KR20100071514A - Photocureing type addhesive composition and process for transcribing by using it - Google Patents

Abstract

PURPOSE: A photo-curing type adhesive composition and a transferring method using thereof are provided to prevent the degradation of the print quality by hot-pressing without containing a volatile component. CONSTITUTION: A photo-curing type adhesive composition contains a urethane (meth)acrylate pre-polymer, an epoxy (meth)acrylate pre-polymer, and an acryl (meth)acrylate pre-polymer. The average molecular weight of the urethane (meth)acrylate pre-polymer is 3,000~10,000. A photo-curing type adhesive is manufactured from the photo-curing type adhesive composition. A transferring method using the composition comprises the following steps: spreading the adhesive(2) on a substrate(1); laminating a transfer paper(3) on the adhesive layer; and curing by the light irradiation.

Description

Photocurable adhesive composition and transfer method using same {PHOTOCUREING TYPE ADDHESIVE COMPOSITION AND PROCESS FOR TRANSCRIBING BY USING IT}

The present invention relates to a photocurable adhesive composition that can be used in the process of transferring the transfer film used in interior and exterior materials, furniture, automotive interior materials using ultraviolet rays and a transfer method using the same.

In general, various materials such as ceramics, glass, metal, and plastics are used as materials for interior and exterior materials, furniture, and interior materials for automobiles, and various transfer methods are used when printing or printing patterns on the surface of such materials.

In the conventional transfer method, a printing layer containing a picture is transferred from a transfer paper such as paper to a to-be-adhered object on top of an adhesive varnish, and then the release paper of the transfer paper is peeled off, leaving only the picture. Paint and finish In welfare, the earth can be detached and transferred. In particular, such a transfer method is characterized by being capable of curved printing, and in ceramics and the like, when it is baked at about 80 ° C. again, the pigment may be fused.

In particular, conventional transfer methods include thermal transfer, wet transfer, sublimation transfer, pressure transfer, and the like. Recently, the most widely used method is a thermal pressurization transfer method using an adhesive considering properties of transfer printing. Solvent-type acrylic, urethane, vinyl (hot-melt type) and water-soluble vinyl are mainly used as adhesives for thermal pressure transfer.

Among them, the adhesive of the oil type causes environmental pollution by releasing volatile organic substances in the air and time required for evaporation of the solvent, and has a disadvantage of severe energy consumption due to high temperature pressure. In addition, the water-soluble adhesive cannot satisfy the perfect adhesion with various highly functional materials (base coat, plastic, glass), and the strength of the hardened coating film is weak to protect the print layer from external pressure or impact. There is a problem in that the productivity is poor because the continuous operation is not possible because it requires a drying time of several minutes to several tens of minutes during drying.

In addition, in the heating and pressing type thermal transfer method in which a high temperature curable adhesive layer is applied to the object to be deposited and then the transfer paper is laminated and then compressed by a high temperature press to produce a transfer product, continuous operation is impossible, and the adhesive layer is applied and the diluent is volatilized. Energy consumption by air pollution and high-temperature curing of volatile organic material is severe by transferring after it is transferred, whereas photocuring type transfer method is a method of simply transferring transfer papers after applying an adhesive layer and simply transferring them with light. It is not only excellent in wear resistance, chemical resistance and impact resistance, but also in terms of economic and environmental aspects. This photocurable transfer method can create a new type of printing culture as a new method worldwide.

Therefore, while providing a cured coating film of perfect adhesion and excellent strength between the to-be-adhered object and the printed layer, it is possible to secure the process stability by minimizing the curing drying time and more eco-friendly transfer process is not accompanied by a separate volatile components There is a need for research on developing transferable adhesives.

The present invention provides a photocurable adhesive composition and a transfer method using the same as an adhesive composition which can be used in a transfer process, which can prevent deterioration in print quality due to excellent adhesion and thermal pressure without containing volatile components harmful to the environment. To provide.

The present invention provides a photocurable adhesive composition comprising a urethane (meth) acrylate prepolymer, an epoxy (meth) acrylate prepolymer, and an acrylic (meth) acrylate prepolymer and a photocurable adhesive prepared therefrom.

The present invention also provides a photocurable transfer method comprising applying the adhesive on a substrate, laminating a transfer paper on the adhesive coating layer, and curing the light by irradiation after the transfer paper is laminated.

Hereinafter, the present invention will be described in more detail.

The present invention does not involve volatile components harmful to the environment and the like in the process of transferring the transfer film to the interior and exterior materials, furniture, automotive interior materials with ultraviolet rays or electron beams, and can produce a cured coating film having excellent adhesion and excellent strength between the substrate and the printed layer. A photocurable adhesive composition which can be characterized by comprising a specific three component prepolymer, namely urethane (meth) acrylate prepolymer, epoxy (meth) acrylate prepolymer, and acrylic (meth) acrylate prepolymer. In particular, the photocurable adhesive prepared from the composition can be effectively used as a transfer primer in the transfer process.

Conventional transfer method is a heating and pressing type thermal transfer method that produces a transfer product by applying a high-temperature hardening adhesive layer to the object to be deposited, then laminating the transfer paper and pressing it with a high-pressure press to apply continuous adhesive, coating the adhesive layer and diluent After volatilizing and transferring, energy consumption due to air pollution and high temperature curing for volatile organics is high. On the other hand, in the case of using a photocurable adhesive such as the present invention, the transfer paper can be easily transferred by laminating the transfer paper immediately after applying the adhesive layer and irradiating light, and the basic physical properties such as printability, wear resistance, chemical resistance, and impact resistance Not only is it excellent, it can also provide excellent transfer characteristics both economically and environmentally.

In particular, the photocurable adhesive composition according to the present invention includes a prepolymer of the three components, based on a 100% solids adhesive with no volatile content can be printed in a short time to improve productivity, substrate and transfer paper printing Excellent adhesion to the layer and excellent workability, there is an advantage that can protect the printed layer from external impact.

As described above, the photocurable adhesive composition of the present invention uses three components, namely, a combination of a urethane (meth) acrylate prepolymer, an acrylic (meth) acrylate prepolymer, and an epoxy (meth) acrylate prepolymer, The disadvantages of the three components of the prepolymer can be secured to each other and maximize the advantages to provide an adhesive of excellent adhesion and strength. In particular, urethane (meth) acrylate prepolymers have good water resistance, but have poor adhesion due to shrinkage during curing, while acrylic (meth) acrylate prepolymers have a good average molecular weight and good adhesion, but have high adhesive strength. There is a problem that the scratches are greatly generated from the external pressure or impact. In addition, the epoxy acrylate prepolymer is excellent in curability and can be cured even in a thick printing layer. However, the epoxy acrylate prepolymer has a high hardness and tends to cause breakage in external impact and inferior adhesion. Thus, by using the three components of the present invention in combination, it is possible to secure the disadvantages of the individual prepolymers to each other and maximize the advantages.

The urethane (meth) acrylate prepolymer usable in the present invention may be a copolymer of a (ol) acrylate having a polyol and a hydroxyl group. In particular, the urethane (meth) acrylate prepolymer may be a copolymer of a hydroxyl group-containing (meth) acrylate to a mixture of the diisocyanate compound and a monomolecular diol having a molecular weight of less than 200 and a polyol, and having a monomer having a molecular weight of less than 200 Molecular diols include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, reduced bisphenol A, reduced bisphenol F, dicyclopentanediol, tricyclodecanediol or mixtures thereof, and the like, and compounds having three or more hydroxyl groups in the molecule, ie, glycerol, trimethylolethane, Trimethylolpropane, pentaerithritol, sorbose, and sorbitol may be mixed and used. Preferably, 1,4-butanediol, 1,6-hexanediol, neopentylglycol or mixtures thereof are used.

In addition, the polyol is a polyol having a weight average molecular weight of 200 to 3000, preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, or a polycaprolactone polyol. Examples of the polyether polyol may include copolymerization forms of polyethylene glycol, 1,2-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, and the like, and polyols. Examples of the polyester polyol include ethylene glycol, Polyethylene glycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 1,4-cyclo Diols such as hexanedimethanol and 3-methyl-1,8-octanediol and acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and azelic acid Polyester polyols or copolymers thereof can be exemplified. As polycarbonate polyol, 1,6-hexane polycarbonate is preferable, and as polycaprolactone polyol, ε-caprolactone and ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1, The form which the diol, such as 4-butanediol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentylglycol, 1, 4- cyclohexane dimethanol, reacted can be illustrated. .

The urethane (meth) acrylate prepolymer of the present invention may have a weight average molecular weight of 1,000 to 10,000, preferably 3,000 to 5,000, 3 to 20, preferably 4 to 15, the average urethane bonds per molecule, More preferably, 5 to 10 are present. If the weight average molecular weight is less than 3,000, the tensile strength and hardness of the cured coating film are too high, the elongation is poor, and the adhesion is poor. If the weight average molecular weight is greater than 5,000, the reverse It is preferable to have a molecular weight distribution as described above because the result of. And carboxylated (meth) acrylate monomer has a big influence on the effect of adhesiveness and thickening.

Moreover, the epoxy (meth) acrylate prepolymer which can be used for this invention is a phenyl epoxy acrylate, bisphenol epoxy diacrylate, an aliphatic alkyl diacrylate, fatty acid modified epoxy (meth) acrylate, and an aliphatic epoxy epoxy (meth). It may be one or more types, such as an acrylate, a cresol noblock epoxy acrylate, a phenol noble epoxy epoxy acrylate, and it is especially preferable to use bisphenol epoxy diacrylate.

In the composition of the present invention, the acrylic (meth) acrylate prepolymer may have a weight average molecular weight of 5,000 to 20,000, preferably 10,000 to 15,000, and 1 to 20 average double bonds per molecule, preferably It is preferred that 1 to 12, more preferably 2 to 8, are present. If the weight average molecular weight is less than 10,000, the adhesion is good, but the adhesion is poor, the adhesion is poor, the adhesion is poor, if the weight average molecular weight is greater than 5,000, the opposite result occurs, it is preferable to have the above molecular weight distribution. And carboxylated (meth) acrylate monomer has a big influence on the effect of adhesiveness and thickening.

The photocurable adhesive composition of the present invention is 1 to 40 parts by weight of urethane (meth) acrylate prepolymer, preferably 10 to 100 parts by weight of the total composition, so as to maximize the synergistic effect of the combination of the three prepolymers. To 20 parts by weight, 1 to 40 parts by weight of acrylic (meth) acrylate prepolymer, preferably 10 to 20 parts by weight, and 1 to 40 parts by weight, preferably 20 to 30 parts by weight of epoxy (meth) acrylate prepolymer. can do.

Particularly, when the urethane acrylate prepolymer is more than 20 parts by weight, the tensile strength and shrinkage of the cured coating film may be severe, resulting in poor adhesiveness. When the urethane acrylate prepolymer is more than 10 parts by weight, poor solvent resistance and strength may result. It is preferable to have a content such as. And, when the acrylic acrylate is more than 20 parts by weight, the strength of the cured coating film is too low and the curing resistance may be poor water resistance, if less than 10 parts by weight may result in poor adhesion with the printed layer may be the same content as described above It is preferable to have. In addition, when the epoxy acrylate is more than 30 parts by weight, the hardness of the adhesive film is too high and elongation is low so that it can easily crack the external impact, and if it is less than 20 parts by weight, the hardening may be poor and the adhesion between the material layer and the adhesion may be reduced. It is preferable to have the same weight part.

The photocurable adhesive composition of the present invention may further include a phosphate (meth) acrylate to improve the adhesion. The ester (meth) acrylate may be one or more of methacryloyloxyethyl acid phosphate, acryloyloxyethyl phosphate, methacryloyloxypropyl acid phosphate, acryloyloxybutyl phosphate, and the like. In particular, it is preferable to use acryloyloxyethyl phosphate. In addition, the phosphate (meth) acrylate may be included in 1 to 20 parts by weight, preferably 2 to 5 parts by weight with respect to 100 parts by weight of the total composition, in the content range in terms of ensuring excellent print adhesion It is good to add.

In addition, the present invention may further include a (meth) acrylate monomer reacting with the urethane (meth) acrylate, epoxy (meth) acrylate prepolymer, acrylic (meth) acrylate prepolymer, and the (meth) acrylic The rate monomer may be at least one of a monofunctional monomer or a polyfunctional monomer.

More specifically, the monofunctional monomers among the (meth) acrylate monomers usable in the photocurable adhesive composition of the present invention include diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-octyl ( Meta) acrylate, N, N-dimethyl (meth) acrylate, N-vinyl caprolactam, N-vinylpyrrolidone, isobutoxy (meth) acrylamide, diacetone (meth) acrylamide, carbonyl (meth) acryl Elate, isobonyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, Methoxy polyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate Polyethylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, epoxydiethylene glycol (meth) acrylate, butoxyethyl ( Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styryl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (Meth) acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, butyl ( Metha) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, or a mixture thereof is preferable. Moreover, as a polyfunctional monomer, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, tri Propylene glycol diacrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol diacrylate, or a mixture thereof is preferable.

The (meth) acrylate monomer may be included in 10 to 60 parts by weight, preferably 20 to 30 parts by weight with respect to 100 parts by weight of the total composition, it is preferable to add in the content range in terms of workability.

The present invention may further include one or more selected from the group consisting of photoinitiators, pressure-sensitive adhesives, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, and antifoaming agents.

In particular, the transfer paper is generally printed on the polyester film with a vinyl-based ink, the photocurable adhesive should be cured through the polyether film layer and the ink layer. Therefore, it is necessary to use a wavelength of light having good transmittance and to be made of a photocurable adhesive composition that can be cured in the wavelength range.

Accordingly, the selection of the photoinitiator in the photocurable adhesive composition of the present invention is important, the photoinitiator is 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, benzaldehyde, anthraquinone, 3 -Methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoinpropyl ether, benzoin ethyl ether, 1- (4-isopropyl-phenol) -2-hydroxy-2-methyl One or more types can be used among a propane-1-one, thioxanthone, benzophenone, etc. Commercially available products as photoinitiators include Irgacure184, 651, 500, 819, 907, and 1800 (Shibagai Corporation) and Darocure 1116, 1173 (Merck), Lucirine LR8728 (BASF), Micure HP-8, TPO, CP -4, BK ?? 6 (Miwon Corporation) etc., Among these, it is preferable to mix and use 2 or more types including 2,4,6- trimethyl benzoyl- diphenyl phosphine.

The photoinitiator may be included in an amount of 0.5 to 10 parts by weight, preferably 3 to 6 parts by weight based on 100 parts by weight of the total composition, but is not particularly limited thereto.

In addition, the pressure-sensitive adhesive which may be further included in the curable adhesive composition of the present invention includes acrylic, polyester, polybutadiene, polyether, polyethylene, polypropylene, polyvinyl caprolactam and mixtures thereof. It can use more than 1 type, Preferably it is good to use a polybutadiene system.

The pressure-sensitive adhesive may be included in 1 to 30 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the total composition, but is not particularly limited to the above content range.

In addition, the photocurable adhesive composition of the present invention may further include one or more selected from the group consisting of a silane coupling agent, a thermal polymerization inhibitor, a smoothing agent, a surfactant, and an antifoaming agent.

In one preferred embodiment of the present invention, the photocurable adhesive composition is 1 to 40% by weight of the urethane (meth) acrylate prepolymer, 1 to 40% by weight of the acrylic (meth) acrylate prepolymer, epoxy ( 1 to 40% by weight of meta) acrylate prepolymer, 0.5 to 10% by weight of phosphorus (meth) acrylate, 10 to 65% by weight of (meth) acrylate monomer, 0.5 to 10% by weight of photoinitiator, and 1 to 30% by weight of adhesive It may include.

In another preferred embodiment, the photocurable adhesive composition of the present invention, based on the total amount of the total composition, 5 to 10% by weight of urethane (meth) acrylate prepolymer, 5 to 30% by weight of acrylic (meth) acrylate prepolymer, epoxy 5 to 30% by weight of (meth) acrylate prepolymer, 0.5 to 4% by weight of ester (meth) acrylate, 30 to 60% by weight of (meth) acrylate monomer, 1 to 7% by weight of photoinitiator, and 5 to 10% of pressure sensitive adhesive May contain%.

This composition ratio is calculated | required from the reaction equivalent ratio of each compound converted into weight ratio.

On the other hand, the present invention is a photocurable adhesive prepared from the composition is excellent in transfer paper printability and provides a stable adhesion to the print layer to the physical impact on the outside.

The present invention also provides a photocurable transfer method comprising applying the photocurable adhesive on a substrate, laminating a transfer sheet on the adhesive coating layer, and curing the photosensitive adhesive after light lamination. .

The photocurable transfer process may further include irradiating light after laminating the transfer paper.

In addition, in performing the light irradiation in the above process, it is preferable to irradiate the amount of light of 50 to 3000 mJ / ㎠, preferably 800 to 1500 mJ / ㎠ in terms of printing stability and adhesion.

In particular, as shown in Figure 1, according to one embodiment of the present invention, the photocurable transfer process, the adhesive coating is a roll coat, and the continuous automatic process by connecting the adhesive coating, transfer paper transfer, roll pressing and release paper removal with a belt It can be done with

The photocurable adhesive composition and the photocurable adhesive prepared therefrom according to the present invention are applied by the photocurable transfer method and may be used as an adhesive for transfer printing in interior and exterior materials, furniture and interior materials for automobiles.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

According to the present invention, by using a combination of specific three-component prepolymers on the basis of a solid component without a volatile component, printing can be performed in a short time to improve productivity. It can secure the adhesion. In addition, it is possible to impart excellent solvent resistance, water resistance, chemical resistance and physical properties to the cured coating film after adhesion with the photocurable adhesive, and to secure the excellent strength to effectively protect the printed layer from external impact.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

In the following Examples 1 to 3 and Comparative Examples 1 to 3 denoted by%, unless indicated otherwise, all represent by weight.

Example 1

30 wt% urethane (meth) acrylate prepolymer, 20 wt% epoxy (meth) acrylate prepolymer, 20 wt% acrylic (meth) acrylate prepolymer, 14.5 wt% isobornyl methacrylate, photoinitiator 4.5 Mixing weight%, pressure-sensitive adhesive 10% by weight, 1% by weight of the ester (meth) acrylate and stirred at 500 rpm for 30 minutes, vacuum degassing for 10 minutes while maintaining at 25 ℃ completely remove the air bubbles, then transfer photocurable adhesive Was prepared.

Example 2

10 wt% urethane (meth) acrylate prepolymer, 30 wt% epoxy (meth) acrylate prepolymer, 30 wt% acrylic (meth) acrylate prepolymer, 24.5 wt% trimethylolpropanetriacrylate, photoinitiator in reactor with stirrer 4.5% by weight, pressure-sensitive adhesive 10% by weight, 1% by weight of the ester (meth) acrylate was mixed and stirred at 500 rpm for 30 minutes, vacuum degassing for 10 minutes while maintaining at 25 ℃ completely remove the air bubbles for transfer A burn adhesive was prepared.

Example 3

20 wt% urethane (meth) acrylate prepolymer, 30 wt% epoxy (meth) acrylate prepolymer, 30 wt% acrylic (meth) acrylate prepolymer, 25.5 wt% trimethylolpropanetriacrylate, photoinitiator in reactor with stirrer 4.5 wt% of the mixture was stirred at 500 rpm for 30 minutes, and vacuum degassed for 10 minutes while maintaining at 25 ° C. to completely remove air bubbles, thereby preparing a photocurable adhesive for transfer.

Comparative Example 1

40 wt% of the urethane (meth) acrylate prepolymer, 30 wt% of the acrylic (meth) acrylate prepolymer, 25.5 wt% of the trimethylolpropane triacrylate, 4.5 wt% of the photoinitiator, and 10 wt% of the adhesive were mixed in a reactor equipped with a stirrer. Stirring at 500 rpm for 30 minutes, vacuum degassing for 10 minutes while maintaining at 25 ℃ to remove the bubbles completely to prepare a photocurable adhesive for transfer.

Comparative Example 2

40 wt% urethane (meth) acrylate prepolymer, 30 wt% epoxy (meth) acrylate prepolymer, 25.5 wt% trimethylolpropanetriacrylate, 4.5 wt% photoinitiator, and 10 wt% adhesive were mixed in a reactor equipped with a stirrer. After stirring for 30 minutes at 500 rpm, while maintaining at 25 ℃ vacuum degassing for 10 minutes to completely remove the bubbles to prepare a photocurable adhesive for transfer.

Comparative Example 3

40 wt% of epoxy (meth) acrylate prepolymer, 30 wt% of acrylic (meth) acrylate prepolymer, 25.5 wt% of trimethylolpropanetriacrylate, 4.5 wt% of photoinitiator, and 10 wt% of adhesive were mixed in a reactor equipped with a stirrer. After stirring at 500 rpm for 10 minutes and vacuum degassing for 10 minutes while maintaining at 25 ℃ completely remove the bubbles to prepare a photocurable adhesive for transfer.

Each component content of the photocurable adhesive composition according to Examples 1 to 3 and Comparative Examples 1 to 3 is shown in Table 1 below. Here, the content unit is weight percent.

ingredient Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Urethane (meth) acrylate 30 10 20 40 40 - Epoxy (meth) acrylate 20 30 30 - 20 40 Acrylic (meth) acrylate 20 20 20 20 - 20 Isobonyl methacrylate /
Trimethylolpropanetriacrylate 14.5 24.5 25.5 25.5 25.5 25.5 Phosphate (meth) acrylate One One - - - - Photoinitiator 4.5 4.5 4.5 4.5 4.5 4.5 adhesive 10 10 0 10 10 10 Sum 100 100 100 100 100 100

Experimental Example

In the process as shown in FIG. 1, it applied to the photocurable adhesive glass plate obtained by the said Examples 1-3 and Comparative Examples 1-3, at the thickness of 0.05 mm, and formed the photocurable adhesive coating layer. After laminating the transfer paper on the adhesive coating layer, it was temporarily cured by irradiating 300 mJ / ㎠ light amount with a light irradiator, and then the release film of the transfer paper was removed. Thereafter, using a light irradiator, the cured product was completely cured at an amount of light of 1000 mJ / cm 2, thereby producing a cured product in which the printing layer of the transfer paper was transferred onto a glass plate.

As mentioned above, the following physical properties were measured about the glass plate transfer product manufactured using the photocurable adhesive agent obtained by the said Examples 1-3 and Comparative Examples 1-3.

Adhesion

After complete curing as described above it was carried out by the method of ASTM D 3359-87.

Printability (% ink transfer)

After curing by irradiating 300 mJ / ㎠ light quantity, the transfer paper release film was removed and completely cured to 1,000 mJ / ㎠ and then the amount of ink transferred to the material was measured by volume ratio to determine the transfer characteristics.

Hardness

Hardness was measured about the cured coating film manufactured by the said method. First, the core of the KS G2603's ordinary pencil was sharply trimmed to expose about 3mm, and then, at 400 or more abrasive papers placed on a solid plane at a right angle, the core was sharply polished in a circle, and the tip was flat and the angle was sharpened. . The shim was newly ground and used each time it was tested. The hardness was measured by drawing a pencil in the obtuse direction while applying a load of about 10 N (1 kg) while maintaining the prepared pencil about 45 kPa to the cured coating film.

MEK Rubbing

For the cured coating film prepared by the above method, methyl ethyl ketone was wetted with cotton, and then rubbed five times on the transfer surface to observe a print change.

Water Resistance (MEK Rubbing)

For the cured coating film prepared by the above method, distilled water was wetted with cotton, and then rubbed five times on the transfer surface to observe a print change.

The adhesiveness, printability, pencil hardness, solvent resistance, and water resistance of the cured coating film drawn by the above method with the adhesives of Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the same method as described above. The measurement results of the physical properties are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Adhesion 100/100 100/100 95/100 75/100 50/100 30/100 Printability (%) 100 100 100 90 90 90 Pencil hardness B HB HB B H HB Solvent resistance Good Good Good usually Good Good Water resistance Good Good Good Good Good Good

As shown in the measurement results of the physical properties of Table 2, the adhesives of Examples 1 to 3 according to the present invention including urethane (meth) acrylate prepolymer, epoxy (meth) acrylate, and acrylic (meth) acrylate are compared. It was excellent in adhesiveness and printability compared with Examples 1-3. Adhesion is a method of measuring the degree of adhesion of the transfer ink to the material. And, as shown in Table 2, the conventional thermal transfer adhesive has very poor water resistance and solvent resistance, so that the printing ink is dissolved in water or solvent, while all photocurable adhesives have good water resistance and solvent resistance and are printed with water or solvent. Wiping the cotton did not change. In essence, it can be seen that solvent resistance and water resistance of photocurable adhesives are superior to existing transfer methods.

The present invention provides a photocurable adhesive composition comprising a prepolymer of three components, that is, a urethane (meth) acrylate, an epoxy (meth) acrylate prepolymer, and an acrylic (meth) acrylate prepolymer together, whereby a volatile component is completely absent. It is possible to improve productivity by printing in a short time based on 100% solid adhesive which is not available.In the process of transferring the transfer film used for interior and exterior materials, furniture and car interior materials using ultraviolet rays or electron beams, Excellent adhesion and workability, and excellent workability, environmental friendliness, solvent resistance, productivity, and the like compared to the conventional oil-based adhesives can be said that the industrial applicability is very large.

1 is a view schematically showing a transfer process using a photocurable adhesive according to an embodiment of the present invention.

* Explanation of the main symbols in the drawings

① Base material ② Photocurable adhesive ③ Transfer paper

④ Roller ⑤ Light Lamp

Claims (23)

A photocurable adhesive composition comprising a urethane (meth) acrylate prepolymer, an epoxy (meth) acrylate prepolymer, and an acrylic (meth) acrylate prepolymer. The method of claim 1, The urethane (meth) acrylate prepolymer has a weight average molecular weight of 3000 to 10000 photocurable adhesive composition. The method of claim 1, The urethane (meth) acrylate prepolymer is a photocurable adhesive composition that has an average of 3 to 20 urethane bonds per molecule. The method of claim 1, The epoxy (meth) acrylate prepolymers are phenyl epoxy acrylate, bisphenol epoxy diacrylate, aliphatic acyl diacrylate, fatty acid modified epoxy (meth) acrylate, aliphatic acyl epoxy citric (meth) acrylate, cresol noblock epoxy At least one photocurable adhesive composition selected from the group consisting of acrylates and phenol noble epoxy acrylates. The method of claim 1, The acrylic (meth) acrylate prepolymer has a weight average molecular weight of 3000 to 10000 photocurable adhesive composition. The method of claim 1, The acrylic (meth) acrylate prepolymer is a photocurable adhesive composition that has an average of 1 to 20 double bonds per molecule. The method of claim 1, Per 100 parts by weight of the total composition, 1 to 40 parts by weight of urethane (meth) acrylate prepolymer, 1 to 40 parts by weight of acrylic (meth) acrylate prepolymer, and 1 to 40 parts by weight of epoxy (meth) acrylate prepolymer Photocurable adhesive composition comprising a. The method of claim 1, A photocurable adhesive composition further comprising a phosphate (meth) acrylate. The method of claim 7, wherein The phosphoric ester (meth) acrylate is at least one selected from the group consisting of methacryloyloxyethyl acid phosphate, acryloyloxyethyl phosphate, methacryloyloxypropyl acid phosphate, and acryloyloxybutyl phosphate Burning adhesive composition. The method of claim 1, The photocurable folding agent composition containing 5-20 weight part of phosphate (meth) acrylate with respect to 100 weight part of total compositions. The method of claim 1, The photocurable adhesive composition which further contains a (meth) acrylate monomer. The method of claim 11, The (meth) acrylate monomers include diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-octyl (meth) acrylate, N, N-dimethyl (meth) acrylate, and N-vinyl. Caprolactam, N-vinylpyrrolidone, isobutoxy (meth) acrylamide, diacetone (meth) acrylamide, carbonyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acryl Latex, methoxy ethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, between Clohexyl (meth) acrylate, benzyl (meth) acrylate, epoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styryl (meth) acrylic Laterate, octadecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Isoamyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, ethyl ( Meta) acrylate, methyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanedioldi (meth )acryl Sites, tripropylene glycol diacrylate, trimethylolpropane tri oxyethyl (meth) acrylate, and tri sayikeu in decane dimethanol di least one member photocurable adhesive composition selected from the group consisting of acrylate. The method of claim 1, A photocurable adhesive composition comprising 10 to 60 parts by weight of the (meth) acrylate monomer, based on 100 parts by weight of the total composition. The method of claim 1, A photocurable adhesive composition further comprising at least one selected from the group consisting of a photoinitiator, an adhesive, a silane coupling agent, a thermal polymerization inhibitor, a smoothing agent, a surfactant, and an antifoaming agent. The method of claim 14, The photoinitiator 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenyl-acetophenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxy Benzophenone, benzoinpropyl ether, benzoin ethyl ether, 1- (4-isopropyl-phenol) -2-hydroxy-2-methylpropan-1-one, thioxanthone, benzophenone, and 2,4,6 -Trimethylbenzoyl-diphenylphosphine further comprising at least one member selected from the group consisting of photocurable adhesive composition. The method of claim 14, The photocurable adhesive composition containing 0.5-10 weight part of photoinitiators with respect to 100 weight part of total compositions. The method of claim 14, The pressure-sensitive adhesive photocurable adhesive composition further comprises one or more selected from the group consisting of acrylic, polyester, polybutadiene, polyether, polyethylene, polypropylene, polyvinyl caprolactam. The method of claim 14, The photocurable adhesive composition containing the said adhesive in 1-30 weight part with respect to 100 weight part of total compositions. The method of claim 14, 1 to 40% by weight of urethane (meth) acrylate prepolymer, 1 to 40% by weight of acrylic (meth) acrylate prepolymer, 1 to 40% by weight of epoxy (meth) acrylate prepolymer, 0.5-10 wt% of phosphate (meth) acrylate, 10 to 65% by weight of (meth) acrylate monomer, Photoinitiator 0.5-10 wt%, and 1 to 30 wt% of adhesive Photocurable adhesive composition comprising a. 20. A photocurable adhesive prepared from a composition according to claim 1. Applying the adhesive according to claim 20 onto a substrate, Laminating a transfer paper on the adhesive coating layer, and After laminating the transfer paper, curing with light irradiation Photocurable transfer method comprising a. The method of claim 21, The photocurable transfer method further comprises the step of irradiating light after laminating the transfer paper. The method of claim 21, A photocurable transfer method for performing the light irradiation with a light amount of 50 to 3000 mJ / ㎠.

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