KR101357270B1 - Primer composition for difficulty adhesion shoe material without halogen - Google Patents

Abstract

The present invention relates to a primer composition for non-halogen-type non-adhesive shoe material, specifically 2 to 6% by weight of polyurethane acrylate resin, 1.0 to 2.5% by weight of thermoplastic polyurethane resin and 0.5 to 1.5% by weight of nanocomposite. 0.5 to 1.5% by weight of a tackifier is added to the main component, and 88.5 to 96% by weight of the solvent is prepared to prepare a primer composition for hard-adhesive shoe material, without using a hazardous aromatic solvent and a halogen-containing resin. The wettability and cohesive force of the primer composition is improved, and thus the adhesion of hard-adhesive shoe materials, such as biodegradable ethylene vinyl acetate foam, is improved. It is not only eco-friendly because it does not use A non-halogen type egg that can select the composition type and composition ratio from the molecular design considering the interaction between the adhesive shoe material and the adhesive, and improve the compatibility between the solvent and the biodegradable ethylene vinyl acetate foam parts except the aromatic hydrocarbon type. Primer composition for adhesive shoe material

Description

Primer composition for non-halogen type non-adhesive shoes material {PRIMER COMPOSITION FOR DIFFICULTY ADHESION SHOE MATERIAL WITHOUT HALOGEN}

The present invention relates to a primer composition for non-halogen-type hard-adhesive shoe materials, and more particularly, does not use harmful aromatic solvents and halogen-containing resins while having excellent adhesion to biodegradable ethylene vinyl acetate-based foams which are hard-adhesive shoe materials. It relates to a primer composition for environmentally friendly non-halogen type non-adhesive shoe material.

Currently, in the shoe industry, ethylene vinyl acetate foam materials are used for midsoles and insoles as shoe parts, and since the ethylene vinyl acetate foam materials are non-polar, they are difficult to bond, and thus, after surface treatment by primer treatment, UV is usually applied. Was investigated and applied in the order of primer and adhesive in order to bond the shoe parts, but there was a problem that the storage stability and adhesion strength is not reliable.

Therefore, in order to improve the adhesion of the hard-adhesive shoe material, such as the ethylene vinyl acetate foam material, a primer was prepared using a polar solvent, which impairs the health of workers and causes discomfort during work and is also good in terms of environmental protection. The research and development has been actively carried out to reduce the use of irritating solvents as possible and to improve adhesive properties such as primer adhesion.

Accordingly, the present applicant has filed a primer composition such as Korean Patent Application Publication No. 10-2010-0078473, which is Patent Document 1, wherein the primer composition is applied to a thermoplastic polyurethane resin, a polyolefin resin, an adhesion promoter, a silane coupling agent, By preparing a primer using a low toxicity solvent, while improving the adhesion to the hard-adhesive shoe material while reducing the damage to the hygiene from workers volatile organic solvents to maintain a comfortable working environment.

However, in recent years, various kinds of component materials used in various industries are considering efforts to manufacture shoe parts using biodegradable materials that are naturally decomposed in an ecosystem after product use in consideration of functionality and environmental friendliness.

Therefore, the biodegradable shoe foam is manufactured using about 30 to 40% of polylactic acid, which can be naturally decomposed, to the ethylene vinyl acetate foam that is not naturally decomposed.

However, the present applicant is a primer composition such as the Republic of Korea Patent Publication No. 10-2010-0078473, although it is possible to improve the adhesion to the non-adhesive shoe material, such as ethylene vinyl acetate foam material, biodegradability such as polylactic acid There has been a limit to improving the adhesion of the hard-adhesive shoe material containing the material.

The reason for this is that simply using an aromatic low toxicity solvent in a hard-adhesive shoe material containing biodegradable substances such as polylactic acid is not easy to dissolve the polymer, which is the main component of the primer, and the wettability of the biodegradable ethylene vinyl acetate foam is reduced. Not only that, there was a problem that the dimensional stability was lowered and the surface of the part was damaged, resulting in a drop in product value.

That is, in the related art, a primer composition which can improve adhesion of hard-adhesive shoe materials such as biodegradable ethylene vinyl acetate foam, but does not use harmful aromatic solvents and compounds and halogen-containing resins that can harm the health and environment of workers in the long term, The situation is absent, the development of this is constantly required.

: Republic of Korea Patent Publication No. 10-2010-0078473 "Adhesive reinforcing primer composition"

The present invention is to solve the above problems, by providing a primer composition consisting of a polyurethane acrylate resin, a thermoplastic polyurethane resin, a nanocomposite, a tackifier and three or more solvents, a hazardous aromatic solvent and a halogen-containing resin It is an object of the present invention to provide a primer composition for a non-halogen type non-adhesive shoe material that improves the wettability and cohesive force without improving the adhesion of the non-adhesive shoe material such as biodegradable ethylene vinyl acetate foam.

In addition, in using the solvent in the primer composition, it does not use harmful aromatic solvents such as phenol, benzene, toluene, and xylene, which is not only environmentally friendly, but also the interaction between adhesive materials such as biodegradable ethylene vinyl acetate foam and adhesives. To provide a primer composition for the non-halogen type, non-adhesive shoe material that improves the compatibility of the solvent and the biodegradable ethylene vinyl acetate foam parts except the aromatic hydrocarbon type from the molecular design in consideration of It is a task.

The present invention is a primer composition for hard-adhesive shoe material, 2 to 6% by weight of polyurethane acrylate resin, 1.0 to 2.5% by weight of thermoplastic polyurethane resin, 0.5 to 1.5% by weight of nanocomposite, 0.5 to 1.5% by weight of tackifier And the primer composition for non-halogen type hard-adhesive shoe material which consists of 88.5 to 96 weight% of solvents as a solution to a subject.

In this case, the polyurethane acrylate resin is a polyurethane prepolymer containing a hydroxyl group at the end by using 50 mole% of diisocyanate to 35 to 45 mol% of polycaprolactone having a hydroxyl group at the end, and hydroxy as a chain extender It is preferable to use the polyurethane acrylate compound synthesize | combined using 5-15 mol% of ethyl methacrylate.

In addition, the nanocomposite, PEGMA / (Na-MMT) -co-MMA / MA nanocomposite, poly (ethylene glycol) methyl ether methacrylate (PEGMA, Poly (ethylene glycol) methyl ether methacrylate) to sodium montmorillonite ( The compound is inserted between the layers of Na-MMT and Na-montmorillonite, and then copolymerized with methyl methacrylate (MMA) and methyl acrylate (MA) monomers.

In addition, the solvent is preferably used in combination of three or more of the group consisting of normal hexane, ethyl acetate, methyl ethyl ketone, acetone, isopropyl alcohol, ethanol, methanol, cyclohexane, and methyl cyclohexane.

The present invention provides a primer composition consisting of a polyurethane acrylate resin, a thermoplastic polyurethane resin, a nanocomposite, a tackifier, and three or more solvents, thereby avoiding the use of hazardous aromatic solvents and halogen-containing resins, thereby being environmentally friendly and biodegradable ethylene. In addition to improving the adhesive strength of the material, such as vinyl acetate foam, there is an advantage that can be widely applied to a variety of industries, such as the shoe industry, furniture industry, the field in which the material is used.

The present invention for achieving the above effect relates to a primer composition for non-halogen type non-adhesive shoe material, only the parts necessary for understanding the technical configuration of the present invention is described, the description of other parts scatter the gist of the present invention. Note that it will be omitted so as not to fall short.

Hereinafter, the primer composition for a non-halogen type hard-adhesive shoe material according to the present invention will be described in detail.

The present invention is a primer composition for non-adhesive shoe material,

2 to 6% by weight of polyurethane acrylate resin, 1.0 to 2.5% by weight of thermoplastic polyurethane resin, 0.5 to 1.5% by weight of nanocomposite, 0.5 to 1.5% by weight of tackifier and 88.5 to 96% by weight of solvent. .

Polyurethane acrylate resin used in the present invention serves to improve the surface wettability and cohesion of the adherend, it is preferable to use 2 to 6% by weight. If the content of the polyurethane acrylate resin is less than 2% by weight, chemical performance such as adhesion to the substrate, wettability, etc. may be degraded, thereby reducing the adhesion. There is a concern that the viscosity of the resin solution increases and the workability and solubility in the solvent decrease.

On the other hand, the polyurethane acrylate resin is a polyurethane prepolymer containing a hydroxyl group at the end by using 50 mol% of diisocyanate in 35 ~ 45 mol% of polycaprolactone having a hydroxyl group at the end, and a hydro-extension agent The polyurethane acrylate compound synthesize | combined using 5-15 mol% of oxyethyl methacrylate is used.

At this time, when the amount of the polycaprolactone is less than 35 mol%, there is a risk that the physical properties of the polyurethane acrylate is too hard (hard), the initial fixability is lowered, if it exceeds 45 mol%, cohesive force is lowered primer There is a risk of reducing the adhesive strength of the.

In addition, when the usage-amount of diisocyanate exceeds 50 mol%, there exists a possibility that a polyurethane may not fully synthesize | combine.

On the other hand, when the amount of the chain extender is less than 5 mol%, the soft segment content increases to increase the flexibility, but the mechanical properties may be weak, and when the content exceeds 15 mol%, the hard segment There is a fear that the content of is increased and becomes hard.

The thermoplastic polyurethane resin used in the present invention is excellent in adhesive strength, aging resistance, cohesion and high strength, and is easy to handle and easy to mix with other resins, which is within the range of 1.0 to 2.5% by weight. It is preferable to use. If the content of the thermoplastic polyurethane resin is less than 1.0% by weight, the cohesive force may be reduced to reduce the adhesive strength. If the content of the thermoplastic polyurethane resin is more than 2.5% by weight, the viscosity of the primer may be increased to improve workability. This may cause poor adhesion, and the amount of primer used increases, resulting in lower economic efficiency.

The nanocomposite used in the present invention is used to improve the cohesion and wettability of the primer, and the amount thereof is preferably used in the range of 0.5 to 1.5% by weight. When the content of the nanocomposite is less than 0.5% by weight, the addition effect is reduced, so that the cohesive strength of the primer is lowered. When the content of the nanocomposite is more than 1.5% by weight, the storage stability of the primer may be reduced by the nano-inorganic material contained in the nanocomposite.

On the other hand, the nanocomposite is a poly (ethylene glycol) methyl ether methacrylate (PEGMA, Poly (ethylene glycol) methyl ether methacrylate) is inserted into sodium montmorillonite (Na-MMT, Na-montmorillonite) and then methyl methacrylate ( PEGMA / (Na-MMT) -co-MMA / MA nanocomposites synthesized by copolymerization with MMA, Methyl Methacrylate) and Methyl Acrylate (MA) monomers are used.

The amount of the tackifier used in the present invention is preferably 0.5 to 1.5% by weight. When the content of the tackifier is less than 0.5% by weight, the initial adhesive strength may decrease, and the content of the tackifier is 1.5% by weight. When it exceeds%, there are many low molecular weights in the primer composition, so that the cohesive force of the primer decreases, and in particular, the adhesive force is high, so that the physical properties of the primer may be deteriorated.

The tackifier is preferably used by selecting one or more of petroleum resin, modified petroleum resin, alkylphenol resin, thermoplastic terpene modified phenol resin, rosin and rosin ester resin, and coumarone indene resin.

The content of the solvent used in the present invention is preferably 88.5 to 96% by weight, it is preferable to adjust the viscosity so that the solid content of the primer composition is 6 to 10% by weight. In particular, since toluene is not used, solubility of the primer is remarkably decreased, so three or more solvents must be used.

Solvents usable in the present invention are preferably used in combination of three or more from the group consisting of normal hexane, ethyl acetate, methyl ethyl ketone, acetone, isopropyl alcohol, ethanol, methanol, cyclohexane, and methyl cyclohexane.

On the other hand, the primer composition for the non-adhesive shoe material of the present invention as described above should be used by mixing isocyanate-based curing agent at the time of use.

It is preferable to use 5-10 weight part of isocyanate with respect to 100 weight part of said primer compositions as a conventional hardening | curing agent which can be used by this invention.

When the mixing amount of the curing agent is less than 5 parts by weight, the primer composition for the thermoplastic polyurethane-based elastomer may not be cured properly due to the lack of the isocyanate mixing amount, and when the mixing amount of the curing agent exceeds 10 parts by weight, the curing rate is increased. As the working time gets shorter as soon as possible, there is a risk of defective rate.

Isocyanate usable in the present invention can be used as a conventional solvent type curing agent having an NCO content of 6 to 20% range.

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

1. Preparation of polyurethane acrylate resin

Methylene bis (p-cyclohexyl isocyanate) (H ₁₂ MDI) with respect to 40 mol% of methyl ethyl ketone and polycaprolactone (Aldrich, Mw = 2000) in a 500 ml reactor equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen injection device. 50 mol% was added, followed by stirring at 70 ° C. for 3 hours at a stirring speed of 100 rpm to prepare a polyurethane prepolymer. Next, 10 mol% of hydroxyethyl methacrylate was added thereto, followed by stirring at 40 ° C. for 3 hours at a stirring speed of 80 rpm to evaporate the solvent to prepare a polyurethane acrylate resin.

2. Preparation of Nanocomposites

70% by weight of vacuum-dried sodium montmorillonite (Na-MMT) (Southern Clay), poly (ethylene glycol) methyl ether methacrylate in a 250 ml reactor equipped with a reflux cooler containing a mixed solvent, a stirrer, a thermometer, and a nitrogen injector. PEGMA) 30% by weight was added and stirred at room temperature with a stirrer for 24 hours, and centrifuged and washed repeatedly with a mixed solvent, which was dried at 25 ° C. for 48 hours in a vacuum dryer to prepare an intercalated PEGMA / Na-MMT. ,

Ethyl acetate as a solvent was added to a 1 L four-necked reactor equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen injector. 5 wt% of PEGMA or PEGMA / Na-MMT was added thereto, followed by dispersion for 3 hours at room temperature. To 100% by weight of the mixed acrylate monomer, 1.5% by weight of the mecartop was added as a chain extender and 0.5% by weight of azobisisobutyronitrile as the initiator, followed by radical polymerization at 70 ° C. for 15 hours to give PEGMA / (Na-MMT) -co -MMA / MA was prepared.

3. Preparation of primer composition for non-adhesive shoe material

(Example 1)

Tackifier (SU-120) in 2% by weight of polyurethane acrylate resin, 2.5% by weight of thermoplastic polyurethane resin (pearstic 45-50 / 18, MERQINSA) and 1% by weight of nanocomposite in a mixing vessel with temperature and speed control 1% by weight of Kolon Emulsifier), 50% by weight of methyl ethyl ketone, 24.5% by weight of normal hexane, and 19% by weight of cyclohexane were added and stirred at a temperature of 50 ° C. for 8 hours to dissolve the total solids. This 6.5 wt% primer composition was prepared.

(Example 2)

Tackifier (SU-120) in 5% by weight of polyurethane acrylate resin, 2% by weight of thermoplastic polyurethane resin (pearstic 45-50 / 18, MERQINSA), and 1.5% by weight of nanocomposite in a mixing vessel with temperature and speed control , Kolon Emulsifier) 0.5% by weight of methyl ethyl ketone, 27% by weight of normal hexane and 15% by weight of cyclohexane were added as a solvent, and the total solid content of the mixed solution was dissolved by stirring at a temperature of 50 ° C for 8 hours. A primer composition of 8% by weight was prepared.

(Example 3)

Tackifier (SU-120) in 3% by weight of polyurethane acrylate resin, 2.5% by weight of thermoplastic polyurethane resin (pearstic 45-50 / 18, MERQINSA) and 1.5% by weight of nanocomposite in a mixing vessel with temperature and speed control , Kolon Emulsifier) 0.5% by weight of methyl ethyl ketone, 27% by weight of normal hexane and 15.5% by weight of cyclohexane were added as a solvent, and the total solid content of the mixed solution was dissolved by stirring at a temperature of 50 ° C for 8 hours. A 7.5 wt% primer composition was prepared.

(Example 4)

3% by weight of polyurethane acrylate resin, 1% by weight of thermoplastic polyurethane resin (pearstic 45-50 / 18, MERQINSA), 1.5% by weight of nanocomposite in mixed container with temperature control and speed control (SU-120 , Kolon Emulsification) 1.5% by weight of methyl ethyl ketone, 26% by weight of normal hexane and 17% by weight of cyclohexane were added as a solvent, and the total solid content of the mixed solution was dissolved by stirring at a temperature of 50 ° C for 8 hours. A 7 wt% primer composition was prepared.

(Comparative Example 1)

Tackifier (SU-120) in 2% by weight of chlorinated polyolefin resin, 2.5% by weight of thermoplastic polyurethane resin (pearstic 45-50 / 18, MERQINSA), 1% by weight of nanocomposite material , Kolon Emulsifier) 1% by weight of methyl ethyl ketone, 24.5% by weight of normal hexane and 19% by weight of cyclohexane were added as a solvent, and the total solid content of the mixed solution was dissolved by stirring at a temperature of 50 ° C for 8 hours. A 6.5 wt% primer composition was prepared.

(Comparative Example 2)

Tackifier (SU-120, Kolon Emulsifier) in 5% by weight of thermoplastically modified chlorinated polyolefin resin and 1% by weight of thermoplastic polyurethane resin (pearstic 45-50 / 18, MERQINSA) in a mixing vessel capable of temperature control and speed control 1 After adding the wt%, 50% by weight of methyl ethyl ketone, 27% by weight of normal hexane, and 16% by weight of cyclohexane were added as a solvent, and the mixture was stirred for 8 hours at a temperature of 50 ° C. The total solid content of the mixed solution was 7% by weight. The composition was prepared.

(Comparative Example 3)

PR-708, a primer product produced by Hwaseung T & C, was used.

4. Evaluation of primer composition for non-adhesive shoe material

5 parts by weight of isocyanate, which is a curing agent, was mixed with respect to 100 parts by weight of the primer composition for the non-adhesive shoe material prepared according to the above Examples and Comparative Examples, and then applied to a biodegradable ethylene vinyl acetate foam part, thereby adhering the adhesive strength with the rubber to the following method. The results are summarized in [Table 1] below.

Adhesion between Biodegradable Ethylene Vinyl Acetate Foam and Rubber Specimens

After washing with methyl ethyl ketone on a functional ethylene vinyl acetate foam part having a size of 25 × 100 mm and drying, 5 parts by weight of a curing agent (Dynamic Chemical DRF) was mixed and applied to 100 parts by weight of the prepared primer, and applied at 60 ° C. for 5 minutes. Dried.

In addition, the rubber sheet was also prepared in the size of 25 × 100mm, washed and dried, and then coated with a rubber primer (Hwaseung T & C PR-700) and dried at 60 ℃ for 5 minutes.

Next, after applying the adhesive to each of the above two adherends, and then dried for 5 minutes at 60 ℃ and bonded by pressing with a load of 10kg. At this time, five test specimens used in the same test was used.

B, initial adhesion evaluation

The prepared adhesive specimen was left at room temperature for 30 minutes, and then peeled at a tensile speed of 100 mm / min using a universal tensile tester to measure adhesive strength.

C, state adhesion evaluation

The prepared adhesive specimen was left at room temperature for 24 hours, and then peeled at a tensile speed of 100 mm / min using a universal tensile tester (UTM) to measure adhesive strength.

characteristic Example Comparative Example One 2 3 4 One 2 3 Initial Adhesion (kg _f / cm) 2.9 2.8 2.9 2.5 3.1 1.8 2.6 Adhesive state (kg _f / cm) 3.8 3.6 3.4 3.4 3.6 2.2 2.9 Dimensional stability Good Good Good Good Good Good Bad

As shown in Table 1, Examples 1 to 4 according to the present invention were excellent in both the initial adhesive force and the state adhesive force, compared to Comparative Examples 1 to 3 without using a hazardous aromatic solvent and a halogen-containing resin, in particular It was evaluated that the state adhesion was excellent.

In addition, compared with Comparative Example 3, the dimensional stability was significantly improved, the adhesion was also excellent.

As described above, the primer composition for non-halogen-type hard-adhesive shoe material according to the present invention has been described through the above-described preferred embodiments, and the superiority thereof has been confirmed, but those skilled in the art will appreciate the present invention described in the following claims. It will be understood that various modifications and changes can be made in the present invention without departing from the spirit and scope of the invention.

Claims (4)

In the primer composition for hard-adhesive shoe material,
2 to 6 wt% of polyurethane acrylate resin, 1.0 to 2.5 wt% of thermoplastic polyurethane resin, 0.5 to 1.5 wt% of nanocomposite, 0.5 to 1.5 wt% of tackifier and 88.5 to 96 wt% of solvent,
The nanocomposite is a PEGMA / (Na-MMT) -co-MMA / MA nanocomposite, wherein poly (ethylene glycol) methyl ether methacrylate (PEGMA) is converted into sodium montmorillonite (Na-). After intercalation between MMT and Na-montmorillonite (MMT), copolymerization with methyl methacrylate (MMA) and methyl acrylate (MA) monomer,
The solvent is non-halogen type hard adhesive, characterized in that used in combination of three or more from the group consisting of normal hexane, ethyl acetate, methyl ethyl ketone, acetone, isopropyl alcohol, ethanol, methanol, cyclohexane, methyl cyclohexane Primer composition for footwear material.
The method of claim 1,
The polyurethane acrylate resin,
To prepare a polyurethane prepolymer containing a hydroxyl group at the terminal using 35 to 45 mol% of polycaprolactone having a hydroxyl group at the end and 50 mol% of diisocyanate, and 5 to 15 mol of hydroxyethyl methacrylate as a chain extender. A primer composition for a non-halogen type hard-adhesive shoe material, characterized in that a polyurethane acrylate compound synthesized using% is used.
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