KR102541682B1 - Surface protection tape - Google Patents

Abstract

The present invention relates to an industrial surface protection tape, and more particularly, to an industrial surface protection tape comprising a transparent base film and an adhesive layer formed on at least one surface of the base film, wherein the adhesive layer comprises 100 parts by weight of an acrylic copolymer, 0.2 to 10 parts by weight of an isocyanate-based curing agent, 5 to 20 parts by weight of metal-based fine particles, 0.1 to 5 parts by weight of a ketoenol tautomer compound, 1 to 10 parts by weight of a polyether-modified siloxane compound, and 0.1 to 10 parts by weight of an antistatic agent to be characterized The industrial surface protection tape of the present invention has advantages of having excellent adhesion, adhesive retention, durability, and antistatic properties as well as having low contamination of adherends after peeling. Therefore, the surface protection tape according to the present invention has the advantage that it can be used in all fields for industrial purposes.

Description

Industrial surface protection tape {SURFACE PROTECTION TAPE}

The present invention relates to an industrial surface protection tape, and more particularly, by forming an adhesive layer including an acrylic copolymer, a diisocyanate-based curing agent, a metal-based fine particle, a ketoenol tautomer compound, a polyether-modified siloxane compound, and an antistatic agent. , It relates to an industrial surface protection tape having excellent adhesion, adhesive retention, low adherend contamination after peeling, antistatic property and durability.

In general, surface protection adhesive tapes are installed on indoor floors or walls, or applied in the form of films to IT products such as mobile phones, LCDs and LEDs, home appliances and electronic products, furniture, building materials, and automobile parts, so that various products can be transported and stored for a long period of time. It is used to prevent scratches and contamination of the material surface from the outside. In addition, the surface protection adhesive tape is also used to temporarily protect the surfaces of optical parts and electronic parts in a product manufacturing process using optical parts and electronic parts.

Such a surface protection adhesive tape has excellent adhesion and cohesion (adhesive retention) in order to prevent scratches and contamination of the surface of the material, and improvement is required so that the adherend is not contaminated after peeling. In addition, antistatic properties are also required to prevent contamination due to electrostatic charging.

In order to improve the physical properties of the surface protection adhesive tape, technologies related to the material or surface structure of the base film constituting the surface protection adhesive tape, the combination of components constituting the adhesive, and the combination of each layer constituting the surface protection adhesive tape have been developed. come.

As such a prior art, Korean Patent Registration No. 10-0926022 discloses a protective film having an adhesive layer containing an ionic antistatic agent. However, the adhesive layer of the protective film has a disadvantage in that the protective film is lifted due to poor durability.

In addition, Korean Patent Registration No. 10-1989877 discloses a surface protection adhesive having excellent adhesion, adhesive retention, light resistance, UV protection, and low contamination of the adherend after peeling due to a combination of an acrylic copolymer, a specific photochromic material, and a specific curing agent. A tape is disclosed. However, the surface protection adhesive tape has a disadvantage in that it is difficult to apply to optical parts and electronic parts because it lacks antistatic properties.

KR 10-0926022 B1 KR 10-1989877 B1

Accordingly, an object of the present invention is to provide an industrial surface protection tape having excellent adhesive strength, adhesive retention, low adherend contamination after peeling and antistatic properties.

Another object of the present invention is to provide an industrial surface protection tape with excellent durability.

Industrial surface protection tape of the present invention for achieving the above object is an industrial surface protection tape comprising a transparent base film and an adhesive layer formed on at least one surface of the base film, wherein the adhesive layer is an acrylic copolymer 100 parts by weight, 0.2 to 10 parts by weight of a diisocyanate-based curing agent, 5 to 20 parts by weight of metal-based fine particles, 0.1 to 5 parts by weight of a ketoenol tautomer compound, 1 to 10 parts by weight of a polyether-modified siloxane compound, and 0.1 to 10 parts by weight of an antistatic agent characterized by

The pressure-sensitive adhesive layer is characterized in that it further comprises 1 to 5 parts by weight of plate-shaped inorganic particles.

The pressure-sensitive adhesive layer is characterized in that it further comprises 1 to 5 parts by weight of a tin-based catalyst.

The antistatic agent is Li[(FSO ₂ ) ₂ N], Na[(FSO ₂ ) ₂ N], K[(FSO ₂ ) ₂ N], Ca[(FSO ₂ ) ₂ N] ₂ and Mg[(FSO ₂ ) ₂ N] characterized in that at least one selected from the group consisting of ₂ .

The pressure-sensitive adhesive layer is characterized in that it further comprises 1 to 5 parts by weight of cotton fiber powder.

The cotton fiber powder is coated with silver nitrate and has an average particle diameter of 10 to 1,000 nm.

The industrial surface protection tape of the present invention has advantages of having excellent adhesion, adhesive retention, durability, and antistatic properties as well as having low contamination of adherends after peeling. Therefore, the surface protection tape according to the present invention has the advantage that it can be used in all fields for industrial purposes.

Hereinafter, the present invention will be described in detail.

Conventionally, industrial surface protection tapes have disadvantages such as poor adhesion and cohesiveness, and poor antistatic properties, and the present invention solves these disadvantages through an adhesive layer.

The industrial surface protection tape of the present invention is an industrial surface protection tape comprising a transparent base film and a pressure-sensitive adhesive layer formed on at least one surface of the base film, wherein the pressure-sensitive adhesive layer contains 100 parts by weight of an acrylic copolymer and 0.2 to 10 parts by weight of a diisocyanate-based curing agent. parts by weight, 5 to 20 parts by weight of metal-based fine particles, 0.1 to 5 parts by weight of a ketoenol tautomer compound, 1 to 10 parts by weight of a polyether-modified siloxane compound, and 0.1 to 10 parts by weight of an antistatic agent.

First, the type of the transparent base film is not particularly limited as long as it is commonly used for known surface protection tapes, and may be selected from various known transparent base films. Illustratively, the transparent base film may be made of polyolefin-based resin, polyester-based resin, polycarbonate resin, polyurethane resin, engineering plastics, synthetic rubbers, thermoplastic elastomers, polyimide resins, and the like. The polyolefin resin is polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer , ethylene-acrylic acid copolymer or ionomer may be selected from resins composed of homopolymers or copolymers of monomers containing an ethylenically unsaturated group.

In addition, the pressure-sensitive adhesive layer formed on at least one surface of the base film is formed of the pressure-sensitive adhesive composition described below, and its thickness and formation method are known methods. That is, it is natural to form a pressure-sensitive adhesive layer by further mixing the pressure-sensitive adhesive composition with a solvent and then removing the solvent to form the pressure-sensitive adhesive layer. A detailed description of the method for forming the pressure-sensitive adhesive layer will be omitted.

The pressure-sensitive adhesive composition according to the present invention contains 100 parts by weight of an acrylic copolymer, 0.2 to 10 parts by weight of a diisocyanate-based curing agent, 5 to 20 parts by weight of metal fine particles, 0.1 to 5 parts by weight of a ketoenol tautomer compound, and polyether-modified siloxane compound 1 ~ 10 parts by weight and 0.1 to 10 parts by weight of an antistatic agent.

The acrylic copolymer is formed by polymerization of a soft monomer having an ethylenically unsaturated bond, a hard monomer having an ethylenically unsaturated bond, and a carboxylic acid monomer having an ethylenically unsaturated bond.

The soft monomer having an ethylenically unsaturated bond is to improve the flowability and wettability of the pressure-sensitive adhesive layer to impart initial adhesive strength, and contains an ethylenically unsaturated bond such as an acryl group, an allyl group, and a vinyl group, and its homopolymer is adhesive at room temperature refers to the phosphorus monomer. In the present invention, the kind of soft monomer having an ethylenically unsaturated bond is not particularly limited as long as it satisfies the above characteristics, and examples thereof include 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, methyl acrylate, and ethyl acrylate. rate, normal butyl acrylate, isobutyl acrylate, and may be composed of one or more selected from the group consisting of octadecyl methacrylate.

The hard monomer having an ethylenically unsaturated bond is used to impart adhesive strength and adhesive retention of the pressure-sensitive adhesive layer, and contains an ethylenically unsaturated bond such as an acryl group, an aryl group, or a vinyl group, and its homopolymer is not adhesive at room temperature refers to monomers. In the present invention, the type of hard monomer having an ethylenically unsaturated bond is not particularly limited as long as it satisfies the above characteristics, and examples thereof include methyl methacrylate, ethyl methacrylate, normal butyl methacrylate, and isobutyl methacrylate. , It may be composed of one or more selected from the group consisting of acrylonitrile, vinyl chloride, vinyl acetate and styrene.

The carboxylic acid monomer having an ethylenically unsaturated bond is used to prevent whitening due to water dispersibility under moist heat conditions as a function of the carboxyl group, remove air bubbles in the pressure-sensitive adhesive composition, and improve adhesive retention by enabling hydrogen bonding.

The type of the carboxylic acid monomer having an ethylenically unsaturated bond is not particularly limited as long as it has an ethylenically unsaturated bond for polymerization with other monomers, and examples thereof include acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, It may be composed of at least one selected from the group consisting of 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl maleic acid.

And the acrylic copolymer is 5 to 15% by weight of a hard monomer having an ethylenically unsaturated bond and 1 to 5% by weight of a carboxylic acid monomer having an ethylenically unsaturated bond % and the remainder by polymerization of soft monomers having ethylenically unsaturated bonds.

Hereinafter, 'parts by weight' is based on 100 parts by weight of the acrylic copolymer.

The diisocyanate-based curing agent is a material that causes crosslinking of polymers and improves durability and heat resistance of the pressure-sensitive adhesive. The diisocyanate-based curing agent may be used regardless of its type, and examples thereof include dimer acid diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), and 2,6-toluene diisocyanate. Isocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4 -Aromatic diisocyanates such as phenylene diisocyanate, xylene diisocyanate (XDI), and tetramethylxylidene diisocyanate (TMXDI); aliphatic diisocyanates such as hexemethylene diisocyanate (HDI) and trimethylhexamethylene diisocyanate (TMHDI); or alicyclic diisocyanates such as isophorone diisocyanate (IPDI) and trans-cyclohexane-1,4-diisocyanate; and the like, and 2,4-toluene diisocyanate or 2,6-toluene diisocyanate can be used.

The diisocyanate-based curing agent is preferably used in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer, which improves the physical properties of the adhesive layer.

The metal-based fine particles serve to improve durability by increasing the mechanical strength of the pressure-sensitive adhesive layer, and silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, ceria, zinc oxide, iron oxide, and germanium oxide , indium oxide, silicon nitride, boron nitride, potassium titanate, wollastonite, sepiolite, acicular tin oxide, acicular magnesium hydroxide, and layered clay minerals. The shape of the metal-based fine particles may be a bulk shape such as a spherical shape, a rectangular parallelepiped shape, or a deformed shape thereof, a needle shape, or a plate shape, and the average particle diameter is preferably 5 to 100 nm. This is to improve the dispersibility of the metal-based fine particles. However, even if metal-based particles having an average particle diameter of 5 to 100 nm are used, dispersibility may be poor, and the problem of dispersibility of metal-based particles can be solved by using an antistatic agent and metal-based particles in combination.

The metal-based fine particles are preferably used in an amount of 5 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is too low, mechanical strength improvement is insignificant, and if the content is excessive, dispersibility, transparency, etc. are not good. .

The ketoenol tautomer compound is for lengthening the pot life of the pressure-sensitive adhesive layer, such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, etc. At least one of β-ketoesters, acetylacetone, 2,4-hexanedione, and benzoylacetone may be used.

The ketoenol tautomer compound is preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is too low, the effect is insignificant, and if the content is excessive, crosslinking is delayed, thereby reducing the physical properties of the pressure-sensitive adhesive layer. because this isn't good.

The polyether-modified siloxane compound is for improving adhesion and adhesive retention, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer , dimethylsiloxane/methyl (polyoxypropylene) siloxane polymers, at least one of which can be used.

The polyether-modified siloxane compound is preferably used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is too low, the effect is insignificant. Because.

The antistatic agent is to improve the antistatic property of the pressure-sensitive adhesive layer, Li[(FSO ₂ ) ₂ N], Na[(FSO ₂ ) ₂ N], K[(FSO ₂ ) ₂ N], Ca[(FSO ₂ ) ₂ N] ₂ and Mg[(FSO ₂ ) ₂ N] ₂ may be used at least one selected from the group consisting of.

The antistatic agent is preferably included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is low, the effect is insignificant, and if the content is excessive, the stability of the pressure-sensitive adhesive layer may be deteriorated.

The industrial surface protection tape of the present invention configured as described above has the advantages of having excellent adhesive strength, adhesive retention, low adherend contamination after peeling, antistatic property, and durability.

Meanwhile, the pressure-sensitive adhesive layer preferably further includes plate-shaped inorganic particles.

The plate-shaped inorganic particles are components that block or hinder the movement of moisture, and may be, for example, nanoclay. Layered silicates may be used as the nanoclay, and examples of the layered silicates include montmorillonite, saponite, hectorite, vermiculite, bentonite, and attapulgite ( attapulgite), sepiolite, halloysite, and the like.

The nanoclay may be modified with an organic modifier to improve compatibility with the binder resin. The organic modifier includes dimethyl benzyl hydrogenated tallow quaternary ammonium ion, bis (hydrogenated tallow) dimethyl quaternary ammonium ion, methyl tallow bis-2-hydroxyethyl quaternary ammonium ion, dimethyl hydrogenated tallow 2-ethylhexyl Quaternary ammonium ions or dimethyl dehydrogenation tallow quaternary ammonium ions and the like are exemplified.

The plate-shaped inorganic particles are preferably included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer, which takes into account adhesive strength and durability.

In addition, the pressure-sensitive adhesive layer of the present invention preferably further includes a tin-based catalyst.

The tin-based catalyst is for improving cohesion, that is, adhesive retention, and at least one of dibutyltindilaurate, dibutyltindiethylhexoate, and dioctyltindilaurate may be used.

The tin-based catalyst is preferably included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is too small, sufficient cohesive force is not exhibited, and if the content is excessive, the stability of the pressure-sensitive adhesive layer is deteriorated.

In addition, the pressure-sensitive adhesive layer of the present invention preferably further comprises cotton fiber powder.

The cotton fiber powder serves to improve cohesion, low post-peel contamination and durability without affecting the adhesive strength of the pressure-sensitive adhesive layer. In addition, when using the cotton fiber powder coated with silver nitrate, there is an advantage that the antistatic property is also further improved.

The method of coating cotton fibers with silver nitrate is sufficient according to the conventionally posted method, and it is preferable to use those having an average particle diameter of 10 to 1,000 nm. This is in consideration of its dispersibility and the like.

The cotton fiber is preferably included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is too small, a sufficient effect may not be exerted, and if the content is excessive, the adhesive strength of the pressure-sensitive adhesive layer may decrease.

Hereinafter, the present invention will be described in detail through specific examples.

(Example 1)

500 g of toluene, 410 g of 2-ethylhexyl acrylate, 450 g of normal butyl acrylate, 110 g of vinyl acetate, 10 g of styrene, and 20 g of acrylic acid were put in a mixing container and stirred to prepare a monomer mixture solution.

In addition, 2 g of potassium persulfate and 4 g of ammonium persulfate, which are polymerization initiators, were separately added to 1,000 g of ethyl acetate and sufficiently dissolved to prepare a polymerization initiator mixture solution. Thereafter, the monomer mixture solution accommodated in the mixing vessel was stirred at a speed of 200 rpm, the temperature was raised to about 60 ° C, and the polymerization initiator mixture solution was added in a constant amount over about 4 hours while maintaining the stirring speed and temperature to perform polymerization. The reaction was induced and a solution containing an acrylic copolymer was obtained.

Next, while stirring the acrylic copolymer-containing solution contained in the mixing vessel at a speed of 100 rpm, a 28 wt% aqueous ammonia solution was added thereto to adjust the pH to about 7.5. Thereafter, in a mixing container, 50 g of 70 nm zinc oxide, 10 g of methyl acetoacetate, 20 g of dimethylsiloxane-methyl(polyoxyethylene)siloxane copolymer, 20 g of Ca[(FSO ₂ ) ₂ N] ₂ and toluene diisocyanate (TDI) as a curing agent were mixed. 10 g was added and dissolved to prepare an adhesive composition.

The adhesive composition is coated to a thickness of 10 μm on one side of a 60 μm PE (Polyethylene) film using a gravure coating device, dried at 80 ° C for 30 minutes to remove all solvents, and aged at 60 ° C for 24 hours to obtain a PE film A surface protection tape having an adhesive layer formed thereon was prepared.

(Example 2)

It was carried out in the same manner as in Example 1, but when the curing agent was added, 20 g of montmorillonite and 20 g of dibutyltin dilaurate were further mixed.

(Example 3)

It was carried out in the same manner as in Example 2, but 20 g of cotton fibers were further mixed when the curing agent was added.

At this time, the cotton fiber was prepared and used as follows. After adding 10 g of sodium hydroxide (NaOH) to 90 mL of deionized water and stirring, cotton wool was sufficiently immersed, obtained, and then dried. Then, 20 g of 0.5 M silver nitrate and 20 mL of 28% aqueous ammonia were added to 50 mL of deionized water, stirred, and electroless coating was performed by immersing the pretreated cotton wool, followed by addition of 50 mL of 1 M glucose for 15 minutes. After the reaction, cotton wool was obtained and dried to obtain a 700 nm powder.

(Comparative Example 1)

It was carried out in the same manner as in Example 1, except that zinc oxide, methyl acetoacetate, a dimethylsiloxane-methyl(polyoxyethylene)siloxane copolymer, and Ca[(FSO ₂ ) ₂ N] ₂ were not used.

(Test Example 1)

Initial Adhesion Test

The initial adhesive strength was measured using the rolling ball tack test method. Specifically, an iron ball with a diameter of 11 mm and a weight of 56 g was used and measured at 23 ± 1 ° C and a relative humidity of 50 ± 5%, and the angle of the inclined plane was 213 °. In addition, after cutting the sample into a width of 2 mm × length of 50 mm, the sample was fixed when contacting the base film of the sample to the polycarbonate plate constituting the inclined surface. Then, an iron ball was rolled at the top of 10 cm from the fixed sample. In addition, the distance at which the steel ball stopped after rolling as it began to contact the adhesive layer of the tape was measured. The initial adhesion normally required for good adhesion balance is 5 ± 1 mm.

adhesion test

The sample was attached to a SUS304 plate by reciprocating twice at a speed of 300 mm/min with a roller with a load of 2 kg, and left for 60 hours at a temperature of 23 ± 2 ° C and a relative humidity of 50 ± 5%. Thereafter, the attached sample was peeled 180 degrees at a speed of 300 mm/min to measure the adhesive force. Typically required adhesion for good adhesion balance is 280 to 450 gf/inch.

Contamination of adherend after peeling

Contamination of the adherend after peeling was measured using the above adhesion test. Specifically, in the adhesion test, while peeling off the sample attached to the adherend by hand, it was confirmed whether residues remained on the adherend or whether the adherend was damaged. If residue or damage remained on the adherend, it was evaluated as 'X', and if it did not remain, it was evaluated as '○'.

adhesive retention

In an environment set at a temperature of 23 ± 2 ° C and a relative humidity of 50 ± 5%, a sample cut into 20 mm wide × 20 mm long was attached to a SUS304 plate. Thereafter, a weight of 500 g was weighed in the direction of gravity at 40 ° C., and the time (minutes) during which the weight fell was measured three or more times, and the adhesive retention was evaluated as an average value. Results were rounded to the ones place to correct for errors. The adhesive holding power of the tape normally required is 300 minutes or more.

durability

After leaving the sample for 250 hours in an atmosphere of 60° C. and 90% RH, it was taken out at room temperature, and after further leaving for 12 hours, the adhesive force was measured and it was confirmed that there was no clear increase compared to the initial adhesive force. As for the evaluation target criterion, the case where the adhesive strength after the test was 15 times or less of the initial adhesive strength was evaluated as '○', and the case where it exceeded 15 times was evaluated as 'X'.

Test Example 1 Results division initial adhesion
(mm) adhesiveness
(gf/inch) Contamination of adherend after peeling adhesive retention
(minute) durability Example 1 5.1 380 ○ 370 ○ Example 2 5.0 400 ○ 410 ○ Example 3 5.1 400 ○ 420 ○ Comparative Example 1 3.7 150 × 250 ×

As shown in Table 1, it was confirmed that the examples of the present invention were superior to Comparative Example 1 in initial adhesive strength, adhesive strength, adherend contamination after peeling, adhesive retention, and durability.

Through the above description, those skilled in the art will know that various changes and modifications are possible without departing from the technical spirit of the present invention. Therefore, the technical scope of the present invention is not limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (6)

An industrial surface protection tape comprising a transparent base film and an adhesive layer formed on at least one surface of the base film,
The pressure-sensitive adhesive layer includes 100 parts by weight of an acrylic copolymer, 0.2 to 10 parts by weight of a diisocyanate-based curing agent, 5 to 20 parts by weight of metal fine particles, 0.1 to 5 parts by weight of a ketoenol tautomer compound, and 1 to 10 parts by weight of a polyether-modified siloxane compound. 0.1 to 10 parts by weight of an antistatic agent and 1 to 5 parts by weight of cotton fiber powder,
The cotton fiber powder is coated with silver nitrate and has an average particle diameter of 10 to 1,000 nm.
According to claim 1,
The adhesive layer,
Industrial surface protection tape further comprising 1 to 5 parts by weight of plate-shaped inorganic particles.
According to claim 1,
The pressure-sensitive adhesive layer,
An industrial surface protection tape further comprising 1 to 5 parts by weight of a tin-based catalyst.
According to claim 1,
The antistatic agent is Li[(FSO ₂ ) ₂ N], Na[(FSO ₂ ) ₂ N], K[(FSO ₂ ) ₂ N], Ca[(FSO ₂ ) ₂ N] ₂ and Mg[(FSO ₂ ) ₂ N] Industrial surface protection tape, characterized in that at least one selected from the group consisting of ₂ .
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