WO2017191960A1 - Uv curable resin composition, method for curing same, and cured product using same - Google Patents

Uv curable resin composition, method for curing same, and cured product using same Download PDF

Info

Publication number
WO2017191960A1
WO2017191960A1 PCT/KR2017/004622 KR2017004622W WO2017191960A1 WO 2017191960 A1 WO2017191960 A1 WO 2017191960A1 KR 2017004622 W KR2017004622 W KR 2017004622W WO 2017191960 A1 WO2017191960 A1 WO 2017191960A1
Authority
WO
WIPO (PCT)
Prior art keywords
curable resin
resin composition
weight
curing
parts
Prior art date
Application number
PCT/KR2017/004622
Other languages
French (fr)
Korean (ko)
Inventor
이호준
신학열
Original Assignee
지스마트 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 지스마트 주식회사 filed Critical 지스마트 주식회사
Publication of WO2017191960A1 publication Critical patent/WO2017191960A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/57—Physical properties photorefractive, e.g. change of refractive index
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/63—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the present invention relates to a UV (ultraviolet) curable resin composition, a curing method thereof and a cured product using the same, and more particularly, a transparent UV curable resin composition based on aliphatic urethane acrylate oligomers having a viscosity of less than 100 mPa ⁇ s and By controlling to have a glass-like density, using a UV curable resin composition, a method for curing the UV curable resin composition and the UV curable resin composition, which can be applied to the glass surface and prevent scattering and refraction upon light transmission after UV curing. It relates to a cured product.
  • UV curable resin composition generally consists of an oligomer, a reactive monomer, a photoinitiator, an additive, etc.
  • the UV curable resin composition is irradiated with ultraviolet rays, radicals are generated from the photoinitiator, and the generated radicals attack the double bonds in the oligomer and the reactive monomer to induce crosslinking of the three-dimensional network structure, thereby curing the UV curable resin composition.
  • a solid coating will be formed.
  • the urethane acrylate oligomer has the advantages of good reactivity and excellent hardness, adhesion, chemical resistance, etc. of the cured coating film, but has a disadvantage of poor workability and poor weather resistance due to the high viscosity of the paint.
  • the viscosity (25 ° C) of the composition is 100 mPa ⁇ s or more, bubbles are likely to occur in the blending process, and bubbles may also occur in the process of applying or injecting the object for application according to the use. Workability is thereby reduced.
  • the composition is used as a pressure-sensitive adhesive layer in the optical device, such as the Korean Patent Publication, if bubbles exist inside the pressure-sensitive adhesive layer, this may cause scattering of light, which may degrade the performance of the optical device.
  • JP 05-039343 A describes a photocurable composition using a urethane (meth) acrylate oligomer.
  • the photocurable composition of the JP Patent Application can be applied to glass
  • the UV curable resin composition applied to the glass surface preferably has affinity with the glass surface without spoiling the transparency of the glass.
  • the photocurable composition disclosed in Japanese Patent Laid-Open is designed to paint a plastic surface, and has a low affinity with glass, which makes it difficult to use in glass, that is, the transparency of glass may be impaired. When the prepared coating film is applied to the glass surface, surface adhesion and workability may be reduced.
  • the first object of the present invention for solving this problem is to control the transparent UV curable resin composition based on aliphatic urethane acrylate oligomer to have a viscosity of less than 100 mPa ⁇ s and a density comparable to glass. It is to provide a UV curable resin composition that can minimize scattering and prevent refraction when applied to a glass surface.
  • a 2nd objective is to provide the hardening method of a UV curable resin composition for applying the said UV curable resin composition to a glass surface.
  • a third object is to provide a cured product using the UV curable resin composition, which can prevent scattering and refraction when applied to glass.
  • the present invention comprises an aliphatic urethane acrylate oligomer, reactive monomer, adhesion promoter, photoinitiator, antifoaming agent, wetting agent, and coupling agent, characterized in that the viscosity at 25 °C is less than 100 mPa ⁇ s It provides a UV curable resin composition.
  • the UV curable resin composition comprises about 65 parts by weight to about 70 parts by weight of the aliphatic urethane acrylate oligomer, about 19 parts by weight to about 32 parts by weight of the reactive monomer, and about 2 parts by weight to about 6 parts by weight of the adhesion promoter.
  • the UV curable resin composition may have a density of about 0.85 to about 3 g / cm 3 .
  • the UV curable resin composition may have a contact angle with respect to glass of about 10 degrees or less.
  • the UV curable resin composition may have a light transmittance of about 95% or more.
  • the UV curable resin composition may be less than 15% by volume shrinkage upon curing.
  • the present invention provides a curing method of the UV curable resin composition, comprising the step of completely curing the UV curable resin composition by irradiating the UV curable resin composition with UV.
  • the maximum temperature at the time of curing may be less than 100 °C.
  • the present invention provides a cured product, wherein the cured product is a cured product using the UV curable resin composition, wherein the UV curable resin composition is completely cured.
  • the cured product may have a refractive index of about 1.4 to about 1.6.
  • the cured product may have a haze value of less than 1%.
  • the cured product may have an elongation at break of about 100% to about 1000%.
  • the cured product may have a light transmittance of about 95% or more.
  • the UV curable resin composition of this invention When the UV curable resin composition of this invention is used, hardened
  • the UV curable resin composition is a transparent UV curable resin composition based on aliphatic urethane acrylate oligomer and controlled to have a viscosity of less than 100 mPa ⁇ s and a glass-like density, so that when applied to the glass surface and cured, Light scattering and refraction can be prevented.
  • the UV curable resin composition of the present invention has the property of being easily cured in response to UV, it can be used for the use of adhesives or sealants.
  • a and / or B means A or B, or A and B.
  • the present invention includes an aliphatic urethane acrylate oligomer, a reactive monomer, an adhesion promoter, a photoinitiator, an antifoaming agent, a wetting agent, and a coupling agent, and the UV curable resin composition is characterized in that the viscosity at 25 ° C. is less than 100 mPa ⁇ s. do.
  • the UV curable resin composition has a viscosity close to water, so that the flow is smooth when injected, and workability is excellent, and bubble generation is minimized. Can be. If bubbles are generated inside the UV-curable resin composition, light scattering may appear, which is inappropriate. That is, minimizing bubble generation by adjusting the viscosity at 25 ° C. to less than 100 mPa ⁇ s is preferable because it can prevent scattering of light. More preferably, the viscosity is about 1 mPa ⁇ s to about 10 mPa ⁇ s at 25 ° C., but may not be limited thereto.
  • the UV curable resin composition may have a density of about 0.85 g / cm 3 to about 3 g / cm 3 at 23 ° C.
  • the UV curable resin composition When the UV curable resin composition is applied to the glass, it is adjusted to have a density similar to that of the glass, so that light passes through the UV light through the UV curable resin composition, and the light at the interface between the glass and the UV curable resin composition It is desirable to prevent the refraction of from occurring.
  • the glass may be ordinary glass, and may be tempered glass having improved heat resistance and / or impact resistance.
  • the UV curable resin composition may have a contact angle with respect to glass of about 10 degrees or less, for example, about 0.5 degrees to about 10 degrees.
  • the contact angle of the UV curable resin composition to the glass is about 0.5 degrees to about 10 degrees, or about 0.5 degrees to about 5 degrees, or about 0.5 degrees to about 3 degrees, or about 5 degrees to about 10 degrees, or about 8 degrees. It is preferably from about 10 degrees, and more preferably, about 8 degrees to about 9 degrees, but may not be limited thereto.
  • the contact angle with respect to glass is 10 degrees or less, the UV curable resin composition has affinity for glass, and when the UV curable resin composition is applied to the glass surface, the UV curable resin composition bonds with the glass with a strong bonding force.
  • contact angle means that when a drop of a liquid of the UV curable resin composition is dropped on a glass surface existing in air, a droplet of the UV curable resin composition is generated, and the solid, liquid, and gas of the droplet are generated. It means the angle of the glass surface and the liquid surface measured inside the liquid at the three-phase contact point of.
  • the UV curable resin composition may have a light transmittance of about 95% to about 100% or about 98% to about 100%.
  • light transmittance of 95% or more can be achieved. It becomes impossible.
  • the UV curable resin composition may have a shrinkage rate of about 0% by volume to about 14.9% by volume during UV curing, most preferably no shrinkage, and close to 0% by volume at less than 15% by volume. It may not be limited.
  • the shrinkage ratio during curing of the UV curable resin composition is 15% by volume or more, bubbles may occur in the cured product, which is not suitable. If bubbles exist in the cured product, light scattering occurs in the cured product, and thus light refraction also appears. Since it is the final object of the present invention to prevent scattering and refraction of light in the cured product, it is important to control properties such as viscosity, density, light transmittance, shrinkage ratio and the like of the UV curable resin composition.
  • the shrinkage at the time of UV curing is about 0% by volume to about 10% by volume, and more preferably, the shrinkage at the time of UV curing is about 0% by volume to about 5% by volume.
  • this may not be limited.
  • the UV curable resin composition may contain about 65 parts by weight to about 70 parts by weight of the aliphatic urethane acrylate oligomer and about 19 parts by weight to about 32 parts by weight of the reactive monomer. From about 2 to about 6 parts by weight of the enhancer, from about 1 to about 2 parts by weight of the photoinitiator, from about 0.2 to about 0.8 parts by weight of the antifoaming agent, and from about 0.2 to about 0.8 parts by weight of the humectant. And from about 0.2 part to about 0.8 part by weight of the coupling agent.
  • the aliphatic urethane acrylate oligomer is a yellowing type and good flexibility can improve the adhesion of the UV curable resin composition. It is preferable that the said aliphatic urethane acrylate oligomer has a 2-10 functional group, and it is more preferable to have a bifunctional group.
  • the UV curable resin composition contains an aliphatic urethane acrylate oligomer of less than 65 parts by weight, it may cause adhesion and flexibility deterioration after UV curing, when contained in more than 70 parts by weight, the viscosity of the composition is increased Workability can be reduced.
  • the photoinitiator can be used that becomes active by UV.
  • the photoinitiator is 1-hydroxy cyclohexyl phenyl ketone, 1-hydroxy-2-methyl-1-phenylpropane-1-ketone (1-hydroxy-2-methyl
  • the content of the photoinitiator in the UV-curable resin composition is less than 1 part by weight, there is a high possibility that the curing does not proceed sufficiently, and when it exceeds 2 parts by weight, the production cost may increase and unreacted photoinitiator may remain in the cured product. Storage stability may be reduced.
  • the antifoaming agent serves to remove bubbles present in the composition, and may use one or two or more selected from the group consisting of silicone oil, ethanol, octanol, cyclohexanol, ethylene glycol, and higher alcohols.
  • silicone oil ethanol, octanol, cyclohexanol, ethylene glycol, and higher alcohols.
  • the wetting agent serves to reduce the surface tension of the composition, and is used to make the surface tension of the composition similar to water so that the contact angle to the glass is about 8 to 9 degrees.
  • the content of the wetting agent in the UV curable resin composition may be adjusted to about 0.2 parts by weight to about 0.8 parts by weight to create a surface tension similar to water. When the amount of the wetting agent is less than 0.2 parts by weight, the surface tension reduction effect is minimal.
  • the contact angle with respect to it may exceed 10 degrees, and if it contains more than 0.8 parts by weight, it will lead to an increase in production cost and is not suitable.
  • the coupling agent serves to increase the interfacial adhesion between the UV curable resin composition and glass and to improve the adhesion of the composition.
  • a silane coupling agent may be used.
  • the silane coupling agent for example, vinyl tris (2-methoxyethoxy) silane, vinyl triethoxysilane, vinyl trimethoxysilane (vinyl) trimethoxysilane), and one or two or more selected from the group consisting of vinyl methyldimethoxysilane.
  • the content of the coupling agent in the UV-curable resin composition is less than 0.2 parts by weight, the effect of improving the adhesion of the composition is insignificant, and thus it is impossible to achieve an improvement in the bonding strength between the cured product and the glass. It is not suitable to cause.
  • the said UV curable resin composition is a solvent-free state which does not contain a solvent, and it is preferable that a property is colorless and transparent. Accordingly, as the components forming the UV curable resin composition of the present invention, it is preferable to use colorless and transparent ones, but is not limited thereto.
  • the UV curable resin composition may be used for the use of an adhesive or sealant, and may be cured by UV after being applied or injected into the use of the adhesive or sealant.
  • the present invention provides a curing method of the UV curable resin composition, comprising the step of completely curing the UV curable resin composition by irradiating UV to the UV curable resin composition.
  • the step is to perform curing by UV, it is possible to obtain a cured product from the UV curable resin composition.
  • Curing at this time may be carried out in a UV curing apparatus, the temperature inside the UV curing apparatus is preferably less than 100 °C, or less than about 90 °C, for example, about 40 °C to about 90 °C.
  • the UV curable resin composition may optionally be used as an adhesive or sealant in a light emitting device such as an LED chip.
  • the UV curable resin composition may be coated or injected into the light emitting device, and then subjected to curing. If the curing temperature exceeds 100 ° C. in the process, the light emitting device may be injured by heat. Therefore, the temperature inside the UV curing device may be controlled to less than 100 ° C., but may not be limited thereto. .
  • Curing in this step may be carried out by UV having an energy density of about 1000 mJ / cm 2 to about 2500 mJ / cm 2 .
  • the UV is about 1000 mJ / cm 2 to about 2500 mJ / cm 2 , or about 1000 mJ / cm 2 to about 2000 mJ / cm 2 , or about 1000 mJ / cm 2 to about 1500 mJ / cm 2 , or about 1500 irradiated with a UV lamp having a dosage of mJ / cm 2 to about 2500 mJ / cm 2 , or about 2000 mJ / cm 2 to about 2500 mJ / cm 2 .
  • the UV curable resin composition comprises about 65 parts by weight to about 70 parts by weight of the aliphatic urethane acrylate oligomer, about 19 parts by weight to about 32 parts by weight of the reactive monomer, and about 2 parts by weight to about 6 parts by weight of the adhesion promoter.
  • the UV curable resin composition may shrink in response to UV, so that the shrinkage of the UV curable resin composition may be reduced to suppress bubbles in the cured product. It is preferably less than 15% by volume.
  • the UV curable resin composition further increases light transmittance upon curing.
  • the cured product is completely cured. If the cured product contains an unreacted photoinitiator so that the cured product can be cured again by UV, the storage stability is inferior.
  • the cured product preferably has a light transmittance of about 95% or more, or about 95% to about 100%, or about 98% to about 100%. This is important for having good transparency, and in order for the cured product to have excellent transparency, a haze (haze value) must achieve a value close to zero. Accordingly, the haze value of the cured product is preferably less than 1%, for example about 0.01% to about 0.99%. When the haze value exceeds 1%, light scattering occurs and the cured product is difficult to have transparency, and irregular refraction of light occurs.
  • the UV curable resin composition further increases light transmittance upon curing.
  • the cured product preferably has a refractive index of about 1.4 to about 1.6.
  • the cured product is adjusted to have a refractive index similar to that of glass, and then the glass and the cured product are exposed when the cured material is brought into intimate contact with the glass and irradiated with light passing through the glass to transmit the cured product. It can be controlled so that the refraction of light does not occur at the interface.
  • the glass may be plain glass or tempered glass.
  • the cured product preferably has flexibility, tack, and excellent physical strength.
  • the elongation of the cured product may be about 100% or more.
  • the elongation may be about 100% to about 1000%, or about 100% to about 750%, or about 100% to about 500%, or about 100% to about 250%, or about 100% to about 200% , Or about 200% to about 1000%, or about 250% to about 1000%, or about 500% to about 1000%, or about 750% to about 1000%, or about 400% to about 600%.
  • the cured product may be applied to a light emitting device such as an LED chip, it should not appear a color change phenomenon in response to light.
  • the cured product may be used as an adhesive or a sealant in a glass having an LED chip, in which case the light of the LED light is completely transmitted without being scattered by the cured product or refracted at the interface with the glass. Clear light transmission is possible.
  • UV-curable resin compositions were prepared to have the compositions (weight ratios) of Tables 1 and 2 below.
  • Example 1 Example 2 Example 3 Aliphatic urethane acrylate oligomer 68 65 70 Acryloyl morpholine 13 10 15 Isobonyl Acrylate 8 6 10 Tetrahydrofurfuryl acrylate 5 3 7 Adhesion promoter 4 2 6 Photoinitiator 1.5 One 2 Antifoam 0.5 0.2 0.8 Humectant 0.5 0.2 0.8 Coupling agent 0.5 0.2 0.8
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Aliphatic urethane acrylate oligomer 60 75 68 68 68 68 68 Acryloyl morpholine 13 13 13 13 13 13 13 Isobonyl Acrylate 8 8 8 8 8 8 8 Tetrahydrofurfuryl acrylate 5 5 5 5 5 5 5 5 5 5 5 Adhesion promoter 4 4 4 4 4 4 4 Photoinitiator 1.5 1.5 3 1.5 1.5 1.5 1.5 1.5 1.5 Antifoam 0.5 0.5 0.5 0 0.5 0.5 0 Humectant 0.5 0.5 0.5 0.5 0 0.5 0 Coupling agent 0.5 0.5 0.5 0.5 0.5 0 0 0
  • Comparative Example 1 is a case containing a small amount of aliphatic urethane acrylate oligomer compared to Example 1
  • Comparative Example 2 is a case containing an excess of aliphatic urethane acrylate oligomer compared to Example 1
  • Comparative Example 3 Compared with Example 1, the photoinitiator is contained in an excessive amount
  • Comparative Example 4 is a case containing no antifoaming agent
  • Comparative Example 5 is a case containing no humectant
  • Comparative Example 4 is a case containing no coupling agent.
  • Example 1 was found to have a viscosity of less than 10 mPa ⁇ s at a level similar to water, and the contact angle was also found to have a level of 7 degrees, similar to that of water. In particular, Example 1 achieved a very high light transmittance of 97%.
  • UV curable resin compositions prepared in Examples and Comparative Examples were irradiated with UV of 2000 mJ / cm 2 for 2 minutes to photocure the UV curable resin compositions.
  • the temperature of the UV curable resin composition may be increased by UV irradiation, but it is preferable to control the temperature so that the temperature does not exceed 100 ° C during the curing reaction.
  • each UV curable resin composition prepared in Examples and Comparative Examples was applied to a glass plate with a thickness of 2 mm and then photocured with the UV lamp, according to JIS D 0202 The adhesion of each cured product was tested.
  • Example 1 was confirmed to have flexibility by having a significantly superior elongation compared to the comparative examples after curing, the refractive index was 1.46, which is similar to that of ordinary glass, and the haze value was confirmed as 0.3% of light It can be expected that there will be little scattering. It can be seen that the light transmittance of Example 1 was increased after curing.
  • Comparative Example 5 without the wetting agent, Comparative Example 6 without the coupling agent, and Comparative Example 7 without the antifoaming agent, the wetting agent, and the coupling agent were all deteriorated in adhesion, and the aliphatic urethane acrylate oligomer 60
  • Comparative Example 1 including parts by weight and Comparative Example 3 including 3 parts by weight of the photoinitiator can be seen that the adhesion and weather resistance is reduced.
  • Comparative Examples 4 and 7 that do not contain an antifoaming agent is confirmed that does not satisfy the refractive index and haze value of the present invention, from which the scattering and refraction of light is likely to occur.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention relates to a UV curable resin composition, a method for curing the same, and a cured product using the same and, more specifically to a UV curable resin composition which can prevent scattering and refraction upon transmitting light after being applied to a glass surface and UV curing, by controlling a transparent UV curable resin composition based on an aliphatic urethane acrylate oligomer to have a viscosity of less than 100 mPa s and a density similar to glass, a curing method of the UV curable resin composition, and a cured product using the UV curable resin composition.

Description

UV 경화형 수지 조성물, 이의 경화 방법 및 이를 이용한 경화물 UV curable resin composition, curing method thereof, and cured product using same
본 발명은 UV (ultraviolet) 경화형 수지 조성물, 이의 경화 방법 및 이를 이용한 경화물에 관한 것으로, 더욱 상세하게는 지방족 우레탄 아크릴레이트 올리고머를 기반으로 한 투명 UV 경화형 수지 조성물을 100 mPa·s 미만의 점도 및 유리와 유사한 밀도를 갖도록 제어함으로써, 유리 표면에 적용하고 UV 경화 후 빛 투과 시 산란 및 굴절을 방지할 수 있는, UV 경화형 수지 조성물, 상기 UV 경화형 수지 조성물의 경화 방법 및 상기 UV 경화형 수지 조성물을 이용한 경화물에 관한 것이다.The present invention relates to a UV (ultraviolet) curable resin composition, a curing method thereof and a cured product using the same, and more particularly, a transparent UV curable resin composition based on aliphatic urethane acrylate oligomers having a viscosity of less than 100 mPa · s and By controlling to have a glass-like density, using a UV curable resin composition, a method for curing the UV curable resin composition and the UV curable resin composition, which can be applied to the glass surface and prevent scattering and refraction upon light transmission after UV curing. It relates to a cured product.
UV 경화형 수지 조성물은 일반적으로, 올리고머, 반응성 모노머, 광개시제, 및 첨가제 등으로 이루어진다. 이러한 UV 경화형 수지 조성물에 자외선이 조사되면 광개시제로부터 라디칼이 생성되고, 생성된 라디칼이 올리고머와 반응성 모노머에 있는 이중결합을 공격하여 3차원 망상 구조의 가교 결합을 유도함으로써, UV 경화형 수지 조성물이 경화되고 결국 견고한 도막을 형성하게 된다.UV curable resin composition generally consists of an oligomer, a reactive monomer, a photoinitiator, an additive, etc. When the UV curable resin composition is irradiated with ultraviolet rays, radicals are generated from the photoinitiator, and the generated radicals attack the double bonds in the oligomer and the reactive monomer to induce crosslinking of the three-dimensional network structure, thereby curing the UV curable resin composition. Eventually a solid coating will be formed.
이때, 올리고머의 특성이 도막의 물성을 결정하는 요인으로 작용하므로, 올리고머의 선택이 무엇보다 중요하다. 특히, 우레탄 아크릴레이트 올리고머는 반응성이 좋고 경화된 도막의 경도, 부착성, 내약품성 등이 우수하다는 장점을 가지고 있지만, 도료의 점도가 높아 작업성이 좋지 않고 내후성이 약한 단점이 있다. 예를 들어, 한국 공개특허 제10-2013-0071267호에는 우레탄 (메타)아크릴레이트 공중합체를 포함하는 광학 점착제 조성물이 개시되어 있고, 이 조성물은 25℃에서 점도가 2000 내지 4000 cps (= 2000 내지 4000 mPa·s)인 것으로 개시되어 있다. 이와 같이, 조성물의 점도 (25℃)가 100 mPa·s 이상일 경우, 배합 과정에서 기포가 발생하기 쉽고, 용도에 맞춰 적용하기 위해 대상물에 도포 또는 주입하는 과정에서도 기포가 발생할 수 있으며, 높은 점도로 인해 작업성은 저감된다. 상기 한국 공개특허와 같이 조성물이 광학장치에 점착층으로 사용되는 경우, 점착층 내부에 기포가 존재한다면, 이로 인해 빛의 산란이 발생할 수 있어, 광학장치의 성능을 떨어뜨리게 될 수 있다.At this time, since the properties of the oligomer acts as a factor for determining the properties of the coating film, the selection of the oligomer is more important than anything. In particular, the urethane acrylate oligomer has the advantages of good reactivity and excellent hardness, adhesion, chemical resistance, etc. of the cured coating film, but has a disadvantage of poor workability and poor weather resistance due to the high viscosity of the paint. For example, Korean Patent Laid-Open Publication No. 10-2013-0071267 discloses an optical pressure-sensitive adhesive composition comprising a urethane (meth) acrylate copolymer, the composition having a viscosity of 2000 to 4000 cps (= 2000 to c) at 25 ° C. 4000 mPa · s). As such, when the viscosity (25 ° C) of the composition is 100 mPa · s or more, bubbles are likely to occur in the blending process, and bubbles may also occur in the process of applying or injecting the object for application according to the use. Workability is thereby reduced. When the composition is used as a pressure-sensitive adhesive layer in the optical device, such as the Korean Patent Publication, if bubbles exist inside the pressure-sensitive adhesive layer, this may cause scattering of light, which may degrade the performance of the optical device.
또한, 일본 공개특허 평05-039343호에는 우레탄 (메타)아크릴레이트 올리고머를 이용한 광 경화 조성물이 기재되어 있다. 상기 일본 공개특허의 광 경화 조성물이 유리에 적용할 수 있음이 개시되어 있지만, 유리 표면에 적용되는 UV 경화형 수지 조성물은 유리의 투명성을 헤치지 않으면서 유리 표면과 친화성을 갖는 것이 바람직한데, 상기 일본 공개특허에 개시된 광 경화 조성물은 플라스틱 표면을 도장하기 위해 설계된 것으로, 유리와는 친화성이 적어 유리에 사용하기에는 무리가 있고, 즉, 유리의 투명성을 헤치게 될 수 있으며, 상기 광경화 조성물로 제조된 도막을 유리 표면에 적용할 경우 표면 부착성, 가공성이 저하될 수 있다.In addition, JP 05-039343 A describes a photocurable composition using a urethane (meth) acrylate oligomer. Although it is disclosed that the photocurable composition of the JP Patent Application can be applied to glass, the UV curable resin composition applied to the glass surface preferably has affinity with the glass surface without spoiling the transparency of the glass. The photocurable composition disclosed in Japanese Patent Laid-Open is designed to paint a plastic surface, and has a low affinity with glass, which makes it difficult to use in glass, that is, the transparency of glass may be impaired. When the prepared coating film is applied to the glass surface, surface adhesion and workability may be reduced.
따라서 이러한 문제점을 해결하기 위한 본 발명의 첫 번째 목적은, 지방족 우레탄 아크릴레이트 올리고머를 기반으로 한 투명 UV 경화형 수지 조성물을 100 mPa·s 미만의 점도 및 유리와 유사한 수준의 밀도를 갖도록 제어함으로써, 빛 산란을 최소화하고 유리 표면에 적용 시 굴절을 방지할 수 있는, UV 경화형 수지 조성물을 제공하는 것이다.Therefore, the first object of the present invention for solving this problem is to control the transparent UV curable resin composition based on aliphatic urethane acrylate oligomer to have a viscosity of less than 100 mPa · s and a density comparable to glass. It is to provide a UV curable resin composition that can minimize scattering and prevent refraction when applied to a glass surface.
또한, 두 번째 목적은 상기 UV 경화형 수지 조성물을 유리 표면에 적용하기 위한, UV 경화형 수지 조성물의 경화 방법을 제공하는 것이다.Moreover, a 2nd objective is to provide the hardening method of a UV curable resin composition for applying the said UV curable resin composition to a glass surface.
그리고 세 번째 목적은 유리에 적용 시 산란 및 굴절을 방지할 수 있는, 상기 UV 경화형 수지 조성물을 이용한 경화물을 제공하는 것이다.And a third object is to provide a cured product using the UV curable resin composition, which can prevent scattering and refraction when applied to glass.
그러나, 본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.
상기 첫 번째 목적을 달성하기 위하여 본 발명은 지방족 우레탄 아크릴레이트 올리고머, 반응성 모노머, 부착증진제, 광개시제, 소포제, 습윤제, 및 커플링제를 포함하며, 25℃에서의 점도가 100 mPa·s 미만인 것임을 특징으로 하는, UV 경화형 수지 조성물을 제공한다.In order to achieve the first object, the present invention comprises an aliphatic urethane acrylate oligomer, reactive monomer, adhesion promoter, photoinitiator, antifoaming agent, wetting agent, and coupling agent, characterized in that the viscosity at 25 ℃ is less than 100 mPa · s It provides a UV curable resin composition.
상기 UV 경화형 수지 조성물은, 상기 지방족 우레탄 아크릴레이트 올리고머를 약 65 중량부 내지 약 70 중량부로, 상기 반응성 모노머를 약 19 중량부 내지 약 32 중량부로, 상기 부착증진제를 약 2 중량부 내지 약 6 중량부로, 상기 광개시제를 약 1 중량부 내지 약 2 중량부로, 상기 소포제를 약 0.2 중량부 내지 약 0.8 중량부로, 상기 습윤제를 약 0.2 중량부 내지 약 0.8 중량부로, 및 상기 커플링제를 약 0.2 중량부 내지 약 0.8 중량부로 포함하는 것일 수 있다.The UV curable resin composition comprises about 65 parts by weight to about 70 parts by weight of the aliphatic urethane acrylate oligomer, about 19 parts by weight to about 32 parts by weight of the reactive monomer, and about 2 parts by weight to about 6 parts by weight of the adhesion promoter. To about 1 part to about 2 parts by weight of the photoinitiator, about 0.2 part to about 0.8 part by weight of the antifoaming agent, about 0.2 part to about 0.8 part by weight of the wetting agent, and about 0.2 part by weight of the coupling agent. It may be to include from about 0.8 parts by weight.
상기 UV 경화형 수지 조성물은 밀도가 약 0.85 내지 약 3 g/cm3인 것일 수 있다.The UV curable resin composition may have a density of about 0.85 to about 3 g / cm 3 .
상기 UV 경화형 수지 조성물은 유리에 대한 접촉각이 약 10도 이하인 것일 수 있다.The UV curable resin composition may have a contact angle with respect to glass of about 10 degrees or less.
상기 UV 경화형 수지 조성물은 광투과율이 약 95% 이상인 것일 수 있다.The UV curable resin composition may have a light transmittance of about 95% or more.
상기 UV 경화형 수지 조성물은 경화시 수축율이 15 부피% 미만인 것일 수 있다.The UV curable resin composition may be less than 15% by volume shrinkage upon curing.
상기 두 번째 목적을 달성하기 위하여 본 발명은, 상기 UV 경화형 수지 조성물에 UV를 조사하여 상기 UV 경화형 수지 조성물을 완전히 경화시키는 단계를 포함하는, UV 경화형 수지 조성물의 경화 방법을 제공한다.In order to achieve the second object, the present invention provides a curing method of the UV curable resin composition, comprising the step of completely curing the UV curable resin composition by irradiating the UV curable resin composition with UV.
상기 단계에서 경화 시의 최고온도가 100℃ 미만인 것일 수 있다.The maximum temperature at the time of curing may be less than 100 ℃.
상기 세 번째 목적을 달성하기 위하여 본 발명은, 상기 UV 경화형 수지 조성물을 이용한 경화물로서, 상기 경화물은 상기 UV 경화형 수지 조성물이 완전 경화된 것임을 특징으로 하는, 경화물을 제공한다.In order to achieve the third object, the present invention provides a cured product, wherein the cured product is a cured product using the UV curable resin composition, wherein the UV curable resin composition is completely cured.
상기 경화물은 굴절률이 약 1.4 내지 약 1.6인 것일 수 있다.The cured product may have a refractive index of about 1.4 to about 1.6.
상기 경화물은 헤이즈 값 (haze value)이 1% 미만인 것일 수 있다.The cured product may have a haze value of less than 1%.
상기 경화물은 연신율 (elongation at break)이 약 100% 내지 약 1000%인 것일 수 있다.The cured product may have an elongation at break of about 100% to about 1000%.
상기 경화물은 광투과율이 약 95% 이상인 것일 수 있다.The cured product may have a light transmittance of about 95% or more.
본 발명의 UV 경화형 수지 조성물을 이용하면 우수한 경화성을 갖고 유리에 친화성을 갖는 경화물을 제조할 수 있다. 상기 UV 경화형 수지 조성물은 지방족 우레탄 아크릴레이트 올리고머를 기반으로 한 투명 UV 경화형 수지 조성물로서 100 mPa·s 미만의 점도 및 유리와 유사한 밀도를 갖도록 제어함으로써, 유리 표면에 적용하고 경화할 경우, 빛 투과 시 빛 산란 및 굴절을 방지할 수 있게 된다.When the UV curable resin composition of this invention is used, hardened | cured material which has excellent curability and has affinity for glass can be manufactured. The UV curable resin composition is a transparent UV curable resin composition based on aliphatic urethane acrylate oligomer and controlled to have a viscosity of less than 100 mPa · s and a glass-like density, so that when applied to the glass surface and cured, Light scattering and refraction can be prevented.
본 발명의 UV 경화형 수지 조성물은 UV에 반응하여 쉽게 경화되는 특성을 가지므로 접착제 또는 실란트의 용도로 사용될 수 있다.Since the UV curable resin composition of the present invention has the property of being easily cured in response to UV, it can be used for the use of adhesives or sealants.
아래에서는 첨부한 도면을 참조하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예를 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 그리고 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.
본 발명의 명세서 및 청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 한정 해석되지 아니하며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the specification and claims of the present invention are not to be construed in a conventional or dictionary sense, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way. Based on the principle, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.
*본 발명의 명세서 전체에 있어서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.* Throughout the specification of the present invention, when a part is said to "include" a certain component, it means that it may further include other components, except to exclude other components unless specifically stated otherwise. do.
본 발명의 명세서 전체에 있어서, "A 및/또는 B"는, A 또는 B, 또는 A 및 B를 의미한다.In the specification of the present invention, "A and / or B" means A or B, or A and B.
이하, 첨부된 도면을 참조하여 본 발명을 구체적으로 설명하였으나, 본 발명이 이에 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited thereto.
본 발명은 지방족 우레탄 아크릴레이트 올리고머, 반응성 모노머, 부착증진제, 광개시제, 소포제, 습윤제, 및 커플링제를 포함하며, 25℃에서의 점도가 100 mPa·s 미만인 것임을 특징으로 하는, UV 경화형 수지 조성물을 제공한다.The present invention includes an aliphatic urethane acrylate oligomer, a reactive monomer, an adhesion promoter, a photoinitiator, an antifoaming agent, a wetting agent, and a coupling agent, and the UV curable resin composition is characterized in that the viscosity at 25 ° C. is less than 100 mPa · s. do.
25℃에서의 점도가 약 1 mPa·s 내지 약 99.9 mPa·s 인 경우, 상기 UV 경화형 수지 조성물은 물과 가까운 점도를 갖게 되어, 주입 시 흐름이 원활하여 작업성이 우수하고, 기포발생이 최소화될 수 있다. UV 경화형 수지 조성물 내부에 기포가 발생하면, 빛의 산란이 나타날 수 있어 부적합하다. 즉, 25℃에서의 점도를 100 mPa·s 미만으로 조절하여 기포발생을 최소화하는 것이 빛의 산란을 방지할 수 있어 바람직하다. 상기 점도는 25℃에서 약 1 mPa·s 내지 약 10 mPa·s 인 것이 더 바람직하나, 이에 제한되지 않을 수 있다.When the viscosity at 25 ° C. is about 1 mPa · s to about 99.9 mPa · s, the UV curable resin composition has a viscosity close to water, so that the flow is smooth when injected, and workability is excellent, and bubble generation is minimized. Can be. If bubbles are generated inside the UV-curable resin composition, light scattering may appear, which is inappropriate. That is, minimizing bubble generation by adjusting the viscosity at 25 ° C. to less than 100 mPa · s is preferable because it can prevent scattering of light. More preferably, the viscosity is about 1 mPa · s to about 10 mPa · s at 25 ° C., but may not be limited thereto.
상기 UV 경화형 수지 조성물은 23℃에서의 밀도가 약 0.85 g/cm3 내지 약 3 g/cm3인 것일 수 있다. 상기 UV 경화형 수지 조성물이 유리에 적용될 경우, 유리의 밀도와 유사한 수준의 밀도를 갖도록 조절하여, 빛이 유리를 거쳐 상기 UV 경화형 수지 조성물을 투과하게 할 경우 유리와 상기 UV 경화형 수지 조성물의 경계면에서 빛의 굴절이 발생하지 않도록 하는 것이 바람직하다. 이때, 상기 유리는 일반유리일 수 있으며, 내열 특성 및/또는 내충격 특성을 향상시킨 강화유리일 수 있다. The UV curable resin composition may have a density of about 0.85 g / cm 3 to about 3 g / cm 3 at 23 ° C. When the UV curable resin composition is applied to the glass, it is adjusted to have a density similar to that of the glass, so that light passes through the UV light through the UV curable resin composition, and the light at the interface between the glass and the UV curable resin composition It is desirable to prevent the refraction of from occurring. In this case, the glass may be ordinary glass, and may be tempered glass having improved heat resistance and / or impact resistance.
상기 UV 경화형 수지 조성물은 유리에 대한 접촉각이 약 10도 이하, 예를 들어, 약 0.5도 내지 약 10도인 것일 수 있다. 상기 UV 경화형 수지 조성물의 유리에 대한 접촉각은 약 0.5도 내지 약 10도, 또는 약 0.5도 내지 약 5도, 또는 약 0.5도 내지 약 3도, 또는 약 5도 내지 약 10도, 또는 약 8도 내지 약 10도인 것이 바람직하며, 특히, 약 8도 내지 약 9도인 것이 더 바람직하나, 이에 제한되지 않을 수 있다. 유리에 대한 접촉각이 10도 이하인 경우, 상기 UV 경화형 수지 조성물은 유리에 대한 친화성을 가져 상기 UV 경화형 수지 조성물을 유리 표면에 적용 시 강한 결합력으로 유리와 결합하게 된다.The UV curable resin composition may have a contact angle with respect to glass of about 10 degrees or less, for example, about 0.5 degrees to about 10 degrees. The contact angle of the UV curable resin composition to the glass is about 0.5 degrees to about 10 degrees, or about 0.5 degrees to about 5 degrees, or about 0.5 degrees to about 3 degrees, or about 5 degrees to about 10 degrees, or about 8 degrees. It is preferably from about 10 degrees, and more preferably, about 8 degrees to about 9 degrees, but may not be limited thereto. When the contact angle with respect to glass is 10 degrees or less, the UV curable resin composition has affinity for glass, and when the UV curable resin composition is applied to the glass surface, the UV curable resin composition bonds with the glass with a strong bonding force.
본 발명의 명세서 전체에서, 용어 "접촉각"은, 공기 중에 존재하는 유리면 상에 상기 UV 경화형 수지 조성물의 액체 한 방울을 떨어뜨리면 상기 UV 경화형 수지 조성물의 액적이 생기는데, 이 액적의 고체·액체·기체의 삼상접촉점에서 유리면과 액체 표면의 각을 액체 안쪽에서 측정한 값을 의미한다.Throughout the specification of the present invention, the term "contact angle" means that when a drop of a liquid of the UV curable resin composition is dropped on a glass surface existing in air, a droplet of the UV curable resin composition is generated, and the solid, liquid, and gas of the droplet are generated. It means the angle of the glass surface and the liquid surface measured inside the liquid at the three-phase contact point of.
상기 UV 경화형 수지 조성물은 광투과율이 약 95% 내지 약 100% 또는 약 98% 내지 약 100%인 것일 수 있다. 상기 UV 경화형 수지 조성물을 형성하는 각 성분이 서로 완전히 용해되지 않아 형성된 UV 경화형 수지 조성물이 탁해진다거나, UV 경화형 수지 조성물의 제조과정에서 내부에 기포가 존재하게 된다면, 95% 이상의 광투과율을 달성할 수 없게 된다. 전술한 바와 같이, 빛의 산란 및 굴절을 방지하기 위해서는, 상기 UV 경화형 수지 조성물의 광투과율이 약 95% 이상이 되게 조절하는 것이 바람직하다.The UV curable resin composition may have a light transmittance of about 95% to about 100% or about 98% to about 100%. When the components forming the UV curable resin composition are not completely dissolved in each other and the formed UV curable resin composition becomes cloudy or bubbles are present in the process of manufacturing the UV curable resin composition, light transmittance of 95% or more can be achieved. It becomes impossible. As described above, in order to prevent scattering and refraction of light, it is preferable to adjust the light transmittance of the UV curable resin composition to be about 95% or more.
상기 UV 경화형 수지 조성물은 UV 경화 시의 수축율이 약 0 부피% 내지 약 14.9 부피%인 것일 수 있으며, 수축이 없는 것이 가장 바람직하고 수축율이 15 부피% 미만에서 0 부피%에 가까운 것이 바람직하나, 이에 제한되지 않을 수 있다. 상기 UV 경화형 수지 조성물의 경화시 수축율이 15 부피% 이상일 경우, 경화물 내에 기포가 발생할 수 있어 부적합하다. 경화물 내에 기포가 존재하면, 경화물 내에서 빛의 산란이 발생하게 되고 이에 따라 빛의 굴절 또한 나타나게 된다. 경화물에서의 빛의 산란 및 굴절을 방지하는 것이 본 발명의 최종 목적이기 때문에, 상기 UV 경화형 수지 조성물의 점도, 밀도, 광투과율, 수축율 등의 특성을 제어하는 것이 중요하다. 상기 UV 경화형 수지 조성물에 있어, 더 바람직한 것은 UV 경화 시의 수축율이 약 0 부피% 내지 약 10 부피% 인 것이며, 특히 더 바람직한 것은 UV 경화 시의 수축율이 약 0 부피% 내지 약 5 부피% 인 것이나, 이에 제한되지 않을 수 있다.The UV curable resin composition may have a shrinkage rate of about 0% by volume to about 14.9% by volume during UV curing, most preferably no shrinkage, and close to 0% by volume at less than 15% by volume. It may not be limited. When the shrinkage ratio during curing of the UV curable resin composition is 15% by volume or more, bubbles may occur in the cured product, which is not suitable. If bubbles exist in the cured product, light scattering occurs in the cured product, and thus light refraction also appears. Since it is the final object of the present invention to prevent scattering and refraction of light in the cured product, it is important to control properties such as viscosity, density, light transmittance, shrinkage ratio and the like of the UV curable resin composition. In the above UV curable resin composition, more preferably, the shrinkage at the time of UV curing is about 0% by volume to about 10% by volume, and more preferably, the shrinkage at the time of UV curing is about 0% by volume to about 5% by volume. However, this may not be limited.
전술한 바와 같은 특성들을 만족하기 위해, 상기 UV 경화형 수지 조성물은, 상기 지방족 우레탄 아크릴레이트 올리고머를 약 65 중량부 내지 약 70 중량부로, 상기 반응성 모노머를 약 19 중량부 내지 약 32 중량부로, 상기 부착증진제를 약 2 중량부 내지 약 6 중량부로, 상기 광개시제를 약 1 중량부 내지 약 2 중량부로, 상기 소포제를 약 0.2 중량부 내지 약 0.8 중량부로, 상기 습윤제를 약 0.2 중량부 내지 약 0.8 중량부로, 및 상기 커플링제를 약 0.2 중량부 내지 약 0.8 중량부로 포함하는 것이 바람직하다.In order to satisfy the above-described properties, the UV curable resin composition may contain about 65 parts by weight to about 70 parts by weight of the aliphatic urethane acrylate oligomer and about 19 parts by weight to about 32 parts by weight of the reactive monomer. From about 2 to about 6 parts by weight of the enhancer, from about 1 to about 2 parts by weight of the photoinitiator, from about 0.2 to about 0.8 parts by weight of the antifoaming agent, and from about 0.2 to about 0.8 parts by weight of the humectant. And from about 0.2 part to about 0.8 part by weight of the coupling agent.
상기 지방족 우레탄 아크릴레이트 올리고머는 무황변 타입이고 유연성이 좋아 UV 경화형 수지 조성물의 부착성을 향상시킬 수 있다. 상기 지방족 우레탄 아크릴레이트 올리고머는 2 내지 10의 관능기를 가지는 것이 바람직하며, 2 관능기를 가지는 것이 더 바람직하다. 상기 UV 경화형 수지 조성물은 지방족 우레탄 아크릴레이트 올리고머를 65 중량부 미만으로 함유할 경우, UV 경화 후 부착성 및 유연성 저하를 야기할 수 있으며, 70 중량부를 초과하여 함유할 경우, 조성물의 점도가 증대되어 작업성이 저감될 수 있다.The aliphatic urethane acrylate oligomer is a yellowing type and good flexibility can improve the adhesion of the UV curable resin composition. It is preferable that the said aliphatic urethane acrylate oligomer has a 2-10 functional group, and it is more preferable to have a bifunctional group. When the UV curable resin composition contains an aliphatic urethane acrylate oligomer of less than 65 parts by weight, it may cause adhesion and flexibility deterioration after UV curing, when contained in more than 70 parts by weight, the viscosity of the composition is increased Workability can be reduced.
상기 반응성 모노머는 하나 이상의 관능기를 가지는 아크릴계 모노머일 수 있으며, 예를 들어, 아크릴로일모르폴린 (acryloylmorpholine), 이소보닐 아크릴레이트 (isobornyl acrylate), 이소보닐 메타아크릴레이트 (isobornyl methacrylate), 테트라하이드로퓨퓨릴 아크릴레이트 (tetrahydrofurfuryl acrylate), 2-페녹시에틸 아크릴레이트 (2-phenoxyethyl acrylate), 스테아릴 아크릴레이트 (stearyl acrylate), 카프로락톤 아크릴레이트 (caprolactone acrylate), 트리프로필렌글리콜 디아크릴레이트 (tripropyleneglycol diacrylate), 1,6-헥산디올 디아크릴레이트 (1,6-hexanediol diacrylate), 트리메틸올프로판 트리아크릴레이트 (trimethylolpropane triacrylate), 에톡시화 트리메틸올프로판 트리아크릴레이트 (ethoxylated trimethylolpropane triacrylate), 펜타에리쓰리톨 트리아크릴레이트 (pentaerythritol triacrylate), 및 디펜타에리쓰리톨 헥사아크릴레이트 (dipentaerythritol hexaacrylate)로 이루어진 군으로부터 선택된 하나 또는 둘 이상을 포함하는 것일 수 있다. 상기 UV 경화형 수지 조성물은 상기 반응성 모노머를 19 중량부 미만으로 함유할 경우, 조성물의 점도가 증대되어 작업성이 저감될 수 있으며, 32 중량부를 초과하여 함유할 경우, 상기 지방족 우레탄 아크릴레이트 올리고머의 물성을 침해하게 될 수 있다.The reactive monomer may be an acrylic monomer having one or more functional groups, for example, acryloylmorpholine, isobornyl acrylate, isobornyl methacrylate, tetrahydropu Tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, stearyl acrylate, caprolactone acrylate, tripropyleneglycol diacrylate 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate Latex (pentaerythritol triacrylate), and dipentaerythritol It may be one containing at least one or two selected from the group consisting of hexadecyl acrylate (dipentaerythritol hexaacrylate). When the UV curable resin composition contains less than 19 parts by weight of the reactive monomer, the viscosity of the composition may be increased, and workability may be reduced. When the UV curable resin composition contains more than 32 parts by weight, the physical properties of the aliphatic urethane acrylate oligomer May be infringed.
상기 부착증진제는 경화물의 부착력을 향상시키기 위해 사용된다. 상기 부착증진제로는 아크릴기를 갖는 C1-20의 알칸 화합물을 포함하는 수지일 수 있다. 상기 아크릴기를 갖는 C1-15의 알칸 화합물은 아크릴기외에 다른 관능기는 가지지 않는 것일 수 있으며, 2-에틸헥실 아크릴레이트 (2-ethylhexyl acrylate)가 바람직하나, 이에 제한되지 않을 수 있다. 상기 UV 경화형 수지 조성물이 부착증진제를 2 중량부 미만으로 함유될 경우, 부착 효과가 미미하고, 6 중량부를 초과하여 함유할 경우, 조성물의 물성 저하 또는 겔화를 초래할 수 있다.The adhesion promoter is used to improve the adhesion of the cured product. The adhesion promoter may be a resin containing a C 1-20 alkane compound having an acrylic group. The alkane compound of C 1-15 having the acryl group may be one having no functional group other than the acryl group, and 2-ethylhexyl acrylate is preferred, but may not be limited thereto. When the UV curable resin composition contains an adhesion promoter less than 2 parts by weight, the adhesion effect is insignificant, and when it contains more than 6 parts by weight, the physical properties of the composition may be reduced or gelation.
상기 광개시제는 UV에 의해 활성을 갖게 되는 것을 사용할 수 있다. 예를 들어, 상기 광개시제로는 1-하이드록시 사이클로헥실 페닐 케톤 (1-hydroxy cyclohexyl phenyl ketone), 1-하이드록시-2-메틸-1-페닐프로판-1-케톤 (1-hydroxy-2-methyl-1-phenylpropane-1-ketone), 2-클로로티옥산톤 (2-chlorothioxantone), 2-이소프로필티옥산톤 (2-isopropylthioxantone), 및 벤조페논 (benzophenone)으로 이루어진 군으로부터 선택된 하나 또는 둘 이상을 사용할 수 있으며, 1-하이드록시 사이클로헥실 페닐 케톤을 사용하는 것이 더 바람직하나, 이에 제한되지 않을 수 있다. 상기 UV 경화형 수지 조성물에서의 상기 광개시제의 함량이 1 중량부 미만일 경우, 경화가 충분히 진행되지 않을 가능성이 높으며, 2 중량부를 초과할 경우, 생산 비용이 증가하고 미반응 광개시제가 경화물에 남아있을 수 있어 저장 안정성이 저하될 수 있다. The photoinitiator can be used that becomes active by UV. For example, the photoinitiator is 1-hydroxy cyclohexyl phenyl ketone, 1-hydroxy-2-methyl-1-phenylpropane-1-ketone (1-hydroxy-2-methyl One or two or more selected from the group consisting of -1-phenylpropane-1-ketone, 2-chlorothioxantone, 2-isopropylthioxantone, and benzophenone It may be used, it is more preferred to use 1-hydroxy cyclohexyl phenyl ketone, but may not be limited thereto. When the content of the photoinitiator in the UV-curable resin composition is less than 1 part by weight, there is a high possibility that the curing does not proceed sufficiently, and when it exceeds 2 parts by weight, the production cost may increase and unreacted photoinitiator may remain in the cured product. Storage stability may be reduced.
상기 소포제는 조성물 내에 존재하는 기포를 제거하는 역할을 하는 것으로, 실리콘유, 에탄올, 옥탄올, 사이클로헥산올, 에틸렌글리콜, 고급알코올류로 이루어진 군으로부터 선택된 하나 또는 둘 이상을 사용할 수 있다. 상기 UV 경화형 수지 조성물 중 소포제의 함량이 0.2 중량부 미만일 경우 기포 제거 효과가 미미하여 조성물 내 기포로 인한 빛의 산란을 막을 수 없게 되고, 0.8 중량부를 초과할 경우, 생산 비용 증가를 초래하여 적합하지 않다.The antifoaming agent serves to remove bubbles present in the composition, and may use one or two or more selected from the group consisting of silicone oil, ethanol, octanol, cyclohexanol, ethylene glycol, and higher alcohols. When the content of the antifoaming agent in the UV curable resin composition is less than 0.2 parts by weight, the bubble removal effect is insignificant to prevent scattering of light due to bubbles in the composition, and when it exceeds 0.8 parts by weight, it is not suitable because it leads to an increase in production cost. .
상기 습윤제는 조성물의 표면장력을 감소시키는 역할을 하는 것으로, 조성물의 표면장력을 물과 유사하게 만들어 유리에 대한 접촉각을 약 8 내지 9도가 되도록 하기 위해 사용한다. 상기 UV 경화형 수지 조성물 중 습윤제의 함량을 약 0.2 중량부 내지 약 0.8 중량부로 조절하여 물과 유사한 표면장력을 만들 수 있으며, 0.2 중량부 미만으로 습윤제가 함유될 경우, 표면장력 감소 효과가 미미하여 유리에 대한 접촉각이 10도를 초과하게 될 수 있으며, 0.8 중량부를 초과하여 함유될 경우, 생산 비용 증가를 초래하여 적합하지 않다.The wetting agent serves to reduce the surface tension of the composition, and is used to make the surface tension of the composition similar to water so that the contact angle to the glass is about 8 to 9 degrees. The content of the wetting agent in the UV curable resin composition may be adjusted to about 0.2 parts by weight to about 0.8 parts by weight to create a surface tension similar to water. When the amount of the wetting agent is less than 0.2 parts by weight, the surface tension reduction effect is minimal. The contact angle with respect to it may exceed 10 degrees, and if it contains more than 0.8 parts by weight, it will lead to an increase in production cost and is not suitable.
상기 커플링제는 상기 UV 경화형 수지 조성물과 유리의 계면접착성을 높여 조성물의 부착성을 향상시키는 역할을 하는 것으로, 실란계 커플링제를 사용할 수 있다. 상기 실란계 커플링제로는 예를 들어, 비닐 트리스(2-메톡시에톡시)실란 [vinyl tris(2-methoxyethoxy)silane], 비닐 트리에톡시실란 (vinyl triethoxysilane), 비닐 트리메톡시실란 (vinyl trimethoxysilane), 및 비닐 메틸디메톡시실란 (vinyl methyldimethoxysilane)으로 이루어진 군으로부터 선택된 하나 또는 둘 이상을 사용할 수 있다. 상기 UV 경화형 수지 조성물 중 커플링제의 함량이 0.2 중량부 미만일 경우 조성물의 부착성 향상 효과가 미미하여 경화물과 유리 사이의 결합력 향상을 달성할 수 없게 되고, 0.8 중량부를 초과할 경우, 생산 비용 증가를 초래하여 적합하지 않다.The coupling agent serves to increase the interfacial adhesion between the UV curable resin composition and glass and to improve the adhesion of the composition. A silane coupling agent may be used. As the silane coupling agent, for example, vinyl tris (2-methoxyethoxy) silane, vinyl triethoxysilane, vinyl trimethoxysilane (vinyl) trimethoxysilane), and one or two or more selected from the group consisting of vinyl methyldimethoxysilane. When the content of the coupling agent in the UV-curable resin composition is less than 0.2 parts by weight, the effect of improving the adhesion of the composition is insignificant, and thus it is impossible to achieve an improvement in the bonding strength between the cured product and the glass. It is not suitable to cause.
상기 UV 경화형 수지 조성물은 용매를 함유하지 않는 무용매 상태인 것이 바람직하며, 성상은 무색·투명한 것이 바람직하다. 이에 따라, 본 발명의 UV 경화형 수지 조성물을 형성하는 성분들로는 무색·투명한 것을 사용하는 것이 바람직하나, 이에 제한되는 것은 아니다.It is preferable that the said UV curable resin composition is a solvent-free state which does not contain a solvent, and it is preferable that a property is colorless and transparent. Accordingly, as the components forming the UV curable resin composition of the present invention, it is preferable to use colorless and transparent ones, but is not limited thereto.
상기 UV 경화형 수지 조성물은 접착제 또는 실란트 (sealant)의 용도로 사용될 수 있으며, 접착제 또는 실란트의 용도로 도포 또는 주입된 뒤에는 UV에 의해 경화될 수 있다.The UV curable resin composition may be used for the use of an adhesive or sealant, and may be cured by UV after being applied or injected into the use of the adhesive or sealant.
아울러, 본 발명은, 상기 UV 경화형 수지 조성물에 UV를 조사하여 상기 UV 경화형 수지 조성물을 완전히 경화시키는 단계를 포함하는, UV 경화형 수지 조성물의 경화 방법을 제공한다.In addition, the present invention provides a curing method of the UV curable resin composition, comprising the step of completely curing the UV curable resin composition by irradiating UV to the UV curable resin composition.
상기 단계는 UV에 의한 경화를 실시하는 단계로, 상기 UV 경화형 수지 조성물로부터 경화물을 수득할 수 있다. 이때의 경화는 UV 경화 장치 내에서 수행될 수 있으며, 상기 UV 경화 장치 내부의 온도는 100℃ 미만, 또는 약 90℃ 이하, 예를 들어, 약 40℃ 내지 약 90℃ 인 것이 바람직하다. 상기 UV 경화형 수지 조성물은 경우에 따라 LED 칩과 같은 발광장치에서 접착제 또는 실란트의 용도로 사용될 수 있는데, 이러한 발광장치에 상기 UV 경화형 수지 조성물이 도포되거나 상기 발광장치 내부에 주입된 다음, 경화를 거치는 과정에서 경화 온도가 100℃를 초과할 경우 상기 발광장치가 열해 (heat damage)를 입을 가능성이 있으므로, 상기 UV 경화 장치 내부의 온도를 100℃ 미만으로 제어하는 것이 바람직하나, 이에 제한되지 않을 수 있다.The step is to perform curing by UV, it is possible to obtain a cured product from the UV curable resin composition. Curing at this time may be carried out in a UV curing apparatus, the temperature inside the UV curing apparatus is preferably less than 100 ℃, or less than about 90 ℃, for example, about 40 ℃ to about 90 ℃. The UV curable resin composition may optionally be used as an adhesive or sealant in a light emitting device such as an LED chip. The UV curable resin composition may be coated or injected into the light emitting device, and then subjected to curing. If the curing temperature exceeds 100 ° C. in the process, the light emitting device may be injured by heat. Therefore, the temperature inside the UV curing device may be controlled to less than 100 ° C., but may not be limited thereto. .
상기 단계에서 경화는 약 1000 mJ/cm2 내지 약 2500 mJ/cm2의 에너지 밀도를 갖는 UV에 의해 실시될 수 있다. 상기 UV는 약 1000 mJ/cm2 내지 약 2500 mJ/cm2, 또는 약 1000 mJ/cm2 내지 약 2000 mJ/cm2, 또는 약 1000 mJ/cm2 내지 약 1500 mJ/cm2, 또는 약 1500 mJ/cm2 내지 약 2500 mJ/cm2, 또는 약 2000 mJ/cm2 내지 약 2500 mJ/cm2의 조사량을 갖는 UV 램프에 의해 조사될 수 있다. Curing in this step may be carried out by UV having an energy density of about 1000 mJ / cm 2 to about 2500 mJ / cm 2 . The UV is about 1000 mJ / cm 2 to about 2500 mJ / cm 2 , or about 1000 mJ / cm 2 to about 2000 mJ / cm 2 , or about 1000 mJ / cm 2 to about 1500 mJ / cm 2 , or about 1500 irradiated with a UV lamp having a dosage of mJ / cm 2 to about 2500 mJ / cm 2 , or about 2000 mJ / cm 2 to about 2500 mJ / cm 2 .
상기 UV 경화형 수지 조성물은, 상기 지방족 우레탄 아크릴레이트 올리고머를 약 65 중량부 내지 약 70 중량부로, 상기 반응성 모노머를 약 19 중량부 내지 약 32 중량부로, 상기 부착증진제를 약 2 중량부 내지 약 6 중량부로, 상기 광개시제를 약 1 중량부 내지 약 2 중량부로, 상기 소포제를 약 0.2 중량부 내지 약 0.8 중량부로, 상기 습윤제를 약 0.2 중량부 내지 약 0.8 중량부로, 및 상기 커플링제를 약 0.2 중량부 내지 약 0.8 중량부로 포함하는 것이 바람직하며, 이 경우 단시간에 상기 UV 경화형 수지 조성물을 완전 경화시킬 수 있다.The UV curable resin composition comprises about 65 parts by weight to about 70 parts by weight of the aliphatic urethane acrylate oligomer, about 19 parts by weight to about 32 parts by weight of the reactive monomer, and about 2 parts by weight to about 6 parts by weight of the adhesion promoter. To about 1 part to about 2 parts by weight of the photoinitiator, about 0.2 part to about 0.8 part by weight of the antifoaming agent, about 0.2 part to about 0.8 part by weight of the wetting agent, and about 0.2 part by weight of the coupling agent. It is preferable to include from about 0.8 parts by weight, in this case, the UV curable resin composition can be completely cured in a short time.
본 발명의 일 구현예에 따른 UV 경화형 수지 조성물의 경화 방법에 있어서, 상기 UV 경화형 수지 조성물은 UV에 반응하여 수축될 수 있는데, 경화물 내 기포발생을 억제하기 위해 상기 UV 경화형 수지 조성물의 수축율이 15 부피% 미만인 것이 바람직하다. In the method of curing the UV curable resin composition according to an embodiment of the present invention, the UV curable resin composition may shrink in response to UV, so that the shrinkage of the UV curable resin composition may be reduced to suppress bubbles in the cured product. It is preferably less than 15% by volume.
상기 UV 경화형 수지 조성물은 경화 시 광투과도가 더 증대되는 것이 바람직하다.Preferably, the UV curable resin composition further increases light transmittance upon curing.
나아가, 본 발명은 상기 UV 경화형 수지 조성물을 이용한 경화물을 제공한다.Furthermore, this invention provides the hardened | cured material using the said UV curable resin composition.
상기 경화물은 완전 경화된 것이 바람직하다. 상기 경화물이 미반응 광개시제를 함유하고 있어 UV에 의해 다시 경화될 수 있는 상태라면 저장 안정성이 떨어져 부적합하다.Preferably, the cured product is completely cured. If the cured product contains an unreacted photoinitiator so that the cured product can be cured again by UV, the storage stability is inferior.
상기 경화물은 광투과율이 약 95% 이상, 또는 약 95% 내지 약 100%, 또는 약 98% 내지 약 100%인 것이 바람직하다. 이는 우수한 투명성을 갖기 위해 중요한 것이며, 또한, 상기 경화물이 우수한 투명성을 갖기 위해서는 탁도 (헤이즈 값)가 0에 가까운 값을 달성해야 한다. 이에 따라, 상기 경화물의 헤이즈 값은 1% 미만, 예를 들어 약 0.01% 내지 약 0.99%인 것이 바람직하다. 헤이즈 값이 1%를 초과할 경우, 빛의 산란이 일어나 경화물이 투명성을 갖기 어려우며, 빛의 불규칙한 굴절이 발생하게 된다. 상기 UV 경화형 수지 조성물은 경화 시 광투과도가 더 증대되는 것이 바람직하다.The cured product preferably has a light transmittance of about 95% or more, or about 95% to about 100%, or about 98% to about 100%. This is important for having good transparency, and in order for the cured product to have excellent transparency, a haze (haze value) must achieve a value close to zero. Accordingly, the haze value of the cured product is preferably less than 1%, for example about 0.01% to about 0.99%. When the haze value exceeds 1%, light scattering occurs and the cured product is difficult to have transparency, and irregular refraction of light occurs. Preferably, the UV curable resin composition further increases light transmittance upon curing.
상기 경화물은 굴절률이 약 1.4 내지 약 1.6인 것이 바람직하다. 상기 경화물은 유리와 비슷한 수준의 굴절률을 갖도록 조절한 다음, 상기 경화물을 유리와 밀접하게 접촉하게 두고 유리를 통과한 빛이 상기 경화물을 투과할 수 있게 빛을 조사할 경우 유리와 경화물의 경계면에서 빛의 굴절이 발생하기 않게 제어할 수 있다. 상기 유리는 일반유리 또는 강화유리일 수 있다.The cured product preferably has a refractive index of about 1.4 to about 1.6. The cured product is adjusted to have a refractive index similar to that of glass, and then the glass and the cured product are exposed when the cured material is brought into intimate contact with the glass and irradiated with light passing through the glass to transmit the cured product. It can be controlled so that the refraction of light does not occur at the interface. The glass may be plain glass or tempered glass.
상기 경화물은 유연성, 점착성, 및 우수한 물리적 강도를 가지는 것이 바람직하다. 특히, 상기 경화물의 연신율은 약 100% 이상일 수 있다. 예를 들어, 상기 연신율이 약 100% 내지 약 1000%, 또는 약 100% 내지 약 750%, 또는 약 100% 내지 약 500%, 또는 약 100% 내지 약 250%, 또는 약 100% 내지 약 200%, 또는 약 200% 내지 약 1000%, 또는 약 250% 내지 약 1000%, 또는 약 500% 내지 약 1000%, 또는 약 750% 내지 약 1000%, 또는 약 400% 내지 약 600% 인 것일 수 있다.The cured product preferably has flexibility, tack, and excellent physical strength. In particular, the elongation of the cured product may be about 100% or more. For example, the elongation may be about 100% to about 1000%, or about 100% to about 750%, or about 100% to about 500%, or about 100% to about 250%, or about 100% to about 200% , Or about 200% to about 1000%, or about 250% to about 1000%, or about 500% to about 1000%, or about 750% to about 1000%, or about 400% to about 600%.
상기 경화물은 LED 칩과 같은 발광장치에 적용될 수 있으므로, 빛과 반응하여 변색되는 현상이 나타나지 않아야 할 것이다. 예를 들어, 상기 경화물은 LED 칩이 구비되는 유리에 접착제 또는 실란트의 용도로 사용될 수 있으며, 이 경우, LED 조명의 빛이 경화물에 의해 산란되거나 유리와의 계면에서 굴절됨 없이 온전히 투과되어 선명한 빛 전달이 가능하다.Since the cured product may be applied to a light emitting device such as an LED chip, it should not appear a color change phenomenon in response to light. For example, the cured product may be used as an adhesive or a sealant in a glass having an LED chip, in which case the light of the LED light is completely transmitted without being scattered by the cured product or refracted at the interface with the glass. Clear light transmission is possible.
이하, 본원에 대하여 실시예를 이용하여 좀 더 구체적으로 설명하지만, 하기 실시예는 본원의 이해를 돕기 위하여 예시하는 것일 뿐, 본원의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only provided to aid the understanding of the present application, and the contents of the present application are not limited to the following Examples.
[실시예]EXAMPLE
1. UV 경화형 수지 조성물의 제조1. Preparation of UV Curable Resin Composition
하기 표 1 및 2의 조성 (중량 비율)을 갖도록 UV 경화형 수지 조성물을 제조하였다. UV-curable resin compositions were prepared to have the compositions (weight ratios) of Tables 1 and 2 below.
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3
지방족 우레탄 아크릴레이트 올리고머Aliphatic urethane acrylate oligomer 6868 6565 7070
아크릴로일모르폴린Acryloyl morpholine 1313 1010 1515
이소보닐 아크릴레이트Isobonyl Acrylate 88 66 1010
테트라하이드로퓨퓨릴 아크릴레이트Tetrahydrofurfuryl acrylate 55 33 77
부착증진제Adhesion promoter 44 22 66
광개시제Photoinitiator 1.51.5 1One 22
소포제Antifoam 0.50.5 0.20.2 0.80.8
습윤제Humectant 0.50.5 0.20.2 0.80.8
커플링제Coupling agent 0.50.5 0.20.2 0.80.8
비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6 비교예 7Comparative Example 7
지방족 우레탄 아크릴레이트 올리고머Aliphatic urethane acrylate oligomer 6060 7575 6868 6868 6868 6868 6868
아크릴로일모르폴린Acryloyl morpholine 1313 1313 1313 1313 1313 1313 1313
이소보닐 아크릴레이트Isobonyl Acrylate 88 88 88 88 88 88 88
테트라하이드로퓨퓨릴 아크릴레이트Tetrahydrofurfuryl acrylate 55 55 55 55 55 55 55
부착증진제Adhesion promoter 44 44 44 44 44 44 44
광개시제Photoinitiator 1.51.5 1.51.5 33 1.51.5 1.51.5 1.51.5 1.51.5
소포제Antifoam 0.50.5 0.50.5 0.50.5 00 0.50.5 0.50.5 00
습윤제Humectant 0.50.5 0.50.5 0.50.5 0.50.5 00 0.50.5 00
커플링제Coupling agent 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 00 00
표 2에서, 비교예 1은 실시예 1에 비해 지방족 우레탄 아크릴레이트 올리고머를 소량 함유한 경우이고, 비교예 2는 실시예 1에 비해 지방족 우레탄 아크릴레이트 올리고머를 과량 함유한 경우이고, 비교예 3은 실시예 1에 비해 광개시제를 과량 함유한 경우이고, 비교예 4는 소포제를 함유하지 않은 경우이고, 비교예 5는 습윤제를 함유하지 않은 경우이고, 비교예 4는 커플링제를 함유하지 않은 경우이다.In Table 2, Comparative Example 1 is a case containing a small amount of aliphatic urethane acrylate oligomer compared to Example 1, Comparative Example 2 is a case containing an excess of aliphatic urethane acrylate oligomer compared to Example 1, Comparative Example 3 Compared with Example 1, the photoinitiator is contained in an excessive amount, Comparative Example 4 is a case containing no antifoaming agent, Comparative Example 5 is a case containing no humectant, and Comparative Example 4 is a case containing no coupling agent.
배합과정Formulation Process
무용매 조건에서, 지방족 우레탄 아크릴레이트 올리고머에 아크릴로일 모르포린, 이소보닐 아크릴레이트, 테트라하이드로퓨퓨릴 아크릴레이트, 부착증진제, 소포제, 습윤제, 커플링제를 순차적으로 각각 투입하고 균일하게 혼합하여 혼합물을 제조하였다. 각 성분이 용해될 때까지 교반하였다. 각 성분이 완전히 용해된 혼합물에 광개시제 (1-하이드록시 사이클로헥실 페닐 케톤)를 투입하고 균질 교반시킴으로써, 무색 투명한 성상의 UV 경화형 수지 조성물을 수득하였다.In the solvent-free condition, acryloyl morpholine, isobornyl acrylate, tetrahydrofurfuryl acrylate, adhesion promoter, antifoaming agent, wetting agent, and coupling agent were sequentially added to the aliphatic urethane acrylate oligomer and mixed uniformly. Prepared. Stir until each component is dissolved. A photoinitiator (1-hydroxy cyclohexyl phenyl ketone) was added to the mixture in which each component was completely dissolved, and homogeneous stirring was carried out to obtain a colorless and transparent UV curable resin composition.
결과result
실시예 및 비교예에서 제조된 UV 경화형 수지 조성물의 물성을 확인하여 표 3에 나타내었다.The physical properties of the UV curable resin compositions prepared in Examples and Comparative Examples are shown in Table 3.
실시예 1Example 1 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6 비교예 7Comparative Example 7
색color 무색투명transparent 무색투명transparent 무색투명transparent 무색투명transparent 무색투명transparent 무색투명transparent 무색투명transparent 무색투명transparent
광투과율 (%)Light transmittance (%) 9797 9696 9494 9191 9595 9696 9595 9494
점도 (mPa·s, 25℃)Viscosity (mPas, 25 ° C) <10<10 <10<10 130130 125125 108108 118118 7272 167167
밀도(g/cm3, 23℃)Density (g / cm 3 , 23 ℃) 0.90.9 0.70.7 1.051.05 0.90.9 0.820.82 0.90.9 0.80.8 0.80.8
수축율 (부피%)Shrinkage (volume%) 1212 3636 2929 2525 1616 1414 2121 2424
접촉각(°)Contact angle (°) 77 88 1818 88 77 1313 1111 1717
표 3을 참조하면, 실시예 1은 물과 유사한 수준으로 10 mPa·s 보다 적은 값의 점도를 갖는 것으로 확인되었으며, 접촉각 또한, 물과 유사한 수준인 7도를 갖는 것으로 확인되었다. 특히 실시예 1은 97%의 매우 높은 광투과율을 달성하였다.Referring to Table 3, Example 1 was found to have a viscosity of less than 10 mPa · s at a level similar to water, and the contact angle was also found to have a level of 7 degrees, similar to that of water. In particular, Example 1 achieved a very high light transmittance of 97%.
2. 경화물의 제조2. Preparation of Cured Product
실시예 및 비교예에서 제조된 UV 경화형 수지 조성물에 2000 mJ/cm2 의 UV를 2 분 동안 조사하여 상기 UV 경화형 수지 조성물을 광경화시켰다. 이때, UV 조사에 의해 상기 UV 경화형 수지 조성물의 온도가 상승될 수 있으나, 경화반응 시 온도가 100℃를 넘지 않게 조절하는 것이 바람직하다.UV curable resin compositions prepared in Examples and Comparative Examples were irradiated with UV of 2000 mJ / cm 2 for 2 minutes to photocure the UV curable resin compositions. At this time, the temperature of the UV curable resin composition may be increased by UV irradiation, but it is preferable to control the temperature so that the temperature does not exceed 100 ° C during the curing reaction.
유리에 대한 부착성을 확인하기 위하여, 실시예 및 비교예에서 제조된 각각의 UV 경화형 수지 조성물을 유리판에 2 mm의 두께로 도포한 후 상기 UV 램프로 광경화시켰으며, JIS D 0202에 의거하여 각 경화물의 부착력을 시험하였다.In order to confirm the adhesion to glass, each UV curable resin composition prepared in Examples and Comparative Examples was applied to a glass plate with a thickness of 2 mm and then photocured with the UV lamp, according to JIS D 0202 The adhesion of each cured product was tested.
내후성을 평가하기 위하여, 실시예 및 비교예에서 제조된 각각의 UV 경화형 수지 조성물을 유리판에 2 mm의 두께로 도포한 후 상기 UV 램프로 광경화시켰으며, 각 경화물을 내후성시험기에 넣고 200 시간 동안 자외선에 노출시킨 다음, 변색 정도를 시험하였다.In order to evaluate the weather resistance, each UV curable resin composition prepared in Examples and Comparative Examples was applied to a glass plate with a thickness of 2 mm and then photocured with the UV lamp, and each cured product was put into a weather resistance tester for 200 hours. Exposure to ultraviolet light for a period of time and then the degree of discoloration was tested.
경화물의 물성을 확인하여, 표 4에 나타내었다.The physical properties of the cured product were confirmed and shown in Table 4.
실시예 1Example 1 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6 비교예 7Comparative Example 7
연신율 (%)Elongation (%) 500500 410410 330330 460460 486486 441441 425425 401401
인장강도 (MPa)Tensile Strength (MPa) 0.650.65 0.400.40 1.081.08 0.910.91 0.600.60 0.540.54 0.620.62 0.400.40
탄성계수(MPa)Modulus of elasticity (MPa) 0.20.2 0.220.22 1.71.7 0.30.3 0.240.24 0.20.2 0.150.15 0.230.23
밀도(g/cm3, 23℃)Density (g / cm 3 , 23 ℃) 1.021.02 1.301.30 1.641.64 1.181.18 0.800.80 1.281.28 1.101.10 1.291.29
유리전이온도 (℃)Glass transition temperature (℃) -25-25 3434 5959 -19-19 -11-11 -18-18 -14-14 -10-10
광투과율 (%)Light transmittance (%) 9999 9595 9292 8989 9393 9696 9494 9494
굴절률Refractive index 1.461.46 1.331.33 1.691.69 1.531.53 1.341.34 1.241.24 1.381.38 1.361.36
헤이즈값 (%)Haze value (%) 0.30.3 33 1.91.9 88 1616 1111 88 1717
부착성* Adhesion * ◎◎ ×× ○○ ○○ ◎◎ ○○ △△ △△
내후성*(황변)Weatherability * (yellowing) ◎◎ ○○ ○○ △△ ◎◎ ○○ ○○ ○○
*부착성 및 내후성에서, ◎: 우수 ○: 양호 △: 보통 ×: 불량 * In adhesion and weather resistance, ◎: Excellent ○: Good △: Normal ×: Poor
표 4를 참조하면, 실시예 1은 경화 후 비교예들에 비해 현저히 우수한 연신율을 가져 유연성을 갖는 것으로 확인되며, 굴절률은 일반유리와 비슷한 수치인 1.46이었고, 헤이즈 값은 0.3%로 확인되어 빛의 산란이 거의 없을 것임을 예상할 수 있다. 실시예 1의 광투과율은 경화 후 증가되었음을 알 수 있다.Referring to Table 4, Example 1 was confirmed to have flexibility by having a significantly superior elongation compared to the comparative examples after curing, the refractive index was 1.46, which is similar to that of ordinary glass, and the haze value was confirmed as 0.3% of light It can be expected that there will be little scattering. It can be seen that the light transmittance of Example 1 was increased after curing.
습윤제를 포함하지 않은 비교예 5, 커플링제를 포함하지 않은 비교예 6과, 소포제, 습윤제, 커플링제를 모두 포함하지 않은 비교예 7은 부착성이 저하됨을 알 수 있고, 지방족 우레탄 아크릴레이트 올리고머 60 중량부를 포함하는 비교예 1 및 광개시제 3 중량부를 포함하는 비교예 3은 부착성 및 내후성이 저하됨을 알 수 있다. 소포제를 포함하지 않은 비교예 4 및 7은 본 발명의 굴절률과 헤이즈 값을 만족하지 않는 것으로 확인이 되며, 이로부터 빛의 산란 및 굴절이 발생할 것으로 보여진다.It can be seen that Comparative Example 5 without the wetting agent, Comparative Example 6 without the coupling agent, and Comparative Example 7 without the antifoaming agent, the wetting agent, and the coupling agent were all deteriorated in adhesion, and the aliphatic urethane acrylate oligomer 60 Comparative Example 1 including parts by weight and Comparative Example 3 including 3 parts by weight of the photoinitiator can be seen that the adhesion and weather resistance is reduced. Comparative Examples 4 and 7 that do not contain an antifoaming agent is confirmed that does not satisfy the refractive index and haze value of the present invention, from which the scattering and refraction of light is likely to occur.
전술한 바와 같이, 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 기술을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로, 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며, 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다.As described above, the description of the present invention is for the purpose of illustration, and those skilled in the art to which the present invention belongs may easily change to other specific forms without changing the technical spirit or essential features of the present invention. I can understand. Therefore, it is to be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

Claims (13)

  1. 지방족 우레탄 아크릴레이트 올리고머, 반응성 모노머, 부착증진제, 광개시제, 소포제, 습윤제, 및 커플링제를 포함하며,Aliphatic urethane acrylate oligomers, reactive monomers, adhesion promoters, photoinitiators, antifoams, wetting agents, and coupling agents,
    25℃에서의 점도가 100 mPa·s 미만인 것임을 특징으로 하는, UV (ultraviolet) 경화형 수지 조성물.UV (ultraviolet) curable resin composition, characterized in that the viscosity at 25 ℃ is less than 100 mPa · s.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 지방족 우레탄 아크릴레이트 올리고머를 65 내지 70 중량부로, 상기 반응성 모노머를 19 내지 32 중량부로, 상기 부착증진제를 2 내지 6 중량부로, 상기 광개시제를 1 내지 2 중량부로, 상기 소포제를 0.2 내지 0.8 중량부로, 상기 습윤제를 0.2 내지 0.8 중량부로, 및 상기 커플링제를 0.2 내지 0.8 중량부로 포함하는 것인, UV 경화형 수지 조성물.65 to 70 parts by weight of the aliphatic urethane acrylate oligomer, 19 to 32 parts by weight of the reactive monomer, 2 to 6 parts by weight of the adhesion promoter, 1 to 2 parts by weight of the photoinitiator, 0.2 to 0.8 parts by weight of the antifoaming agent. , 0.2 to 0.8 parts by weight of the wetting agent, and 0.2 to 0.8 parts by weight of the coupling agent, UV curable resin composition.
  3. 제 1 항에 있어서,The method of claim 1,
    밀도가 0.85 내지 3 g/cm3인 것임을 특징으로 하는, UV 경화형 수지 조성물.UV-curable resin composition, characterized in that the density is 0.85 to 3 g / cm 3 .
  4. 제 1 항에 있어서,The method of claim 1,
    유리에 대한 접촉각이 10도 이하인 것임을 특징으로 하는, UV 경화형 수지 조성물.UV-curable resin composition, characterized in that the contact angle to the glass is 10 degrees or less.
  5. 제 1 항에 있어서,The method of claim 1,
    광투과율이 95% 이상인 것임을 특징으로 하는, UV 경화형 수지 조성물.The light transmittance is 95% or more, UV curable resin composition, characterized in that.
  6. 제 1 항에 있어서,The method of claim 1,
    경화시 수축율이 15 부피% 미만인 것임을 특징으로 하는, UV 경화형 수지 조성물.UV curing curable resin composition, characterized in that the shrinkage at curing is less than 15% by volume.
  7. 제 1 항에 따른 UV 경화형 수지 조성물에 UV를 조사하여 상기 UV 경화형 수지 조성물을 완전히 경화시키는 단계Irradiating UV to the UV curable resin composition according to claim 1 to completely cure the UV curable resin composition
    를 포함하는, UV 경화형 수지 조성물의 경화 방법.Curing method of a UV curable resin composition containing.
  8. 제 7 항에 있어서,The method of claim 7, wherein
    상기 단계에서 경화 시의 최고온도가 100℃ 미만인 것임을 특징으로 하는, UV 경화형 수지 조성물의 경화 방법.Curing method of the UV curable resin composition, characterized in that the maximum temperature at the time of curing in the step is less than 100 ℃.
  9. 제 1 항에 따른 UV 경화형 수지 조성물을 이용한 경화물로서,As hardened | cured material using the UV curable resin composition of Claim 1,
    상기 경화물은 상기 UV 경화형 수지 조성물이 완전 경화된 것임을 특징으로 하는, 경화물.The cured product is a cured product, characterized in that the UV curable resin composition is completely cured.
  10. 제 9 항에 있어서,The method of claim 9,
    굴절률이 1.4 내지 1.6인 것임을 특징으로 하는, 경화물.Hardened | cured material characterized by the refractive index being 1.4-1.6.
  11. 제 9 항에 있어서,The method of claim 9,
    헤이즈 값이 1% 미만인 것임을 특징으로 하는, 경화물.Hardened | cured material characterized by the haze value being less than 1%.
  12. 제 9 항에 있어서,The method of claim 9,
    연신율이 100% 내지 1000%인 것임을 특징으로 하는, 경화물.Cured product, characterized in that the elongation is 100% to 1000%.
  13. 제 10 항에 있어서,The method of claim 10,
    광투과율이 95% 이상인 것임을 특징으로 하는, 경화물.Hardened | cured material characterized by the light transmittance being 95% or more.
PCT/KR2017/004622 2016-05-03 2017-05-01 Uv curable resin composition, method for curing same, and cured product using same WO2017191960A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160054484A KR101683800B1 (en) 2016-05-03 2016-05-03 Ultraviolet curing resin composition, method of preparing the same and cured product using the same
KR10-2016-0054484 2016-05-03

Publications (1)

Publication Number Publication Date
WO2017191960A1 true WO2017191960A1 (en) 2017-11-09

Family

ID=57574545

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/004622 WO2017191960A1 (en) 2016-05-03 2017-05-01 Uv curable resin composition, method for curing same, and cured product using same

Country Status (2)

Country Link
KR (1) KR101683800B1 (en)
WO (1) WO2017191960A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101683800B1 (en) * 2016-05-03 2016-12-09 지스마트 주식회사 Ultraviolet curing resin composition, method of preparing the same and cured product using the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100385910B1 (en) * 1995-12-30 2003-08-21 고려화학 주식회사 Photocurable coating composition containing urethane acrylate oligomer
KR20080061581A (en) * 2006-12-28 2008-07-03 (주)디피아이 홀딩스 Photo-curable paint composition and coating method using the same
KR20080109853A (en) * 2006-03-31 2008-12-17 미쓰이 가가쿠 가부시키가이샤 Photocurable coating material
JP2012131900A (en) * 2010-12-21 2012-07-12 Sumitomo Bakelite Co Ltd Cured product of ultraviolet-curable resin composition, resin laminate and ultraviolet-curable resin composition
JP2013237863A (en) * 2013-08-07 2013-11-28 Autonetworks Technologies Ltd Ultraviolet curable composition and cured product using the same
KR20150005552A (en) * 2012-04-27 2015-01-14 아라까와 가가꾸 고교 가부시끼가이샤 Ultraviolet light curing adhesive composition and adhesive layer
KR101683800B1 (en) * 2016-05-03 2016-12-09 지스마트 주식회사 Ultraviolet curing resin composition, method of preparing the same and cured product using the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3251608B2 (en) 1991-06-17 2002-01-28 広栄化学工業株式会社 Method for producing urethane (meth) acrylate oligomer and photocurable resin composition using the same
KR960006840B1 (en) * 1992-12-29 1996-05-23 고려화학주식회사 Process for the preparation of urethane acrylate oligomer and coating composition thereof
KR101397698B1 (en) 2011-12-20 2014-05-26 제일모직주식회사 Optical adhesive composition and display apparatus including the adhesive layer comprising the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100385910B1 (en) * 1995-12-30 2003-08-21 고려화학 주식회사 Photocurable coating composition containing urethane acrylate oligomer
KR20080109853A (en) * 2006-03-31 2008-12-17 미쓰이 가가쿠 가부시키가이샤 Photocurable coating material
KR20080061581A (en) * 2006-12-28 2008-07-03 (주)디피아이 홀딩스 Photo-curable paint composition and coating method using the same
JP2012131900A (en) * 2010-12-21 2012-07-12 Sumitomo Bakelite Co Ltd Cured product of ultraviolet-curable resin composition, resin laminate and ultraviolet-curable resin composition
KR20150005552A (en) * 2012-04-27 2015-01-14 아라까와 가가꾸 고교 가부시끼가이샤 Ultraviolet light curing adhesive composition and adhesive layer
JP2013237863A (en) * 2013-08-07 2013-11-28 Autonetworks Technologies Ltd Ultraviolet curable composition and cured product using the same
KR101683800B1 (en) * 2016-05-03 2016-12-09 지스마트 주식회사 Ultraviolet curing resin composition, method of preparing the same and cured product using the same

Also Published As

Publication number Publication date
KR101683800B1 (en) 2016-12-09

Similar Documents

Publication Publication Date Title
US6376571B1 (en) Radiation-curable composition having high cure speed
KR102062177B1 (en) Ultraviolet light curing adhesive composition and adhesive layer
WO2012070796A2 (en) Adhesive composition for touch panel, adhesive film, and touch panel
CN110713818B (en) Ultraviolet/moisture dual fast-curing polysiloxane adhesive composition
CN103974826A (en) Optical member, ultraviolet curable resin composition, and cured product
JP2008291114A (en) Photosetting resin composition, photosetting and moistureproof insulating paint for mounted circuit board, electronic component and method for manufacturing the component
KR20160064082A (en) Photocurable resin composition, image display device and method for manufacturing image display device
KR20140099836A (en) An antistatic agent for active energy-ray curable resin composition, an active energy-ray curable composition, a cured film and an antistatic treated optical film
WO2018199686A1 (en) Optical transparent adhesive sheet, composition for preparing same, and flat display device using same
KR101257753B1 (en) Photocurable compositions for discoloration, insulated electronic parts using the compositions, and a method of production thereof
WO2017078488A1 (en) Optical adhesive composition and optical adhesive film
WO2010021490A2 (en) Uv curable resin composition
WO2017191960A1 (en) Uv curable resin composition, method for curing same, and cured product using same
CN111675999A (en) Photocurable adhesive layer composition and protective film thereof
KR102155180B1 (en) Dual cure adhesive composition
KR101161014B1 (en) Methacryl modified polyurethane, photocurable composition for discoloration comprising the same, and insulated electronic parts using the composition
KR20190098761A (en) Photo-curable adhesive compositions, cured products and uses thereof
JP2017218477A (en) Photocurable resin composition for curved surface coating, image display device and method for manufacturing the same
JP2003073429A (en) Resin composition for cast photopolymerization and optical member
KR20150075943A (en) UV curable composition containing inorganic particles to seal electrode from humidity in plasma display panel
CN114181660A (en) Ultraviolet curing adhesive composition for MiniLED packaging and preparation method and application thereof
JP3198285B2 (en) Liquid curable resin composition
WO2011115374A2 (en) Uv-curable adhesive composition
KR101467394B1 (en) Photocurable and optical resin compositions with various properties and flat panel display using the compositions
JP5050517B2 (en) Manufacturing method of photocurable resin composition, photocurable moisture-proof insulating coating for mounting circuit board, mounting circuit board, and manufacturing method of mounting circuit board

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17792862

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17792862

Country of ref document: EP

Kind code of ref document: A1