increased, and efficient extrusion processing was possible.

And, when the MAH content in the mixed resin was 2.0% by weight, the overall graft ratio was 2.1 to 3.1%.

And, comparing the graft rates of Examples 1 to 4, the graft rate increases as the BPO input content increases, but in Example 4, which exceeds 4 wt%, the graft rate significantly slows down and the problem is stagnant. there was.

A polypropylene-based polymer (PP-g-MA-St) sample having a graft ratio of 2.7% in Example 2 using 2 wt% of BPO and 3.1% in Example 4 using 10 wt% of BPO was obtained. The margin of error by the experiment was not large.

The grafting of MAH to the polypropylene-based polymer is to impart a hydrophilic group to the surface of the reactive thermal extrudate (sheet or film) of the present invention. However, if too much MAH is grafted, it is important to control the graft rate not to become too large because the melting characteristics of the polypropylene-based polymer itself are likely to change.

Under the experimental conditions, if the BPO content is greater than 2% by weight, the graft rate does not increase any more, and it is judged that the injury of the polypropylene-based polymer will be increased by an excess of the reaction initiator, and the BPO treatment concentration is reduced to about 2% by weight. It is considered appropriate to use

In addition, Examples 1 to 4 in which styrene and MA were used simultaneously showed a relatively high graft rate and improved mechanical properties compared to Examples 1-5 in which styrene was not used. This is considered to be due to the effect of increasing the graft amount and preventing chain scission due to radical formation as MAH and styrene in the polymer are alternately polymerized to PP.

Experimental Example 2: Surface hydrophilicity measurement and analysis of sheet-type semi-silver hot-extrusion molded articles made of reactive thermo-extrusion molding resin (PP-g-MA-St)

The hydrophilic layer on the surface of the sheet prepared in Comparative Example 1 and Examples 1 to 4 was measured, and the results are shown in Table 3 below. In this case, the control is a co-PP sheet (or film) purely prepared in Comparative Example 1.

In addition, the hydrophilicity was measured after dropping water droplets on the surface of the sheet, and the contact angle was measured, and the lower the contact angle, the higher the hydrophilicity.

composition MAH
Graft rate (%) male contact angle
(water contact angle, °) surface free energy
(dyne/cm) control 0.0 91.3 31,90 Example 1 2.1 74.0 34.20 Example 2 2.7 69.2 36.90 Example 3 2.9 68.80 39.80 Example 4 3.1 68.3 39.95

It was determined that the surface properties of the copolymer sheet prepared by introducing a hydrophilic group to the MAH-grafted PP would be different. In order to measure the contact angle to confirm this, the film was manufactured and the contact angle was measured. Measurements of the contact angles of the samples with water are shown in Table 3 above. Looking at the hydrophilicity measurement results, the control group, which is the water contact angle of the control group (MAH 0%), has an average of 92°, and the surface free energy is 31.90 dyne/cm, which is a difficult-to-adhesive shape that does not absorb moisture as shown in A of FIG. 1 below. However, in Examples 1 to 4 grafted with MAH, the water contact angle was 67° on average, and the surface free energy was 39.80 dyne/cm. can be checked

The change in surface hydrophilicity (contact angle) according to the results is shown in FIG. 2 as a graph. As the graft rate increased, the contact angle of the sheets with water decreased almost linearly from A to B in FIG. 1 , indicating a change in surface hydrophilization.

As the graft ratio increased, the contact angle of the film samples with water decreased almost linearly, and the degree of decrease was slightly slowed at a graft ratio of 3% or more. The contact angle of the control group was 91.3 ^o , and Example 4 having a graft rate of 3.1% had a contact angle of 68.3 ^o . While the control was hydrophobic, the PP modified by grafting MAH significantly reduced the contact angle with respect to distilled water, confirming that PP- g -MAH became hydrophilic. That is, it can be seen that the contact angle with respect to water is reduced by the grafted MAH. As described above, MAH is grafted onto the surface, but when it is manufactured into a sheet, the grafted samples exist not only on the surface of the sheet, but throughout the sheet. Therefore, it is judged that the hydrophilicity of the actual sheet surface is much greater than the measured hydrophilicity.

Experimental Example 3: Surface SEM photograph for confirming the surface hydrophilicity of a sheet-type reactive hot-extrusion molded article made of reactive thermo-extrusion molding resin (PP-g-MA-St)

The comparative example 1 (control group) and the upper surface of the sheet prepared in Example 1 were compared by SEM imaging, and this was shown in FIG. 3 (magnification × 500).

Although MAH is grafted onto the co-PP polymer, when it is made into a sheet, it is present throughout the sheet and not just on the surface of the sheet. Therefore, it was determined that the hydrophilicity of the actual surface was much greater than the hydrophilicity measured with the film sample as shown in FIG. 3 .

In the process of manufacturing PP- g -MAH, if styrene is used as a reaction medium, the PP powder does not dissolve in styrene, but as the grafting proceeds, the particles swell. Comparing the same surface SEM (a) and (b) photos, the degree of swelling of the PP- g -MAH powder expanded as the graft rate increased, and the number of pores created on the film surface increased. After reaction extrusion of PP- g -MAH, the sample was soxhlet-extracted with acetone for more than 24 hours, so it can be considered that all styrene that may remain in the sample was removed. Therefore, as the graft rate increases, PP- g -MAH swells in xylene, and it is determined that this state is maintained on the film surface. In particular, it can be confirmed that the sample with a graft rate of 3.1% has severe swelling and many micropores, so whether the final film surface is hydrophilic or hydrophobic can act as a more important factor. Therefore, it was confirmed that the larger the graft rate in PP- g - MAH , the larger the contact angle with water was increased by the hydrophobicity of the samples.

Preparation Examples 1 to 4: Preparation of flocking fabric (sealing molding material)

(1) Preparation of equipment

A sheet (thickness 150 μm), which is a reactive thermo-extrusion molded article prepared in Example 4, was prepared as a substrate.

(2) Preparation of solvent-free urethane-type binder resin

Using a solvent-free urethane-type binder resin while changing the type and content of the hydroxyl-terminated prepolymer, isocyanate compound, surfactant, and crosslinking curing catalyst under the compounding quantity and process conditions shown in Table 4 below, the binder layer is formed as follows. And a flocking process was performed to prepare a flocking fabric.

The prepared prepolymer was heated and melted in a temperature range of 60° C. or less, and then maintained at an appropriate temperature (about 60° C.) in an insulated container. In addition, each of the isocyanate-based compound, the surfactant, and the crosslinking curing catalyst were maintained at 30° C. in a heat-retaining tank to prepare them respectively.

After quantitatively inputting each component in a certain amount in a high-speed reaction molding machine (see Table 4 below), high-speed stirring was performed at 4,000 to 5,000 rpm for 3 to 5 seconds to prepare a solvent-free urethane-type binder resin.

Next, a binder layer is formed by applying the solvent-free urethane-type binder resin on the substrate, which is the reactive hot-extrusion molded article (sheet). In this case, the binder layer was formed by knife coating.

Next, a hair transplantation process was performed in which the fiber piles were stacked upright at high density on the binder layer. Then, by heating to a temperature of 60 ~ 90 ℃ cross-linking and primary curing of the hair-transplantation layer and the binder layer to complete the sheet, followed by aging and secondary curing at 60 ℃ for 12 hours to prepare each flocking fabric 1 to 4 were performed.

The prepolymer of Table 4 below means a prepolymer including a hydroxyl group at the terminal, RH-2020-1 is a urethane prepolymer having a melt viscosity of 20,000cps at 60°C, and RH-2020-2 is a melt viscosity of 15,000 at 60°C It is a urethane prepolymer with cps. And, C-1000 has a melt viscosity of 10,000 cps, and TKA-200 has a melt viscosity of 10,000 cps.

In addition, a non-silicone type surfactant was used, and an amine type was used as a crosslinking curing catalyst.

division prepolymer
(100 parts by weight) isocyanate type
Compound (parts by weight) Surfactants
(parts by weight) crosslinking curing catalyst
(parts by weight) Preparation Example 1 RH-2020-1 C-1000 (23) 0.5 0.3 Preparation Example 2 RH-2020-2 C-1000 (23) 0.5 0.3 Preparation 3 RH-2020-1 TKA-200(13) 0.5 0.4 Preparation 4 RH-2020-2 TKA-200(13) 0.5 0.4

The measured physical properties of the flocking fabrics of Preparation Examples 1 to 4 are shown in Table 5 below.

division Peel strength (N/30mm) Molding/
Heat resistance (180℃) light fastness wear resistance 1 day aging 2 days aging Preparation Example 1 25.8 ~ 30.1 30.1 to 34.5 ◎ 4th grade 3rd grade Preparation Example 2 25.6 ~ 29.5 29.4 to 32.4 ◎ 4th grade 3rd grade Preparation 3 26.9 ~ 28.9 30.1 to 32.9 ○ 4-5 grades 3rd grade Preparation 4 25.8 ~ 29.8 28.7 to 30.8 ○ 4-5 grades 3rd grade ◎ Very good, ○ Good, peel strength, light fastness and abrasion resistance are MS300-31 test results

As can be seen in Tables 4 and 5, the system that heats and cures and matures at an appropriate temperature has good reproducibility due to little change in physical properties, and its properties such as heat resistance, light resistance, and flame retardancy are suitable for automotive interior materials, efficient in productivity, good heat resistance, and good adhesion It was confirmed that this had a high effect.

Preparation Examples 5-1 to 5-5: Preparation of flocking fabric (sealing molding material)

(1) Preparation of equipment

A sheet (thickness 150 μm), which is a reactive thermo-extrusion molded article prepared in Example 4, was prepared as a substrate.

(2) Preparation of solvent-free urethane-type binder resin and flocking fabric

If the molecular design of the solvent-free urethane binder resin formulation satisfies the properties of interior materials for automobiles such as heat resistance and light resistance, and the viscosity during the process is appropriately adjusted, various types of coatings are possible at a certain temperature and it is effective in improving the working environment.

Therefore, in consideration of heat resistance, processability, mechanical properties, and durability, a solvent-free urethane resin was selected as an eco-friendly resin for hair transplantation. In consideration of not only mechanical properties but also processability, flexibility, heat resistance, and adhesion to the substrate, the content of urethane prepolymer and isocyanate compound as a crosslinking agent was fixed as shown in Table 5 below because it showed suitability as an adhesive resin material for hair transplantation. After each flocking fabric was prepared by applying from a high-speed reaction molder while changing the content of the crosslinking curing catalyst and performing a hair transplantation process as in Preparation Example 1, adhesive strength properties and gelation time were measured, and the results are shown in the table below. 6 is shown.

Category (parts by weight) Preparation 5-1 Preparation 5-2 Preparation 5-3 Preparation 5-4 Preparation 5-5 RH-2020-1 100 100 100 100 100 C-1000 13 13 13 13 13 crosslinking curing catalyst 0.3 0.35 0.45 0.5 0.55 Adhesive strength (kgf/cm) 2.6 2.7 2.9 3.2 3.0 Gelation time (min) 16 13 10 8 5

Referring to Table 6, the adhesive strength and heat resistance tended to increase as the amount of the crosslinking curing catalyst increased. Physical properties such as adhesion and heat resistance improve production stability as the catalyst content increases. Up to 0.5 parts by weight of the cross-linking curing catalyst, the production processability, miscellaneous power, and durability are improved, but beyond that, the gelation time is too short and product stability is lowered. As shown in the series of test results, considering the adhesive strength and production stability, it is judged that it is appropriate to use the crosslinking curing catalyst content in an amount of 0.50 parts by weight or less.

Preparation Examples 6-1 to 6-5: Preparation of flocking fabric (sealing molding material)

(1) Preparation of equipment

A sheet (thickness 150 μm), which is a reactive thermo-extrusion molded article prepared in Example 4, was prepared as a substrate.

(2) Preparation of solvent-free urethane-type binder resin and flocking fabric

100 parts by weight of hydroxyl-terminated urethane prepolymer (RH-2020-1) was heated and melted at 60 ° C., then maintained at 60 ° C. in a thermal insulation tank, and modified MDI, an isocyanate compound (trade name: Cosmonate LL, Kumho Mitsui Chemicals, NCO content 28.5 13 parts by weight) and 0.30 to 0.55 parts by weight of N,N-dimethylcyclohexylamine (trade name: Polycat-8, manufacturer: Air products) as a crosslinking curing catalyst and a non-silicone surfactant (trade name: Dabco LK-443) Each of 0.5 parts by weight was transferred to a high-speed stirring molding machine by a separate line while maintaining at 30°C.

Next, the composition transferred to the high-speed stirring molding machine was stirred at 5,000 rpm for 3 seconds at high speed to prepare a mixed resin, and then applied and knife coated on the upper surface of the sheet, which is the reactive thermo-extrusion molded article formed on release paper, A binder layer having a thickness of 400 μm was formed.

Next, a fiber material pile (fiber length 0.4 to 2.0 mm) of a polyethylene terephthalate (PET) homopolymer material is planted on the upper portion of the binder layer at about 70 to 75 g/m2, and heat-dried at a temperature of about 80° C. for 3 minutes. After primary crosslinking and curing, it was left at about 50° C. for 12 hours to mature and secondary curing to prepare flocking fabrics (see Table 7).

Category (parts by weight) production example
6-1 production example
6-2 production example
6-3 production example
6-4 production example
6-5 RH-2020-1
(Hydroxy-terminated urethane prepolymer) 100 100 100 100 100 Modified MDI
(isocyanate compound) 13 13 13 13 13 N,N-dimethylcyclohexyl amine
(Crosslinking Curing Catalyst) 0.3 0.35 0.45 0.5 0.55 Non-silicone surfactant 0.5 0.5 0.5 0.5 0.5

Experimental Example 4: Measurement of physical properties of flocking fabric 1

Tensile properties, heat resistance, hydrolysis resistance and peel strength of the flocking fabrics prepared in Preparation Examples 6-1 to 6-5 were measured, and the results are shown in Table 8 below.

At this time, the tensile properties were measured according to KS M 6782, modulus and tensile strength.

For heat resistance, after the sheet was left at 120° C. for 3 weeks, the tensile properties were measured by the same test method as above.

In addition, for hydrolysis resistance, the tensile properties were measured by the same test method as above after the sheet was left at 70° C. and 95% relative humidity for 3 weeks.

The peel strength was measured by heat-sealing a 25 mm wide hot melt cloth tape on both sides of the flocking fabric at 130° C. for 5 seconds, based on KS M 0533, and measuring the interlayer peel strength of the sheet.

In addition, an SEM image of the cross section of the flocking fabric of Preparation Example 6-2 is shown in FIG. 4 .

Product Category Preparation 6-1 Preparation 6-2 Preparation 6-3 Preparation 6-4 Preparation 6-5 ripening time (hr) 12 12 12 12 12 Tensile properties modulus
(kgf/cm) 10.5 10.9 12.1 12.8 11.9 The tensile strength
(kgf/cm) 31.6 30.90 33.1 32.5 32.9 heat resistance Elongation (%) 720 750 710 716 730 modulus
(kgf/cm) 10.3 10.0 12.4 11.6 11.1 The tensile strength
(kgf/cm) 33.1 30.5 32.7 33.8 31.6 Elongation (%) 720 728 733 718 729 I can sing
degradability modulus
(kgf/cm) 10.01 10.3 12.4 11.7 11.1 The tensile strength
(kgf/cm) 31.5 31.3 32.6 32.9 31.3 Elongation (%) 688 726 702 706 721 Peel strength (kgf/cm) 3.4 3.3 3.7 3.4 3.5

Looking at the results of the physical properties of the flocking fabrics in Tables 7 and 8, physical properties such as tensile strength, elongation and peel strength at break, hydrolysis resistance, heat resistance, etc. were stable.

In addition, although the aging time was set to 12 hours, the urethane binder was excellent in crosslinking and hardening properties and solidification speed was fast due to optimization of the conditions.

And, it showed a tendency of physical properties similar to Table 5, but in the case of Preparation Example 6-5, in which the amount of the crosslinking curing catalyst exceeded 0.5 parts by weight, compared to Preparation Example 6-4, rather poor heat resistance and hydrolysis resistance were obtained. seemed

Through the measurement of the physical properties in Table 8, it was confirmed that the flocking fabric of the present invention had excellent mechanical properties and excellent heat resistance and hydrolysis resistance.

Experimental Example 5: Measurement of physical properties of flocking fabric 2

The abrasion resistance, sliding resistance test and sliding resistance test of the flocking fabric of the flocking fabric prepared in Preparation Examples 6-1 to 6-5 were measured, and the results are shown in Table 9 below. And, the method of measuring the physical properties is as follows.

1) Measurement of wear resistance

The abrasion resistance was performed using the MS 2621 test method using the device as shown in FIG. 5A to determine whether or not the hair transplantation was lost under the same conditions of the actual vehicle chassis and the glass (see FIG. 5A ).

And, if the loss of hair transplantation was not visually confirmed, it was passed, and if it was confirmed, it was rejected.

2) Sliding resistance test

In the sliding resistance test, a specimen is prepared using a flocking fabric as a sealing molding material, and 100 mm of the specimen is attached to the contact resistance measurement tooth of the inoculation resistance meter, and a load of 29.4 N (3 kgf) is applied to the glass tube and reciprocating motion at 200 mm/min. It is a device that measures the sliding resistance applied to the glass plate when moving the glass plate with the friction value through This means that there is no strain on the vehicle's powertrain.

3) Semi-dry sliding resistance test

For the semi-dry sliding resistance test, a specimen (100 mm) is prepared using flocking fabric as a sealing molding material, the specimen is mounted on an abrasion tester, moisture is applied to the lower glass tube, and a load of 29.4 N (3 kgf) is applied to 200 mm The friction value through the reciprocating motion during 100 reciprocating motions at /min was measured in the same manner as in FIG. 5C.

It is a device that estimates the coefficient of friction that occurs during the reciprocating motion of a glass window in rain. The smaller the measured value, the less the friction force decreases, meaning that there is no strain on the vehicle's powertrain.

division wear resistance Sliding resistance (kgf) Semi-dry lubricity (kgf) Preparation 6-1 pass up to 0.10 Maximum friction 0.145, average friction 0.1313 Preparation 6-2 pass up to 0.09 Maximum friction 0.089, average friction 0.0755 Preparation 6-3 pass up to 0.10 Maximum friction 0.099, average friction 0.0855 Preparation 6-4 pass up to 0.09 Maximum friction 0.093, average friction 0.0942 Preparation 6-5 pass up to 0.10 Maximum friction 0.098, average friction 0.0895

Through the physical property measurement results in Table 9, it was confirmed that the flocking fabric of the present invention was excellent in abrasion resistance, sliding resistance and semi-dry sliding resistance.

Claims (10)

It contains a reactive thermal extrudate of a polypropylene-based polymer grafted with maleic anhydride,
The polypropylene-based polymer grafted with maleic anhydride,
A mixed resin comprising 1.5 to 5.0 wt% of maleic anhydride, 1.0 to 10.0 wt% of a reaction initiator, and a polypropylene-based polymer that is a semi-crystalline polymer of the remaining balance of the total weight is prepared by performing a maleation reaction did it,
The polypropylene-based polymer is a polypropylene in which an ethylene monomer is introduced into a polypropylene chain, and the polypropylene-based polymer is a semi-crystalline co-PP obtained by copolymerizing 90 to 95% by weight of a polypropylene monomer and 5 to 10% by weight of a polyethylene monomer. (co-propylene) copolymer; including,
The reactive hot-extrusion molded article is a reactive hot-extrusion molded article for flocking fabric substrate, characterized in that it is a sheet or film type that is completed by performing calendaring on a release paper after reaction extrusion, performing a hair transplantation process on the upper part, and peeling. According to claim 1, wherein the reaction initiator DCP (di-cumyl peroxide), BP (benzophenone), and BPO (benzoyl peroxide) Reactive thermo-extrusion molded article for a flocking fabric substrate, characterized in that it comprises at least one selected from the group consisting of. According to claim 1, wherein the mixed resin is a reactive thermo-extrusion molded article for flocking fabric substrate, characterized in that it further comprises 1 to 5 parts by weight of styrene as a graft enhancer based on 100 parts by weight of the semi-crystalline co-PP copolymer. According to claim 1, wherein the polypropylene-based polymer grafted with maleic anhydride,
A reactive thermo-extrusion molded article for flocking fabric base material, characterized in that the maleic anhydride graft rate (MAH graft rate) is 1.0 to 10.0%. delete delete A base layer comprising the reactive thermo-extrusion molded article of any one of claims 1 to 4;
a binder layer formed of a solvent-free urethane-type binder resin on the base layer; and
Flocking fabric comprising a; a pile layer comprising fibers implanted in the binder layer. The flocking fabric according to claim 7, wherein the fiber comprises at least one selected from polyethyleneterephthalate (PET)-based fibers and recycled PET-based composite short fibers. According to claim 7, wherein the flocking fabric is a vehicle headliner (head liner), a weather strip (weather strip), tailgate sealing (tailgate sealing), body sealing (body sealing), door sealing (door sealing), hood sealing ( Flocking fabric, characterized in that it is used for hood sealing) or sunroof sealing. (a) preparing a urethane prepolymer containing a hydroxyl group at the terminal having a melt viscosity of 2,000 to 20,000 cps at 60° C. or less;
(b) heating and melting the urethane prepolymer at 58 to 62°C;
(c) preparing a solvent-free urethane-type binder resin by adding a mixture containing a molten urethane prepolymer, an isocyanate-based compound, a crosslinking curing catalyst, and a surfactant into a high-speed reaction molding machine and mixing at high speed;
(d) discharging the solvent-free urethane-type binder resin on the upper surface of the reactive thermal extrusion molded article of any one of claims 1 to 4, and then performing knife coating or comma coating to form a binder layer;
(E) planting a fiber pile in the binder layer, crosslinking and primary curing under 60 ~ 90 ℃; and
(f) aging and secondary curing at 40 ~ 60 ℃; Method for producing flocking fabric, characterized in that performing a process comprising.

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