KR20150039981A - Adhesive composition and method of producing anti-fingerprint film - Google Patents

Abstract

The present invention relates to an adhesive composition and a manufacturing method for an anti-fingerprint layer and, more specifically, to an adhesive composition capable of greatly reducing the process time and process costs since additional facilities and equipment are not required as compared with an existing solution coating method and an existing depositing method by forming an anti-fingerprint layer via a method of performing transcription on glass by using the adhesive composition containing anti-fingerprint agents; and to a method for manufacturing an anti-fingerprint layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a pressure-sensitive adhesive composition,

The present invention relates to a pressure-sensitive adhesive composition comprising a fingerprint-preventing agent and a method for producing the fingerprint-preventing layer using the same.

In an information terminal, for example, a mobile phone, a personal computer, a navigation system, a cash dispenser, etc., a display and a touch panel are mounted on the input / output unit. However, when such an information terminal is used, since the display surface is manipulated by touching with the finger, the fingerprint due to the lipid component originating from the living body such as sebum or the like adheres to the display surface, which makes it difficult to recognize letters and numbers .

Therefore, measures have been taken to prevent the fingerprint from adhering to the display surface by directly coating the display and the touch panel.

For example, a method of forming a film containing water-repellent and oil-repellent fluorine, a method of introducing a water-repellent silicone resin skeleton such as polydimethylsiloxane, a method of attaching fine irregularities to the surface to further improve water repellency and oil repellency, And a method of making it less susceptible to dirt are performed.

Such an anti-fingerprint layer is formed directly on the substrate surface of glass or the like (Japanese Patent Application Laid-Open No. 2000-327818) or deposited (Korean Patent No. 1,242,591). The above-described method has a disadvantage in that equipment and equipment for separate coating and deposition processes are required.

An object of the present invention is to provide a method for manufacturing a fingerprint preventing layer which can form a fingerprint preventing layer on a glass, without requiring any equipment and equipment using a pressure sensitive adhesive composition containing a fingerprint preventing agent .

In order to achieve the above object, the present invention provides a pressure-sensitive adhesive composition containing a fingerprint-preventing agent.

The anti-fingerprinting agent may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition may be a fluorine-containing pressure-sensitive adhesive composition or a silicon-containing pressure-sensitive adhesive composition.

The fluorine-containing pressure-sensitive adhesive composition may contain a fingerprint inhibitor, a (meth) acrylate monomer having a C ₁ -C ₁₂ alkyl group, a crosslinkable monomer having a crosslinkable functional group, and a fluorine-containing monomer.

The silicone-containing pressure-sensitive adhesive composition may contain an anti-fogging agent, an organopolysiloxane containing a vinyl group, an organohydrogenpolysiloxane, and an addition reaction catalyst.

The silicon-containing pressure-sensitive adhesive layer may contain an acrylic monomer containing a (meth) acrylate monomer having a C ₁ -C ₁₂ alkyl group, and a trimethylsilane group.

The present invention also provides a protective film with a pressure-sensitive adhesive, wherein a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition is laminated on at least one surface of the protective film.

The present invention also provides an optical laminate in which the above protective film with a pressure-sensitive adhesive is laminated on at least one surface of a glass.

Further, the present invention provides a method for manufacturing a pressure sensitive adhesive sheet, comprising: forming a pressure sensitive adhesive layer by coating a pressure sensitive adhesive composition on at least one surface of a protective film; Bonding the glass onto the pressure-sensitive adhesive layer to form an optical laminate; And heat-treating the optical laminate at a temperature of 50 ° C or higher, and then removing the protective film to produce a glass having a fingerprint-preventing layer formed thereon.

Preferably, the heat treatment may be performed at 50 to 150 < 0 > C.

The present invention has an advantage that a fingerprint blocking layer can be formed by a method of transferring to a glass using a pressure sensitive adhesive composition of a protective film used for preventing contamination and scratching of a glass during a manufacturing process such as a touch panel process.

Since the transfer method is performed by heat treatment, there is no need for additional equipment and equipment as compared with the conventional solution coating method and vapor deposition method, and thus there is an advantage that the processing time and cost can be drastically reduced.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive composition comprising a fingerprint-preventing agent and a method for producing the fingerprint-

Hereinafter, the present invention will be described in detail.

The pressure-sensitive adhesive composition of the present invention contains a printing inhibitor.

The anti-fingerprinting agent is generally used in the art and is not particularly limited. Specifically, the adhesive layer containing the anti-fingerprinting agent has a water contact angle of 100 ° or more, preferably 110 to 120 °.

It is preferable that at least one compound selected from the group consisting of the following formulas (1), (2) and (3) is contained.

이고, R₄는 H 또는

이고, R₅는 C₁-C₈의 지방족 탄화수소기, N 또는 O에 의해 중단된 C₁-C₈의 지방족 탄화수소기 또는 알킬실록산기이고, Y는 O 또는 NH이며, n 및 m은 각각 독립적으로 1 내지 20의 정수임). Wherein X is a halogen group, a C ₁ -C ₈ alkoxy group, or an acetoxy group, R ₁ is a C ₁ -C ₈ aliphatic hydrocarbon group, C (O) interrupted by N or O, C ₁ -C ₈ aliphatic hydrocarbon group or alkylsiloxane group, R ₂ and R ₃ each independently represents a halogen group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ acetoxy group, a C ₁ -C ₄ Of an aliphatic hydrocarbon group or

, R < ₄ > is H or

, R ₅ is a C ₁ -C ₈ aliphatic hydrocarbon group, a C ₁ -C ₈ aliphatic hydrocarbon group or an alkyl siloxane group interrupted by N or O, Y is O or NH, n and m are each independently Is an integer of 1 to 20).

The anti-fingerprinting agent is preferably contained in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the pressure-sensitive adhesive composition. If the content is less than 0.1 part by weight, the transfer amount of the anti-fingerprint agent may be insufficient to prevent the fingerprint. If the amount exceeds 10 parts by weight, excessive peeling of the anti-fingerprint agent may cause bleeding-out of the anti- .

The pressure-sensitive adhesive composition of the present invention is preferably a fluorine-containing pressure-sensitive adhesive composition or a silicon-containing pressure-sensitive adhesive composition having a surface energy in a similar range in consideration of compatibility with a fingerprint inhibitor.

For example, the fluorine-containing pressure-sensitive adhesive composition may contain a printing inhibitor, a (meth) acrylate monomer having a C ₁ -C ₁₂ alkyl group, a crosslinkable monomer having a crosslinkable functional group, and a fluorine-containing monomer.

In the present invention, (meth) acrylate means acrylate and methacrylate, and the content is based on the solid content

Examples of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms include (meth) acrylates derived from an aliphatic alcohol having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, (meth) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t- (Meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate. These may be used alone or in combination of two or more. Of these, n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof is preferable.

Examples of the polymerizable monomer having a crosslinkable functional group include a monomer having a hydroxy group, a monomer having an amide group, a monomer having a tertiary amine group, and a monomer having a carboxyl group. These monomers may be used alone or in combination.

,

,

,

,

,

,

및

로 이루어진 군에서 선택된 1종 이상일 수 있다. The fluorine-containing monomer is an aliphatic fluorinated hydrocarbon-containing acrylate, for example,

,

,

,

,

,

,

And

And the like.

The fluorine-containing pressure-sensitive adhesive composition may further contain a crosslinking agent capable of improving adhesion and durability and maintaining reliability at a high temperature and a shape of a pressure-sensitive adhesive. The cross-linking agent may be an isocyanate-based, epoxy-based, melamine-based, peroxide-based, metal chelating-based, oxazoline-based, or the like. Preferred is a double isocyanate-based or epoxy-based.

The content of each component contained in such a fluorine-containing pressure-sensitive adhesive composition can appropriately be controlled to such an extent as to fulfill its role as a pressure-sensitive adhesive composition and to satisfy the range of surface energy. The double fluorine containing monomer is used as an important factor for controlling the surface energy. The fluorine-containing monomer is preferably contained in an amount of 20 to 70 parts by weight based on 100 parts by weight of the total amount of the pressure-sensitive adhesive composition. When the content is less than 20 parts by weight, the compatibility with the anti-fingerprinting agent is lowered, and excessive peeling-out of the anti-fingerprinting agent may cause peeling failure of the protective film during the process. When the content exceeds 70 parts by weight , The low adhesive force between the adhesive of the protective film and the glass is excessively lowered, and peeling between the adhesive layer and the glass may occur during the process.

In one example, the silicone-containing pressure-sensitive adhesive composition may contain a print inhibitor, a vinyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and an addition reaction catalyst.

The vinyl group-containing organopolysiloxane is used as a main component of the composition, and is a compound containing two or more vinyl groups in one molecule, and is preferably a branched or solid phase branched structure. The organohydrogenpolysiloxane is preferably a crosslinking component having at least two Si-H bonds per molecule.

The addition reaction catalyst may be a platinum group metal selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium or iridium metals and organometallic compounds thereof, and combinations thereof for promoting the curing reaction have.

The content of each component of such a silicone-containing pressure-sensitive adhesive composition can be appropriately adjusted to such an extent that the pressure-sensitive adhesive composition fulfills its role as a pressure-sensitive adhesive composition and compatibility with the anti-fingerprint agent is satisfied.

Further, for example, the silicone-containing pressure-sensitive adhesive composition may contain a (meth) acrylate monomer having a C ₁ -C ₁₂ alkyl group and an acrylic monomer containing a trimethylsilane group.

,

,

및

로 이루어진 군에서 선택된 1종 이상일 수 있다.
Such an acryl monomer containing a trimethylsilane group is, for example,

,

,

And

And the like.

The present invention also provides a pressure-sensitive adhesive sheet, comprising: a protective film with a pressure-sensitive adhesive layer on which a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition is laminated on at least one surface of a protective film; And is characterized in that the protective film with the adhesive is laminated on at least one surface of the glass.

The protective film is not particularly limited as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. Specifically, polyester resins such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin-based resins such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefin, and ethylene propylene copolymer; Vinyl chloride resin; Polyamide resins such as nylon and aromatic polyamide; Imide resin; Polyether sulfone type resin; Sulfone based resin; Polyether ketone resin: a polyphenylene sulfide resin; Vinyl alcohol-based resin; Vinylidene chloride resins; Vinyl butyral resin; Allylate series resin; Polyoxymethylene type resin; Epoxy resin, and the like, and a film composed of the blend of the thermoplastic resin may also be used. Further, a film made of a thermosetting resin such as (meth) acrylic, urethane, epoxy, or silicone or a film made of an ultraviolet curable resin may be used.

The present invention also provides a method for manufacturing a pressure sensitive adhesive, comprising: forming a pressure sensitive adhesive layer on at least one surface of a protective film by coating the pressure sensitive adhesive composition; Bonding the glass onto the pressure-sensitive adhesive layer to form an optical laminate; And a step of heat treating the optical laminate at a temperature of 50 ° C or higher and then removing the protective film to produce a glass having an anti-fingerprint layer formed thereon.

The heat treatment is preferably performed at 50 to 150 ° C, and may be performed for 1 to 24 hours.

By the heat treatment process, the anti-fingerprint agent contained in the adhesive layer is transferred to the glass to form the anti-fingerprint layer, and the adhesive composition is removed together with the protective film. That is, the present invention can form an anti-fingerprint layer on a glass by joining a protective film formed with a pressure-sensitive adhesive layer and a glass and peeling the protective film.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  One

1) Pressure-sensitive adhesive composition

50중량부, 히드록시에틸아크릴레이트(HEA) 1중량부를 투입한 후, 용제로 아세톤 100 중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1 시간 동안 퍼징한 후, 70 ℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비 스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량 100만 이상의 아크릴계 공중합체를 제조하였다. 49 parts by weight of n-butyl acrylate (BA) was added to a 1 L reactor equipped with a cooling device for regulating the temperature of the reflux of nitrogen gas,

, And 1 part by weight of hydroxyethyl acrylate (HEA), and 100 parts by weight of acetone was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 70 ° C. After the mixture was homogenized, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of at least 1,000,000.

(TCI사) 3중량부를 혼합한 후 코팅성을 고려하여 유기 용매에 희석하여 점착제 조성물을 제조하였다.100 parts by weight of the above acrylic copolymer, 0.5 part by weight of a TMP adduct of TDI (Nippon Urethane Saccharonate L) as a crosslinking agent,

(TCI) were mixed and diluted in an organic solvent in consideration of coating properties to prepare a pressure-sensitive adhesive composition.

2) Anti-fingerprint layer  Produce

The pressure-sensitive adhesive composition was dried on a polyethylene terephthalate (PET) film, coated to a thickness of 25 μm, and dried at 100 ° C. for 5 minutes to form a pressure-sensitive adhesive layer. And then laminated on a Corning glass treated with plasma to prepare a laminate. Thereafter, the laminate was heat-treated at 100 ° C for 1 hour, the protective film was removed, and the film was allowed to stand at room temperature for 24 hours to prepare a glass having an anti-fingerprint layer.

Example  2

대신에

을 사용하여 광학적층체를 제조하였다.
The procedure of Example 1 was repeated,

Instead of

To prepare an optical laminate.

Example  3

대신에

을 사용하여 광학적층체를 제조하였다.
The procedure of Example 1 was repeated,

Instead of

To prepare an optical laminate.

Example  4

30 중량부, 히드록시에틸아크릴레이트(HEA) 1 중량부를 사용하여 광학적층체를 제조하였다.
The procedure of Example 1 was repeated except that 69 parts by weight of n-butyl acrylate (BA)

, And 1 part by weight of hydroxyethyl acrylate (HEA) were used to prepare an optical laminate.

Example  5

The procedure of Example 1 was repeated except that 1) an addition type organopolysiloxane composed of an organopolysiloxane and an organohydrogenpolysiloxane having a siloxane bond as a main skeleton and having a vinyl group (manufactured by Shin-Etsu Chemical Co., Ltd. (Manufactured by Shin-Etsu Chemical Co., Ltd., PL-50T) was added to 100 parts by weight of a polypropylene resin (product of KS-847H, KS-847H) and diluted to a solid content concentration of about 20% by weight in methyl ethyl ketone Was used to produce a glass having an anti-fingerprint layer.

Example  6

대신에

을 사용하여 지문방지층이 형성된 글래스를 제조하였다.
The procedure of Example 1 was repeated,

Instead of

To prepare a glass having an anti-fingerprint layer formed thereon.

Example  7

대신에

을 사용하여 지문방지층이 형성된 글래스를 제조하였다.
The procedure of Example 1 was repeated,

Instead of

To prepare a glass having an anti-fingerprint layer formed thereon.

Example  8

(TCI사) 12중량부를 사용하여 지문방지층이 형성된 글래스를 제조하였다.
The procedure of Example 1 was repeated,

(TCI) were used to prepare a glass having an anti-fingerprint layer formed thereon.

Example  9

The procedure of Example 1 was repeated, The optical layered body was heat-treated at 60 캜 for 5 hours, and then the protective film was removed to produce a glass having the anti-fingerprint layer.

Example  10

The procedure of Example 1 was repeated, The optical laminate was heat-treated at 160 캜 for 5 hours, and then the protective film was removed to prepare a glass having the anti-fingerprint layer.

Comparative Example  One

(TCI사) 1g을 CF₃CHFCHFCF₂CF₃ 100g에 녹인 용액에, 글라스를 10초간 딥핑(dipping)한 후, 80℃ 열풍건조기에서 1분간 건조하고, 50℃ 50%RH 조건에서 1일간 방치하여 지문방지층이 형성된 글래스를 제조하였다.

(TCI Inc.) 1g of CF ₃ CHFCHFCF ₂ in solution in CF ₃ 100g, and then the glass 10 seconds dipping (dipping), 1 minutes. Thereafter at 80 ℃ hot-air dryer and by one days allowed to stand at 50% RH conditions 50 ℃ A glass having an anti-fingerprint layer was prepared.

Comparative Example  2

구조의 용액이 포함된 타블렛(Tablet)에 열을 가하여 기화된 용액을 글래스 상에 80초동안 증착하여 지문 방지층이 형성된 글래스를 제조하였다. 타블렛(Tablet)에 열을 가하는 방법으로는 E-Beam 방식을 사용하였으며, 증착 과정 중 챔버내 온도는 80℃를 유지하였다.
A glass was introduced into the chamber to form a vacuum atmosphere up to 5 ^-5 Torr,

And the vaporized solution was deposited on the glass for 80 seconds to prepare a glass having the anti-fading layer formed thereon. The E-Beam method was used to apply heat to the tablet, and the temperature in the chamber was maintained at 80 ° C during the deposition process.

Comparative Example  3

The procedure of Example 1 was repeated, The optical layered body was heat-treated at 30 DEG C for 5 hours, and then the protective film was removed to prepare a glass having the anti-fingerprint layer.

Test Example

The physical properties of the glass with the anti-fingerprint layer formed in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

One. Fingerprint Prevention  ( Water contact angle )

The water contact angle of the glass on which the fingerprint blocking layer was formed was measured.

2. Coating uniformity

A sample of the glass with the fingerprint blocking layer thus formed was displayed in a size of 10 cm x 10 cm and the water contact angle was measured at ten positions within the displayed area and the difference between the maximum value and the minimum value of the water contact angle was calculated.

3. Reliability (Fingerprint prevention Maintainability )

The surface of the glass on which the fingerprint blocking layer was formed was repeatedly rubbed 10 times at a constant pressure, and then the contact angle of the friction surface was measured.

division Fingerprint Prevention Coating uniformity responsibility Example 1 112 3 110 Example 2 110 3 108 Example 3 111 3 109 Example 4 114 3 109 Example 5 113 3 110 Example 6 115 2 112 Example 7 114 2 113 Example 8 112 3 109 Example 9 112 3 110 Example 10 112 3 109 Comparative Example 1 113 2 110 Comparative Example 2 112 3 110 Comparative Example 3 102 2 100

As shown in Table 1, it was confirmed that the anti-fingerprint layers of Examples 1 to 10 produced according to the present invention maintained the same or better fingerprint preventive properties, coating uniformity, and reliability as compared with Comparative Examples 1 to 3.

Claims (10)

A pressure-sensitive adhesive composition containing an anti-fingerprinting agent.
The pressure-sensitive adhesive composition according to claim 1, wherein the anti-fingerprinting agent contains 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the pressure-sensitive adhesive composition.
The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is a fluorine-containing pressure-sensitive adhesive composition or a silicon-containing pressure-sensitive adhesive composition.
[4] The pressure-sensitive adhesive composition according to claim 3, wherein the fluorine-containing pressure-sensitive adhesive composition comprises a fingerprint inhibitor, a (meth) acrylate monomer having a C ₁ -C ₁₂ alkyl group, a crosslinkable monomer having a crosslinkable functional group, and a fluorine-containing monomer.
4. The pressure-sensitive adhesive composition according to claim 3, wherein the silicone-containing pressure-sensitive adhesive composition contains a fingerprint-preventing agent, an organopolysiloxane, an organohydrogenpolysiloxane and an addition reaction catalyst.
A pressure-sensitive adhesive composition according to claim 3, wherein the silicon-containing pressure-sensitive adhesive composition is containing a monomer containing a (meth) acrylate monomer, trimethylsilane having an alkyl group of fingerprint agent, C ₁ -C _12.
A protective film with a pressure-sensitive adhesive, wherein a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition according to any one of claims 1 to 6 is laminated on at least one surface of the protective film.
And an adhesive protective film of claim 7 is laminated on at least one side of the glass.
Coating a pressure-sensitive adhesive composition according to any one of claims 1 to 8 on at least one side of a protective film to form a pressure-sensitive adhesive layer;
Bonding the glass onto the pressure-sensitive adhesive layer to form an optical laminate; And
A step of heat-treating the optical laminate at a temperature of 50 ° C or higher and then removing the protective film to produce a glass having a fingerprint-preventing layer formed thereon;
The method according to claim 9, wherein the heat treatment is performed at 50 to 150 ° C.