KR102116588B1 - An article comprising a film on a carrier or release substrate - Google Patents

Abstract

The present invention generally relates to an article comprising a curable film on a carrier substrate and / or release substrate. More particularly, the curable film comprises at least one specific cyanoacrylate monomer and at least one film forming (co) polymer. The article may take the form of a label, single-sided tape, transfer tape or double-sided tape.

Description

Articles containing film on carrier or release substrate {AN ARTICLE COMPRISING A FILM ON A CARRIER OR RELEASE SUBSTRATE}

The present invention is an article comprising a curable film on a carrier substrate and / or a release substrate, the film comprising one or more specific cyanoacrylate monomers and one or more film forming (co) polymers It is about the goods to be.

Adhesive tapes and labels are attractive to consumers in that they are easily manipulated and stored and used in a wide range of bonding and shielding applications, including bonding of electrical, electronic, aerospace and audio / video components.

Pressure sensitive adhesives are a common type of adhesive tape. The pressure sensitive adhesive is a viscoelastic material, which can be provided in the form of a transfer tape as a carrierless or carrier-based, single-sided or double-sided tape. It maintains permanent tack for a long period of time, and bonding to a surface such as polyethylene or polypropylene is difficult, but only minimal pressure is required for adhesion to the surface. In general, they can be removed without leaving any adhesive residue and without breaking the bonded portion.

The application of prior art pressure sensitive adhesives has generally been limited to operations where the requirements regarding bond strength and / or heat resistance are not demanding. Accordingly, there is a need for a heat resistant adhesive tape that combines high initial tackiness and high structural bonding strength and exhibits excellent adhesion to various different substrates.

For example, U.S. A pressure sensitive adhesive tape is disclosed in Patent Publication No. 2012/0082818 (Nitto Denko Corporation). In particular, U.S. The pressure sensitive adhesive tape disclosed in 2012/0082818 includes a silicone based release layer coated on a water dispersible pressure sensitive adhesive layer. The water-dispersible pressure-sensitive adhesive layer contains a tackifier resin acrylic polymer dispersed in water. U.S. The pressure sensitive adhesive tape disclosed in 2012/0082818 does not contain any aromatic hydrocarbon-based solvents such as toluene. Consequently, volatile organic carbon (VOC) emissions from the tape are minimized.

Prior art pressure sensitive adhesive tapes can be single-sided or double-sided. Double-sided pressure-sensitive adhesive tape, for example, U.S. It is reported in Patent Publication No. US2012 / 0115405 (Nitto Denko Corporation). In the above patent, the double-sided tape consists of a substrate on which the first side is coated with a rubber-based pressure sensitive adhesive and the second side is coated with an acrylic pressure-sensitive adhesive.

International Patent Publication No. WO2010 / 069800 (Tesa Se et al. ) Has a pressure consisting of a homogeneous mixture of at least one natural rubber component and at least one polyacrylate component to achieve improved properties in coagulation, aging and also weatherability. Sensing adhesives are described. The pressure sensitive adhesive can be used for tape.

European Patent No. EP2283100 B1 (Tesa Se) discloses a pressure-sensitive adhesive material comprising a mixture of a polymer blend of thermoplastic and / or non-thermoplastic elastomers and a vinyl aromatic block copolymer and an adhesive resin, among others. The pressure sensitive adhesive can be used for tape.

International Patent Publication No. WO2010 / 023229 (Loctite (R & D) Limited and Henkel AG & Co. KGaA) discloses a curable cyanoacrylate-based film that does not require a release substrate. One particular film disclosed consists of a combination of neopentyl cyanoacrylate and rubber components. The manufacturing process associated with this particular film is expensive due to the vapor pressure of neopentyl cyanoacrylate.

Guseva et al. (Russian Chemical Bulletin Volume 43, Issue 4, pp 595-598) describes the synthesis conditions of the functionalized 2-cyanoacrylate. Synthesis and performance of 1-adamantylmethyl 2-cyanoacrylate and 1,10-decanediol bis-2-cyanoacrylate in Khrustalev et al (Russian Chemical Bulletin Volume 45, Issue 9, pp 2172-2176). X-ray structure studies have been disclosed.

EP0470722 describes instant adhesives comprising neopentyl alpha-cyanoacrylates, which have advantageous adhesive properties at high temperatures and also whitening-preventing properties.

Nevertheless, even at the current technical level, there is still a need for alternative adhesive tape formulations that exhibit improved coating properties for carrier and release substrates, exhibit high initial tack, and exhibit improved bond strength. Thus, it may be desirable to provide articles such as (transfer) tapes that have good storage stability, exhibit good adhesion to various substrates, are easy to manufacture and inexpensive, and exhibit a combination of high initial tack and strong bond strength. have.

Adhesive articles such as adhesive tapes, transfer tapes, labels and laminates, which have high flexibility and high bonding strength, are for example for bonding parts in the electronics industry or for stitching in the textile industry for example As an alternative, it can be particularly advantageous. In particular, it is desirable to provide a robust fabric assembly with a durable joint that provides flexibility from a design and aesthetic point of view.

Adhesive articles, such as adhesive tapes, transfer tapes, labels and laminates, which are easily applied and can be cut by die cutting, are highly desirable for use in, for example, automated manufacturing processes. Adhesive articles such as adhesive tapes, transfer tapes, labels and laminates, which are effective for bonding substrates such as fabrics, which can withstand physical pressures such as being subjected to high humidity environments during cleaning, high temperatures and cleaning and drying cycles, for example For the manufacture of clothing it is very desirable.

Adhesive articles such as adhesive tapes, transfer tapes, labels and laminates are used in a variety of applications including bonding and shielding applications, especially in the construction industry. However, exposure to moisture and / or exposure to harsh environmental conditions that occur under high humidity conditions often reduces their applicability.

Adhesive articles, such as adhesive tapes, transfer tapes, labels, and laminates, that are resilient to high humidity, such as in a humid environment, can create bonds in which such articles, such as bathrooms, have weakened bonding strength, or Alternatively, the strength of the bond may degrade to an unsatisfactory level over time, which can be very advantageous in such cases.

Adhesive articles, such as adhesive tapes, transfer tapes, labels and laminates, which are effective for bonding ceramics, steel, wood, glass, rubber and plastics, are often bonded with strong and / or durable bonds to at least some of these substrates Because of this difficulty, it is very preferable in the case described above. This is particularly the case when the environment can also weaken the initial or aged bond strength, for example in an environment where exposure to harsh conditions and / or moisture is present.

[Summary of invention]

The present invention provides adhesive articles such as adhesive tapes, transfer tapes, labels, laminates, and the like.

In a first aspect, the present invention is an article comprising a curable film on a release substrate and / or a carrier substrate, wherein the film

(a) one or more cyanoacrylate monomers selected from compounds of formula (I)

[Wherein, R ¹ is a divalent linking group having 1 to 10 carbon atoms, and A represents a C ₅ -C ₅₀ aryl residue or a C ₂ -C ₅₀ heteroaryl residue]; And

(b) one or more film-forming (co) polymers

It provides an article comprising a.

As used herein, the term aryl residue refers to a monocyclic or polycyclic (non-fused or fused) aromatic carbocyclic structure. Similarly, the term heteroaryl refers to an aromatic heterocyclic structure having two or more different elements as ring atoms. Heteroaryl residues can be monocyclic or polycyclic (non-fused or fused). The carbon atom of the aryl or heteroaryl residue is, for example, one or more cyano groups, nitro groups, halogens, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ ethers, C ₁ -C ₁₀ thioethers, C ₁ -C ₁₀ ester, C ₁ -C ₁₀ ketone, C ₁ -C ₁₀ ketamine, C ₁ -C ₁₀ sulfone, C ₁ -C ₁₀ sulfoxide, C ₁ -C ₁₀ primary amide or C ₁ -C ₂₀ secondary It may be optionally substituted one or more times with an amide.

As used herein, the term release substrate is a material that acts as a protective coating of the curable film and prevents unwanted adhesion and contamination of the adhesive surface during transportation and manipulation. The release substrate can be coated on one or both sides with a release agent and can be removed to release an adhesive material, such as a pressure sensitive adhesive, without adversely affecting the integrity of the curable film.

With regard to the articles of the invention, the release substrate may be a plastic-based (eg PET, PE, HDPE, PP) material or paper optionally coated with a release agent.

The release agent can easily transfer the adhesive film of the article of the invention from the release substrate to the article of interest. The release agent may be selected from the group consisting of polyvinyl alcohol, clay, siloxane and combinations thereof. Suitable release agents, especially siloxane-based release agents, are those sold under the trade name SILCOLEASE®.

As used herein, the term carrier substrate means a material that can be coated on a curable film to stabilize the adhesive. The carrier substrate can increase the thickness of the article to improve manipulation. The carrier substrate differs from the release substrate in that it cannot be removed from the curable film without adversely affecting the intact shape of the curable film.

The carrier substrate can be flexible, and can be, for example, a flexible sheet. The carrier substrate can be selected from polymeric films, metal foils, foams, fabrics and combinations thereof. For example, the carrier substrate can be selected from the group consisting of polyester, polypropylene, polyethylene, foam and paper.

In the context of the present specification, the term (co) polymer means a polymer derived from a single monomeric species or a polymer derived from two (or more) monomeric species.

The term film forming (co) polymer refers to a (co) polymer material that, when formulated with a cyanoacrylate monomer of formula (I), provides a curable film.

The film-forming component can help solidify any liquid component in the composition. This increases the total viscosity of the combined material and allows the combined material to remain on the transfer substrate. The film-forming component may include a film-forming agent, which may be one or more elastic additive components. When solid cyanoacrylates are used, the addition of a film former is less required since the curable component can be present on the substrate after it is typically applied. When a composition comprising a mixture of solid and liquid cyanoacrylates is used, an appropriate amount of film-forming component can be added to the composition as a compensation for the level of liquid curable component present. In particular, solid monomeric materials can form non-cohenrent films due to, for example, crystalline properties for application, but film-forming components provide suitable structures or frameworks to provide agglomerated films do. Aggregated films can be achieved with a combination of film-forming components and co-curatives.

Advantageously, the curable films of the articles of the present invention exhibit pressure sensitive adhesive properties at 23 ° C. Subsequent curing of the film can be initiated as appropriate. For example, if desired, external stimuli such as heat or radiation (such as UV curing) can be applied to induce curing of the curable film.

As used herein, the term “pressure-sensitive adhesive properties” means that the materials and formulations are permanently tacky and adhere under pressure. More particularly, the term means that the material or formulation has a glass transition temperature (T _g ) of less than 25 ° C and a storage modulus G 'of 3.3 x 10 ⁵ Pa or less at 23 ° C, where the glass transition temperature (T _g ) Is measured by differential scanning calorimetry (DSC), and the storage modulus G 'is measured by dynamic mechanical analysis (DMA) at 1 Hz and 23 ° C.

Many materials (eg, epoxy and silicon based materials) with high bond strengths used in packaging and encapsulant technology have stiffness. The lack of flexibility often excludes these materials from application to flexible optical elements. The application of liquid adhesives involves the formation of droplets, which makes accurate and thin distribution on the substrate difficult. The articles of the present invention are typically very flexible, and the amount of adhesive applied to the substrate can be very accurately determined by the amount of the article of the invention used. This means that the articles of the present invention are particularly useful in applications where flexibility is desired across the bond line.

Thin film adhesives with high flexibility, high bond strength and high refractive index are used in optical devices (sensors, diodes, fibers, lenses, etc.), flexible (touch-) screens (LCDs, plasma screens, etc.), photovoltaic industry and chip bonding, etc. It is preferred for flexible encapsulation, packaging and fixation, which can be achieved using articles of the invention, for example tapes of the invention.

The term divalent linking group refers to the portion connecting the unsaturated oxygen and aryl residue of the ester functional group.

With regard to the cyanoacrylate monomers of the articles of the invention, the variable A can be a C ₅ -C ₅₀ aryl residue.

For example, the cyanoacrylate monomer can be selected from compounds of formula (II):

[Wherein n is 0 to 5, R ² is a C _1-5 alkylene group, and each R ³ , when present, is independently C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, fluorine, Chlorine, bromine, cyano and nitro.

As used herein, the term "C _x -C _y alkyl" includes C _x -C _y unbranched alkyl, C _x -C _y branched alkyl and combinations thereof. The term "C _x -C _y alkylene group" may be configured as "C _x -C _y alkyl".

The cyanoacrylate monomer can have a melting point above 10C at 1013.25 mbar.

Regarding the compound of formula (II), n may be 0 to 2, R ² may be a C _1-3 alkylene group, and each R ³ , when present, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, fluorine, chlorine, bromine, cyano and nitro. For example, n can be 0 to 2, R ² can be a C _1-3 alkylene group, and each R ³ , if present, is independently selected from fluorine, chlorine, bromine, cyano and nitro. Can be. In another embodiment, n can be 0 and R ² can be a C _1-5 alkylene group. For example, n may be 0 and R ² may be a C _1-3 alkylene group.

The cyanoacrylate monomer may be (2-phenylethyl) 2-cyanoacrylate, that is, R ² is C ₂ H ₄ and n is 0 (II).

The cyanoacrylate monomer of general formula (I) may be present in an amount of at least 15% by weight, based on the total weight of the film. For example, the cyanoacrylate monomer can be present in an amount of 20% to 80% by weight, based on the total weight of the curable film.

The cyanoacrylate monomer of formula (I) may also be present in an amount of at least 10% by weight, based on the total weight of the film. For example, the cyanoacrylate monomer can be present in an amount of 10% to 90% by weight, based on the total weight of the curable film.

The film-forming (co) polymer may be present in an amount of 20% to 85% by weight, based on the total weight of the film.

The film-forming (co) polymer may be present in an amount of 10% to 90% by weight, based on the total weight of the film.

The film-forming (co) polymer is poly (meth) acrylate, polyvinyl ether, natural rubber, polyisoprene, polybutadiene, polyisobutylene, polychloroprene, butadieneacrylonitrile polymer, thermoplastic elastomer, styrene-isoprene, styreneisoprene -Styrene block copolymers, ethylene-propylene-diene polymers, styrene-butadiene polymers, poly-alpha-olefins, silicones, ethylene-containing copolymers, ethylene vinyl acetate and combinations thereof. Preferably, the film-forming (co) polymer may include poly (meth) acrylate and / or ethylene vinyl acetate.

The film-forming (co) polymer may have a glass transition temperature (Tg) of less than 30 ° C. as measured by differential scanning calorimetry (DSC).

The film-forming (co) polymer may be a (co) polymer having pressure-sensitive adhesive properties at 23 ° C.

The film forming (co) polymer can be a (co) polymer of (meth) acrylic acid, (meth) acrylic acid ester and optionally other comonomers.

The film-forming (co) polymer may have an acid number from about 0 to about 30. Preferably, the film-forming (co) polymer has an acid value of less than 15. The acid value is the weight in mg of KOH required to neutralize the pendant carboxylate groups in 1 g of the (co) polymer. The method for measuring the acid value of the (co) polymer is described in the experimental section below.

The film forming (co) polymer can be an ethylene vinyl acetate copolymer. The ethylene vinyl acetate copolymer may have a vinyl acetate content of 50% to 98% by weight based on the total weight of the ethylene vinyl acetate copolymer.

The curable film of the article of the present invention exhibits pressure sensitive adhesive properties at 23 ° C. The curable film of the articles of the present invention may have a storage modulus G 'of about 3.3 x 10 ⁵ Pa or less, as measured by dynamic mechanical analysis (DMA) at 1 Hz and 23 ° C.

The curable film of the article of the present invention can return to a tack value of about 3 N or greater, as measured by DIN EN 1719 in a standard loop tack test.

The curable film of the article of the invention may have a glass transition temperature (Tg) of less than 10 ° C. as measured by differential scanning calorimetry (DSC). For example, the curable film may have a glass transition temperature in the range of -60 to +10 ° C as measured by DSC.

The curable film of the articles of the invention may have a 180 ° peel strength of 3 N / 25 mm to 50 N / 25 mm after 10 minutes, as measured by DIN EN 1939 (Afera 5001) on a steel substrate at 23 ° C.

The curable film used in the present invention, in an uncured state, may have an elastic modulus G 'of about 3.3 x 10 ⁵ Pa or less at room temperature, as measured by DMA at 1 Hz, in accordance with DIN EN 1719 in a standard loop adhesion test. Upon measurement by, it can return to an adhesive value of 3 N or more, preferably 5 N or more.

The curable film used in the articles of the present invention may have an elastic modulus G 'of about 3.3 x 10 ⁵ Pa or less at room temperature when measured by DMA at 1 Hz in an uncured state, and differential scanning calorimetry (DSC) As measured by, it may have a glass transition temperature (Tg) of less than 10 ° C, for example -60 to + 10 ° C.

The curable film used in the article of the present invention has a glass transition temperature (Tg) of less than 10 ° C, for example -60 to + 10 ° C, as measured by differential scanning calorimetry (DSC) in an uncured state. It may have, and can be returned to the adhesive value of 3 N or more, preferably 5 N or more, as measured by DIN EN 1719 in the standard loop adhesion test.

The curable film used in the article of the present invention, in an uncured state, when measured by DMA at 1 Hz, at a room temperature of about 3.3 x 10 ⁵ Pa or less elastic modulus G 'and when measured by differential scanning calorimetry (DSC) , May have a glass transition temperature (Tg) of less than 10 ° C., for example -60 to + 10 ° C., as measured by DIN EN 1719 in a standard loop adhesion test, 3 N or higher, preferably 5 N or higher You can return to the value.

The curable film used in the article of the present invention, in addition to the solid cyanoacrylate of formula (I), poly (meth) acrylate, polyvinyl ether, natural rubber, polyisoprene, polybutadiene, polyisobutylene, polychloroprene , Butadieneacrylonitrile polymer, thermoplastic elastomer, styrene-isoprene, styreneisoprene-styrene block copolymer, ethylene-propylene-diene polymer, styrene-butadiene polymer, poly-alpha-olefin, silicone, ethylene-containing copolymer, ethylene vinyl Film forming (co) polymer matrix materials selected from the group consisting of acetates and combinations thereof. Preferably, the film-forming (co) polymer matrix material can include poly (meth) acrylate and / or ethylene vinyl acetate.

With regard to the articles of the present invention, based on the total weight of the film, the film may include:

(a) 15 to 80% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) 20 to 85% by weight of one or more film-forming (co) polymers; And

(c) 0 to 65% by weight of one or more additives.

For example, based on the total weight of the film, the film may include:

(a) 40 to 60% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) 40 to 60% by weight of one or more film-forming (co) polymers; And

(c) 0 to 20% by weight of one or more additives.

With regard to the articles of the present invention, based on the total weight of the film, the film may include:

(a) 10 to 90% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) 10 to 90% by weight of one or more film-forming (co) polymers; And

(c) 0 to 65% by weight of one or more additives.

Films of the articles of the invention further comprise one or more additives selected from cyanoacrylate polymers, tackifiers, plasticizers, toughening agents, antioxidants, stabilizers, dyes, absorbents and / or combinations thereof. Can be.

Suitable dyes include, but are not limited to, Naphthol Green, Coumarin, Carotene, m-Cresol purple, Copper (II) phthalocyanine (Cu (II) phthalocyanine), Phenol, anthraquinone, benzofuranone, polymethine, styryl, carbonium, triphenylmethane, diphenylmethane, trifendioxazine, phthalocyanine, quinophthalone, naphthol, stilbene, formazan, xanthene, Triarylmethane, carotenoids, flavonols, flavones, chromans, caramel poly (hydroxyethyl methacrylate) copolymers, riboflavin and derivatives and mixtures thereof.

The curable film is randomly selected from the group consisting of Naphthol Green, Coumarin, Carotene, m-Cresol purple, Copper (II) phthalocyanine An article further comprising a dye.

Examples of filler components include, but are not limited to, silica, quartz, alumina, calcium, clay, talc and other inorganic filler materials such as polycarbonate and other polymer powders, including, for example, with certain acrylate components.

Examples of stabilizer components that can be suitably used in the adhesive film of the present invention include hydroquinone, pyrocatechol, resorcinol or derivatives thereof, phenol, sulfur dioxide, sulfuric acid, alkyl sulfonic acid, aromatic sulfonic acid, borane and combinations thereof. Is included. For example, the stabilizer can be selected from methanesulfonic acid (MSA), BF ₃ , SO ₂ and combinations thereof. Suitably, the stabilizer can be selected from camphor sulfonic acid (CSA) or hydroquinone and combinations thereof.

Preferred examples of dyes that can be suitably used in the adhesive film of the present invention include carotene, naphthol green, coumarin, m-cresol purple, copper (II) phthalocyanine.

Cyanoacrylate compositions are usually relatively sensitive to certain materials, such as nucleophiles, because they tend to react with the cyanoacrylate component. However, the curable film of the present invention is quite strong and not as sensitive to nucleophiles as expected.

These unexpected results can be used in a number of ways. One of many ways is the optical component industry. A number of color-imparting components (often referred to as colorants, dyes and pigments) used in electronic or optical components or devices, such as LEDs, portable devices and LCDs, contain nucleophilic groups such as -OH, -NH, etc. . Accordingly, the curable film of the present invention may surprisingly contain components comprising nucleophilic groups, such as color-imparting components, without adversely affecting the initial or aged binding performance. This means that the articles of the invention are readily used in a variety of applications, including optical devices, as the invention can be used in applications where the color-imparting component having one or more nucleophilic groups is part of the curable film.

In one embodiment of the invention, the article of the invention is at least translucent and preferably transparent. Transparent materials (lenses, encapsulants, etc.), such as transparent tapes used in optoelectronics and optical packaging, should provide the maximum refractive index. The articles of the present invention may exhibit better results than existing high refractive index tapes (eg, some commercially available products have a refractive index value of 1.47). Preferred refractive index values for the cured form of the curable film range from about 1.45 to about 1.6. Preferred refractive index values for the cured form of the curable film range from about 1.47 to about 1.55. The refractive index can be further increased by mixing with other polymers or exchanging with a film-forming polymer.

The liquid adhesive forms, for example, water droplets. The size of these droplets can vary depending on the amount of adhesive applied. It may be difficult to apply the liquid form of the adhesive in exactly the required amount, and even because of the additional difficulty spreading on the applied adhesive surface, this may not be possible. The layer of adhesive is often thick, not flexible enough, or even brittle, which weakens the bond strength. The advantage of a liquid adhesive is its bond strength.

Articles of the invention comprising a curable film can be made thin and flexible, have a uniform shape, for example, have a flat surface, and can be repositioned and cut into any shape or shape desired. Yes (for example using die-cutting). For the above reasons, adhesive articles of the present invention, such as tapes, are preferred in some applications.

The development of articles such as tapes that simultaneously provide optical clarity, flexibility and high bond strength remains a challenging task. As a result, liquid adhesives that provide high bond strength are often used in electronic devices, such as cell phones exposed to mechanical stress, shock or heat, for example. Preferably, the article of the invention, for example in the form of a tape, is thin. The articles of the present invention can exhibit high bond strength, flexibility, optical clarity, refractive index, and can be die-cut.

In fact, the articles of the present invention can be used for such applications, as well as substrates of all types, including glass and anodized aluminum, PC / ABS, and others frequently used in devices such as optical components. It has been found to be suitable for other substrates. The bonds provided by the present invention are typically superior to conventional tapes.

The articles of the invention, for example tapes, are not only thin, but also provide a strong bond while maintaining flexibility.

The combination of these features makes the tape of the present invention very useful in applications where flexibility is required, for example when joining flexible substrates such as the laminate and textile manufacturing industries. Sometimes, it is desirable that stitches and seams are not used for aesthetic or other reasons (for example, stitchless seams in sports clothing and shoes such as running shoes and hiking shoes).

The tape spreads mechanical stress over a wider surface, and no weakness due to puncturing with a thread is found. Examples of those whose functionality is the first criterion are high performance fabrics / laminates used in applications such as parachutes, military uniforms, bulletproof vests, sports apparel and sports equipment, automotive and agricultural fabrics.

The multiple hotmelts used in the lamination process have several disadvantages. They must be applied at high temperatures (> 100 ° C), and once applied, repositioning is no longer possible, and some polyurethane-based hot melts tend to have an unpleasant odor. Because the hot melt is a liquid as described above, it is desirable to provide an alternative adhesive article, such as a tape.

In contrast to these shortcomings, articles of the invention, such as tapes, have a uniform thickness before lamination and subsequent processing is possible without loss of performance. Furthermore, high temperatures are not required during the application process and there is no unpleasant odor during the manufacturing process.

A time consuming manufacturing process can be avoided by relatively short exposure to temperature and pressure (hot press) followed by activation of the articles of the invention, such as tapes. Tests performed under precise conditions, impact times in the seconds range, provide very narrow and strong bonds.

Even today, in bathrooms and kitchens, the most common way to secure items such as appliances to mounting surfaces is to drill holes for screws, such as screws, on mounting surfaces such as walls, ceilings, and tiles. .

In contrast to many commercial adhesives, the high humidity environment promotes the curing process of the adhesive articles of the present invention on a number of different substrates (metal, glass, ceramic, aluminum, etc.). It is ideal for bathrooms, kitchens, swimming pools and outdoor applications.

In tensile strength tests on ceramic and metal surfaces, at different temperatures and relative humidity, the tapes according to the invention showed better results than commercially available adhesive products. Preferably, many of the articles of the invention have been found to increase bond strength under high temperature and high humidity conditions.

Other disadvantages of liquid formulations may include the need for additional dispensing aids such as dispensing containers, nozzles or adapters. The amount of adhesive used when applying liquid formulations is much higher than the amount required when using the tape of the present invention. Finally, the curing time of liquid adhesives is quite long.

Advantageously, the adhesive article of the present invention avoids waste, only minimally reactive materials are used, and pre-cutting such as die-cutting can cut the length of the tape into the desired shape. The residue of the tape can be easily removed from the walls and tiles by washing it with ethyl acetate. This feature makes the product of the present invention very versatile and desirable.

With respect to the articles of the present invention, the weight ratio of the cyanoacrylate monomer of the formula (I) to the film-forming (co) polymer in the film may be 1: 8 to 8: 1. Suitably, the weight ratio of cyanoacrylate monomer of formula (I) to film forming (co) polymer in the film may be 1: 4 to 4: 1.

With regard to the articles of the present invention, the curable film, based on the total weight of the curable film, may include:

(a) 10 to 90, for example 15 to 80% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) 10 to 90, for example 20 to 85% by weight of one or more film forming (co) polymers (wherein the film forming copolymers have pressure sensitive adhesive properties at 23 ° C.); And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, the curable film, based on the total weight of the curable film, may include:

(a) 10 to 90, for example 15 to 80% by weight of (2-phenylethyl) 2-cyanoacrylate;

(b) 10 to 90, for example 20 to 85% by weight of one or more film forming (co) polymers; And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, the curable film, based on the total weight of the curable film, may include:

(a) 10 to 90, for example 15 to 80% by weight of (2-phenylethyl) 2-cyanoacrylate;

(b) 10 to 90, for example 20 to 85% by weight of one or more film forming (co) polymers (wherein the film forming copolymers have pressure sensitive adhesive properties at 23 ° C.); And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, based on the total weight of the film, the film may include:

(a) 10 to 90, for example 15 to 80% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) from 10 to 90, for example from 20 to 85% by weight, of one or more film forming (co) polymers of (meth) acrylic acid, (meth) acrylic acid ester and optionally other (co) monomers; And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, based on the total weight of the film, the film may include:

(a) 10 to 90, for example 15 to 80% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) from 10 to 90, for example from 20 to 85% by weight, of one or more (co) polymers of (meth) acrylic acid, (meth) acrylic acid esters and optionally other comonomers, wherein the (co) polymer is 23 ° C. At pressure sensitive adhesive properties); And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, the curable film, based on the total weight of the curable film, may include:

(a) 10 to 90, for example 15 to 80% by weight of one or more cyanoacrylate monomers selected from compounds of formula (I);

(b) 10 to 90, for example 20 to 85% by weight of one or more film-forming ethylene vinyl acetate copolymers; And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, the curable film, based on the total weight of the curable film, may include:

(a) 10 to 90, for example 15 to 80% by weight of (2-phenylethyl) 2-cyanoacrylate;

(b) 10 to 90, for example 20 to 85% by weight of one or more film-forming ethylene vinyl acetate copolymers; And

(c) 0 to 65% by weight of one or more additives.

With regard to the articles of the present invention, the curable film, based on the total weight of the curable film, may include:

(a) 10 to 90, for example 15 to 80% by weight of (2-phenylethyl) 2-cyanoacrylate;

(b) from 10 to 90, for example from 20 to 85% by weight, of one or more film forming (co) polymers of (meth) acrylic acid, (meth) acrylic acid ester and optionally other (co) monomers; And

(c) 0 to 65% by weight of one or more additives.

Alternatively, the curable film may include the following, based on the total weight of the curable film:

(a) 10 to 90, for example 15 to 80% by weight of (2-phenylethyl) 2-cyanoacrylate;

(b) from 10 to 90, for example from 20 to 85% by weight, of one or more (co) polymers of (meth) acrylic acid, (meth) acrylic acid esters and optionally other (co) monomers, wherein the (co) polymer is Pressure sensitive adhesive properties at 23 ° C.); And

(c) 0 to 65% by weight of one or more additives.

Suitable poly (meth) acrylate (co) polymers include DuroTAK ^® 2123. Suitable ethylene vinyl acetate copolymers include Levamelt ^® 900.

Suitable additives can be selected from cyanoacrylate polymers, tackifiers, plasticizers, toughening agents, antioxidants, stabilizers, absorbents and / or combinations thereof.

Suitable tackifiers are known to those skilled in the art. The source of tackifiers can be found in the standard literature on pressure sensitive adhesives, for example in "Handbook of Pressure Sensitive Adhesive" from Donata Satas (van Notstrand, New York, 1989).

The article of the present invention may take the form of an adhesive transfer tape, including:

-A curable film according to the invention located on a release substrate (the curable film has two adhesive surfaces), and optionally

-A second release substrate (covering substrate) placed on top of the curable film,

-Release substrate (s) having a release function for the film.

The first and second release substrates can be paper, cloth or plastic based materials or combinations thereof, optionally coated with a release agent. The release agent can easily transfer the adhesive film of the article of the invention from the release substrate to the article of interest. The release agent may be selected from the group consisting of polyvinyl alcohol, clay, siloxane and combinations thereof. Suitable release agents, especially siloxane-based release agents, are those sold under the trade name SILCOLEASE®.

Advantageously, the adhesive transfer film with the first and second release substrates enables easy manipulation of the film between two release layers and safe protection of the film.

When using the first and second release substrates, it is clear which release layer should be removed first, so they must have different release properties for the film.

When only the first release substrate is used and the second or covering release substrate is not used, the first release substrate should preferably have release properties on both sides. Preferably, the release characteristics are different on both sides. When winding a product (substrate and film) with a roll, there may be a clear difference between the release effects of the two sides. Consequently, the film will preferably adhere to one side during unwinding.

The articles of the invention may also take the form of single-sided adhesive tapes, including:

-A curable film according to the invention located on a carrier substrate, and optionally

-A release substrate on a curable film, the release substrate having a release function for the film.

The carrier substrate that stabilizes the film can be selected from paper, polymeric films, metal foils, foams, fabrics, and combinations thereof. It can include several layers, for example a primer layer that contrasts with the film to bond the film and a carrier substrate, or a release layer that is present on the opposite side of the film.

The articles of the invention may take the form of double-sided adhesive tapes, including:

-A first curable film according to the invention located on the first side of the carrier substrate,

A second curable film according to the invention located on the second side of the carrier substrate, wherein the carrier substrate is disposed between the first film and the second film, and optionally

-A first release substrate on the first curable film, and / or

-A second release substrate on the second curable film

(The release substrate (s) has a release function with respect to the film (s)).

The first and second curable films can be the same or different, that is, they can include the same or different combinations of one or more cyanoacrylates of formula (I) and a film forming (co) polymer. The first and second release substrates can have different release properties for the first and second curable films. The first and second curable films can be the same or different, that is, they can include the same or different combinations of one or more cyanoacrylates of formula (I) and a film-forming (co) polymer, the first And the second release substrate may have different release properties for the first and second curable films.

The carrier substrate between the two film layers can be selected from paper, polymeric films, metal foils, foams, fabrics, viscoelastic materials and combinations thereof. Examples of the viscoelastic material include poly (meth) acrylate, polyvinyl ether, natural rubber, polyisoprene, polybutadiene, polyisobutylene, polychloroprene, butadiene acrylonitrile polymer, thermoplastic elastomer, styrene-isoprene, styrene-isoprene -Styrene block copolymers, ethylene-propylene-diene polymers, styrene-butadiene polymers, poly-alpha-olefins, silicones, ethylene-containing copolymers, ethylene vinyl acetate and / or combinations thereof. The carrier substrate may include tackifiers, plasticizers, toughening agents, antioxidants, stabilizers, absorbents and / or combinations thereof. The carrier substrate can be in the form of a foam of this material.

The first and second release substrates can be paper, cloth or plastic based materials or combinations thereof, optionally coated with a release agent. The release agent can easily move the adhesive film of the article of the present invention from the release substrate and rewind the article into a roll. The release agent may be selected from the group consisting of polyvinyl alcohol, clay, siloxane and combinations thereof. Suitable release agents, especially siloxane-based release agents, are those sold under the trade name SILCOLEASE®.

Articles of the invention, such as transfer films, single-sided tapes, double-sided tapes, or labels, can be protected from ambient conditions such as light, heat or moisture to extend their shelf life.

The article according to the invention can be made by coating a curable film on a carrier substrate or release substrate, and then laminating it on a further release substrate or carrier substrate. The coating process may be a hot melt-process, a solid-based process (ie, no solvent), a solvent-based process, or a dispersion process.

In a hot melt process, the components of the film of the present invention are mixed by a suitable mixing device such as an extruder, the mixture is melted through a suitable device such as an extruder, and the mixture is formed into a film through a suitable device such as an extruder and a substrate. It is coated onto and formed into a film of suitable thickness through a die. Such hot melt mixing and coating processes are well known in the adhesive and tape industry.

In a solid-based process (i.e., no solvent), the curable film contains only solids, i.e., the film is 100% solids. In the dispersion process, the components of the curable film are mixed in a liquid phase, for example an aqueous liquid phase. The aqueous liquid phase can be water.

In a solvent process, the components of the film of the invention are mixed in one or more solvents, such as benzene, toluene, acetone, ethyl acetate and other organic solvents or combinations thereof. After dissolving / dispersing and mixing the components, the mixture is coated on a release substrate or carrier substrate, the solvent is removed by drying, and the film is rolled up. Such solvent mixing, coating and drying processes are well known in the adhesive and tape industries.

Preferably, the film of the present invention is produced by a solvent process. Preferably, the solvent is ethyl acetate.

Since the article of the present invention can exhibit pressure sensitive adhesive properties at 23 ° C., it can initially adhere or adhere to the target surface. Preferably, other stimuli such as heat and / or radiation (such as UV radiation) are used to promote curing of the adhesive film. If radiation is used to initiate or promote, additional cure shields may be used to selectively induce cure.

In a further aspect, the present invention provides a method of attaching a curable film to a surface, comprising the following steps:

(a) providing an article according to the invention;

(b) attaching the curable film of the article to one or more surfaces to form an assembly;

(c) exposing the assembly to conditions sufficient to cure the curable film of the article,

Here, the release substrate (s) of the article, if present, are removed before and / or after step (b).

The article of the present invention can be a transfer tape, a single-sided adhesive tape or a double-sided adhesive tape. Since the articles of the present invention can exhibit pressure sensitive adhesive properties at 23 ° C., attaching the curable film of the article to one or more surfaces can be accomplished by applying pressure to the curable film on the surface.

Articles of the present invention, such as transfer films, single-sided tapes, double-sided tapes, or labels, include, but are not limited to, metals, metal alloys, glass, enamel, wood, natural or synthetic fabrics and fibers, leather, stones, ceramics, plastics, paper or It can be used for bonding multiple substrates or surfaces, including cards, plastics, composites, and living tissues and organs.

Conditions sufficient to cure the curable film of the articles of the invention may include heat and / or radiation (such as UV radiation).

In a further aspect, the present invention provides a method of adhering parts to one another, comprising the following steps:

(i) providing an article according to the invention;

(ii) attaching the curable film of the article to one or more parts;

(iii) mating the parts; And

(iv) curing the adhesive film between them so that the parts are adhered to each other,

Here, the release substrate of the article, if present, is removed before and / or after step (ii).

Since the articles of the present invention can exhibit pressure sensitive adhesive properties at 23 ° C., attaching the curable film of the article to one or more parts can be achieved by applying pressure to the curable film on the part.

Conditions sufficient to cure the curable film of the articles of the invention may include heat and / or radiation (such as UV radiation).

For example, the method of the present invention is a method of adhering parts to each other using a transfer tape according to the present invention, and may include a method comprising the following steps:

(i) providing a transfer tape according to the invention;

(ii) attaching the curable film of the transfer tape to one or more parts;

(iii) matching the parts; And

(iv) curing the adhesive film between them so that the parts are adhered to each other,

Here, the release substrate (s) of the transfer tape, if present, are removed before and / or after step (ii).

Substrates joined by articles of the present invention may include one or more flexible substrates, for example, one or more substrates may be fabric or flexible laminate material.

Conditions sufficient to cure the curable film of the articles of the invention may include heat, humidity, and / or radiation (such as UV radiation).

When bonding fabrics, conditions sufficient to cure the curable film of the articles of the invention may suitably include the application of short heat exposures, such as short heat bursts, such as heat shock.

The transfer tape can include one or two release substrates as illustrated in Figures 3 and 4 below. As used herein, the term transfer tape means an article in which a release substrate can be used to move a curable film to a target substrate or surface.

Advantageously, the method of using the article of the invention, such as the transfer tape described above, can be used as an alternative to stitching. Such a method can be described as a stitch-free seam.

Preferably, the method of using the article of the present invention, such as a transfer tape for bonding fabrics, is completely flexible and at the same time provides very strong bonding.

Compared to a liquid adhesive, the method of using the article of the present invention, such as a transfer tape, does not cause the liquid adhesive to penetrate into the fabric and does not leave stains or traces when applied.

Advantageously, the method of using the article of the invention, such as a transfer tape, leads to the formation of a fabric assembly with excellent solvent resistance, which can withstand high temperature cleaning and high temperature drying processes. The method of using the articles of the present invention, such as transfer tapes, is particularly suitable for use in the manufacture of high performance mechanical fabrics, ie those with a first functional criterion, for example protective garments, agricultural fabrics, automotive fabrics and the like.

Advantageously, the method of adhering parts together in a high humidity environment using an article of the invention, such as a transfer tape, provides an alternative to drilling holes in the tile, thereby possibly damaging the intact form of the hidden pipe or decorative tile. Remove it.

Another aspect of the present invention is a method of adhering one or more electronic components to a substrate, including, for example, joining two electronic components to each other in the following manner:

(i) providing an article according to the invention;

(ii) attaching the curable film of the article to one or more parts;

(iii) matching the parts; And

(iv) curing the adhesive film between them so that the parts are adhered to each other,

Here, the release substrate of the article, if present, is removed before and / or after step (ii).

Other components that can be combined using the articles according to the invention include components in optical elements and optoelectronics.

In a further aspect of the invention, the adhesive article, such as the transfer tape described in the present invention, can be used for, for example, electronic chip bonding, sensors, diodes, fibers, lenses, LCDs, plasma screens, etc. It can be used for encapsulation and / or packaging.

Thin film adhesives with high flexibility, high bond strength and high refractive index are used for sensors, diodes, fibers, lenses, photodiodes, phototransistors, photomultipliers, integrated optical circuit elements, photoresistors, photoconductive cameras tubes, charge-coupled imaging devices, laser diodes, optical devices such as quantum cascade lasers, light-emitting diodes, flexible (touch-) screens (LCD, plasma screens, etc.), photovoltaic cells It is very suitable for flexible encapsulation, packaging and fixing in industrial and chip bonding.

In a further embodiment, the method of the present invention is a method of attaching parts to each other using a single-sided adhesive tape according to the present invention, wherein the single-sided adhesive comprises one of the parts, a method comprising the following steps: May contain:

(i) providing a single-sided adhesive tape according to the invention;

(ii) attaching the curable film of the single-sided adhesive tape to the component; And

(iii) curing the adhesive film,

Here, the release substrate of the single-sided adhesive tape, if present, is removed prior to step (ii).

Generally, single-sided adhesive tapes do not include release substrates or have one release substrate as illustrated in Figures 1 and 2 below.

In another further embodiment, the method of the present invention is a method of adhering parts to each other using a double-sided adhesive tape according to the present invention, which may include a method comprising the following steps:

(i) providing a double-sided adhesive tape according to the present invention;

(ii) attaching the first curable film of the double-sided adhesive tape to one or more parts;

(iii) attaching the second curable film of the double-sided adhesive tape to other parts; And

(iv) curing the curable film between them so that the parts are adhered to each other,

Here, the release substrate (s) of the double-sided adhesive tape, if present, are removed before and / or after step (ii).

The double-sided adhesive tape can include one or two release substrates as illustrated in FIGS. 5 and 6 below.

The articles of the present invention are more particularly for a wide range of applications, such as, but not limited to, lamination, binding, shoe assembly, parts of automobiles, air conditioning systems, parts of electrical or electronic devices or other durable consumer goods, parts used in the construction industry [eg For example, it can be used industrially throughout assembly, packaging, die attach applications, wound closure, suturing, medical device applications and all kinds of labeling of insulation / sound insulation (thermal and acoustic). The parts may be bonded to the longitudinal ends of the material, for example, rolls of two materials may be spliced with each other.

The articles of the invention can be used for stacking or shielding a substrate, covering part or all of a substrate, bonding both sides of a gap to each other, packaging a substrate or bundle portion together, and / or combinations thereof. have.

In industrial processes, articles of the present invention, such as transfer films, single-sided tapes, double-sided tapes, or labels, can be used in a continuous feed process. For example, a carrier or release substrate can be continuously supplied into the device for moving the adhesive film onto the carrier or release substrate, and the thus formed article can be contacted with the (part) for its bonding.

All numerical ranges and ratios disclosed herein include the last point presented.

It is understood that, where appropriate, all optional and / or preferred features of one embodiment of the present invention may be combined with all optional and / or preferred features of another / other embodiment (s) of the present invention.

Additional features and advantages of the invention are described in the detailed description and drawings of the invention, from which additional features and advantages of the invention can be clarified:
1 illustrates a single-sided tape without a release substrate according to the invention;
2 illustrates an embodiment of an article of the invention that may correspond to a single-sided tape or label with a release substrate;
3 illustrates a transfer tape with one release substrate according to the invention;
Figure 4 Illustrates a transfer tape with two release substrates according to the invention;
5 illustrates a double-sided tape with one release substrate according to the invention;
6 illustrates a double-sided tape with two release substrates according to the invention; And
7 illustrates the refractive index values of different curable films.

The examples disclosed herein below are merely examples, and other methods and methods capable of replicating the present invention are possible, and it will be apparent to those skilled in the art that they are included in the present invention.

1 , single-sided tape 101 is shown. The single-sided tape 101 consists of a carrier substrate 102 and a curable film 103, and the curable film 103 comprises at least one cyanoacrylate of formula (I) and a film-forming (co) polymer (above). The surface of the carrier substrate opposite the curable film may be a specific release agent-treated surface.

2 may be a single-sided tape or label 201. The single-sided tape or label 201 consists of a carrier substrate 102 and a curable film 103; Curable film 103 comprises at least one cyanoacrylate of formula (I) and a film forming (co) polymer. The curable film 103 is covered with a release substrate 104 to protect the curable film and prevent unwanted adhesion of the curable film 103.

3 and 4 show a transfer tape according to the invention. Transfer tapes are particularly useful for moving a curable film from a release substrate to a target surface. In Fig. 3 , the transfer tape 301 consists of a release substrate 104 coated with a curable film 103. Curable film 103 comprises at least one cyanoacrylate of formula (I) and a film forming (co) polymer. The release substrate 104 should preferably have release properties on both sides. Preferably, the release characteristics are different on both sides. Therefore, when the transfer tape 301 is wound and unwound with a roll, there may be a difference in the release effect on both sides of the release substrate 104.

In Fig. 4 , the transfer tape 401 consists of a curable film 103, comprising at least one cyanoacrylate of formula (I) and a film forming (co) polymer sandwiched between the first and second release substrates 104 and 105 have. The first and second release substrates 104 and 105 may have different release properties for curable films. This enables the first and second release substrates 104 and 105 to be removed independently of each other.

Double-sided adhesive tape 501 is shown in FIG. 5 . The tape 501 consists of a carrier substrate 102 having a first curable film 103 on a first side of the carrier substrate 102 and a second curable film 106 on a second side of the carrier substrate 102. The first and second curable films 103 and 106 can be the same or different, that is, can include the same or different combinations of one or more cyanoacrylates of formula (I) and a film forming (co) polymer. The release substrate 104 covers and protects the second curable film 106. The release substrate 104 should preferably have release properties on both sides. Preferably, the release characteristics are different on both sides. Therefore, when winding and unwinding the double-sided tape 501 with a roll, there may be a difference in the release effect on both sides of the release substrate 104.

A second embodiment of double-sided adhesive tape 601 is provided in FIG. 6 . The tape 601 consists of a carrier substrate 102 having a first curable film 103 on a first side of the carrier substrate 102 and a second curable film 106 on a second side of the carrier substrate 102. The first and second curable films 103 and 106 can be the same or different, that is, can include the same or different combinations of one or more cyanoacrylates of formula (I) and a film forming (co) polymer. The first release substrate 104 covers and protects the first curable film 103. The second release substrate 105 covers and protects the second curable film 106. The first and second release substrates 104 and 105 may have different release properties for curable films 103 and 106.

7 shows several indexes of refraction of some tapes obtained from different formulations. Levamelt (bar 1 of the bar chart) represents the curable film obtained from tape 1, bars 2 to 4 represent tapes obtained by mixing styrene-PheCA copolymers, bars 5 to 7 represents the tape obtained by replacing the lebamel with a binol type polymer, and finally the last bar is a dye / colorant such as naphthol green, coumarin, carotene, m-cresol purple, copper (II) phthalocyanine and other substances or The tape obtained by adding pigment to the adhesive material is indicated.

Example

material

Levamelt ^® 900 is a film-forming ethylene vinyl acetate copolymer having a vinyl acetate content of about 90% by weight (commercially available from Lanxess AG, Leverkusen, Germany).

Durota ^® 2123 is a solution of a film-forming (meth) acrylic acid ester copolymer in ethyl acetate (commercially available from Henkel AG & Co. KGaA, Dusseldorf, Germany).

Neopentyl 2-cyanoacrylate (NCA) is a solid cyanoacrylate (melting point 41 ° C.), which can be synthesized according to WO2010 / 023229.

(2-phenylethyl) 2-cyanoacrylate (PheCA) is a solid cyanoacrylate (melting point 30-32 ° C), which is a Knoevenagel using 2-phenician acetate, formaldehyde and catalyst. ) After reaction according to the method, it may be synthesized through a cracking process. Suitable synthesis is [Sato, Mitsuyoshi, Okuyama and Toshio, Jpn. Kokai Tokkyo Koho (1994)] and JP 06192202A.

Release substrate 1 (RS 1) is a 50 μm thick polyester film covered on both sides with a silicone coating.

Release substrate 2 (RS 2) is a polyethylene film with a thickness of 50 μm, both sides covered with a silicone coating.

The super glue is a typical cyanoacrylate adhesive. This is Henkel AG & Co. KGaA, available from Dusseldorf, Germany as Loctite 4062.

Tape manufacturing

Different curable film formulations were prepared in HDPE bottles according to the following procedure: The film forming (co) polymer was dissolved in ethyl acetate to obtain a 50% by weight solution. The cyanoacrylate monomer and additional ethyl acetate were added to obtain a 50% by weight (cyanoacrylate monomer + film forming (co) polymer) solution in ethyl acetate. All formulations were stable in the presence of sulfonic acid, BF ₃ or SO ₂ as stabilizer.

To prepare the tape, the curable film formulation was coated on a release substrate using a blade-mounted draw-down coater. The wet curable film was left at 22 ° C for 10 minutes. The release liner and the curable film are further dried in an oven with air-flow at 90 ° C. for 5 minutes, or ethyl acetate is removed to a residual solvent level of less than 1% by weight. Dried as much as possible. The following tapes were prepared:

Tape 1 (PheCA + Levamelt ^® 900)

Curable film formulation: 25% by weight PheCA, 25% by weight Levamelt ^® 900, 49.957% by weight ethyl acetate, 0.04% by weight hydroquinone, 0.003% by weight camphor-10-sulfonic acid;

Substrates: RS 1 and RS 2;

Curing film basis weight: 40 g / m ²

Tape 2 (PheCA + Durotak ^®  2123)

Curable film formulation: 35 wt% PheCA, 15 wt% Durotak 2123 (polymer), 49.957 wt% ethyl acetate, 0.04 wt% hydroquinone, 0.003 wt% camper-10-sulfonic acid;

Substrates: RS 1 and RS 2;

Curing film basis weight: 40 g / m ²

Comparison Tape 1 (NCA + Levamelt ^®  900)

Curable film formulation: 25 wt% NCA, 25 wt% Levamelt® 900, 49.957 wt% ethyl acetate, 0.04 wt% hydroquinone, 0.003 wt% camper-10-sulfonic acid;

Substrates: RS 1 and RS 2;

Curing film basis weight: 40 g / m ²

Comparative Tape 2 (Durotak ^®  2123)

The curable film ^{formulation: Durotak ® 2123 (68.7% Durotak} 2123 polymer by weight or 31.3% by weight of ethyl acetate);

Substrates: RS 1 and RS 2;

Curing film basis weight: 40 g / m ²

The properties of the different tapes were evaluated using the following test method.

Test Methods

Loop tack

Loop tack was measured according to DIN EN 1719: The curable film was laminated on aluminum and cut into strips with a width of about 25 mm and a length of about 300 mm. The strip was immediately measured on a "Zwick" tensile tester Z010 at a speed of 100 mm / min.

To measure loop tack after curing, specimens were prepared as described above. Before placing the specimen on the "Zwick" tensile tester Z010, the curable film was cured under the conditions described and loop tack was measured as described above.

Shear resistance

The film was laminated on a polyester film and cut into strips about 25 mm wide and about 50 mm long. The strip was placed on a steel plate to cover an area of about 25 mm x 25 mm at the edge of the steel plate. Immediately after manufacturing the steel plate, it was placed vertically in a suitable device and pressed with a load of 1 N to 160 N. The shear value was the maximum stress (in Newton) when the strip was still attached to the plate after 4 hours.

To measure shear resistance after curing, specimens were prepared as described above. The curable film was cured under the conditions described before measuring the shear resistance as described above.

Lap shear test

Grit blasted mild steel (GBMS) panels: GBMS panels consist of grit blasted mild steel. Grit blasting should be performed less than 24 hours prior to testing. Blasting medium: Corundum, diameter 0.21-0.3 mm, blasting pressure 3 bar. The curable film was moved to a GBMS steel panel (25 mm width) to cover the 25 mm x 12.5 mm (312.5 mm ² ) area of the edge of the first steel panel. A second steel panel was placed on the first panel so that the covered area completely overlapped. The steel panels were compressed together using two clamps (the load of each of these is 45-90 N). Thereafter, the obtained specimens were stored under predetermined temperature and time conditions.

Wrap shear strength was measured using a “Zwick” tensile tester Z010. Speed: 2 mm / min; Initial load: 5 N. The value obtained was the maximum force before the specimen failed.

To measure the wrap shear strength after curing, specimens were prepared as described above. The curable film was cured under the conditions described before measuring the wrap shear strength as described above.

Differential Scanning Calorimetry (DSC)

For DSC measurement, a NETZSCH DSC204F1 instrument was used and the measurement conditions were as follows: injection temperature range -80 ° C to 200 ° C (at a rate of 10 K / min), sample weight: 5 mg.

Dynamic Mechanical Analysis (DMA)

For DMA measurements, a METTLER TOLEDO DMA / SDTA861e instrument was used and the measurement conditions were as follows: Harmonic shear load 1 Hz, maximum force 1.5 N, maximum distance 10 μm, scan temperature range -150 ° C to 200 ℃. The storage modulus G 'was determined from the DMA results.

Example 1

The curable film of tape 1 exhibited high initial tack and excellent pressure-sensitive adhesive properties at 23 ° C. The curable film could be completely cured by exposing the film at a temperature of 65 ° C. for 1 hour and then at a temperature of 23 ° C. for 24 hours. The glass transition temperature (T _g ) of the curable film was -40 ° C, while the glass transition temperature (T _g ) of the cured film was 15 ° C. For the curable film, the storage modulus G 'was measured to be 3 · 10 ³ Pa.

Table 1 shows some material properties of tape 1.

The importance of the curing process is further shown in Table 2, where different curing conditions were used. High shear strength was observed only when the sample was exposed to conditions that could cause curing of the curable film.

Example 2

The curable film of tape 2 showed very high initial tack and very good pressure-sensitive adhesive properties at 23 ° C. The curable film could be completely cured by exposing the film at a temperature of 65 ° C. for 1 hour and then at a temperature of 23 ° C. for 24 hours.

Table 3 shows some material properties of tape 2.

Example 3 (comparative example)

Curing of the curable film for 1 hour at a temperature of 65 ° C. and then for 24 hours at a temperature of 23 ° C. did not sufficiently increase the wrap shear strength for GBMS, which makes the tape unsuitable for various structural bonding applications. It means that it may not.

Table 4 shows some material properties of Comparative Tape 1.

Example 4 (comparative example)

The film of Comparative Tape 2 showed high initial tack and pressure sensitive adhesive properties at 23 ° C. However, exposing the film to different conditions (see Table 5) did not lead to a significant increase in bond strength to GBMS, which means that the tape is not suitable for all structural bonding applications.

Procedure for measuring (co) polymer acid value

Replace the lid of the sample container with a lid equipped with a thermometer to check if the sample is at room temperature. Measure the temperature. When the temperature is 20 to 30 ° C., analysis can be started in a set order. If the temperature is not within the above range, the sample is placed in a water bath at 25 ° C, and the temperature is checked regularly until the temperature reaches a value between 20 and 30 ° C. Since some (co) polymers may contain volatile compounds, it is recommended to start with the analysis of the most critical parameters.

Way:

1. Weigh (co) polymer of Xg in a 250 cc sample bottle.

2. Add acetone. Before use, acetone is neutralized with 0.05 N KOH using phenolphthalein.

3. Shake the sample bottle until the (co) polymer is dissolved.

4. Cool the sample bottle (0-5 ° C) and titrate from clear to light pink using 0.05 N KOH. The color change should be maintained for 30 seconds.

5. If the (co) polymer has a low acid value (1.0 mg KOH / g maximum dry resin), a small 10 ml burette should be used.

The acid value of the (co) polymer is measured according to the following equation:

Total solids in the sample means% of dry polymer in (co) polymer. Generally, the (co) polymer is a solvent system. The typical value of total solids in the sample is 30-60%.

Fabric assembly method

Structural adhesive transfer tapes as described in the present invention are particularly useful for fabric assembly.

Fabric substrate

Commercial nylon, cotton and cotton-polyester (33% / 66%) x 2.5 cm Cut into 12.5 cm pieces, fabric specimens were prepared for lab shear or peel experiments.

Comparative experiments were performed using Henkel Technomelt PUR 7549, a polyurethane reactive hot melt liquid adhesive. Samples of Technomelt PUR 7549 fabric pre-laminated on nylon made in China were used for cleaning experiments and peeling measurements as received.

Plastic wrap shear specimen

The plastic wrap shear specimen was assembled according to STM 700 using a clamp (Wilton, model 365) and cured. Fabric wrap shear specimens were clamped between mild steel wrap shears using a clamp (Wilton, model 365) according to STM 700 and cured.

Heat shock press

A thermal shock press Fermant 400T was used for sealing experiments in a stitch free application. Using impact strength 5 (8 seconds), 2.5 cm x A 0.2 cm cured surface was produced. Subsequently, the bonded material was applied directly to a cleaning experiment or tensile strength test, respectively.

Heat press

For heat press experiments in tape applications, 320 cm x A piece of 320 cm fabric is cut, the tape is moved onto one piece of fabric, and the opened layer of tape is another 320 cm x Covered with a piece of 320 cm fabric.

For heat press experiments using competitive hot melt adhesives, 320 cm x A piece of 320 cm fabric is cut, one piece is placed on a hot plate (100 ° C.), the hot melt is moved onto the piece of fabric at 100 ° C. using a 40 μm coating knife, and finally the piece of fabric is of the same size. Covered with a second fabric layer.

320 cm x Heat Press Fontune TP-400 Pressure and heat were applied over 320 cm to cure the adhesive article of interest on a fully covered surface with a force of 20 kN for 2 minutes. Temperature during compression: 100 ° C.

Cleaning experiment

After heat press, 2.5 cm x Specimens with dimensions of 12.5 cm were cut from the laminated fabric, transferred into a glass 1 L round bottom flask equipped with a mechanical stir bar, and then 700 mL to 800 mL of tap water and half of a commercial somat tablet were added. The mixture was stirred at 100-250 rpm and heated to 100 ° C, 60 ° C, 40 ° C or room temperature. After 2 hours (or 24 hours if the experiment was performed at room temperature), the fabric specimens were removed, washed 3 times with clean tap water, and transferred to an oven at 60 ° C or 70 ° C. Dry for 2 hours. The piece of fabric was cooled to room temperature and allowed to stand at ambient temperature for 1-2 days before peeling or tensile strength was measured.

Tensile strength measurement

On Instron 5567 with 30kN, 1kN and 100N load cells respectively, on Zwick tensile tester Z100 with 100kN and 1kN load cells, on Zwick tensile tester type 144501 with 1kN load cell and on Zwick tensile tester KAF-Z, STM Wrap shear strength was measured according to 700. The test was repeated twice.

Peel experiment

Peeling was measured according to DIN EN 1939 modified on a Zwick tensile tester KAF-Z using a 1 kN load cell:

Specimen 2.5 cm x Cut to 12.5 cm.

Remove the sample to have a 5-6 cm opening, and verify that both open ends can be secured to the grip of the tensile tester.

· Set up the tensile tester:

· Grip to grip distance 60 mm

Pre-load 2 cN

Peak definition 0.1 N

Measurement path 100 mm

Pre-measurement path 2 mm

· Maximum extension 100 mm

Measurement speed 100 mm / min

・ Set the power again.

Fix the sample (without tension) and start.

・ When finished, return the grip.

・ Print the graph.

Calculate the average from all peaks above 0.1 N.

Repeat for all samples (2-3 times).

Example 5

A transfer tape, Tape 1, was applied to one of the two pieces of fabric, a second piece of fabric was superimposed on the tape, and a short thermal shock was applied to create a neat joint. An 8 second heat shock was applied to obtain a 2 mm wide neat seamless stitch with a total bound area of 50 mm ² .

Substrate failure (SF) means that the bulk strength of the fabric is much less than the bond strength of the bond. Failure of this type means successful treatment and selection of adhesives.

As shown in Table 6 below, after high temperature cleaning and drying, the adhesive strength was maintained.

Fabric wrap shear experiment

Tables 7 and 8 below show the results of lab shear tests on various fabrics. Different curing conditions have been suggested, including the effects of various cleaning and drying cycles.

Tables 9 and 10 show the lap shear results for tape 1 and comparative hot melt Technomelt PUR 7549 under different curing conditions.

Peeling experiment

Tables 11 and 12 show the results of the peeling test of the tape 1, which is a structural adhesive transfer tape as described in the present invention, and a commercial Technomelt PUR 7549.

Tape 1 showed better results than the comparative samples in experiments on cotton and cotton-polyester substrates.

Table 13 shows a 2 hour washing cycle at 60 ° C. and a 2 hour drying cycle; And after a 2 hour washing cycle and a 2 hour drying cycle at 40 ° C., the results of the peeling experiment of tape 1 on nylon, cotton and cotton-polyester materials are summarized.

Tables 14 and 15 show the results for Technomelt PUR 7549 when the peeling experiment was performed with the same cleaning and drying cycle.

Example 6

Structural adhesive transfer tapes as described in the present invention are particularly useful in high humidity environments.

material

Board

Wood specimens for lab shear testing were cut from commercially available red beech wood to the dimensions of conventional lab shear panels. Ceramic tile specimens were cut from commercially available tiles purchased from a DIY store to the dimensions of a typical wrap shear panel. The plane of the ceramic tile was used for the assembly of the bond. Mild steel wrap shear specimens were grit blasted using silicon carbide (manufactured by Gyson) at 4 bar pressure on a 1ULA 1400 grit blasting machine according to STM 700 before use. All tensile strength studies using lap shear specimens were performed according to STM 700.

Competitive sample

For comparative testing, "Nie wieder bohren (TEROSTAT MS 9380 WEISS DK310ML)", "Unibond No More Nails (original)", "Tesa Powerstrips" and "3M 467MP" were used. All competitive samples were applied as recommended by the supplier. Preparation of wrap shear specimens, application of the product and tensile strength tests were performed according to STM 700.

"Nie wieder bohren (TEROSTAT MS 9380 WEISS DK310ML)" is a 1K (1-part), silane modified polyether adhesive in the form of a white paste. It is suitable for application on smooth and rough surfaces. It is not a disposable adhesive and requires air and time (12 hours) to cure. Certain dispensing adapters sold separately are also required. The smallest commercially available dispensing adapter has a diameter of 35 mm and permanently carries a weight of 5 kg (0.5 MPa).

"Unibond No More Nails (original)" is a styrene acrylate copolymer commercially available from Henkel.

"Tesa Powerstrips" is wide; It is a double-sided adhesive strip (commercially available from Tesa AG).

3M 467MP is a 200MP adhesive, acrylic adhesive, double-sided transfer tape.

Tensile strength measurement

On Instron 5567 with 30kN, 1kN and 100N load cells respectively, on Zwick tensile tester Z100 with 100kN and 1kN load cells, on Zwick tensile tester type 144501 with 1kN load cell and on Zwick tensile tester KAF-Z, STM Tensile strength of the lap shear bond was measured according to 700.

Ceramics and steel using adhesive transfer tapes as described in the present invention; Ceramic and ceramic and rubber and steel were combined.

The bonding assembly was exposed to the following conditions for 24 hours:

20% RH, 20 ℃-Drying room condition

85% RH, 30 ℃-bathroom condition

98% RH, 40 ℃-bathroom condition

98% RH, 65 ℃-bathroom condition

The bonding area was 0.5 inch ² (322.6 mm ² ).

The results are summarized in Table 16 below. Curing conditions: carried out according to STM 700, using clamping for 24 hours at the indicated conditions. Bond strength was measured at room temperature.

Substrate failure means that the bulk strength of the material is much smaller than the adhesive and adhesive strength. Failure of this type means successful treatment and selection of adhesives.

In very high-humidity environments (> 85% room humidity (RH) and> 30 ° C), Tape 1 with a combined area of 0.5 inch ² (12.7 mm ² ) weighs about 65-270 Kg, depending on the substrate. Support.

Substrate failure at 98% humidity and 40 ° C. indicates very strong bond strength.

The adhesive strength is better in high humidity environments compared to standard room conditions.

Results of tape 1 bonding at different humidity levels to different substrates:

Curing 85% RH, 30 ° C:

Ceramic-GBMS-Force applied until bond breaks: 4.6 MPa (151 Kg) short term

Ceramic-ceramic-Force applied until bond breaks: 2.6 MPa (85 Kg)

GBMS-GBMS-4.6 MPa (153 Kg)

Curing 98% RH, 40 ° C:

Ceramic-GBMS-Force applied until bond breaks: 2.8 MPa (92 Kg) short term

Ceramic-ceramic-Force applied: 4.2 MPa (138 Kg)-Substrate failure: Stronger adhesion than substrate

GBMS-GBMS-Force applied until bond breaks: 5.5 MPa (181 Kg)

Curing 98% RH, 65 ° C:

Ceramic-GBMS-Force applied until bond breaks: 3.5 MPa (114 Kg) short term

Ceramic-ceramic-Force applied until bond breaks: 1.9 MPa (65 Kg)

GBMS-GBMS-Force applied until bond breaks: 8.2 MPa (270 Kg)

Preferably, the structural adhesive transfer tape is transparent, has a thickness of only a few microns, and adheres to most surfaces.

Table 17-21 compares the suitability of tape 1 to alternative products. The results of the comparative lab shear experiments are presented in Tables 17-21. Curing conditions were performed according to STM 700, using clamping for the indicated curing conditions. Curing was achieved by direct exposure to high temperature and high humidity environments. Bond strength was measured at room temperature.

Structural adhesive transfer tapes as described in the present invention, depending on the material, humidity and temperature, can support 30-270 kg before breaking.

Tape 1 showed better results than the comparative sample for all curing conditions shown in Table 22 in the post-cure wrap shear results for GBMS.

Tables 25-27 are ceramic-ceramics; Ceramic-GBMS; And it shows the results of the wrap shear for the adhesive tape 1 of GBMS-GBMS. Curing conditions: bonds were obtained without clamping, exposed directly to a high temperature and high humidity environment and tested according to STM 700. Bond strength was measured at room temperature.

Tables 27-31 compare the suitability of tape 1 with alternative commercially available products. The results of the comparative lab shear experiments are presented in Tables 25-31. Curing conditions: bonds were obtained without clamping, exposed directly to a high temperature and high humidity environment and tested according to STM 700. Bond strength was measured at room temperature.

Tables 32 and 33 show the suitability of tape 1 and 3M 467MP in a lab shear test after curing and aging at room temperature. Curing conditions: Performed according to STM 700 for GBMS, using clamping for the indicated curing conditions. After the curing time, the clamp was removed, and the specimen was stored at the ambient temperature for the indicated time. Bond strength was measured at room temperature.

Tables 34 and 35 show the suitability of tape 1 and 3M 467MP in a lab shear test over time at different temperatures. Curing conditions: Performed according to STM 700 for GBMS, using clamping for the indicated curing conditions. After the curing time, the clamp was removed, and the specimen was stored at the ambient temperature for the indicated time. Bond strength was measured at room temperature.

Table 36 shows the results of tape 1 and 3M 467MP in a lab shear test after curing at high temperature. Curing conditions: Performed according to STM 700, using clamping for the indicated curing conditions.

As is evident from the results in Table 36: Tape 1 showed better results than the comparative samples, under all high curing temperature conditions tested.

Solvent resistance

GBMS test specimens were cured and clamped according to STM 700. The clamp was removed (then the initial tensile strength was measured) and the bound wrap shear specimen was immersed in the solvent presented or placed under the indicated environmental conditions. After 24 hours, 48 hours, 100 hours and 500 hours, the lab shear was removed from the solvent / environmental conditions, then dried at ambient temperature and tensile strength was measured at room temperature.

Example 7

The adhesive article as described in the present invention, such as Tape 1, supported a weight of 15 kg or less after 9 hours of curing on the surface of 322.6 mm ² , which showed 3 times better results than the comparative sample.

High humidity and high temperature promote curing and develop bond strength. Therefore, when applied to wet areas, the bond may become stronger with time.

Optoelectronics

Structural adhesive transfer tapes as described in the present invention are particularly useful for the manufacture of optoelectronics and optical elements.

The following examples illustrate the suitability of adhesive articles as described herein for applicability in the optical and electronics industries.

material

Board

Wood specimens for lab shear testing were cut from commercial red beech wood to the dimensions of a typical lab shear panel. Nitrile butadiene rubber wrap shear specimens were cut from a wide mat, the width being the dimensions of a typical wrap shear panel but cut in half in length. Mild steel wrap shear specimens and aluminum wrap shear specimens (as shown) were grit blasted using silicon carbide (manufactured by Gyson) at 4 bar pressure on a 1ULA 1400 grit blasting machine, according to STM 700, prior to use. All other wrap shear specimens were used as received. All tensile strength studies using lap shear specimens were performed according to STM 700.

Competitive sample

3M 467MP double sided transfer tape was used as a comparative sample. All competitive samples were applied as recommended by the supplier. Preparation of wrap shear specimens, application of the product and tensile strength tests were performed according to STM 700.

additive

All additives were purchased from Sigma Aldrich and used as received without further purification.

keep

The tape was stored at 5 ° C or room temperature in a sealed aluminum pouch.

Tensile strength measurement

The tensile strength of the lap shear bond was measured on an Instron 5567 using 30kN, 1kN and 100N load cells (Dublin), on a Zwick tensile tester Z100 using 100kN and 1kN load cells (Dublin) and on a Zwick tensile tester type 144501 (Duesseldorf), respectively. Phase, measured according to STM 700.

Refractive index

The refractive index was measured at a temperature of 22 ° C-23 ° C on a Bellingham + Stanley 44-501 Abbe refractometer.

Example 8-Tape 3

The tapes used herein are solid cyanoacrylates (50%, such as neopentyl CA, 2-phenyl ethyl CA), toughening agents such as Levamelt (50%) and dyes in suitable solvents (chloroform, ethyl acetate). , Based on a coatable mixture of additives (several percent by weight), such as colorants and pigments. The mixture should suitably be a liquid for coating and should exhibit suitable stability.

High refractive index (RI) and transparency are required. Coating was performed on the carrier liner from the solution to form a transferable film after drying.

RI could be measured directly from the tape using an Abbey refractometer.

The tape was coated with a release liner with better release properties than those mentioned above. The tape was stored in a sealed pouch for next use or moved from the liner to the portion for immediate or subsequent bonding (or fixation) of the optical element. It can also be used as an encapsulant and in packaging.

The curable composition in Tape 3 was stored with rebamalt (4 g, 36.08% total solid, 11.08 g solution in ethyl acetate), 2-phenyl ethyl cyanoacrylate (4 g), CSA (48 μg, 0.2 g in ethyl acetate) Solution), hydroquinone (6.4 mg, 0.8 g stock solution in ethyl acetate), a mixture of beta carotene (0.04 g) dissolved in ethyl acetate (0.47 g). The coating solution was transferred to a siliconized polyethylene carrier liner using an automatic coating device. The solvent was removed at elevated temperature. The agglomerated uniform film was placed on the liner. The film was then covered with a release liner and stored at low temperature in a heat-sealed aluminum pouch.

Bond strength was measured according to STM-700.

As can be seen from Table 41, Tape 3 showed better results than the comparative sample, for each tested curing condition, in a lab shear test for GBMS.

As can be seen from Table 42, Tape 3 showed better results than the comparative sample, for each curing condition, in the lab shear test on wood.

As can be seen from Table 44, Tape 3 showed better results than the comparative sample, for each curing condition, in a lab shear experiment on glass.

As can be seen in Table 46, tape 3 showed better results than the comparative sample, for each curing condition, in the lab shear test for ABS.

As can be seen from Table 47, Tape 3 showed better results than the comparative sample, for each curing condition, in a lab shear experiment on PC / ABS (polycarbonate / acrylonitrile butadiene styrene). .

Ixef® (arylamide) compounds typically contain 50-60% glass fiber reinforcement, which imparts significant strength and stiffness. What makes it special despite having a high glass load is that the smooth, resin-rich surface provides a high gloss finish ideal for painting, metallization or the creation of natural reflective shells.

As can be seen from Table 48, Tape 3 exhibited similar performance to the comparative sample in a lab shear experiment when curing was performed at room temperature. However, when curing was carried out at 70 ° C. for 1 hour and at room temperature for 24 hours, Tape 3 showed almost better results by about 10 factors than the comparative sample.

As can be seen from Table 49, Tape 3 after curing for 1 week at room temperature showed better results than the comparative sample in a lab shear experiment on zinc bichromate.

As can be seen from Table 50, Tape 3 showed better results than the comparative sample, for all curing conditions, in a lab shear experiment on anodized aluminum.

As can be seen from Table 51, Tape 3 showed better results than the comparative sample for all curing conditions, in a lab shear experiment on the magnesium alloy.

As can be seen in Table 52, Tape 3 showed better results than the comparative sample, for each tested curing condition, in a lab shear experiment on lacquer 0754.

As can be seen from Table 53, Tape 3 showed better results than the comparative sample, for each tested curing condition, in a lab shear test on aluminum.

As can be seen from Table 54, Tape 3 showed better results than the comparative sample, for each tested curing condition, in a lab shear experiment on grit blasted aluminum.

As can be seen in Table 55, Tape 3 showed the same or better results than the comparative samples, for each tested curing condition, in a lab shear experiment on nitrile butadiene rubber.

Tables 56-68 show the results of bonding performance experiments for the modification of curable film formulations of structural adhesive transfer tapes (SATT) as described in the present invention.

Refractive index

The refractive index was measured at 22 ° C-23 ° C on a Bellingham + Stanley 44-501 Abbey refractometer.

Curing conditions: Performed according to STM 700, using clamping for the indicated curing conditions.

Vinol® surface coating resins represent a wide range of vinyl chloride-derived copolymers and terpolymers used in different industrial applications. The main component of this polymer is a different composition of vinyl chloride and vinyl acetate. The vinyl chloride copolymer does not contain any other functional groups. The terpolymer of Vinnol® products additionally contains carboxyl or hydroxyl groups.

The words "comprises / comprising" and the words "having / comprising" as used in connection with the present invention are used to specify the presence of the stated feature, integer, step or component, but one or more other features, integers, steps, The presence or addition of components or groups thereof is not excluded.

For clarity, it is understood that certain features of the invention described in the context of individual embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, various features of the invention described in the context of a single embodiment can also be provided individually or in any suitable sub-combination.

Claims (41)

An article comprising a curable film on a release substrate and / or a carrier substrate, wherein the curable film is
(a) (2-phenylethyl) 2-cyanoacrylate; And
(b) one or more film-forming (co) polymers present in an amount of 20% to 85% by weight, based on the total weight of the curable film
The article containing. delete The article of claim 1, wherein the (2-phenylethyl) 2-cyanoacrylate has a melting point greater than 25 ° C. at 1013.25 mbar. delete The article of claim 1, wherein the (2-phenylethyl) 2-cyanoacrylate is present in an amount of at least 15% by weight, based on the total weight of the curable film. The article of claim 1, wherein (2-phenylethyl) 2-cyanoacrylate is present in an amount of 20% to 80% by weight, based on the total weight of the curable film. The method of claim 1, wherein the film-forming (co) polymer is a poly (meth) acrylate (co) polymer, polyvinyl ether, natural rubber, polyisoprene, polybutadiene, polyisobutylene, polychloroprene; Butadiene-acrylonitrile polymer, thermoplastic elastomer, styrene-isoprene copolymer, styrene-isoprene-styrene block copolymer, ethylene-propylene-diene polymer, styrene-butadiene polymer, poly-alpha-olefin, silicone, ethylene vinyl acetate copolymer And / or combinations thereof. The article of claim 1, wherein the film-forming (co) polymer has a glass transition temperature (T _g ) of less than 30 ° C. as measured by differential scanning calorimetry (DSC). The article of claim 1, wherein the film-forming (co) polymer is a (co) polymer having pressure-sensitive adhesive properties at 23 ° C. The article of claim 1, wherein the film-forming (co) polymer is a copolymer of (meth) acrylic acid, (meth) acrylic acid ester and optionally other comonomers. The article of claim 1, wherein the film forming (co) polymer has an acid number from 0 to 30. The article of claim 1, wherein the film forming (co) polymer is an ethylene vinyl acetate copolymer. 13. The article of claim 12, wherein the ethylene vinyl acetate copolymer has a vinyl acetate content of 50% to 98% by weight based on the total weight of the ethylene vinyl acetate copolymer. delete The article of claim 1, wherein the weight ratio of the total amount of (2-phenylethyl) 2-cyanoacrylate to the total amount of film-forming (co) polymer in the curable film is 1: 8 to 8: 1. The curable film of claim 1, further comprising one or more additives selected from cyanoacrylate polymers, tackifiers, plasticizers, toughening agents, antioxidants, stabilizers, absorbents and / or combinations thereof. article. The article of claim 1, wherein the curable film further comprises a stabilizer present in an amount of 1% by weight or less based on the total weight of the curable film. 18. The article of claim 17, wherein the stabilizer is optionally one of hydroquinone, sulfonic acid, BF ₃ or SO ₂ , boric acid, zinc salt, phosphoric acid, carboxylic acid, or combinations thereof. The article of claim 1, wherein the curable film further comprises an acid, or camphor sulfonic acid. 20. The article of claim 19, wherein the acid is present in an amount of 1% by weight or less based on the total weight of the curable film. The curable film of claim 1, wherein the curable film is Naphthol Green, Coumarin, Carotene, m-Cresol purple, Copper (II) phthalocyanine (Cu (II) phthalocyanine). An article further comprising a dye optionally selected from the group consisting of. The article of claim 21, wherein the dye is present in an amount of 0% to 10% by weight, based on the total weight of the curable film. The article of claim 1, wherein the curable film has a storage modulus G ′ of 3.3 × 10 ⁵ Pa or less, as measured by Dynamic Mechanical Analysis (DMA) at 1 Hz and 23 ° C. The article of claim 1, wherein the curable film has a tack value of 3 N or greater as measured by DIN EN 1719 in a standard loop tack test. The article of claim 1, wherein the curable film has a 180 ° peel strength of 3 N / 25 mm to 50 N / 25 mm after 10 minutes, as measured by DIN EN 1939 on a steel substrate at 23 ° C. The article of claim 1, wherein the curable film has a glass transition temperature (T _g ) of less than 10 ° C. as measured by differential scanning calorimetry (DSC). The article of claim 1, wherein the carrier substrate is selected from polymeric films, foams, metal foils, fabrics and combinations thereof. The article of claim 1, wherein the release substrate is a paper or plastic based material, optionally coated with a release agent. The article of claim 1 which is a label, single sided tape, transfer tape or double sided tape. The article of claim 1, wherein the cured product of the curable film has a refractive index in the range of 1.45 to 1.6, or 1.47 to 1.55. The article of claim 1, wherein the cured product of the curable film is translucent or transparent. A cured product of a curable film as defined in any one of claims 1, 3, 5 to 13 and 15 to 31. The curable film of any one of claims 1, 3, 5 to 13 and 15 to 31, wherein the curable film is optionally cured by exposure to heat, moisture or radiation. Goods available. The curable film of any one of claims 1, 3, 5 to 13 and 15 to 31, wherein the curable film is exposed by exposure for 2 to 360 seconds at a temperature in the range of 0 to 200 ° C. Curable article. 32. The curable film of any one of claims 1, 3, 5-13, and 15-31, wherein the curable film is exposed by exposure for 1 to 24 hours at a humidity in the range of 10 to 100%. Curable article. The article of any of claims 1, 3, 5 to 13 and 15 to 31, wherein the curable film is curable by exposure to radiation, or UV radiation. A method of attaching a film to a curable surface, comprising the steps of:
(a) providing an article according to any one of claims 1, 3, 5 to 13 and 15 to 31;
(b) attaching the curable film of the article to one or more surfaces to form an assembly;
(c) exposing the assembly to conditions sufficient to cure the curable film of the article,
Wherein the release substrate of the article, if present, is removed before and / or after step (b). An article according to any of claims 1, 3, 5 to 13 and 15 to 31 for use in the manufacture of optoelectronic devices. A method of adhering a first substrate to a second substrate, comprising the steps of:
(i) providing an article according to any one of claims 1, 3, 5 to 13 and 15 to 31;
(ii) attaching the curable film of the article to one or more substrates;
(iii) mating the substrates; And
(iv) curing the adhesive film between the components so that the components adhere to each other,
Wherein the release substrate of the article, if present, is removed before and / or after step (ii) of the first substrate to the second substrate. 40. The method of claim 39, wherein the at least one substrate comprises a flexible material. 41. The method of claim 40, wherein the flexible material is at least one of a fabric, fabric, cloth, sheet material, plastic, and combinations thereof.

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