KR102172041B1 - Removable adhesive and reparing method of adhesive material - Google Patents

Abstract

The present invention relates to: a re-releasing type adhesive comprising an acrylic monomer consisting of 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethylhexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid, 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator, a solvent consisting 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene, and 2 to 3 parts by weight of rosin ester; and a method for manufacturing an adhesive material using the same. According to the present invention, it is possible to improve substrate adhesive strength and adhesion, and overcome step characteristics of embossed fabrics.

Description

Removable adhesive and manufacturing method of adhesive material {REMOVABLE ADHESIVE AND REPARING METHOD OF ADHESIVE MATERIAL}

The present invention relates to a re-peelable pressure-sensitive adhesive and a method of manufacturing a pressure-sensitive adhesive material, and more particularly, a re-peelable pressure-sensitive adhesive with improved weather resistance and re-peelability and improved adhesion between a substrate and an adhesive layer, and a pressure-sensitive adhesive material using the same. It relates to a manufacturing method.

Existing OPP tapes or paper tapes are widely used for masking, general packaging, and construction. However, although these tapes are inexpensive, cutting requires additional equipment such as scissors or cutters, and additional work is required accordingly. This leads to an increase in labor costs and process defects due to unclean cut surfaces.

Accordingly, fabric tapes have been developed that make the cut surface clean when cutting the fabric itself by hand without using additional equipment. Such a fabric tape is a generally widely used type of adhesive material that can be torn by hand, and is currently used for various purposes, such as packing or packing work using paper boxes, and curing tape or maintenance tape during construction of buildings. In general, woven tapes are manufactured by laminating a polyethylene film on one side of a plain weave base material and then applying an adhesive layer composed of an adhesive on the opposite side to which lamination has not been performed.

In the case of a fabric tape, the adhesion and cohesiveness of the adhesive to the fabric are not sufficient, and thus improvement is required. When manufacturing a fabric tape, the fabric may be easily peeled off during the adhesive coating process and torn, or irregularities or residues may occur on the cut surface when cutting the adhesive coated fabric. In addition, when using an existing tape-applied adhesive, the molecular weight is low, the adhesive composition is too hard, there is a problem that the adhesion to the substrate is lowered, or the cohesive force is lowered. In particular, in the case of the embossed fabric, there may be a problem in maintaining the adhesion of the substrate and the adhesive force of the adhesive according to the difference in step. In addition, in the case of the curing agent applied to the existing pressure-sensitive adhesive, it cannot provide sufficient adhesion to the substrate, which is a factor causing process defects.

The present invention is to solve the problems of the prior art described above, one object of the present invention is to provide a pressure-sensitive adhesive capable of improving adhesion to a substrate, weather resistance, and re-peelability.

Another object of the present invention is to provide a pressure-sensitive adhesive capable of improving adhesion to a substrate and maintaining adhesion for a long time by overcoming the step characteristics of an embossed easy-cut fabric.

Another object of the present invention is to provide a fabric tape capable of preventing irregularities or residues from occurring on the cut surface when cutting the fabric in the adhesive coating process during the fabrication of the fabric tape.

One aspect of the present invention for achieving the above object,

An acrylic copolymer consisting of 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator; And a solvent consisting of 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene; And it relates to a re-peelable pressure-sensitive adhesive comprising 2 to 3 parts by weight of rosin ester.

Another aspect of the present invention for achieving the above object,

An acrylic monomer consisting of 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator; And 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene are added to the reactor, and the polymerization reaction proceeds for 8 hours while raising the temperature to 80° C.;

After completion of the reaction, aging under natural falling at an ambient temperature of 60° C. for 8 hours, and adding 2 to 3 parts by weight of a rosin ester tackifying resin;

It relates to a method for producing a pressure-sensitive adhesive material comprising the step of mixing 1 to 2 parts by weight of a chelating-based curing agent and 0.2 to 0.6 parts by weight of an isocyanate-based curing agent in the finished pressure-sensitive adhesive and coating the fabric on an easy-cut fabric.

Another aspect of the present invention for achieving the above object,

It relates to a textile tape comprising a laminating film formed on one or both sides of a substrate and an adhesive layer formed on the opposite surface of the laminating film, wherein the adhesive layer is made of the adhesive of the present invention.

The pressure-sensitive adhesive of the present invention is excellent in adhesion and adhesion to the substrate, but is excellent in re-peelability to the extent that there is no transfer of the pressure-sensitive adhesive even if the tape is attached and removed for 6 months when the pressure-sensitive adhesive is applied to the substrate.

According to the present invention, a chelate-based curing agent is used as a crosslinking agent to induce the formation of a coating film, and an isocyanate-based curing agent is used to provide excellent adhesion to the substrate and to maintain the adhesion for a long time.

In addition, another effect of the present invention is to improve the weather resistance of the adhesive composition by improving the cohesive resistance, which is a disadvantage of the existing adhesive.

According to the present invention, in the case of the embossed fabric, it is possible to provide excellent adhesion and adhesion maintenance performance by preventing reduction of the adhesion of the substrate and the adhesion maintenance of the adhesive according to the difference in step.

Hereinafter, embodiments of the present invention will be described in more detail. In addition, in describing the present invention, detailed descriptions of related known general functions or configurations will be omitted.

One aspect of the present invention is an acrylic monomer consisting of 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid ; 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator; And a solvent consisting of 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene; And it relates to a pressure-sensitive adhesive containing 2 to 3 parts by weight of rosin ester.

The pressure-sensitive adhesive of the present invention is composed of a component capable of controlling the crosslinking reaction of the pressure-sensitive adhesive in order to overcome the step characteristics of the easy-cut tape. In the present invention, the chelating curing agent is involved in the initial coating film formation, and the isocyanate curing agent secondly controls the cohesive force.

The pressure-sensitive adhesive of the present invention is an acrylic copolymer comprising 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator; And an acrylic copolymer prepared by copolymerizing a solvent consisting of 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene as a main component, further enhancing the adhesion to the substrate or the strength of the surface adhesion. In order to further improve it, it includes a rosin ester tackifying resin.

The acrylic copolymer can be prepared by polymerizing the monomer component. As the polymerization method, known polymerization methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method may be mentioned. In order to obtain an adhesive having good water resistance, a solution polymerization method or a bulk polymerization method It is preferable to employ a polymerization method. For example, it may be prepared by a solution polymerization method, and may be prepared by performing a polymerization temperature of about 50 to 140°C.

The acrylic copolymer may use a thermal initiator during polymerization, for example, an initiator such as a peroxide such as benzoyl peroxide or acetyl peroxide may be used, and one or two or more of the above may be used in combination.

The pressure-sensitive adhesive of the present invention is a rosin-based tackifying resin, polymerized rosin-based tackifying resin, polymerized rosin ester-based tackifying resin, rosin phenolic tackifying resin, stabilized rosin ester-based tackifying resin, disproportionated rosin ester Tackifier resin, hydrogenated rosin ester tackifier resin, terpene tackifier resin, terpenephenol tackifier resin, petroleum resin tackifier resin, (meth)acrylate resin tackifier resin, etc. have.

In the present invention, the crosslinking agent is preferably used in combination with an isocyanate crosslinking agent and a chelate crosslinking agent, and the use of an isocyanate crosslinking agent in combination is preferable because the adhesion between the adhesive layer and the substrate can be further improved.

As the isocyanate-based crosslinking agent, for example, toluene diisocyanate, naphthalene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, trimethylolpropane-modified toluene diisocyanate, etc. can be used, It is more preferred to use toluene diisocyanate.

The chelating agent used in the present invention may be a chelating agent of a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium or vanadium, preferably an aluminum chelating agent.

In addition, the pressure-sensitive adhesive of the present invention is other additives such as tackifying resin, acrylic low molecular weight material, epoxy resin, curing agent, ultraviolet stabilizer, antioxidant, colorant, reinforcing agent, filler, plasticizer, surfactant, foaming agent, vesicle and organic salt as needed. It may further include.

The pressure-sensitive adhesive of the present invention can perform a uniform coating operation only when the functional group cross-linking reaction of the cross-linking agent hardly occurs in the blending process performed to form the pressure-sensitive adhesive layer. When such a coating operation is completed and drying and aging process is performed, a crosslinked structure is formed, so that an adhesive layer having elasticity and cohesion can be obtained. At this time, the adhesive properties such as durability and cutability of the adhesive product are improved by the strong cohesive force of the adhesive.

In another aspect of the present invention, there is provided an adhesive material having a laminated structure of an adhesive layer formed by thermosetting the adhesive composition on one or both surfaces of a substrate. The thickness of the substrate may be about 4 μm to about 500 μm, and the thickness of the adhesive layer may be about 10 μm to about 100 μm.

Another aspect of the present invention relates to a method of manufacturing the pressure-sensitive adhesive material by coating the pressure-sensitive adhesive composition described above on a substrate. In the present invention, an acrylic monomer consisting of 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of benzyl peroxide thermal initiator; And a solvent consisting of 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene are added to the reactor, and the polymerization reaction is performed for 8 hours while raising the temperature to 80°C. Subsequently, after completion of the reaction, the aging is carried out at an external temperature of 60° C. for 8 hours, and 2 to 3 parts by weight of a rosin ester tackifying resin is added. Subsequently, 1 to 2 parts by weight of a chelating-based curing agent and 0.2 to 0.6 parts by weight of an isocyanate-based curing agent are mixed with the finished adhesive and coated on an easy-cut fabric, thereby preparing a pressure-sensitive adhesive material.
In the present invention, the substrate is an easy-cut fabric composed of synthetic fibers selected from the group consisting of polyester, polyacrylic, polyamide, polyimide, polyethylene and polypropene.

In more detail, first, an acrylic monomer, a thermal initiator, and a solvent are polymerized, and then a rosin ester-based tackifying resin is mixed to mix the adhesive composition, and then the adhesive layer may be coated. The method of forming the adhesive layer on the substrate as described above is not particularly limited, and for example, a method of applying and drying an adhesive using a bar coater, etc., directly on the surface of the fabric substrate, or applying the adhesive to the surface of the releasable substrate and drying After that, a method of transferring and aging the adhesive layer formed on the surface of the peelable substrate to the surface of the substrate may be applied.

The pressure-sensitive adhesive of the present invention lowers the molecular weight before coating after the addition of the curing agent, and then sufficiently wets the embossed surface during coating. Therefore, the step gap is first overcome. The too soft adhesive causes the orange peel of the adhesive during winding, so the chelating curing agent applied first proceeds to form the coating. Secondly, in the case of a chelating hardener, it receives sufficient vertical force, but it is a hardener that is weak in adhesion to the substrate or agglomeration. Accordingly, metastasis and transcription can occur. In order to solve this problem, in the present invention, a three-dimensional crosslinking is performed secondarily using an isocyanate curing agent.

The chelate curing agent and the isocyanate curing agent are preferably included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer, and if the content is less than 0.01 parts by weight, there is a problem that the effect of improving the adhesion of the substrate and the cohesive strength is lowered. When it exceeds parts by weight, there is a problem in that durability reliability is weakened due to a decrease in cohesive strength.

Another aspect of the present invention includes a laminating film formed on one or both sides of a substrate and an adhesive layer formed on the opposite surface of the laminating film, wherein the adhesive layer is 20 to 30 parts by weight of the aforementioned butyl acrylate, 2- An acrylic monomer consisting of 4 to 5 parts by weight of ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator; And a solvent consisting of 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene; And it relates to a fabric tape, characterized in that the re-peelable adhesive comprising 2 to 3 parts by weight of rosin ester.

In the fabric tape according to the present invention, the fabric base material is produced by weaving the weft and warp, and any kind of yarn used for the weft and warp may be used. As the fabric base material, a knitted fabric using warp and weft is mainly used. This knitted fabric is a weft knitting structure in which each warp is in an independent form to form a regular and uniform loop structure, and a weft yarn is inserted between the loops to weave, and the warp is between long fiber filaments, and the weft is formed of long fiber processed yarn (DTY). It is a substrate for fabric tape. The base material of the fabric tape may be a plain weave fabric or may be made of a weft inserting method as proposed by the present applicant in Korean Patent No. 1158529.

The laminating film used in the present invention may be a transparent film or a film of various colors depending on the use of the fabric tape. The laminating film of the fabric tape of the present invention may use a polyethylene resin as a base resin. In addition, in order to improve the lamination strength and tear strength of the polyethylene resin, it is preferably a low density polyethylene resin (LDPE). However, if necessary, in addition to low-density polyethylene, a second polyethylene resin selected from the group consisting of resins such as linear LDPE, very low density polyethylene, high density polyethylene (HDPE), and polypropylene. Can be added.

Of fabric tape The adhesive layer is composed of the adhesive of the present invention uniformly applied to the surface of the fabric substrate. The method of forming the adhesive layer is not particularly limited, and for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip Methods, such as an extrusion coating method using coating, a die coater, etc., are mentioned.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not construed as being limited by the examples. Both parts and percentages in each example are based on weight. Unless otherwise specified below, the conditions for standing at room temperature are all 23°C and 65% RH.

Example

Example 1

(Manufacture of acrylic copolymer)

25 parts by weight of butyl acrylate, 4 parts by weight of 2-ethyl hexyl acrylate, 1 part by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid in a 1 L reactor equipped with a cooling device so that nitrogen gas is refluxed and temperature control is easy. After the acrylic monomer mixture consisting of parts by weight was added, 40 parts by weight of ethyl acetate, 4 parts by weight of acetone, and 2 parts by weight of toluene were added as a solvent. Subsequently, nitrogen gas was purged for 1 hour to remove oxygen, and then maintained at 80°C. After making the mixture uniform, 0.1 parts by weight of benzyl peroxide was added as a thermal initiator and reacted for 8 hours to prepare an acrylic copolymer. Then, 2 parts by weight of rosin ester was added.

(Blending process)

1 part by weight of an aluminum chelate curing agent and 0.3 parts by weight of a toluene diisocyanate curing agent were added to 100 parts by weight of the acrylic copolymer prepared above, diluted to an appropriate concentration in consideration of coatability, and uniformly mixed, and then coated on the substrate and dried. Then, a uniform adhesive layer having a thickness of 25 μm was prepared.

(Adhesive material manufacturing process)

After the prepared adhesive layer was adhesively processed on a polyester plain weave fabric, it was stored for 4 days at a temperature of 23° C. and a relative humidity of 65% for a sufficient aging process. The adhesive material obtained as described above was cut to an appropriate size and used for performance evaluation.

Comparative Example 1

The adhesive material was prepared in the same manner as in Example 1, except that only aluminum chelate, which is a chelate-based curing agent, was used in the manufacture of the adhesive material, and then the performance of the adhesive material was evaluated in the same manner and shown in Table 1 below. Done.

Comparative Example 2

Except that only toluene diisocyanate, which is an isocyanate-based curing agent, was used in the manufacture of the adhesive material, an adhesive material was prepared in the same manner as in Example 1, and then the performance of the adhesive material was evaluated in the same manner and shown in Table 1 below. Indicated.

Comparative Example 3

When preparing an acrylic copolymer, an acrylic monomer mixture consisting of 20 parts by weight of butyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of methyl acrylate, 1 part by weight of 2-hydroxyethyl acrylate, and 3 parts by weight of acrylic acid After injecting, the adhesive material was prepared in the same manner as in Example 1, except that 40 parts by weight of ethyl acetate, 4 parts by weight of acetone, and 2 parts by weight of toluene were added as solvents. Was evaluated in the same manner and shown in Table 1 below.

Test example

1) Durability : After the samples were left for 1,000 hours under conditions of 60°C and 90% relative humidity, it was observed whether bubbles or peeling occurred, and weather resistance was measured according to the following evaluation criteria.

Evaluation standard

○ No air bubbles or peeling phenomenon

× There is air bubble or peeling phenomenon

2) Adhesive force : The adhesive material was adhered to the polyester substrate, and the adhesive force 30 minutes later was measured according to JIS Z0237. The unit is N/25mm. In addition, in order to measure the weather resistance, the adhesion was measured after leaving for 10 hours at 80°C, 60°C, and 12 hours at 90% relative humidity conditions, respectively. At this time, the adhesive strength was measured using a tensile tester at a speed of 300 mm/min and a 180° angle.

durability adhesiveness Initial adhesion Room temperature 10hrs 80℃, 10 hrs 60℃, 90% R.H, 12 hrs Example 1 Great 8N/25mm
(No transcription) 8N/25mm
(No transcription) 9N/25mm
(No transcription) 10N/25mm
(No transcription) Comparative Example 1 Bad 9N/25mm
(No transcription) 12N/25mm
(Transcription) Fabric break Fabric break Comparative Example 2 Bad Blocking
Occur Blocking
Occur Blocking
Occur Blocking
Occur Comparative Example 3 Bad 4N/25mm
(No transcription) 9N/25mm
(No transcription) 12N/25mm
(Transcription) Fabric break

As can be seen from the results of Table 1, in the case of Examples 1 to 2, compared to Comparative Examples 1 or 2, the initial adhesive strength was excellent when attached to the substrate of the fabric tape, and the step characteristics due to embossing were overcome. there was.

In the above, the present invention has been described in detail with reference to the preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and within the scope of the present invention, many persons skilled in the art It will be obvious that transformation is possible. For example, in the above, mainly a fabric tape has been described as an example, but the present invention is not limited thereto, and the present invention is applicable to double-sided tape, decorative ribbon, and the like.

Claims (9)

delete delete delete delete An acrylic monomer consisting of 20 to 30 parts by weight of butyl acrylate, 4 to 5 parts by weight of 2-ethyl hexyl acrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of a benzyl peroxide thermal initiator; And 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene are added to the reactor, and the polymerization reaction proceeds for 8 hours while raising the temperature to 80° C.;
After completion of the reaction, aging under natural falling at an ambient temperature of 60° C. for 8 hours, and adding 2 to 3 parts by weight of a rosin ester-based tackifying resin; And
Including the step of mixing 1 to 2 parts by weight of a chelate-based curing agent and 0.2 to 0.6 parts by weight of an isocyanate-based curing agent in the finished pressure-sensitive adhesive and coating the fabric on the easy-cut fabric,
The easy-cut fabric fabric is a method of manufacturing a pressure-sensitive adhesive material, characterized in that it forms a loop structure having a constant warp, and is a fabric of a weft structure in which a weft is inserted and woven between the loops.
The method for manufacturing a pressure-sensitive adhesive material according to claim 5, wherein an aluminum chelating agent is used as the chelating-based curing agent, and toluene diisocyanate is used as the isocyanate-based curing agent.
Including a laminating film formed on one or both sides of an easy-cut fabric substrate and an adhesive layer formed on the opposite side of the laminating film, wherein the adhesive layer is 20 to 30 parts by weight of butyl acrylate, 4-ethyl nuclear acrylate 4 to An acrylic copolymer consisting of 5 parts by weight, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 3 to 4 parts by weight of acrylic acid; 0.1 to 0.2 parts by weight of benzyl peroxide thermal initiator; And a solvent consisting of 40 to 50 parts by weight of ethyl acetate, 4 to 7 parts by weight of acetone, and 2 to 4 parts by weight of toluene; And 2 to 3 parts by weight of rosin ester, wherein the easy-cut fabric base material forms a loop structure having a constant inclination, and is a fabric of a weft structure in which a weft yarn is inserted between the loops to weave.
The fabric tape of claim 7, wherein the easy-cut fabric substrate is a fabric composed of synthetic fibers selected from the group consisting of polyester, polyacrylic, polyamide, polyimide, polyethylene, and polypropene.
The method of claim 7, wherein the laminating film is composed of a polyethylene film selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (linear LDPE), ultra low density polyethylene (VLDPE), and high density polyethylene (HDPE). Fabric tape characterized by.