KR20150078040A - Photocurable Adhesive Resin Composition And Method for Manufacturing the same - Google Patents
Photocurable Adhesive Resin Composition And Method for Manufacturing the same Download PDFInfo
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- KR20150078040A KR20150078040A KR1020130167095A KR20130167095A KR20150078040A KR 20150078040 A KR20150078040 A KR 20150078040A KR 1020130167095 A KR1020130167095 A KR 1020130167095A KR 20130167095 A KR20130167095 A KR 20130167095A KR 20150078040 A KR20150078040 A KR 20150078040A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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Abstract
The present invention relates to a photo-curable pressure-sensitive adhesive resin composition having a high viscosity and a process for producing the same, and more specifically to a photo-curable pressure-sensitive adhesive resin composition for a display having a viscosity of 25,000 or more and a method for producing the same. The photo-curing type adhesive resin composition of the present invention is applied as an interlayer adhesive of a touch panel, so that it can be directly coated without application of OCR for dams because of its low conductivity after coating due to its high conductivity, Slot die coating is possible, and thus it is advantageous in workability even when coating a large area. In addition, since no OCR for dams is used, bubbles are not generated on the contact surface where the OCR for dams and the low viscosity OCR for low viscosity OCR are used, thereby improving the workability and yield.
Description
TECHNICAL FIELD The present invention relates to a photo-curable pressure-sensitive adhesive resin composition having a high viscosity and a method for producing the same, and more specifically to a photo-curable pressure-sensitive adhesive resin composition for display having a high viscosity and a method for producing the same.
In general, film-type dots and adhesives used in displays have been using heat curing type which is hardened by heat and have a long history. In the case of the thermosetting type, a method is known in which an acrylic resin, a proper equivalent of an isocyanate or epoxy thermosetting agent, and a method of using a UV stabilizer, as the case may be, are known. In the case of acrylic resin, it contains both an acid group, a hydroxy group or two reactors capable of reacting with a thermosetting agent, and the content of the thermosetting agent is determined by the equivalence ratio of these functional groups. In recent years, functional groups have been extended to amine groups and thiol groups in addition to acidic functional groups and hydroxyl groups.
In addition to the thermosetting type, studies are also being made on materials having a photo-curable point, an adhesive, a thermosetting type and a photo-curable type. In the case of photocurable type, most means ultraviolet curing, and some visible light curing type or other types of radiation may be used.
Korean Patent Laid-Open No. 10-2001-0050901 discloses a material which simultaneously introduces a photosensitive group into an acrylic resin and simultaneously introduces a photo-curing initiator and a heat curing agent, thereby satisfying both thermal curing and photo-curing. However, the use of isocyanate thermosetting agents is disadvantageous in that the materials are resistant to heat and have a short shelf life. Materials having both photo-curing and thermal curing have long been commercialized as a photosensitive solder resist (PSR) by a solder resist manufacturer such as Daiyou ink. In recent years, a product obtained by converting a solder resist ink, which has been provided in a liquid state, into a dry film is commercially available, and Japanese Laid-Open Patent Application No. 10-2011-197286 discloses a part of the technology.
The field of dry film photoresists used in printed circuit boards includes a technique including an acrylic multi-functional monomer and an oligomer containing at least one double bond capable of photopolymerization with a developable acrylic resin in a water-soluble alkali developer, and an ultraviolet reactive initiator . Korean Patent Laid-Open No. 10-2005-0107310 discloses a technology flow in this field, and the dry film photoresist field is developing its application field with high resolution and special use. However, the dry film photoresist field also differs from the characteristics required in the display for the requisite characteristics such as reworkability, bubble removing ability, and adhesion.
In the case of thermosetting dots and adhesives used for display dots and adhesives, it is necessary to polymerize dots and adhesives in advance. A liquid or a film type product is produced by blending the polymerized point and adhesive and a curing agent such as isocyanate, an ultraviolet stabilizer and an additive for reinforcing other properties. However, this method requires a high molecular weight in the case of the polymer to increase the reliability. Also, various monomers and oligomers are necessary to meet various requirements, but the reactivity varies depending on the polymerization characteristics, so that there are many limitations in obtaining a uniform polymeric polymer. In addition, in the case of thermosetting dots and adhesive films, a solvent is added for coating properties and it is difficult to obtain a composition having a solid content of 50% or more due to viscosity restrictions. As a result, it is difficult to cope with a product requiring a thick film having a thickness of more than 100 μm such as a capacitive touch screen panel. In the film forming process for thick film, productivity problems such as a long drying length or a low speed Respectively.
On the other hand, in the case of the photocurable composition using ultraviolet rays, it is easy to change the composition because it is necessary to change the composition of the monomer or oligomer used for photo-curing in order to cope with various requirements, and the monomer viscosity is adjusted to a suitable viscosity It is possible to apply a thick film, and it is advantageous that a drying step is unnecessary or short. However, for the thick film coating, it is necessary to adjust the viscosity of the solution by mixing an oligomer or a low molecular weight acrylic resin having an appropriate viscosity with a monomer or oligomer having a low viscosity, and an ultraviolet curing system having an appropriate length is required for producing a thick film product. However, despite these limitations, photo-curable dots and adhesives are easier to control than thermosetting dots and adhesives, have higher coating speed and higher productivity.
Recently, as the use of smart phones in the touch panel field has increased, development of dots and adhesives capable of thick film coating to bond the cover window, the touch panel or the touch panel with the display module has been actively developed. The composition used herein is generally a photo-curing type point adhesive resin composition, and the photo-curable type point adhesive resin composition is mainly reacted with ultraviolet rays to form an optically transparent point-adhesive layer. The dots and adhesives used here generally have a viscosity of 3,000 cps.
Korean Patent Laid-Open Nos. 10-2012-0086310, 10-2012-0087939, and 10-2011-0050711 refer to such an optically clear liquid resin composition (OCR = Optically Clear Resin). The viscosity of the liquid type product proposed in these patents is 2,000 ~ 4,000 cps (1 cps = 1 cP = 1 mPa · s), which is applicable to small devices of 5 or less. However, in products such as 7 or more tablet PC, There is a problem in that an OCR for a dam having a high viscosity is used at an edge portion in order to prevent the liquid from flowing, and there is a disadvantage that the operation is troublesome and the defoaming is not perfect.
Accordingly, the present inventors have attempted to improve the coating properties and workability of the ultraviolet curing type point and adhesive composition used for direct bonding, and to provide a photocuring type point adhesive resin composition which has a high viscosity, .
In order to achieve the above object, the present invention provides a photocurable adhesive resin composition for display having a high viscosity, which comprises a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator, and a method for producing the same.
An example of the present invention may be a photocurable adhesive resin composition for display having a high viscosity of 25,000 cps or more.
Another example of the present invention may be a photocurable type pressure-sensitive adhesive resin composition having a viscosity at 25 DEG C of 25,000 to 100,000 cps.
Another example of the present invention is a photocurable adhesive composition comprising 10 to 89% by weight of a viscosity control compound, 10 to 89% by weight of a photopolymerizable compound having an ethylenically unsaturated bond, 0.01 to 10% by weight of a photopolymerization initiator, Curable pressure-sensitive adhesive resin composition.
Another example of the present invention is that in the photocurable type point adhesive resin composition, the viscosity control compound may be at least one selected from the group consisting of an acrylic resin, an ultraviolet-ray-responsive acrylic resin, and an ultraviolet-curable oligomer.
Another example of the present invention relates to a photocurable pressure-sensitive adhesive resin composition, wherein the photopolymerizable compound is 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2- 2-hydroxypropyl methacrylate, 2-methacryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2- Methoxyethyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, oxyethyl acid phosphate, methacrylates of phthalic acid derivatives, iso-octyl acrylate, iso-vinyl acrylate, phenoxy ethyl acrylate, acryloyl morpholine, , Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene Recolled dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol Dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol penta methacrylate, 2,2-bis (4-methacryloxy diethoxyphenyl) propane, 2-hydroxy- Ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, and glycerin polyglycidyl ether poly Methacrylate, and the like.
In another embodiment of the present invention, in the photocurable pressure-sensitive adhesive resin composition, the photopolymerization initiator is benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, anthraquinone, Naphthoquinone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, pivalone ethyl ether, 1,1- - dimer of 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaaryl-imidazole, 2,2'-diethoxyacetophenone ( 2,2'-diethoxyacetophenone), 2,2'-diethoxy-2-phenyla But are not limited to, 2,2'-diethoxy-2-phenylacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, hydroxy isobutylphenone, dibenzospan, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl- (2-methyl- [4- (methylthio) -2-methyl-1-propanone] ) phenyl] -2-morpholino-1-propanone, tri-bromophenylsulfone, triaryl phosphine oxide and tribromomethylphenylsulfone. It may be more than one species.
Another example of the present invention may be a photocurable type point adhesive resin composition further comprising a photopolymerization sensitizer.
Another example of the present invention is a process for preparing a photoresist composition comprising mixing a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator to prepare a first composition; Curing the primary composition; And a step of blending the photocured primary composition with a secondary composition comprising a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator, to form a photocurable viscous adhesive resin composition have.
In still another embodiment of the present invention, in the photocuring step of the above production method, the primary composition may be a material which undergoes a photo-curing reaction by ultraviolet irradiation while passing through a quartz material inside the ultraviolet irradiation apparatus.
In another embodiment of the present invention, in the step of photo-curing the above-mentioned production method, when passing through the quartz material of the first composition, low-intensity ultraviolet rays may be irradiated and high-intensity ultraviolet rays may be irradiated.
In another embodiment of the present invention, in the above production method, the number of reactors of the viscosity control compound of the first composition may be 0.1 to 2 per 10,000 molecular weight.
In still another embodiment of the present invention, the content of the viscosity control compound in the first composition is 60 to 95% by weight based on the total weight of the first composition, and the photopolymerization initiator of the first composition is a composition of the first composition May be 0.1 to 1% by weight based on the total weight of the viscosity control compound and the photopolymerizable compound.
In another embodiment of the present invention, the content of the viscosity control compound and the photopolymerizable compound in the second composition is 10 to 50% by weight based on the total weight of the photocurable adhesive resin composition, and the content of the photopolymerization initiator in the second composition is May be 0.1 to 10% by weight based on the total weight of the photocurable pressure-sensitive adhesive resin composition.
The photo-curing type adhesive resin composition of the present invention is applied as an interlayer adhesive of a touch panel, so that it can be directly coated without application of OCR for dams because of its low conductivity after coating due to its high conductivity, Slot die coating is possible, which is advantageous in workability even when coating a large area.
Also, since no OCR for dams is used, bubbles are not generated at the contact surface where OCR for dams and low OCR for low densities meet, which is a problem in using low viscosity OCR, and work efficiency and yield are improved.
1 is a schematic view of a UV reactor for producing a photocurable adhesive resin composition for display having a high viscosity.
FIG. 2 is an enlarged view of a UV reactor. FIG. 2 is a schematic view of a quartz quartz crystal tube passing through a primary composition through UV1 (low light intensity) and UV2 (high light intensity).
Hereinafter, the present invention will be described in detail.
The present invention relates to a photo-curable pressure-sensitive adhesive resin composition for display having a high viscosity and a method for producing the same, which comprises a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.
The photocurable type point-adhesive resin composition is characterized by having a high viscosity. As an illustration, the composition may have a viscosity of 25,000 to 100,000 cps, preferably 25,000 to 70,000 cps at 25 ° C.
In addition, the photocurable type point-adhesive resin composition is characterized by having a uniform viscosity. The photo-curable pressure-sensitive adhesive resin composition provides a composition having a uniform viscosity through mixing with a secondary composition by using a composition obtained by photo-curing a primary composition having a high viscosity as a viscosity control compound. In particular, it is possible to provide a composition having a uniform viscosity by overcoming the disadvantage that it is difficult to reproducibly obtain a uniform viscosity in view of the photoreaction characteristic through a reactor, for example, a reactor as shown in FIG. 1 and FIG.
The viscosity control compound may be one or more selected from the group consisting of an acrylic resin, an ultraviolet ray-sensitive acrylic resin, and an ultraviolet ray-curable oligomer.
In the present invention, an ultraviolet reactive acrylic resin refers to a compound having a double bond in a resin and capable of reacting with a monomer or an oligomer. The acrylic resin or ultraviolet reaction type acrylic resin should be provided in a dried state, and there is no particular limitation if it is an acrylic polymer (resin) having optical transparency and dissolved in a monomer or an oligomer.
The acrylic resin or ultraviolet-ray-responsive acrylic resin may be prepared by a conventional method known in the art. For example, the acrylic resin or ultraviolet-reactive acrylic resin can be prepared using monomers capable of acrylic or acrylic and copolymerization. The acrylic resin or ultraviolet-reactive acrylic resin may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- Acrylate, monofunctional (meth) acrylate derivatives such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and glycidyl , Styrene, alpha -methylstyrene, acrylonitrile, vinyl acetate, alkyl vinyl ether, etc., and compounds selected therefrom may be used as a diazo compound such as AIBN (Azobisisobutyronitrile) A linear copolymer having an appropriate molecular weight is obtained by using a peroxide or the like and dried to obtain a desired acrylic resin or a UV- Based resin can be obtained.
The ultraviolet curable oligomer may be a polyfunctional polyurethane (meth) acrylate. The intermediate of the ultraviolet-curable oligomer may be prepared by the reaction of a polyol and a polyisocyanate, and may be prepared by introducing a (meth) acrylate group at both terminals. Further, the properties can be changed by controlling the components of the polyol and the polyisocyanate, and the hygroscopicity or the moisture permeability can be imparted by introducing the hydrophobic group. The polyfunctional polyurethane (meth) acrylate may be a commercialized one. For example, the polyfunctional polyurethane (meth) acrylate is commercially available from Kayakard series of Nippon Kayaku Co., Ltd. of Japan, Shin-Nakamura Chemical Co., Ltd. of Japan. NIK-OLIGO series manufactured by Cytec Industries, Inc., Ebecryl manufactured by Cytec Industries, Inc., or Miramer of Korea Myungwon Specialty Chemicals Co.,
The viscosity control compound may be contained in the photocurable adhesive resin composition in an amount of 10 to 89% by weight, preferably 20 to 80% by weight. When the content of the viscosity control compound is less than 10% by weight or more than 89% by weight, appropriate viscosity may not be provided, and proper elasticity and the like may not be obtained after curing.
The photopolymerizable compound having an ethylenically unsaturated bond is a compound which undergoes compositional change mainly to realize various properties.
The kind of the photopolymerizable compound can be appropriately controlled according to the object of the invention. For example, the main chain may be formed using the viscosity control compound, and the type of the photopolymerizable compound may be selected by dividing the use of the photocurable resin composition as a constituent of an outer layer to be adhered to the adherend or as an intermediate layer.
In general, in the case of an outer layer adhering to the adherend in a multilayer film, the type can be determined by adjusting the properties of the adherend and the glass transition temperature after the reaction. That is, when the adherend is an ITO (Indium Tin Oxide) material used in a touch panel, an acid group may cause ITO corrosion and cause a reliability problem of the product, so it should be selected as a composition excluding organic acid. However, when the adherend does not react with ordinary glass or organic acids, organic acids may be added to improve adhesion. This also applies to viscosity control compounds. The method of introducing the organic acid can be carried out by a known conventional method, for example, a compound for controlling the viscosity can be added to the monomer for reaction or a compound having an organic acid in the photopolymerizable compound can be added. When it is used as an intermediate layer, it can be variously adjusted according to requirements such as transparency, elasticity, and balance.
The photopolymerizable compound may be a compound having a monofunctional group or a compound having a polyfunctional group.
The compound having a monofunctional group is preferably selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-phenoxy- Methacryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, methacrylates of phthalic acid derivatives, May be at least one member selected from the group consisting of iso-octyl acrylate, isobornyl acrylate, phenoxy ethyl acrylate, acryloyl morpholine, 4-hydroxybutyl acrylate and N-methylol methacrylamide .
The compound having a polyfunctional group is preferably selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, Trimethylolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, Methacryloxy diethoxyphenyl) propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl (meth) acrylate, Diallyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate And glycerin polyglycidyl ether polymethacrylate. The composition may be changed through various combinations as long as the object of the present invention is satisfied.
The photopolymerizable compound may be contained in the photocurable adhesive resin composition in an amount of 10 to 89% by weight, preferably 20 to 80% by weight. If the content of the photopolymerizable compound is less than 10% by weight or exceeds 89% by weight, control of physical properties through composition modification is not possible, and an appropriate viscosity may not be provided, so that the effect of improving the coating property may not be obtained.
The photopolymerization initiator may be at least one selected from the group consisting of benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzyl phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, Irgacure series from Ciba Specialty Chemicals, anthraquinone, naphthoquinone, 3, 3-dimethyl-4-methoxybenzophenone, benzophenone, pivalone ethyl ether, 1,1-dichloroacetophenone (1,1- dichloroacetophenone, pt-butyldichloroacetophenone, dimer of hexaaryl-imidazole, 2,2'-diethoxyacetophenone, 2 , 2'-diethoxy-2-phenylacetophe none, 2,2'-dichloro-4-phenoxyacetophenone, phenyl glyoxylate,? -hydroxy isobutylphenone ), Dibenzospan, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl- (methylthio) phenyl] -2-morpholino-1-propanone), 2-methyl- [4- (methylthio) phenyl] , Tri-bromophenylsulfone, triaryl phosphine oxide, and tribromomethylphenylsulfone. In addition, the present invention is not limited thereto.
The photopolymerization initiator may be contained in the photocurable adhesive resin composition in an amount of 0.01 to 10% by weight, preferably 0.02 to 5% by weight. If the content of the viscosity control compound is less than 0.01 wt% or exceeds 10 wt%, it may not be possible to control the photocuring reaction time through appropriate photocuring.
The photo-curable pressure-sensitive adhesive resin composition may further include a photosensitizer. The photopolymerization sensitizer may be selected from the group consisting of p, p'-bis (dimethylamino) benzophenone, p, p'-bis (diethylamino) benzophenone (diethylamino) benzophenone), and p, p'-diethylaminobenzophenone (p, p'-diethylaminobenzophenone). The photopolymerization sensitizer may be further included depending on the type of the photopolymerization initiator. The content of the photopolymerization sensitizer may be adjusted depending on the content of the photopolymerization initiator, and preferably 5 wt% or less.
The photo-curable pressure-sensitive adhesive resin composition may further contain other additives as required.
The other additives may be ultraviolet absorbers, light stabilizers, dyes, silane coupling agents, thickeners, flow inhibitors, and the like.
For example, a UV absorber, a light stabilizer, and a dye may be added to improve the weatherability of the multilayer film and the tape, and a silane coupling agent may be added to improve the adhesive strength to glass and to secure a better point and adhesive strength. Thickening agents and anti-flow agents can be added for precise viscosity control and character control.
The method comprises: preparing a first composition by mixing a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator; Curing the primary composition; And blending the photocured primary composition with a secondary composition comprising a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.
The photo-curing step may be such that the primary composition passes through a quartz material inside the ultraviolet irradiation device and is accompanied by a photo-curing reaction by ultraviolet irradiation. As the photocuring reaction is accompanied, a photocurable type point adhesive resin composition having uniformity and high viscosity can be obtained.
The primary composition may be accompanied with a photo-curing reaction by ultraviolet irradiation while passing through a quartz quartz crystal filter located between the transfer tubes. The shape of the quartz tube may be various, such as a tube, a square, It may be tubular, but there is no particular restriction on its shape. For example, as shown in FIG.
The photo-curing step may be a step of irradiating low-intensity ultraviolet rays at the initial stage when passing through the quartz material of the first composition and irradiating high-intensity ultraviolet rays at the latter stage. The low light intensity in the present invention means 10 watt / cm or less and the high illuminance means 100 watt / cm or more. It is preferable that the ultraviolet ray irradiation apparatus is subjected to low-intensity light curing and then to high-intensity light curing, rather than to a high-intensity one, in the production of a uniform and stable photo-curing type adhesive resin composition. In the case of irradiating only a high degree of intensity, the viscosity increase sharply increases due to the abrupt reaction and the shrinkage is also serious, so that the viscosity of the obtained resin becomes uneven and the workability may be deteriorated.
The viscosity control compound of the first composition may be at least one member selected from the group consisting of an acrylic resin, an ultraviolet-reactive acrylic resin, and an ultraviolet-curable oligomer.
The number of reactors of the viscosity control compound of the primary composition may be from 0.1 to 2, preferably from 0.5 to 1.5, per 10,000 molecular weight. If the number of reactors per molecular weight is more than 2, the viscosity may be too high to cause deterioration of flowability, resulting in a decrease in productivity, and flexibility may be lowered and hardened. On the other hand, when the reactor is less than 0.1, the photocuring reaction is low and it is difficult to increase the viscosity sufficiently.
The content of the viscosity control compound in the first composition may be 60 to 95% by weight, preferably 70 to 90% by weight, based on the total weight of the first composition. If the amount of the viscosity control compound in the first composition is less than 60% by weight, the composition may become hard after photocuring due to too much of the reactor. If the amount exceeds 95% by weight, It can get worse.
The photopolymerization initiator of the first composition is as described above, and may be 0.01 to 1% by weight based on the total weight of the viscosity control compound and the photopolymerizable compound of the first composition. If the amount of the photopolymerization initiator is less than 0.01% by weight, sufficient photoreaction may not occur. If the amount of the photopolymerization initiator is more than 1% by weight, the reaction may be excessively intense and shrinkage may occur rapidly.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the present invention is not limited by the following examples and experimental examples, and various modifications and changes may be made.
Example 1 to 4
The composition of the primary composition described in Table 1 below was mixed and stirred until completely dissolved. The stirred primary composition was pumped through a quartz tube made of quartz as a raw material of the ultraviolet ray irradiation apparatus, and light reaction was performed at low light intensity in the early stage and high light intensity in the latter stage. At this time, Gt; 60 C. < / RTI > Then, the composition of the secondary composition described in Table 1 below was mixed with the primary composition which was subjected to the UV light reaction and stirred until it was completely dissolved to obtain the final composition.
UC203: urethane (meth) acrylate (Kuraray Co., Ltd.)
CN-9004: urethane (meth) acrylate (US satomer)
CN-9018: urethane (meth) acrylate (US satomer)
EHA: 2-ethylhexyl acrylate (2-ethylhexyl acrylate)
IOA: iso-octyl acrylate
IBOA: iso-bornyl acrylate
TPO: triaryl phosphine oxide < RTI ID = 0.0 >
PEA: phenoxy ethyl acrylate
ACMO: Acryloyl morpholine
4-HBA: 4-hydroxy acrylate < RTI ID = 0.0 >
Experimental Example
The viscosity of the primary and final compositions of Examples 1 to 4 was measured at 25 占 폚, and the final composition was coated to a thickness of 175 占 퐉 using a slot die, and optical characteristics and adhesion were evaluated by the following methods.
<Turbidity ( Hz ), Light transmittance ( TT )>
The turbidity (Haze, Hz) was evaluated according to JIS K 7136, the total transmittance (TT) was measured according to JIS K 7361, and the evaluation instrument was HM-150 manufactured by Murakami Color Research Laboratory.
First, the release-release film was removed from the specimen to be evaluated, and laminated to the slide glass without bubbles. The 2 kg rubber roll was rolled and adhered, and left at room temperature for 1 day. After removing the heavy release film, turbidity and light transmittance were evaluated. A total of 5 evaluations were made, and the three highest values were taken as the turbidity and the light transmittance except for the highest value and the lowest value.
≪ Glass adhesion force &
Glass adhesion was evaluated by ASTM D3330 / D3330M-04 (Standard Test Method for Peel Adhesion of Pressure-Sensitive Tape) Modify, and the same method was applied to the above-mentioned evaluation standard JIS Z 0237 8 or Korean Standard KS A 1529.
For evaluation of the glass adhesion, the release film of the multilayered film was removed and a specially coated polyester film having high adhesion to the adhesive layer was laminated without bubbles. The prepared sample was cut into a length of 150 to 200 mm with a width of 25 mm to prepare a sample for evaluation. A sample for evaluation was attached to a glass substrate, and 2 kg of rubber roll was rolled and adhered to the glass substrate. The prepared glass substrate was tested according to ASTM D3330 test method at a speed of 300 mm / sec and a 180 ° peeling angle. Five times, the highest value and the lowest value were excluded and the average value of three times was recorded as adhesion.
< High temperature and high humidity Reliability>
The sample to be evaluated was allowed to stand at 85 ° C and 85hrs for 240hrs, left at room temperature for 1 hour, and then evaluated for Hz, TT and glass adhesion.
Table 2 shows the results of the measurement, showing the viscosity of the first composition and the viscosity, turbidity, light transmittance, glass adhesion, and measurement results of high temperature and high humidity reliability of the final composition.
Composition
(Kgf / 24 mm)
responsibility
(Kgf / 24 mm)
As shown in Table 2, the viscosity of the first-order composition was controlled within ± 5% with a viscosity of 70,000 cps or more, and the finally obtained composition was excellent in optical properties and adhesion, and had excellent properties Respectively.
Claims (13)
And has a high viscosity of 25,000 cps or more.
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-phenoxy-2-hydroxypropyl methacrylate, 2- methacryloyloxy- Hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, methacrylates of phthalic acid derivatives, iso-octyl acrylate, iso-octyl acrylate, Acrylate monomers such as acrylate, methacrylate, methacrylate, acrylate, methacrylate, methacrylate, methacrylate, methacrylate, Dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate Hexane glycol dimethacrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol penta methacrylate Methacryloxy diethoxyphenyl) propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene Wherein the photo-curable pressure-sensitive adhesive resin composition is at least one selected from the group consisting of glycol diglycidyl ether dimethacrylate, diglycidyl ether dimethacrylate phthalate, and glycerin polyglycidyl ether polymethacrylate. Composition.
Curing the primary composition; And
A process for producing a photocurable viscous adhesive resin composition according to claim 1, which comprises blending a secondary composition comprising a viscosity control compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator in the photocured primary composition .
Wherein the photopolymerization initiator of the first composition is 0.1 to 1% by weight based on the total weight of the photopolymerizable compound and the viscosity control compound of the first composition.
Wherein the content of the photopolymerization initiator in the second composition is from 0.1 to 10% by weight based on the total weight of the photocurable type pressure-sensitive adhesive resin composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130167095A KR20150078040A (en) | 2013-12-30 | 2013-12-30 | Photocurable Adhesive Resin Composition And Method for Manufacturing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130167095A KR20150078040A (en) | 2013-12-30 | 2013-12-30 | Photocurable Adhesive Resin Composition And Method for Manufacturing the same |
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| Publication Number | Publication Date |
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| KR20150078040A true KR20150078040A (en) | 2015-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020130167095A KR20150078040A (en) | 2013-12-30 | 2013-12-30 | Photocurable Adhesive Resin Composition And Method for Manufacturing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355022A (en) * | 2018-09-17 | 2019-02-19 | 江苏创客新材料科技有限公司 | Low viscous formula of a kind of binding dust paper roll and preparation method thereof |
-
2013
- 2013-12-30 KR KR1020130167095A patent/KR20150078040A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355022A (en) * | 2018-09-17 | 2019-02-19 | 江苏创客新材料科技有限公司 | Low viscous formula of a kind of binding dust paper roll and preparation method thereof |
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