KR20240025113A - Compositions of environment friendly waterborne polyurethane adhesives for vehicle interior fabric material - Google Patents

Abstract

The present invention relates to an eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials. More specifically, it is environmentally friendly as it does not use harmful substances, and has adequate tackiness after application and drying of the adhesive, so it has initial adhesion and the tackiness disappears afterwards. It relates to an eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials that can sufficiently demonstrate adhesive strength.

Description

Eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials {COMPOSITIONS OF ENVIRONMENT FRIENDLY WATERBORNE POLYURETHANE ADHESIVES FOR VEHICLE INTERIOR FABRIC MATERIAL}

The present invention is eco-friendly as it does not use harmful substances, and has initial adhesion by retaining appropriate tack after adhesive application and drying. Afterwards, the tack disappears to fully demonstrate adhesive strength for automotive interior textile materials. It relates to an eco-friendly water-based polyurethane adhesive composition.

Recently, domestic and foreign textile companies are breaking away from simply producing only textiles and turning their attention to various fields, emphasizing high added value and differentiation. In particular, textiles are used in a variety of ways in the automobile sector, and are gaining new attention for companies seeking sales channels.

Among the fiber materials used in automobile interiors, the most used is the seat part, followed by floor carpet and ceiling skin. Except for some functional parts such as air bags and seat belts, the areas where these textile materials are used are mostly concentrated in the design area, and there is a trend of expanding to areas that were not previously used.

The fiber material seat for automobile interior is the part that the driver's body touches the longest from the moment of entering the vehicle to the time of exiting the vehicle. Since 70% of the vehicle's movement is transmitted through the seat, it affects the riding comfort and safety of the driver and passengers. It is an important factor. Textile materials for automobile interiors generally have the appearance of natural leather by applying a release paper with a separate pattern imprinted on fabric materials and coating the skin layer. Fabric and skin It is manufactured by bonding the middle layer.

Meanwhile, despite the development of various eco-friendly processes as full-fledged environmental regulation policies were implemented in the early 2000s, most domestic textile material manufacturers still use solvents containing DMF (dimethylformamide) during the manufacturing process of synthetic leather, as shown in Patent Document 1. Type adhesive is applied.

This is because DMF is easily soluble in polar and non-polar substances and has several operational advantages, but the most important point is that the adhesives for textile materials released domestically lack tackiness after drying, resulting in poor initial adhesion to the fabric. This is because if the drying time is shortened to control tackiness, the undried adhesive penetrates between the fabrics, damaging the appearance and not developing sufficient adhesive strength. Therefore, even to this day, most water-based adhesives for manufacturing automobile interior materials are imported from Japan and other countries.

In other words, the development of eco-friendly adhesives for automotive interior textile materials is aimed at satisfying the growing demand for eco-friendly products due to heightened awareness of hazardous substances, practical regulations by major overseas companies, and improvement in foreign dependence on core technologies such as water-based adhesives. Development is desperately needed.

Patent Document 1: Republic of Korea Patent Publication No. 10-2022-0036635 “Method for manufacturing synthetic leather made of mesh fabric using hot melt adhesive”

The present invention is intended to improve the above-mentioned problems, and is environmentally friendly as it does not use harmful substances. It has initial adhesion by maintaining appropriate tackiness after adhesive application and drying, and then the tackiness disappears to fully demonstrate adhesive power. The task is to provide an eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials.

The present invention relates to a polyurethane adhesive composition, based on 100 parts by weight of polyol, 40 to 50 parts by weight of isocyanate, 3 to 10 parts by weight of chain extender, and 15 to 20 parts by weight of adhesion reinforcing resin. A means of solving the problem is an eco-friendly water-based polyurethane adhesive composition for automobile interior fiber materials, characterized in that it contains 1 to 7 parts by weight of a tackifier, 0.5 to 5 parts by weight of a curing agent, and 0.5 to 1.5 parts by weight of an adhesion enhancer. Do it as

The present invention is environmentally friendly as it does not use harmful substances, and has an initial adhesion by maintaining appropriate tackiness after adhesive application and drying, and then the tackiness disappears, allowing for sufficient adhesion.

The present invention to achieve the above effects relates to an eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials. Only the parts necessary to understand the technical structure of the present invention are described, and the description of other parts will distract from the gist of the present invention. Please note that it will be omitted to avoid confusion.

Hereinafter, the eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials according to the present invention will be described in detail as follows.

The present invention is based on 100 parts by weight of polyol, 40 to 50 parts by weight of isocyanate, 3 to 10 parts by weight of chain extender, 15 to 20 parts by weight of adhesion reinforcing resin, and tackifier (Tackifier). ) 1 to 7 parts by weight, 0.5 to 5 parts by weight of hardener, and 0.5 to 1.5 parts by weight of adhesion enhancer.

The polyol is a base material for synthesizing polyurethane and is used alone or in combination among polyester polyol or polyether polyol. In other words, adhesion can be secured by applying polyester polyol, and when polyether polyol is mixed, the balance of adhesion and adhesion is maintained.

The isocyanate is a base material for synthesizing polyurethane with polyol, and includes TDI (Toluene Diisocyanate), HDI (Hexamethylene diisocyanate), MDI (Methylene Diphenyl Diisocyanate), IPDI (Isophorone Diisocyanate), H ₁₂ MDI (dicyclohexylmethane diisocyanate), and TMXDI. (Tetramethylxylene Diisocyanate), NDI (naphthalene-1,5-diisocyanate),

The chain extender is added to ensure a certain level of adhesion immediately after adhesive application and drying when attaching to fabric materials and skin layers. It makes the molecular chain more flexible through controlling the polyurethane modulus (PU modulus) to ensure initial fixation. To secure 1,4-butanediol, 1,6-hexane diol, ethylene glycol, diethylene glycol, and ethylene diamine ( It can be used alone or in combination with ethylene diamine, hydrazine, or piperazine.

The adhesion reinforcing resin, when added to a water-based adhesive, improves the initial and state adhesion to the water-based adhesive. Use a water-based polyurethane-based adhesive manufactured according to the ‘Manufacturing method of polyurethane-based adhesive’.

More specifically, the adhesion reinforcing resin is prepared by reacting a polyol, a diol containing a hydrophilic group, and a reactive resin with isocyanate in the presence of a catalyst to produce a polyurethane prepolymer having isocyanate groups at both ends of the molecule (S100). After cooling the prepolymer to 60 to 70°C and neutralizing it to enable water dispersion by adding a neutralizer, an organic solvent was added so that the solid content was 40 to 70% by weight to adjust the viscosity so that the NCO/OH ratio was 0.1 to 1.0. A step of preparing a self-emulsifying prepolymer (S200), adding a chain extender to the self-emulsifying prepolymer to extend the chain to terminate the reaction of the polyurethane-based adhesive, and then adding water to disperse it in water (S300) ) and removing the organic solvent of the water-dispersed polyurethane-based adhesive (S400), and the catalyst is a tin-based (trimethyltin laurate, dibutyltin dilaurate, etc.) catalyst, a lead-based catalyst (octyl acid lead, etc.), salts of organic and inorganic acids, organometallic derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, and the polyol Polyols with a number average molecular weight of 400 to 4000 are used, and diols containing the hydrophilic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N-bishydroxyethylglycine, and N,N. -Bishydroxyethylalanine or 3,4-dihydroxybutanesulfonic acid can be used alone or in combination, and the reactive resin is hydroxy-based, amine-based, alkylphenol-based, terpene-phenol-based, phenol-based, rosin ester-based or It is used alone or in combination among ketone-based resins, and is bound in the range of 1 to 30% by weight in the water-based polyurethane-based adhesive molecule. The isocyanate is isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (1, 6-HDI), 4,4'-methylenebiscyclohexane diisocyanate (4-4'-H ₁₂ MDI), 1,3-xylene diisocyanate (1,3-XDI) or 1,3-tetramethylxyl It is used alone or in combination among lene diisocyanate (1,3-TMXDI), and the neutralizing agent is triethylamine, triethanolamine, dimethylcyclohexylamine, ethyldiisopropylamine, dimethylaminoethanol, and N-methylmorpholine. Or used in combination, the organic solvent is an organic solvent having 3 to 8 carbon atoms and a boiling point of 50 to 160°C at normal pressure, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and N,N-dimethylformamide. or N,N-dimethylacetamide, used alone or in combination, and the chain extender is a diamine-based chain extender such as ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1 ,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, Xylylenediamine, piperazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine hydrazine or diol-based chain extender such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexane Diol, polyethylene glycol, and water can be used alone or in combination.

The tackifier is added to temporarily bond two materials by providing initial fixation by providing tackiness, and includes terpene phenol, rosin ester, petroleum resin, and alkylphenol resin. , Rosin or Coumaroneindene resin can be used alone or in combination.

The curing agent and adhesion enhancer are added to sufficiently develop tackiness in the initial stage of adhesive application and drying, and then completely cure to enable strong adhesion of different materials. The curing agent is 4,4-dicyclohexylmethane di. Isocyanate (4,4-dicyclohexylmethane diisocyanate), naphthalene diisocyanate (naphthalene diisocyanate) or tolidine diisocyanate (tolidine diisocyanate) can be used alone or in combination, and the adhesion enhancer is ethylene oxide propylene oxide copolymer. ), poly(meth)acrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose, Vinyltriethoxysilane, Vinyltrimethoxysilane ) or Vinyltri(2-methoxyethoxy)silane, used alone or in combination.

Here, if the content of each material is outside the above range, there is a risk that it may not be properly synthesized into polyurethane.

Hereinafter, the present invention will be described in more detail based on the examples below, but the present invention is not limited by the examples.

1. Preparation of adhesive

(Example 1)

A prepolymer was prepared by reacting 100 parts by weight of polyol (polyester polyol and polyether polyol 1:1 mixture) and 40 parts by weight of isocyanate (TDI) in a 2L four-necked flask equipped with a stirrer, mantle, cooling pipe, and thermometer. After neutralizing by mixing 0.1 parts by weight of a neutralizing agent (TEA (triethanolamine)), distilled water was added to the neutralized prepolymer to disperse it, 3 parts by weight of chain extender (1,4-butanediol), and 15 parts by weight of adhesion reinforcing resin were added to the neutralized prepolymer. It was prepared by mixing 1 part by weight of tackifier (terpene phenol), 0.5 part by weight of curing agent (naphthalene diisocyanate), and 0.5 part by weight of adhesion enhancer (hydroxyethylcellulose).

Here, the adhesion reinforcing resin used was a water-based polyurethane adhesive in which 1% by weight of a reactive resin was bonded to the water-based polyurethane adhesive molecule. The specific manufacturing method was to measure the molecular weight in a 2L four-necked flask equipped with a stirrer, mantle, cooling pipe, and thermometer. After adding this 400 polyether polyol, 2,2-dimethylolpropionic acid, a diol containing a hydrophilic group, and a ketone resin as a reactive resin, the mixture was stirred uniformly under a dibutyltin dilaurate catalyst, a tin-based catalyst, and 1,6- A polyurethane prepolymer was prepared by adding hexamethylene diisocyanate dropwise and reacting at about 80 to 90°C until the NCO peak disappeared (step S100). After cooling the prepolymer to 60-70°C, triethanolamine (TEA), a neutralizing agent, is added dropwise to neutralize the prepolymer, and methyl ethyl ketone, an organic solvent, is added to control the viscosity to 100 poise or less during the reaction, thereby forming a magnetic product with an NCO/OH ratio of 0.5. An emulsified prepolymer was prepared (step S200). In addition, ethylenediamine, a chain extender, was added to the self-emulsifying prepolymer to extend the chain to terminate the reaction of the polyurethane adhesive. After cooling to 30-40°C, water was added and stirred and dispersed in water (step S300). In addition, methyl ethyl ketone in the polyurethane solution was removed by reduced pressure distillation to prepare a water-based polyurethane-based adhesive with a solid content of 50% by weight and a reactive resin bound to the water-based polyurethane-based adhesive molecule in the range of 1% by weight (step S400).

(Example 2)

A prepolymer was prepared by reacting 100 parts by weight of polyol (polyester polyol and polyether polyol 1:1 mixture) and 50 parts by weight of isocyanate (TDI) in a 2L four-necked flask equipped with a stirrer, mantle, cooling pipe, and thermometer. After neutralizing by mixing 0.1 parts by weight of a neutralizing agent (TEA (triethanolamine)), distilled water was added to the neutralized prepolymer to disperse it, and then 10 parts by weight of chain extender (1,4-butanediol) and 20 parts by weight of adhesion reinforcing resin were added to the neutralized prepolymer. It was prepared by mixing 7 parts by weight of a tackifier (rosin ester), 5 parts by weight of a curing agent (naphthalene diisocyanate), and 1.5 parts by weight of an adhesion enhancer (vinyltrimethoxysilane).

Here, the adhesion reinforcing resin used was a water-based polyurethane-based adhesive in which 30% by weight of a reactive resin was bonded to the water-based polyurethane adhesive molecule. The specific manufacturing method was to measure the molecular weight in a 2L four-necked flask equipped with a stirrer, mantle, cooling pipe, and thermometer. After adding the 4000 polyether polyol, 2,2-dimethylolpropionic acid, a diol containing a hydrophilic group, and rosin ester resin, a reactive resin, the mixture was stirred uniformly under a dibutyltin dilaurate catalyst, a tin-based catalyst, and 1,6- A polyurethane prepolymer was prepared by adding hexamethylene diisocyanate dropwise and reacting at about 80 to 90 degrees C until the NCO peak disappeared (step S100). Then, the prepolymer was cooled to 60 to 70°C and then neutralized by dropwise adding triethanolamine (TEA), a neutralizing agent. During the reaction, methyl ethyl ketone, an organic solvent, was added to control the viscosity to 100 poise or less, so that the NCO/OH ratio was 1.0. An emulsified prepolymer was prepared (step S200). In addition, ethylenediamine, a chain extender, was added to the self-emulsifying prepolymer to extend the chain to terminate the reaction of the polyurethane adhesive. After cooling to 30-40°C, water was added and stirred and dispersed in water (step S300). In addition, methyl ethyl ketone in the polyurethane solution was removed by reduced pressure distillation to prepare a water-based polyurethane-based adhesive with a solid content of 50% by weight and a reactive resin bound in the range of 30% by weight within the water-based polyurethane-based adhesive molecule (step S400).

(Comparative Example 1)

It was prepared in the same manner as in Example 1, but no adhesion reinforcing resin was added.

(Comparative Example 2)

It was prepared in the same manner as in Example 2, but no adhesion reinforcing resin was added.

2. Evaluation of adhesives

go. Specimen preparation

Each surface of the synthetic leather for automotive interior textile material manufactured using the adhesive according to Examples 1 and 2 and Comparative Examples 1 and 2 was applied with a commercial adhesive, adhered to each other, and then moved forward and backward twice using a rubber roller. A specimen was prepared by pressing.

me. Initial adhesion evaluation

The manufactured adhesive specimen was measured at a speed of 200 mm/min using a universal tensile tester (UTM, Zwick model 1435), and the results are shown in [Table 1] below.

all. State adhesion evaluation

The manufactured adhesive specimen was measured at a speed of 200 mm/min using a universal tensile tester (UTM, Zwick model 1435), and the results are shown in [Table 1] below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 initial adhesion
(kgf/cm) 1.5 1.6 1.1 1.1 state adhesion
(kgf/cm) 3.0 3.2 2.7 2.4

As shown in [Table 1], the Examples according to the present invention have initial adhesion by retaining appropriate tackiness after adhesive application and drying compared to the Comparative Examples, and it can be seen that the tackiness disappears thereafter, allowing sufficient adhesion. You can.

As described above, the eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials according to the present invention has been explained through the above preferred embodiments and its excellence has been confirmed, but those skilled in the art will recognize the present invention as described in the patent claims below. It will be understood that the present invention can be modified and changed in various ways without departing from the spirit and scope of the present invention.

Claims (8)

In the polyurethane adhesive composition,
For 100 parts by weight of polyol, 40 to 50 parts by weight of isocyanate, 3 to 10 parts by weight of chain extender, 15 to 20 parts by weight of adhesion reinforcing resin, 1 to 1 part of tackifier. An eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials, comprising 7 parts by weight, 0.5 to 5 parts by weight of a hardener, and 0.5 to 1.5 parts by weight of an adhesion enhancer.
According to clause 1,
The polyol is,
An eco-friendly water-based polyurethane adhesive composition for automobile interior textile materials, characterized in that it is used alone or in combination with polyester polyol or polyether polyol.
According to clause 1,
The isocyanate is,
TDI (Toluene Diisocyanate), HDI (Hexamethylene diisocyanate), MDI (Methylene Diphenyl Diisocyanate), IPDI (Isophorone Diisocyanate), H ₁₂ MDI (dicyclohexylmethane diisocyanate), TMXDI (Tetramethylxylene Diisocyanate), NDI (naphthalene-1,5-diisocyanate), An eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials, characterized in that it is used alone or in combination with XDI (m-xylene diisocyanate), CHDI (1,4-cyclohexyl diisocyanate), or DDI (Diphenylmethane diisocyanate).
According to clause 1,
The chain extender is,
1,4-butanediol, 1,6-hexane diol, ethylene glycol, diethylene glycol, ethylene diamine, An eco-friendly water-based polyurethane adhesive composition for automotive interior textile materials, characterized in that it is used alone or in combination with hydrazine or piperazine.
According to clause 1,
The adhesion reinforcing resin is,
An eco-friendly water-based polyurethane adhesive composition for automobile interior textile materials, characterized in that it is a water-based polyurethane-based adhesive in which 1 to 30% by weight of a reactive resin is bonded to the water-based polyurethane adhesive molecule.
According to clause 1,
The tackifier is,
Automotive interior, characterized in that it is used alone or in combination with terpene phenol, rosin ester, petroleum resin, alkylphenol resin, rosin, or coumaroneindene resin. Eco-friendly water-based polyurethane adhesive composition for textile materials.
According to clause 1,
The hardener is,
Automotive interior fiber, characterized in that it is used alone or in combination with 4,4-dicyclohexylmethane diisocyanate, naphthalene diisocyanate, or tolidine diisocyanate. Eco-friendly water-based polyurethane adhesive composition.
According to clause 1,
The adhesion enhancer is,
Ethylene oxide propylene oxide copolymer, poly(meth)acrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose, vinyl triethoxy For automobile interior textile materials, characterized in that they are used singly or in combination among silane (Vinyltriethoxysilane), Vinyltrimethoxysilane, or Vinyltri(2-methoxyethoxy)silane. Eco-friendly water-based polyurethane adhesive composition.