WO2016003156A1 - Curable composition - Google Patents
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- WO2016003156A1 WO2016003156A1 PCT/KR2015/006699 KR2015006699W WO2016003156A1 WO 2016003156 A1 WO2016003156 A1 WO 2016003156A1 KR 2015006699 W KR2015006699 W KR 2015006699W WO 2016003156 A1 WO2016003156 A1 WO 2016003156A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Definitions
- the present application relates to a curable composition, a cured body and the use of the curable composition and the cured body.
- the display device may include a touch panel 302 mounted on the display panel 301.
- an air gap 304 may be formed between the display panel and the touch panel by interposing a spacer 303 between the display panel and the touch panel.
- light scattering occurs due to the air gap existing between the display panel and the touch panel, and the contrast decreases due to the air gap, and the presence of the air gap hinders the thinning of the panel.
- Patent Document 1 Japanese Patent Laid-Open No. 2005-55641
- OCR Optically Clear Resin
- the physical properties required for such OCR include optical properties, shrinkage, dielectric constant, crosslinking degree, adhesive properties, and the like.
- to show excellent adhesion properties proper correlation between the properties of OCR is required.
- research on each property has been actively conducted.
- the results of researches on the parameters formulating the correlation between properties are insignificant. to be.
- the present application provides a curable composition, a cured body and the use of the curable composition and the cured body.
- the present application relates to a curable composition.
- Applicants have found that by adjusting the correlation between dielectric constant, gel fraction, shrinkage and storage modulus, it is possible to provide a curable composition that can be suitably used in physical properties suitable for optical applications, such as so-called OCR (Optically Clear Resin). It confirmed and completed this invention.
- OCR Optically Clear Resin
- the correlation may be satisfied by adjusting the content ratio and the components included in the curable composition as described below.
- the curable composition satisfies the above correlation, a cured product having low dielectric constant and excellent adhesive properties can be produced.
- Exemplary curable compositions can satisfy, for example, the relationship of the following formula (1).
- A is the dielectric constant at 1 MHz after curing of the composition
- B is the gel fraction after curing of the composition (%)
- C is the shrinkage after curing of the composition (%)
- D is the storage modulus after curing of the composition (Pa).
- the dielectric constant (A) is, for example, using a cured product of the composition, after preparing a standard specimen of a copper plate / hard body / copper plate laminated structure having a size of 2 cm x 2 cm (width x length)
- the dielectric constant can be calculated using the Agilent 4294A Precision Impedance Analyzer device, and by measuring the value for the dielectric constant of the specimen under vacuum.
- the gel fraction (B) is, for example, cut the cured body of the composition to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, which is then immersed in an excess of ethyl acetate (Ethyl acetate) After standing for 24 hours, the uncured portion was melted and filtered using a strainer, and the separated insoluble fraction was dried in an oven at about 150 ° C. for about 30 minutes to 1 hour, and then measured based on the measured mass change before and after drying. It can be calculated as
- the shrinkage ratio (C) is, for example, after cutting the cured product of the composition to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, and after measuring the specific gravity before and after curing, It can be calculated from the rate of change of the specific gravity later.
- the storage modulus (D) is, for example, after cutting the cured body of the composition to a size of 8 mm in diameter and 1 mm in thickness to prepare a circular sample, and then using an Advanced Rheometrics Expansion System (ARES) device Can be measured at 1 Hz frequency in sweep mode.
- RATS Advanced Rheometrics Expansion System
- the value calculated by the formula 1 may be 30 or more. More specifically, the value calculated by Equation 1 may be 35 or more, 40 or more, 45 or more, 50 or more, 55, or more 60 or more or 65 or more. Such curable compositions can exhibit good adhesion properties while exhibiting low dielectric constant.
- the upper limit of the value calculated by Equation 1 is not particularly limited and may be appropriately set according to the intended use. For example, 200 or less, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 145 Or less than 140 or 135 or less.
- Exemplary curable compositions may exhibit low dielectric constant after curing.
- the dielectric constant at 1 MHz after curing of the curable composition may be 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, or 2.5 or less.
- Such a curable composition may be usefully used for adhesion of an optical member that senses a position by sensing an electrical signal such as, for example, a touch panel.
- the lower limit of the dielectric constant is not particularly limited and may be appropriately set according to the intended use.
- the dielectric constant is 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more at 1 MHz after curing of the curable composition. Or 2.5 or more.
- fills the said range can be obtained by including a rubber component mentioned later in a curable composition suitably, for example.
- Exemplary curable compositions may exhibit a gel fraction suitable for adhesion to the optical member after curing.
- the gel fraction after curing of the curable composition may be, for example, at least 30%, at least 30.5%, at least 31%, at least 31.5%, or at least 32.5%.
- the upper limit of the gel fraction may be, for example, 80% or less, 79.5% or less, 79% or less, 78.5% or less, 78% or less, 77.5% or less, 77% or less, 76.5% or less, or 76% or less. Since such a curable composition can exhibit excellent adhesive properties, it can be usefully used for bonding an optical member such as, for example, a touch panel and a display panel.
- fills the said range can be obtained by including a rubber component mentioned later in a curable composition suitably, for example.
- Exemplary curable compositions may also exhibit low shrinkage after curing.
- the curable composition may have a shrinkage after curing of 3.0% or less, 2.95% or less, 2.90% or less, 2.85% or less, 2.80% or less, 2.75% or less, 2.70% or less, or 2.65% or less.
- Such a curable composition can prevent dimensional changes, warpage, etc. of the adherend due to stress upon curing shrinkage of the resin composition, and thus can be usefully used for bonding an optical member such as a touch panel and a display panel.
- the lower limit of the shrinkage rate after curing is not particularly limited and may be appropriately set according to the intended use.
- fills the said range can be obtained by including a rubber component mentioned later in a curable composition suitably, for example.
- Exemplary curable compositions may also exhibit a storage modulus suitable for adhesion of the optical member.
- the storage modulus after curing of the curable composition is 20,000 Pa or less, 19,000 Pa or less, 18,000 Pa, or less, 17,0000 Pa or less, 16,000 Pa or less, 15,000 Pa or less, 14,000 Pa or less, 13,000 Pa or less, 12,000 Pa or less, It may be 11,000 Pa or less, 10,000 Pa or less, 9,500 Pa or less, 9,000 Pa or less, 8,500 Pa or less, 8,000 Pa or less, 7,500 Pa or less, 7,000 Pa or less, 6,500 Pa or less, or 6,000 Pa or less.
- the lower limit of the storage modulus after curing of the curable composition is not particularly limited and may be appropriately set according to the intended use. For example, 1 Pa or more, 100 Pa or more, 500 Pa or more, 1000 Pa or more, 2,000 Pa or more, 2,100 It may be at least Pa, at least 2,200 Pa, at least 2,300 Pa, at least 2,400 Pa, at least 2,500 Pa, or at least 2,600 Pa.
- a storage modulus that satisfies this range can be achieved, for example, by lowering the crosslinking density or gel fraction to lower the storage modulus. For this purpose, for example, by adding a rubber component to the curable composition or by applying an appropriate amount of monomer. Can be used to control the reactivity of the oligomer.
- Exemplary curable compositions may also exhibit good adhesion or adhesion.
- the curable composition has a peel force of 0.3 N / m or more, 0.34 N / m, 0.36 N / m or more, for example, at a room temperature after curing at a peel angle of 180 ° and a peel rate of 300 mm / min. , 0.38 N / m or more, 0.40 N / m or more, or 0.42 N / m or more.
- Excellent peeling force after curing of such a curable composition can be achieved by using a curable composition that satisfies the correlation of the formula (1).
- the upper limit of the peeling force is not particularly limited and may be appropriately set according to the intended use.
- Exemplary curable compositions can also produce a cured product excellent in light transmittance.
- the curable composition includes, for example, at least 80%, at least 82%, at least 84%, at least 86%, at least 88%, at least 90%, at least 92%, at least 94%, at least 96% of the visible light region after curing, At least 98% or at least 99%. Since such a curable composition is excellent in light transmittance, it can be usefully used for bonding between optical members of a display device.
- Exemplary curable compositions can include active energy ray curable oligomers.
- cure by irradiation of an active energy ray, for example, UV can be selected and used,
- a (meth) acrylate oligomer can be selected and used.
- the term (meth) acrylate oligomer may refer to an oligomer having at least one (meth) acryloyl group in a molecule. From the viewpoint of curability, an oligomer having at least two (meth) acryloyl groups in the molecule can be suitably used.
- an oligomer having 2 to 6, 2 to 4 or 2 (meth) acryloyl groups in the molecule may be used, but is not limited thereto.
- the main chain skeleton of the oligomers for example, oligomers having a (meth) acryloyl group, is not particularly limited. It may be at least one selected from a polydiene skeleton having no functional group, a hydrogenated product of polydiene, polyester, dibutylene glycol, polycarbonate and polyether.
- polydiene refers to a polymer prepared by using a monomer having two carbon-carbon double bonds.
- polyisoprene polybutadiene, styrene-butadiene, a copolymer of ethylene and propylene (EPM ) Or terpolymers (EPDM) of ethylene, propylene and nonconjugated dienes, and the like.
- EPM ethylene and propylene
- EPDM terpolymers
- an active energy ray-curable oligomer having a polybutadiene skeleton having a hydroxyl group may be used, but is not limited thereto .
- Examples of the (meth) acrylate oligomer include urethane-based (meth) acrylate oligomers, polyester-based (meth) acrylate oligomers, polyether-based (meth) acrylate oligomers, epoxy-based (meth) acrylate oligomers, One or more types selected from the group consisting of diene polymer-based (meth) acrylate oligomers and oligomers having a main chain of hydrogenated products of diene polymer-based (meth) acrylates can be selected and used.
- the urethane-based (meth) acrylate oligomer may mean, for example, a (meth) acrylate oligomer having a urethane bond in the molecule.
- the urethane-based (meth) acrylate oligomer can be obtained by, for example, esterifying a polyurethane oligomer obtained by the reaction of polybutadienediol, polyether polyol, polyester polyol, polycarbonate diol and the like with polyisocyanate with (meth) acrylic acid.
- Polybutadiene-modified urethane type (meth) acrylate obtained by (meth) acryl modification of polybutadiene is also contained in a urethane type (meth) acrylate oligomer.
- Hydrogenated polybutadiene modified urethane type (meth) acrylate obtained by (meth) acryl modification of the hydrogenated polybutadiene is also contained in a urethane type (meth) acrylate oligomer.
- urethane type (meth) acrylate oligomer 1,2-polybutadiene modified urethane type (meth) acrylate oligomer, polyester urethane type (meth) acrylate oligomer, dibutylene glycol urethane type (meth) acrylate oligomer, polycarbonate urethane type (meth ) Acrylic oligomer, a polyether urethane type (meth) acrylate oligomer, etc. are mentioned.
- the polyester-based (meth) acrylate oligomer may be obtained by esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both terminals obtained by condensation of polyhydric carboxylic acid with a polyhydric alcohol, or with (meth) acrylic acid.
- the terminal hydroxyl group of the oligomer obtained by adding an alkylene oxide can be obtained by esterifying with (meth) acrylic acid.
- a polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of a polyether polyol, for example with (meth) acrylic acid.
- An epoxy-type (meth) acrylate oligomer can be obtained by reacting and esterifying (meth) acrylic acid with the oxirane ring of a bisphenol-type epoxy resin or a novolak-type epoxy resin of comparatively low molecular weight, for example.
- denatured this epoxy type (meth) acrylate oligomer partially by dibasic carboxylic anhydride can also be used.
- the oligomer which has a skeleton of the hydrogenated substance of diene polymer type (meth) acrylate can be obtained by esterifying the hydroxyl group of hydrogenated polybutadiene or hydrogenated polyisoprene which has hydroxyl groups at both terminals, for example (meth) acrylic acid.
- the oligomer which has such a (meth) acryloyl group can be used individually by 1 type, or can be used in combination of 2 or more type.
- a urethane type (meth) acrylate oligomer can be selected and used from a viewpoint of sclerosis
- a bifunctional urethane type (meth) acrylate oligomer can be selected and used.
- a bifunctional urethane type (meth) acrylate oligomer can mean that two (meth) acryloyl groups are contained in 1 molecule of a urethane type (meth) acrylate oligomer.
- a bifunctional urethane type (meth) acrylate oligomer can be obtained by esterifying a polyurethane oligomer with (meth) acrylic acid.
- Polyurethane oligomer can be obtained by reaction of polyisocyanate with polyether polyol, polyester polyol, polycarbonate diol, etc. which have two hydroxyl groups in a molecule
- polyether polyol having two hydroxyl groups examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), polyhexamethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol Neopentylglycol, cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, bisphenol A, or the like, or a compound in which ethylene oxide or propylene oxide is added.
- the polyester polyol which has two hydroxyl groups can be obtained, for example by making an alcohol component and an acid component react.
- Polyester polyols having two hydroxyl groups are, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), 1,3-butylene glycol, 1,4-butylene glycol, 1,6- ⁇ -caprolactone or a compound in which ethylene oxide or propylene oxide is added to hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, bisphenol A, or the like
- the added compound may be used as an alcohol component, dibasic acids such as adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid, and anhydrides thereof as an acid component, and the alcohol component and the acid component may be reacted with each other.
- the weight average molecular weight or the number average molecular weight of the urethane-based (meth) acrylate oligomer may be, for example, in the range of 500 to 100000 or 1000 to 50000 in view of handling properties. This value is not particularly limited, and may be, for example, 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 20000, 30000, 40000, 50000 or 100000.
- This average molecular weight is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the amount of the active energy ray-curable oligomer is, in terms of producing a curable composition that satisfies the relationship of the formula 1, in the curable composition, for example, 10% by weight, 11% by weight, 12% by weight, 13 May be included in an amount of at least 20% by weight, at least 14% by weight, or at least 15% by weight, and at most 20% by weight, 19% by weight, 18% by weight, 17% by weight, 16% by weight or 15% by weight. Can be.
- the curable composition may further include a photopolymerization initiator.
- a photoinitiator as long as it can start superposition
- an ultraviolet-ray polymerization initiator, a visible light polymerization initiator, etc. can be used.
- the ultraviolet polymerization initiator for example, benzoin, benzophenone, acetophenone and the like can be used.
- the visible light polymerization initiator for example, acyl phosphine oxide, thioxanthone, metallocene and quinone.
- ⁇ -aminoalkylphenone series and the like can be used as a photopolymerization initiator.
- Exemplary curable compositions may further include a rubber component.
- the rubber component may comprise polydiene.
- a compound having a polyisoprene skeleton or a polybutadiene skeleton, a styrene-butadiene skeleton, a copolymer of ethylene and propylene (EPM) or a terpolymer of ethylene, propylene, and nonconjugated diene (EPDM) May be used, but is not limited thereto.
- the rubber component may have a functional group such as a hydroxyl group or a carboxyl group at the terminal.
- a functional group such as a hydroxyl group or a carboxyl group
- polydiene having a functional group such as a hydroxyl group or a carboxyl group
- a polybutadiene rubber having a hydroxyl group may be used, but is not limited thereto.
- the weight average molecular weight of the rubber component may be appropriately selected within a range that does not impair the purpose of the present application, for example, in the range of about 1,000 to about 10,000, about 1,000 to about 5,000 or about 2,000 to 3,000 May be, but is not limited thereto.
- the content of the rubber component in the curable composition may be included, for example, at least 50 wt%, at least 52 wt%, at least 54 wt%, at least 56 wt%, at least 58 wt% or at least 60 wt%, and at most 70 wt%. , Up to 68 wt%, up to 66 wt%, up to 64 wt%, up to 62 wt% or up to 60 wt%.
- the curable composition includes the rubber component in the above ratio, it is advantageous to provide a curable composition that satisfies the condition of Formula 1.
- Exemplary curable compositions may further comprise monomers in addition to the oligomers for the purpose of regulating and diluting active energy curable oligomers, for example, (meth) acrylate oligomers.
- the content of such monomers may be included in the curable composition, for example, at least 10 weight percent, at least 12 weight percent, at least 14 weight percent, at least 16 weight percent, at least 18 weight percent, or at least 20 weight percent, and at least 30 weight percent. Or less, 28 wt% or less, 26 wt% or less, 24 wt% or less, 22 wt% or less, or 20 wt% or less.
- a (meth) acrylate monomer can be used, for example, and polyfunctional (meth), such as monofunctional (meth) acrylate and bifunctional, trifunctional, tetrafunctional, 5-functional, and 6 functional, etc. ) Acrylate, etc. can be used variously, For example, monofunctional (meth) acrylate or bifunctional (meth) acrylate can be selected and used.
- polyfunctional (meth) such as monofunctional (meth) acrylate and bifunctional, trifunctional, tetrafunctional, 5-functional, and 6 functional, etc.
- Acrylate, etc. can be used variously,
- monofunctional (meth) acrylate or bifunctional (meth) acrylate can be selected and used.
- (meth) acrylate for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl ( Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxyethyl ( Meta) acrylate, nonylphenoxytetraethylene
- polyfunctional (meth) acrylate di (meth) acrylated isocyanurate, tri (meth) acrylated isocyanurate, 1,3-dibutylene glycol di (meth) acrylate, 1,4-butanedioldi ( Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO (ethylene oxide) modified bisphenol A di (meth) acrylate, diethylene glycol di (Meth) acrylate, ECH (epichlorohydrin) modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, caprolactone modified hydroxide Oxypibaric acid ester neopentylglycol di (meth) acrylate, ste
- the curable composition may further include a known silane coupling agent in order to improve the adhesion to the adherend, for example, the adhesion to glass.
- curable composition may further contain well-known paraffins in order to accelerate hardening of the part which contact
- the curable composition may further include a known antioxidant including a polymerization inhibitor for the purpose of maintaining storage stability.
- the curable compositions may further include known additives such as elastomers, plasticizers, fillers, colorants, or crystals, depending on the intended use.
- exemplary cured bodies may satisfy the relationship of Equation 1 below.
- Equation 1 A is the dielectric constant at 1 MHz of the cured product, B is the gel fraction (%) of the cured product, C is the shrinkage percentage (%) of the cured product, and D is the storage modulus (Pa) of the cured product.
- Exemplary cured bodies may include, for example, the curable composition in a cured state.
- the "cured state” means that the components contained in the composition undergo a crosslinking reaction, a polymerization reaction, or the like. This may mean a case where the state is converted into a hard state.
- Specific information on the dielectric constant, gel fraction, shrinkage and storage modulus in Equation 1 of the cured body may be equally applicable to the dielectric constant, gel fraction, shrinkage and storage modulus described in the item of the curable composition.
- Exemplary cured bodies can be prepared by curing the curable composition.
- the curing method is not particularly limited, and a method of maintaining the composition at an appropriate temperature or irradiating an appropriate active energy ray such that the polymerization reaction may proceed so that the crosslinking reaction of the active energy ray curable oligomer described in the section of the curable composition may proceed. It can be hardened through the process. If the maintenance at the appropriate temperature and the irradiation of the active energy ray is required at the same time, the process can be carried out sequentially or simultaneously.
- the irradiation of the active energy ray may be performed using, for example, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like, and the conditions such as the wavelength and the amount of light of the active energy ray to be irradiated may be the active energy.
- the crosslinking or polymerization of the precurable oligomer may be selected within a range that can be appropriately made.
- This application also relates to the use of the curable composition or cured product. Since the curable composition or the cured product exhibits low dielectric constant and excellent adhesive properties, it may be usefully used for bonding various optical members of the display device.
- the curable composition or cured body can be used to bond the indicator and the optically functional material.
- a display body may be, for example, a display element such as an LCD (Liquid Crystal Display), an EL (Electroluminescence) display device, an EL illumination, an electronic paper or a plasma display, to which a polarizing plate for glass is attached.
- an acrylic plate for example, a hard coating or an antireflective coating may be applied to one or both surfaces
- a PC for example, to improve visibility or to prevent cracking of a display element from external impact
- a transparent plastic plate such as a polycarbonate (PET) plate, a polyethylene terephthalate (PET) plate, and a polyethylene naphthalate (PEN) plate, tempered glass (for example, a shatterproof film may be attached), or a touch panel input sensor.
- PET polycarbonate
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- tempered glass for example, a shatterproof film may be attached
- a touch panel input sensor for example, a touch panel input sensor.
- the curable composition or cured product may also be usefully used for bonding a transparent substrate and a transparent plate on which a transparent electrode is formed, for example, in a capacitive touch panel.
- the material of the transparent substrate may be, for example, PC, polymethyl methacrylate (PMMA), a composite of PC and PMMA, cyclo-olefin copolymer (COC), cyclo-olefin polymer (COP).
- the material of the transparent plate may be, for example, glass, PC, PMMA, composite COC or COP of PC and PMMA.
- cured material can also be usefully used for the use for bonding a touch panel and the sheet
- the sheet may be, for example, an icon sheet, a protective sheet, a makeup sheet, or the like, and the material of the sheet may be, for example, PET, PC, COC, or COP.
- the plate include a decorative plate or a protective plate, and the material of the plate may be, for example, PET glass, PC, PMMA, a composite of PC and PMMA, COC, or COP.
- the material of the touch panel bonded to the sheet or plate may be, for example, glass, PET, PC, PMMA, a composite of PC and PMMA, COC, or COP.
- the curable composition or the cured product may also be usefully used, for example, for direct bonding of a touch panel and a display panel of a display device.
- FIG. 1 exemplarily illustrates a display device including a display panel 101 and a touch panel 102, and the display panel 101 and the touch panel 102 are bonded by the curable composition or the cured body 103. .
- the curable composition or the cured product may also be usefully used for filling a space spaced between the optical functional material spaced by a spacer and a display panel, for example, in a display device.
- 2 exemplarily shows a display device in which the optical functional material is a touch panel.
- the display device may include a display panel 201, a touch panel 202, and a spacer 203 spaced apart from the display panel. In this case, the display panel and the touch panel may be disposed.
- This spaced space, a so-called air gap space may have a structure in which the curable composition or the cured body 204 is filled.
- the curable composition or cured product When the curable composition or cured product is applied to the display device, other components constituting the device or a method of constituting the device are not particularly limited, and any known in the art may be used as long as the curable composition or cured product is used. Both materials and methods may be employed.
- Exemplary curable compositions of the present application can produce a cured product exhibiting low dielectric constant and excellent adhesive properties, and thus are useful for bonding various optical functional members of a display device, for example, bonding a touch panel and a display panel. Can be used.
- FIG. 1 and 2 are schematic views of an exemplary display device of the present application.
- FIG. 3 is a schematic diagram of a display device related to the background art.
- the cured product prepared in Examples and Comparative Examples was cut to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, which was then immersed in an excess of ethyl acetate and left for 24 hours to leave uncured portion. After dissolving and filtering using a strainer, the separated insoluble fraction was dried in an oven at about 150 ° C. for about 30 minutes to 1 hour to calculate a gel fraction based on the measured mass change before and after drying.
- a standard specimen of a copper / hardened body / copper laminated structure having a size of 2 cm ⁇ 2 cm (width ⁇ length) was fabricated, and then the Agilent 4294A Precision Impedance Analyzer was used. The dielectric constant was measured and the dielectric constant was measured by calculating the value for the dielectric constant of the specimen in vacuum.
- a polyurethane acrylate comprising a polybutadiene rubber having a hydroxyl group and having a weight average molecular weight of 15,000 (hereinafter oligomer A) 18 g and a polybutadiene rubber having a hydroxyl group and having a weight average molecular weight of 10,000 (
- 2 g of oligomer B) 60 g of polybutadiene rubber (hereinafter referred to as rubber A) having a hydroxyl group as a rubber component and having a weight average molecular weight of 2,000, 20 parts by weight of isobonyl acrylate as a monomer, and 1 g of Darocur TPO as a photopolymerization initiator Mixing produced a curable composition.
- the cured body After applying the prepared curable composition to about 0.2 mm on a glass substrate, the cured body having a predetermined size according to the measurement sample by irradiating UV of about 365 nm to 400 nm long wavelength using an LED or a metal-halide lamp Prepared.
- a cured product was prepared in the same manner as in Example 1, except that the composition of the curable composition in Example 1 was adjusted as shown in Table 1 below.
- Example Oligomer Rubber Monomer Other A B C A B IBOA S.C Initiator One 18 2 - 60 - 20 - One 2 16 4 - 60 - 20 - One 3 14 6 - 60 - 20 - One 4 18 - 2 60 - 20 - One 5 16 - 4 60 - 20 - One 6 14 - 6 60 - 20 - One 7 20 - - - 60 20 0.5 One 8 20 - - 60 - 20 0.5 One 9 22 - - - 60 18 0.5 One 10 20 - - - 60 20 0.25 One 11 20 - - - 60 20 One One 12 20 - - - 60 20 2 One Content Unit (g)-Oligomer A: Polyurethane acrylate containing polybutadiene rubber having hydroxyl group (weight average molecular weight: 15,000)-Oligomer B: Polyurethane acrylate containing polybutadiene rubber having hydroxyl group (weight average molecular weight : 10,000)-oli
- a cured product was prepared in the same manner as in Example 1 except that the composition of the curable composition in Example 1 was adjusted as shown in Table 2 below.
- Examples 1 to 12 having a value of Equation 1 or more exhibited a low dielectric constant, and at the same time, it was confirmed that the peeling force was remarkably superior to Comparative Examples 1 to 3 having a value of Equation 1 less than 30.
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Abstract
The present application relates to a curable composition, a cured body, and uses of the curable composition and the cured body. An exemplary curable composition can produce a cured body which exhibits a low dielectric constant and has excellent adhesive characteristics, and thus can be favorably used in the bonding of various optical functional members of a display device, for example, the direct bonding of a touch panel and a display panel.
Description
관련 출원들과의 상호 인용
Cross Citation with Related Applications
본 출원은 2014년 06월 30일자 한국 특허 출원 제10-2014-0081020호 및 2014년 06월 30일자 한국 특허 출원 제10-2014-0081022호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0081020 dated June 30, 2014 and Korean Patent Application No. 10-2014-0081022 dated June 30, 2014. All content disclosed in the literature is included as part of this specification.
기술분야Technical Field
본 출원은 경화성 조성물, 경화체 및 경화성 조성물과 경화체의 용도에 관한 것이다.The present application relates to a curable composition, a cured body and the use of the curable composition and the cured body.
디스플레이 장치는, 예를 들면, 도 3에 나타내는 바와 같이 표시 패널(301) 상에 탑재하는 터치 패널(302)을 구비할 수 있다. 이 경우, 표시 패널을 보호하기 위해, 표시 패널과 터치 패널의 사이에 스페이서(303)를 개재시킴으로써, 표시 패널과 터치 패널 사이에 에어갭(304)을 형성할 수 있다. 그러나, 표시 패널과 터치 패널 사이에 존재하는 에어갭에 의해 광 산란이 일어나고 이에 기인하여 콘트라스트가 저하되며 또한 에어갭의 존재는 패널 박형화에 방해가 된다. For example, as shown in FIG. 3, the display device may include a touch panel 302 mounted on the display panel 301. In this case, in order to protect the display panel, an air gap 304 may be formed between the display panel and the touch panel by interposing a spacer 303 between the display panel and the touch panel. However, light scattering occurs due to the air gap existing between the display panel and the touch panel, and the contrast decreases due to the air gap, and the presence of the air gap hinders the thinning of the panel.
이와 같은 문제를 감안하여, 특허문헌 1(일본 공개특허공보 제2005-55641호)에 개시된 바와 같이 표시 패널과 터치 패널 사이의 에어갭에 수지, OCR(Optically Clear Resin)를 충진하는 기술이 제안되고 있다. 이러한 OCR에 요구되는 물성으로는 광학적 특성을 포함하여 수축율, 유전율, 가교도, 접착 특성 등이 있다. 특히 우수한 접착 특성을 나타내기 위해서는 OCR의 각 물성간의 적절한 상관관계가 필요한데, 현재까지 물성 각각의 기준에 대해서는 연구가 활발히 진행되고 있으나, 각 물성 간의 상관 관계를 수식화한 파라미터에 대한 연구 성과는 미미한 실정이다. In view of such a problem, as disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2005-55641), a technique for filling resin and OCR (Optically Clear Resin) in an air gap between a display panel and a touch panel is proposed. have. The physical properties required for such OCR include optical properties, shrinkage, dielectric constant, crosslinking degree, adhesive properties, and the like. In particular, to show excellent adhesion properties, proper correlation between the properties of OCR is required. Until now, research on each property has been actively conducted. However, the results of researches on the parameters formulating the correlation between properties are insignificant. to be.
본 출원은 경화성 조성물, 경화체 및 경화성 조성물과 경화체의 용도를 제공한다. The present application provides a curable composition, a cured body and the use of the curable composition and the cured body.
본 출원은 경화성 조성물에 관한 것이다. 본 출원인은 유전상수, 겔분율, 수축율 및 저장 탄성률 간의 상관 관계를 조절함으로써 광학적 용도에 적합한 물성, 예를 들면, 소위 OCR(Optically Clear Resin)에 적합하게 사용할 수 있는 경화성 조성물의 제공이 가능하다는 것을 확인하고 본 발명을 완성하였다. 명확하지는 않으나, 상기 상관 관계는 후술하는 바와 같이 경화성 조성물에 포함되는 성분과 함량 비율을 조절함으로써 만족시킬 수 있다. 경화성 조성물이 상기 상관 관계를 만족하는 경우 저 유전율을 나타내면서도 우수한 접착 특성을 나타내는 경화체를 제조할 수 있다. 예시적인 경화성 조성물은, 예를 들면, 하기 수식 1의 관계를 만족할 수 있다. The present application relates to a curable composition. Applicants have found that by adjusting the correlation between dielectric constant, gel fraction, shrinkage and storage modulus, it is possible to provide a curable composition that can be suitably used in physical properties suitable for optical applications, such as so-called OCR (Optically Clear Resin). It confirmed and completed this invention. Although not clear, the correlation may be satisfied by adjusting the content ratio and the components included in the curable composition as described below. When the curable composition satisfies the above correlation, a cured product having low dielectric constant and excellent adhesive properties can be produced. Exemplary curable compositions can satisfy, for example, the relationship of the following formula (1).
[수식 1] [Equation 1]
수식 1에서 A는 조성물의 경화 후 1 MHz에서의 유전상수이고, B는 조성물의 경화 후 겔분율(%)이며, C는 조성물의 경화 후 수축율(%)이고, D는 조성물의 경화 후 저장 탄성률(Pa)이다. In Formula 1, A is the dielectric constant at 1 MHz after curing of the composition, B is the gel fraction after curing of the composition (%), C is the shrinkage after curing of the composition (%), and D is the storage modulus after curing of the composition (Pa).
수식 1에서, 유전상수(A)는, 예를 들면, 조성물의 경화체를 이용하여, 2 cm x 2 cm (가로 x 세로)의 크기를 가지는 동판/경화체/동판 적층 구조의 규격 시편을 제작한 후, Agilent 4294A Precision impedance Analyzer 장치를 사용하여 유전율을 측정하고, 진공 상태에서의 상기 시편의 유전율에 대한 값을 측정함으로써 계산될 수 있다. In Equation 1, the dielectric constant (A) is, for example, using a cured product of the composition, after preparing a standard specimen of a copper plate / hard body / copper plate laminated structure having a size of 2 cm x 2 cm (width x length) The dielectric constant can be calculated using the Agilent 4294A Precision Impedance Analyzer device, and by measuring the value for the dielectric constant of the specimen under vacuum.
수식 1에서, 겔 분율(B)은, 예를 들면, 조성물의 경화체를 직경 2.5 mm 및 두께 1 mm의 크기로 절단하여 원형 샘플을 제조한 후, 이를 과량의 에틸아세테이트(Ethyl acetate)에 침적시키고 24시간 동안 방치하여 경화되지 않은 부분을 녹여 거름망을 이용하여 거른 후, 분리된 불용해분을 약 150℃ 오븐에서 약 30분 내지 1시간 동안 건조하여 건조 전·후 질량 변화를 측정한 값을 기초로 계산될 수 있다.In Formula 1, the gel fraction (B) is, for example, cut the cured body of the composition to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, which is then immersed in an excess of ethyl acetate (Ethyl acetate) After standing for 24 hours, the uncured portion was melted and filtered using a strainer, and the separated insoluble fraction was dried in an oven at about 150 ° C. for about 30 minutes to 1 hour, and then measured based on the measured mass change before and after drying. It can be calculated as
수식 1에서, 수축율(C)은, 예를 들면, 조성물의 경화체를 직경 2.5 mm 및 두께 1 mm의 크기로 절단하여 원형 샘플을 제조한 후, 경화 전·후 비중을 측정한 후, 경화 전·후 의 비중의 변화율로부터 계산될 수 있다. In the formula (1), the shrinkage ratio (C) is, for example, after cutting the cured product of the composition to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, and after measuring the specific gravity before and after curing, It can be calculated from the rate of change of the specific gravity later.
수식 1에서, 저장 탄성률(D)은, 예를 들면, 조성물의 경화체를 직경 8 mm 및 두께 1 mm의 크기로 절단하여 원형 샘플을 제조한 후, ARES(Advanced Rheometrics Expansion System) 장치를 사용하여 Frequency Sweep mode로 1 Hz 주파수에서 측정될 수 있다. In Equation 1, the storage modulus (D) is, for example, after cutting the cured body of the composition to a size of 8 mm in diameter and 1 mm in thickness to prepare a circular sample, and then using an Advanced Rheometrics Expansion System (ARES) device Can be measured at 1 Hz frequency in sweep mode.
예시적인 경화성 조성물은, 상기 수식 1로 계산되는 값이 30 이상일 수 있다. 상기 수식 1로 계산되는 값은, 보다 구체적으로, 35 이상, 40 이상, 45 이상, 50 이상, 55, 이상 60 이상 또는 65 이상일 수 있다. 이러한 경화성 조성물은 저 유전율을 나타내면서 우수한 접착 특성을 나타낼 수 있다. 또한, 상기 수식 1로 계산되는 값의 상한은 특별히 제한되지 않고 목적하는 용도에 의하여 적절히 설정될 수 있으며, 예를 들면, 200 이하, 190 이하, 180 이하, 170 이하, 160 이하, 150 이하, 145 이하, 140 이하 또는 135 이하일 수 있다. Exemplary curable compositions, the value calculated by the formula 1 may be 30 or more. More specifically, the value calculated by Equation 1 may be 35 or more, 40 or more, 45 or more, 50 or more, 55, or more 60 or more or 65 or more. Such curable compositions can exhibit good adhesion properties while exhibiting low dielectric constant. In addition, the upper limit of the value calculated by Equation 1 is not particularly limited and may be appropriately set according to the intended use. For example, 200 or less, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 145 Or less than 140 or 135 or less.
예시적인 경화성 조성물은, 경화 후 저 유전율을 나타낼 수 있다. 예를 들면, 상기 경화성 조성물의 경화 후 1 MHz에서 유전상수가 3.5 이하, 3.4 이하, 3.3 이하, 3.2 이하, 3.1 이하, 3.0 이하, 2.9 이하, 2.8 이하, 2.7 이하, 2.6 이하 또는 2.5 이하일 수 있다. 이러한 경화성 조성물은, 예를 들면, 터치 패널과 같은 전기 신호를 감지하여 위치를 센싱하는 광학 부재의 접착에 유용하게 사용될 수 있다. 유전상수의 하한은 특별히 제한되지 않고 목적하는 용도에 따라 적절히 설정될 수 있으며, 예를 들어, 상기 경화성 조성물의 경화 후 1 MHz에서 유전 상수가 2.0 이상, 2.1 이상, 2.2 이상, 2.3 이상, 2.4 이상 또는 2.5 이상일 수 있다. 상기 범위를 만족하는 유전율은, 예를 들면, 경화성 조성물에 후술하는 러버(rubber) 성분을 적절히 포함시킴으로써 얻을 수 있다. Exemplary curable compositions may exhibit low dielectric constant after curing. For example, the dielectric constant at 1 MHz after curing of the curable composition may be 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, or 2.5 or less. . Such a curable composition may be usefully used for adhesion of an optical member that senses a position by sensing an electrical signal such as, for example, a touch panel. The lower limit of the dielectric constant is not particularly limited and may be appropriately set according to the intended use. For example, the dielectric constant is 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more at 1 MHz after curing of the curable composition. Or 2.5 or more. Dielectric constant which satisfy | fills the said range can be obtained by including a rubber component mentioned later in a curable composition suitably, for example.
예시적인 경화성 조성물은, 경화 후 광학 부재에 접착에 적합한 겔분율을 나타낼 수 있다. 예를 들면, 경화성 조성물의 경화 후 겔분율이, 예를 들면, 30% 이상, 30.5% 이상, 31% 이상, 31.5% 이상 또는 32.5% 이상일 수 있다. 또한, 겔분율의 상한은, 예를 들면, 80% 이하, 79.5% 이하, 79% 이하, 78.5% 이하, 78% 이하, 77.5% 이하, 77% 이하, 76.5% 이하 또는 76% 이하일 수 있다. 이러한 경화성 조성물은, 우수한 접착 특성을 나타낼 수 있으므로, 예를 들어, 터치 패널과 표시 패널 등과 같은 광학 부재의 접합에 유용하게 사용될 수 있다. 또한, 상기 범위를 만족하는 겔분율은, 예를 들면, 경화성 조성물에 후술하는 러버(rubber) 성분을 적절히 포함시킴으로써 얻을 수 있다.Exemplary curable compositions may exhibit a gel fraction suitable for adhesion to the optical member after curing. For example, the gel fraction after curing of the curable composition may be, for example, at least 30%, at least 30.5%, at least 31%, at least 31.5%, or at least 32.5%. In addition, the upper limit of the gel fraction may be, for example, 80% or less, 79.5% or less, 79% or less, 78.5% or less, 78% or less, 77.5% or less, 77% or less, 76.5% or less, or 76% or less. Since such a curable composition can exhibit excellent adhesive properties, it can be usefully used for bonding an optical member such as, for example, a touch panel and a display panel. In addition, the gel fraction which satisfy | fills the said range can be obtained by including a rubber component mentioned later in a curable composition suitably, for example.
예시적인 경화성 조성물은, 또한, 경화 후에 저 수축율을 나타낼 수 있다. 예를 들면, 경화성 조성물은 경화 후 수축율이 3.0% 이하, 2.95% 이하, 2.90% 이하, 2.85% 이하, 2.80% 이하, 2.75% 이하, 2.70% 이하 또는 2.65% 이하일 수 있다. 이러한 경화성 조성물은, 수지 조성물의 경화 수축시 응력에 의한 피착체의 치수 변화나 휨 등을 방지할 수 있으므로, 예를 들면, 터치 패널과 표시 패널 등과 같은 광학 부재의 접합에 유용하게 사용될 수 있다. 경화 후 수축율의 하한의 특별히 제한되지 않고 목적하는 용도에 따라 적절히 설정될 수 있으며, 예를 들면, 1% 이상, 1.1% 이상, 1.2% 이상, 1.3% 이상, 1.4% 이상, 1.5% 이상, 1.6% 이상, 1.7% 이상 또는 1.8% 이상일 수 있다. 또한, 상기 범위를 만족하는 수축율은, 예를 들면, 경화성 조성물에 후술하는 러버(rubber) 성분을 적절히 포함시킴으로써 얻을 수 있다.Exemplary curable compositions may also exhibit low shrinkage after curing. For example, the curable composition may have a shrinkage after curing of 3.0% or less, 2.95% or less, 2.90% or less, 2.85% or less, 2.80% or less, 2.75% or less, 2.70% or less, or 2.65% or less. Such a curable composition can prevent dimensional changes, warpage, etc. of the adherend due to stress upon curing shrinkage of the resin composition, and thus can be usefully used for bonding an optical member such as a touch panel and a display panel. The lower limit of the shrinkage rate after curing is not particularly limited and may be appropriately set according to the intended use. For example, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.6 Or at least 1.7% or at least 1.8%. In addition, the shrinkage rate which satisfy | fills the said range can be obtained by including a rubber component mentioned later in a curable composition suitably, for example.
예시적인 경화성 조성물은, 또한, 광학 부재의 접착에 적합한 저장 탄성률을 나타낼 수 있다. 예를 들면, 경화성 조성물의 경화 후 저장 탄성률이 20,000Pa 이하, 19,000Pa 이하, 18,000Pa, 이하, 17,0000Pa 이하, 16,000Pa 이하, 15,000 Pa 이하, 14,000 Pa 이하, 13,000 Pa 이하, 12,000 Pa 이하, 11,000 Pa 이하, 10,000 Pa 이하, 9,500 Pa 이하, 9,000 Pa 이하, 8,500 Pa이하, 8,000 Pa이하, 7,500 Pa이하, 7,000 Pa이하, 6,500 Pa이하 또는 6,000 Pa이하일 수 있다. 이러한, 경화성 조성물은, 예를 들면, 고온 환경에서 피착체의 팽창 수축을 견딜 수 있기 때문에 박리 등을 억제할 수 있으므로, 터치 패널과 표시 패널 등과 같은 광학 부재의 접합에 유용하게 사용될 수 있다. 경화성 조성물의 경화 후 저장 탄성률의 하한은 특별히 제한되지 않고 목적하는 용도에 따라 적절히 설정될 수 있으며, 예를 들면, 1 Pa 이상, 100 Pa 이상, 500 Pa 이상, 1000 Pa 이상, 2,000 Pa이상, 2,100 Pa이상, 2,200 Pa이상, 2,300 Pa이상, 2,400 Pa이상, 2,500 Pa이상 또는 2,600 Pa이상일 수 있다. 이러한 범위를 만족하는 저장 탄성률은, 예를 들면, 가교 밀도나 겔 분율을 낮추어서 저장 탄성률을 낮춤으로써 달성할 수 있으며, 이를 위해, 예를 들면, 경화성 조성물에 러버 성분을 추가하거나 또는 적절한 양의 모노머를 사용하여 올리고머의 반응성을 조절할 수 있다. Exemplary curable compositions may also exhibit a storage modulus suitable for adhesion of the optical member. For example, the storage modulus after curing of the curable composition is 20,000 Pa or less, 19,000 Pa or less, 18,000 Pa, or less, 17,0000 Pa or less, 16,000 Pa or less, 15,000 Pa or less, 14,000 Pa or less, 13,000 Pa or less, 12,000 Pa or less, It may be 11,000 Pa or less, 10,000 Pa or less, 9,500 Pa or less, 9,000 Pa or less, 8,500 Pa or less, 8,000 Pa or less, 7,500 Pa or less, 7,000 Pa or less, 6,500 Pa or less, or 6,000 Pa or less. Since such a curable composition can withstand expansion and contraction of an adherend in a high temperature environment, for example, peeling and the like can be suppressed, so that the curable composition can be usefully used for bonding an optical member such as a touch panel and a display panel. The lower limit of the storage modulus after curing of the curable composition is not particularly limited and may be appropriately set according to the intended use. For example, 1 Pa or more, 100 Pa or more, 500 Pa or more, 1000 Pa or more, 2,000 Pa or more, 2,100 It may be at least Pa, at least 2,200 Pa, at least 2,300 Pa, at least 2,400 Pa, at least 2,500 Pa, or at least 2,600 Pa. A storage modulus that satisfies this range can be achieved, for example, by lowering the crosslinking density or gel fraction to lower the storage modulus. For this purpose, for example, by adding a rubber component to the curable composition or by applying an appropriate amount of monomer. Can be used to control the reactivity of the oligomer.
예시적인 경화성 조성물은, 또한, 우수한 점착력 또는 접착력을 나타낼 수 있다. 경화성 조성물은, 예를 들면, 경화 후 상온에서 180 °의 박리각도 및 300 mm/min의 박리속도로 측정된 유리에 대한 박리력이 0.3 N/m 이상, 0.34 N/m, 0.36 N/m 이상, 0.38 N/m 이상, 0.40 N/m 이상 또는 0.42 N/m 이상일 수 있다. 이러한 경화성 조성물의 경화 후의 우수한 박리력은 상기 수식 1의 상관 관계를 만족하는 경화성 조성물을 이용함으로써 달성될 수 있다. 박리력의 상한은 특별히 제한되지 않고 목적하는 용도에 따라 적절히 설정될 수 있다.Exemplary curable compositions may also exhibit good adhesion or adhesion. The curable composition has a peel force of 0.3 N / m or more, 0.34 N / m, 0.36 N / m or more, for example, at a room temperature after curing at a peel angle of 180 ° and a peel rate of 300 mm / min. , 0.38 N / m or more, 0.40 N / m or more, or 0.42 N / m or more. Excellent peeling force after curing of such a curable composition can be achieved by using a curable composition that satisfies the correlation of the formula (1). The upper limit of the peeling force is not particularly limited and may be appropriately set according to the intended use.
예시적인 경화성 조성물은, 또한, 투광성이 우수한 경화체를 제조할 수 있다. 경화성 조성물은, 예를 들면, 경화 후 가시광 영역의 투과율이 80% 이상, 82 % 이상, 84 % 이상 86 % 이상, 88% 이상, 90% 이상, 92% 이상, 94% 이상, 96% 이상, 98% 이상 또는 99% 이상일 수 있다. 이러한 경화성 조성물은 투광성이 우수하므로 디스플레이 장치의 광학 부재 간의 접합에 유용하게 사용될 수 있다. Exemplary curable compositions can also produce a cured product excellent in light transmittance. The curable composition includes, for example, at least 80%, at least 82%, at least 84%, at least 86%, at least 88%, at least 90%, at least 92%, at least 94%, at least 96% of the visible light region after curing, At least 98% or at least 99%. Since such a curable composition is excellent in light transmittance, it can be usefully used for bonding between optical members of a display device.
예시적인 경화성 조성물은 활성 에너지선 경화성 올리고머를 포함할 수 있다. 이러한, 올리고머로는, 활성 에너지선, 예를 들면, UV 등의 조사 의하여 경화할 수 있는 작용기를 가지는 올리고머를 선택하여 사용할 수 있고, 예를 들어, (메타)아크릴레이트 올리고머를 선택하여 사용할 수 있다. 본 명세서에서 용어 (메타)아크릴레이트 올리고머는 분자 내에 적어도 하나 이상의 (메타)아크릴로일기를 가지는 올리고머를 의미할 수 있다. 경화성의 관점에서 분자 내에 적어도 2개 이상의 (메타)아크릴로일기를 가지는 올리고머를 적합하게 이용할 수 있다. (메타)아크릴레이트 올리고머로는, 예를 들어, 분자 내에 2 내지 6개, 2 내지 4개 또는 2개의 (메타)아크릴로일기를 가지는 올리고머를 사용할 수 있으나 이에 제한되는 것은 아니다. Exemplary curable compositions can include active energy ray curable oligomers. As such an oligomer, the oligomer which has a functional group which can harden | cure by irradiation of an active energy ray, for example, UV, can be selected and used, For example, a (meth) acrylate oligomer can be selected and used. . As used herein, the term (meth) acrylate oligomer may refer to an oligomer having at least one (meth) acryloyl group in a molecule. From the viewpoint of curability, an oligomer having at least two (meth) acryloyl groups in the molecule can be suitably used. As the (meth) acrylate oligomer, for example, an oligomer having 2 to 6, 2 to 4 or 2 (meth) acryloyl groups in the molecule may be used, but is not limited thereto.
상기 올리고머, 예를 들어, (메타)아크릴로일기를 갖는 올리고머의 주쇄 골격은 특별히 제한은 없지만, 예를 들면, 말단에 수산기 또는 카르복실기 등의 관능기를 가지는 폴리디엔 골격, 말단에 수산기 또는 카르복실기 등의 관능기를 가지지 않는 폴리디엔 골격, 폴리디엔의 수소 첨가물, 폴리에스테르, 디부틸렌글리콜, 폴리카보네이트 및 폴리에테르에서 선택되는 1종이상일 수 있다. 본 명세서에서 용어 폴리디엔은 두 개의 탄소-탄소 이중 결합을 갖는 단량체를 이용하여 제조된 폴리머를 의미하는 것으로서, 예를 들어, 폴리이소프렌, 폴리부타디엔, 스티렌-부타디엔, 에틸렌과 프로필렌의 공중합체(EPM) 또는 에틸렌, 프로필렌 및 비공액 디엔의 삼원중합체(EPDM)등이 예시될 수 있으나, 이에 제한되는 것은 아니다. 상기 올리고머의 하나의 구체적인 예로서, 수산기를 가지는 폴리 부타디엔 골격을 가지는 활성 에너지선 경화성 올리고머를 사용할 수 있으나, 이에 제한되는 것은 아니다.
The main chain skeleton of the oligomers, for example, oligomers having a (meth) acryloyl group, is not particularly limited. It may be at least one selected from a polydiene skeleton having no functional group, a hydrogenated product of polydiene, polyester, dibutylene glycol, polycarbonate and polyether. As used herein, the term polydiene refers to a polymer prepared by using a monomer having two carbon-carbon double bonds. For example, polyisoprene, polybutadiene, styrene-butadiene, a copolymer of ethylene and propylene (EPM ) Or terpolymers (EPDM) of ethylene, propylene and nonconjugated dienes, and the like. As one specific example of the oligomer, an active energy ray-curable oligomer having a polybutadiene skeleton having a hydroxyl group may be used, but is not limited thereto .
상기 (메타)아크릴레이트 올리고머는, 예를 들면, 우레탄계 (메타)아크릴레이트 올리고머, 폴리에스테르계 (메타)아크릴레이트 올리고머, 폴리에테르계 (메타)아크릴레이트 올리고머, 에폭시계 (메타)아크릴레이트 올리고머, 디엔 중합체계 (메타)아크릴레이트 올리고머 및 디엔 중합체계 (메타)아크릴레이트의 수소 첨가물의 주쇄를 갖는 올리고머로 이루어진 군으로부터 선택되는 1종 이상을 선택하여 사용할 수 있다. Examples of the (meth) acrylate oligomer include urethane-based (meth) acrylate oligomers, polyester-based (meth) acrylate oligomers, polyether-based (meth) acrylate oligomers, epoxy-based (meth) acrylate oligomers, One or more types selected from the group consisting of diene polymer-based (meth) acrylate oligomers and oligomers having a main chain of hydrogenated products of diene polymer-based (meth) acrylates can be selected and used.
우레탄계 (메타)아크릴레이트 올리고머는 예를 들면 분자 내에 우레탄 결합을 갖는 (메타)아크릴레이트 올리고머를 의미할 수 있다. 우레탄계 (메타)아크릴레이트 올리고머는 예를 들면 폴리부타디엔디올, 폴리에테르폴리올, 폴리에스테르폴리올, 폴리카보네이트디올 등과 폴리이소시아네이트의 반응에 따라 얻어지는 폴리우레탄 올리고머를 (메타)아크릴산으로 에스테르화함으로써 얻을 수 있다. 폴리부타디엔을 (메타)아크릴 변성하여 얻어지는 폴리부타디엔 변성 우레탄계 (메타)아크릴레이트도 우레탄계 (메타)아크릴레이트 올리고머에 포함된다. 수소 첨가한 폴리부타디엔을 (메타)아크릴 변성하여 얻어지는 수소 첨가 폴리부타디엔 변성 우레탄계 (메타)아크릴레이트도 우레탄계 (메타)아크릴레이트 올리고머에 포함된다. 우레탄계 (메타)아크릴레이트 올리고머로서는 1,2-폴리부타디엔 변성 우레탄계 (메타)아크릴레이트 올리고머, 폴리에스테르 우레탄계 (메타)아크릴레이트 올리고머, 디부틸렌글리콜 우레탄계 (메타)아크릴레이트 올리고머, 폴리카보네이트 우레탄계 (메타)아크릴레이트 올리고머, 폴리에테르 우레탄계 (메타)아크릴레이트 올리고머 등을 들 수 있다.The urethane-based (meth) acrylate oligomer may mean, for example, a (meth) acrylate oligomer having a urethane bond in the molecule. The urethane-based (meth) acrylate oligomer can be obtained by, for example, esterifying a polyurethane oligomer obtained by the reaction of polybutadienediol, polyether polyol, polyester polyol, polycarbonate diol and the like with polyisocyanate with (meth) acrylic acid. Polybutadiene-modified urethane type (meth) acrylate obtained by (meth) acryl modification of polybutadiene is also contained in a urethane type (meth) acrylate oligomer. Hydrogenated polybutadiene modified urethane type (meth) acrylate obtained by (meth) acryl modification of the hydrogenated polybutadiene is also contained in a urethane type (meth) acrylate oligomer. As urethane type (meth) acrylate oligomer, 1,2-polybutadiene modified urethane type (meth) acrylate oligomer, polyester urethane type (meth) acrylate oligomer, dibutylene glycol urethane type (meth) acrylate oligomer, polycarbonate urethane type (meth ) Acrylic oligomer, a polyether urethane type (meth) acrylate oligomer, etc. are mentioned.
폴리에스테르계 (메타)아크릴레이트 올리고머는 예를 들면 다가 카르본산과 다가 알코올의 축합에 의해 얻어지는 양 말단에 수산기를 갖는 폴리에스테르 올리고머의 수산기를 (메타)아크릴산으로 에스테르화함으로써, 또는 다가 카르본산에 알킬렌 옥사이드를 부가하여 얻어지는 올리고머의 말단 수산기를 (메타)아크릴산으로 에스테르화함으로써 얻을 수 있다.The polyester-based (meth) acrylate oligomer may be obtained by esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both terminals obtained by condensation of polyhydric carboxylic acid with a polyhydric alcohol, or with (meth) acrylic acid. The terminal hydroxyl group of the oligomer obtained by adding an alkylene oxide can be obtained by esterifying with (meth) acrylic acid.
폴리에테르계 (메타)아크릴레이트 올리고머는 예를 들면 폴리에테르폴리올의 수산기를 (메타)아크릴산으로 에스테르화함으로써 얻을 수 있다.A polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of a polyether polyol, for example with (meth) acrylic acid.
에폭시계 (메타)아크릴레이트 올리고머는 예를 들면 비교적 저분자량의 비스페놀형 에폭시 수지나 노볼락형 에폭시 수지의 옥시란환에 (메타)아크릴산을 반응하고 에스테르화함으로써 얻을 수 있다. 또한, 이 에폭시계 (메타)아크릴레이트 올리고머를 부분적으로 2염기성 카르본산 무수물로 변성한 카르복실 변성형 에폭시 (메타)아크릴레이트 올리고머도 이용할 수 있다.An epoxy-type (meth) acrylate oligomer can be obtained by reacting and esterifying (meth) acrylic acid with the oxirane ring of a bisphenol-type epoxy resin or a novolak-type epoxy resin of comparatively low molecular weight, for example. Moreover, the carboxyl modified type epoxy (meth) acrylate oligomer which modified | denatured this epoxy type (meth) acrylate oligomer partially by dibasic carboxylic anhydride can also be used.
디엔 중합체계 (메타)아크릴레이트 올리고머로서는 예를 들면 액상 스티렌-부타디엔 공중합체를 (메타)아크릴변성하여 얻어지는 SBR 디(메타)아크릴레이트, 폴리이소프렌을 (메타)아크릴 변성하여 얻어지는 폴리이소프렌디(메타)아크릴레이트 등을 들 수 있다.As a diene polymer type (meth) acrylate oligomer, polyisoprene (meth) obtained by (meth) acryl modification of SBR di (meth) acrylate and polyisoprene obtained by (meth) acryl modification of a liquid styrene butadiene copolymer, for example. ) Acrylates and the like.
디엔 중합체계 (메타)아크릴레이트의 수소 첨가물의 골격을 갖는 올리고머는 예를 들면 양 말단에 수산기를 갖는 수소 첨가 폴리부타디엔 또는 수소 첨가 폴리이소프렌의 수산기를 (메타)아크릴산으로 에스테르화함으로써 얻을 수 있다.The oligomer which has a skeleton of the hydrogenated substance of diene polymer type (meth) acrylate can be obtained by esterifying the hydroxyl group of hydrogenated polybutadiene or hydrogenated polyisoprene which has hydroxyl groups at both terminals, for example (meth) acrylic acid.
이러한 (메타)아크릴로일기를 갖는 올리고머는 1종을 단독으로 사용할 수 있고 또는 2종 이상을 조합하여 사용할 수 있다. 올리고머 중에서는 경화성 등의 관점에서 우레탄계 (메타)아크릴레이트 올리고머를 선택하여 사용할 수 있고, 특히 2관능 우레탄계 (메타)아크릴레이트 올리고머를 선택하여 사용할 수 있다. 2관능 우레탄계 (메타)아크릴레이트 올리고머란 우레탄계 (메타)아크릴레이트 올리고머의 1분자 중에 (메타)아크릴로일기가 2개 포함되어 있는 것을 의미할 수 있다. The oligomer which has such a (meth) acryloyl group can be used individually by 1 type, or can be used in combination of 2 or more type. In an oligomer, a urethane type (meth) acrylate oligomer can be selected and used from a viewpoint of sclerosis | hardenability, etc., In particular, a bifunctional urethane type (meth) acrylate oligomer can be selected and used. A bifunctional urethane type (meth) acrylate oligomer can mean that two (meth) acryloyl groups are contained in 1 molecule of a urethane type (meth) acrylate oligomer.
2관능 우레탄계 (메타)아크릴레이트 올리고머는 폴리우레탄 올리고머를 (메타)아크릴산으로 에스테르화함으로써 얻을 수 있다. 폴리우레탄 올리고머는 분자 내에 히드록시기 2개를 갖는 폴리에테르폴리올, 폴리에스테르 폴리올, 폴리카보네이트디올 등과 폴리이소시아네이트의 반응에 의해 얻을 수 있다.A bifunctional urethane type (meth) acrylate oligomer can be obtained by esterifying a polyurethane oligomer with (meth) acrylic acid. Polyurethane oligomer can be obtained by reaction of polyisocyanate with polyether polyol, polyester polyol, polycarbonate diol, etc. which have two hydroxyl groups in a molecule | numerator.
히드록시기 2개를 갖는 폴리에테르폴리올로서는 예를 들면 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌글리콜(폴리부틸렌글리콜), 폴리헥사메틸렌글리콜, 1,3-부틸렌글리콜, 1,4-부틸렌글리콜, 네오펜틸글리콜, 시클로헥산디메탄올, 2,2-비스(4-히드록시시클로헥실)프로판, 비스페놀A 등에 에틸렌 옥사이드 또는 프로필렌 옥사이드 등이 부가된 화합물 등을 이용할 수 있다.Examples of the polyether polyol having two hydroxyl groups include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), polyhexamethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol Neopentylglycol, cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, bisphenol A, or the like, or a compound in which ethylene oxide or propylene oxide is added.
히드록시기 2개를 갖는 폴리에스테르 폴리올은 예를 들면 알코올 성분과 산 성분을 반응시켜 얻을 수 있다. 히드록시기 2개를 갖는 폴리에스테르 폴리올은 예를 들면 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌글리콜(폴리부틸렌글리콜), 1,3-부틸렌글리콜, 1,4-부틸렌글리콜, 1,6-헥산디올, 네오펜틸글리콜, 1,4-시클로헥산디메탄올, 2,2-비스(4-히드록시시클로헥실)프로판, 비스페놀A 등에 에틸렌 옥사이드 또는 프로필렌 옥사이드 등이 부가된 화합물 혹은 ε-카프로락톤이 부가된 화합물 등을 알코올 성분으로 하고, 아디핀산, 세바신산, 아젤라인산, 도데칸디카르본산 등의 2염기산 및 그 무수물을 산 성분으로 하며, 알코올 성분과 산 성분을 반응시켜 사용할 수 있다. 상기 알코올 성분, 산 성분 및 ε-카프로락톤의 삼자를 동시에 반응시킴으로써 얻어지는 화합물도 폴리에스테르 폴리올로서 사용할 수 있다.The polyester polyol which has two hydroxyl groups can be obtained, for example by making an alcohol component and an acid component react. Polyester polyols having two hydroxyl groups are, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), 1,3-butylene glycol, 1,4-butylene glycol, 1,6- Ε-caprolactone or a compound in which ethylene oxide or propylene oxide is added to hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, bisphenol A, or the like The added compound may be used as an alcohol component, dibasic acids such as adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid, and anhydrides thereof as an acid component, and the alcohol component and the acid component may be reacted with each other. The compound obtained by making the said alcohol component, an acid component, and (epsilon) -caprolactone three react simultaneously simultaneously can be used as a polyester polyol.
우레탄계 (메타)아크릴레이트 올리고머의 중량 평균 분자량이나 수평균 분자량은 핸들링성 등의 관점에서 예를 들면 500 내지 100000 또는 1000 내지 50000 범위 내에 있을 수 있다. 이 값은 특별히 한정되지 않으며, 예를 들면 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 20000, 30000, 40000, 50000 또는 100000 일 수 있다. 이러한 평균 분자량은 겔 투과 크로마토그래피(GPC)법에 의해 측정되는 표준 폴리스티렌 환산의 값이다.The weight average molecular weight or the number average molecular weight of the urethane-based (meth) acrylate oligomer may be, for example, in the range of 500 to 100000 or 1000 to 50000 in view of handling properties. This value is not particularly limited, and may be, for example, 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 20000, 30000, 40000, 50000 or 100000. This average molecular weight is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
상기 활성 에너지선 경화성 올리고머의 함량은, 상기 수식 1의 관계를 만족하는 경화성 조성물을 제조한다는 측면에서, 경화성 조성물 내에, 예를 들면, 10 중량% 이상, 11 중량% 이상, 12 중량% 이상, 13 중량% 이상, 14 중량% 또는 15 중량% 이상으로 포함될 수 있고, 20 중량% 이하, 19 중량% 이하, 18 중량% 이하, 17 중량% 이하, 16 중량% 이하 또는 15 중량% 이하의 비율로 포함될 수 있다. The amount of the active energy ray-curable oligomer is, in terms of producing a curable composition that satisfies the relationship of the formula 1, in the curable composition, for example, 10% by weight, 11% by weight, 12% by weight, 13 May be included in an amount of at least 20% by weight, at least 14% by weight, or at least 15% by weight, and at most 20% by weight, 19% by weight, 18% by weight, 17% by weight, 16% by weight or 15% by weight. Can be.
경화성 조성물은, 또한, 광중합 개시제를 추가로 포함할 수 있다. 이러한 광중합 개시제로는, 활성 에너지선 경화성 올리고머, 예를 들면, (메타)아크릴레이트 올리고머의 중합을 개시할 수 있는 것이면 특별한 제한없이 사용할 수 있고, 예를 들면, 자외선 중합 개시제나 가시광 중합 개시제 등을 사용할 수 있다. 자외선 중합 개시제로서는, 예를 들면, 벤조인계, 벤조페논계, 아세토페논계 등을 사용할 수 있고, 가시광 중합 개시제로서는, 예를 들면, 아실포스핀옥사이드계, 티옥산톤계, 메탈로센계, 퀴논계, α-아미노알킬페논계 등을 사용할 수 있다. 구체적으로, 광중합 개시제로서, 벤조페논, 4-페닐벤조페논, 벤조일 안식향산, 2,2-디에톡시아세토페논, 비스디에틸아미노벤조페논, 벤질, 벤조인, 벤조일이소프로필에테르, 벤질디메틸케탈, 1-히드록시시클로헥실페닐케톤, 티옥산톤, 2-메틸티옥산톤, 2,4-디메틸티옥산톤, 이소프로필티옥산톤, 2,4-디에틸티옥산톤, 2,4-디이소프로필티옥산톤, 1-(4-이소프로필페닐)2-히드록시-2-메틸프로판-1-온, 1-(4-(2-히드록시에톡시)-페닐)-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온, 캠퍼퀴논, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2-메틸-1-(4-(메틸티오)페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-1-부타논-1,2-디메틸아미노-2-(4-메틸-벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸-펜틸포스핀옥사이드 등을 사용할 수 있으나, 이에 제한되는 것은 아니다. The curable composition may further include a photopolymerization initiator. As such a photoinitiator, as long as it can start superposition | polymerization of an active energy ray curable oligomer, for example, a (meth) acrylate oligomer, it can use without a restriction | limiting, For example, an ultraviolet-ray polymerization initiator, a visible light polymerization initiator, etc. can be used. Can be used. As the ultraviolet polymerization initiator, for example, benzoin, benzophenone, acetophenone and the like can be used. As the visible light polymerization initiator, for example, acyl phosphine oxide, thioxanthone, metallocene and quinone. , α-aminoalkylphenone series and the like can be used. Specifically, as a photopolymerization initiator, benzophenone, 4-phenylbenzophenone, benzoyl benzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyl dimethyl ketal, 1 -Hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso Propylthioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy- 2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -1-butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -Butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like can be used, but is not limited thereto.
예시적인 경화성 조성물은, 또한 러버(rubber) 성분을 추가로 포함할 수 있다. 상기 러버 성분은 폴리디엔을 포함할 수 있다. 상기 러버 성분으로는, 예를 들면, 폴리이소프렌 골격 또는 폴리부타디엔 골격, 스티렌-부타디엔 골격를 가지는 화합물, 에틸렌과 프로필렌의 공중합체(EPM) 또는 에틸렌, 프로필렌 및 비공액 디엔의 삼원공중합체(EPDM) 등을 사용할 수 있으나, 이에 제한되는 것은 아니다. Exemplary curable compositions may further include a rubber component. The rubber component may comprise polydiene. As the rubber component, for example, a compound having a polyisoprene skeleton or a polybutadiene skeleton, a styrene-butadiene skeleton, a copolymer of ethylene and propylene (EPM) or a terpolymer of ethylene, propylene, and nonconjugated diene (EPDM) May be used, but is not limited thereto.
하나의 예시에서, 상기 러버 성분은 말단에 수산기 또는 카르복실기와 같은 관능기를 가질 수 있다. 하나의 예로, 상기 러버 성분으로는 예를 들어 말단에 수산기 또는 카르복실기와 같은 관능기를 가지는 폴리디엔이 사용될 수 있다. 상기 러버 성분의 구체적인 예로, 수산기를 가지는 폴리 부타디엔 러버를 사용할 수 있으나, 이에 제한되는 것은 아니다. 또한, 상기 러버 성분의 중량평균분자량은 본 출원의 목적을 손상시키지 않는 범위 내에서 적절히 선택될 수 있고, 예를 들어, 약 1,000 내지 약 10,000, 약 1,000 내지 약 5,000 또는 약 2,000 내지 3,000의 범위 내일 수 있으나, 이에 제한되는 것은 아니다.In one example, the rubber component may have a functional group such as a hydroxyl group or a carboxyl group at the terminal. As one example, as the rubber component, for example, polydiene having a functional group such as a hydroxyl group or a carboxyl group may be used. As a specific example of the rubber component, a polybutadiene rubber having a hydroxyl group may be used, but is not limited thereto. In addition, the weight average molecular weight of the rubber component may be appropriately selected within a range that does not impair the purpose of the present application, for example, in the range of about 1,000 to about 10,000, about 1,000 to about 5,000 or about 2,000 to 3,000 May be, but is not limited thereto.
경화성 조성물 내의 러버 성분의 함량은, 예를 들면, 50 중량% 이상, 52 중량% 이상, 54 중량% 이상, 56 중량% 이상, 58 중량% 또는 60 중량% 이상으로 포함될 수 있고, 70 중량% 이하, 68 중량% 이하, 66 중량% 이하, 64 중량% 이하, 62 중량% 이하 또는 60 중량% 이하로 포함될 수 있다. 경화성 조성물이 상기 러버 성분을 상기 비율로 포함하는 경우 상기 수식 1의 조건을 만족하는 경화성 조성물을 제공하는데 유리하다. The content of the rubber component in the curable composition may be included, for example, at least 50 wt%, at least 52 wt%, at least 54 wt%, at least 56 wt%, at least 58 wt% or at least 60 wt%, and at most 70 wt%. , Up to 68 wt%, up to 66 wt%, up to 64 wt%, up to 62 wt% or up to 60 wt%. When the curable composition includes the rubber component in the above ratio, it is advantageous to provide a curable composition that satisfies the condition of Formula 1.
예시적인 경화성 조성물은, 활성 에너지 경화성 올리고머, 예를 들면, (메타)아크릴레이트 올리고머의 반응성 조절 및 희석의 목적으로 상기 올리고머 이외에 모노머를 추가로 더 포함할 수 있다. 이러한 모노머의 함량은, 경화성 조성물 내에, 예를 들면, 10 중량% 이상, 12 중량% 이상, 14 중량% 이상, 16 중량% 이상, 18 중량% 또는 20 중량% 이상으로 포함될 수 있고, 30 중량% 이하, 28 중량% 이하, 26 중량% 이하, 24 중량% 이하, 22 중량% 이하 또는 20 중량% 이하로 포함될 수 있다. Exemplary curable compositions may further comprise monomers in addition to the oligomers for the purpose of regulating and diluting active energy curable oligomers, for example, (meth) acrylate oligomers. The content of such monomers may be included in the curable composition, for example, at least 10 weight percent, at least 12 weight percent, at least 14 weight percent, at least 16 weight percent, at least 18 weight percent, or at least 20 weight percent, and at least 30 weight percent. Or less, 28 wt% or less, 26 wt% or less, 24 wt% or less, 22 wt% or less, or 20 wt% or less.
상기 모노머로는, 예를 들면, (메타)아크릴레이트 모노머를 사용할 수 있고, 구체적으로 단관능 (메타)아크릴레이트나 2관능, 3관능, 4관능, 5관능, 6관능 등의 다관능 (메타)아크릴레이트 등 다양하게 사용할 수 있고, 예를 들면, 단관능 (메타)아크릴레이트 또는 2관능 (메타)아크릴레이트를 선택하여 사용할 수 있다. As said monomer, a (meth) acrylate monomer can be used, for example, and polyfunctional (meth), such as monofunctional (meth) acrylate and bifunctional, trifunctional, tetrafunctional, 5-functional, and 6 functional, etc. ) Acrylate, etc. can be used variously, For example, monofunctional (meth) acrylate or bifunctional (meth) acrylate can be selected and used.
단관능(메타)아크릴레이트로는, 예를 들면, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 테트라히드로푸르푸릴 (메타)아크릴레이트, 카프로락톤 변성 테트라히드로푸르푸릴 (메타)아크릴레이트, 시클로헥실 (메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 벤질 (메타)아크릴레이트, 페닐 (메타)아크릴레이트, 페녹시에틸 (메타)아크릴레이트, 페녹시디에틸렌글리콜 (메타)아크릴레이트, 페녹시테트라에틸렌글리콜 (메타)아크릴레이트, 페녹시폴리에틸렌글리콜 (메타)아크릴레이트, 노닐페녹시에틸 (메타)아크릴레이트, 노닐페녹시테트라에틸렌글리콜 (메타)아크릴레이트, 메톡시디에틸렌글리콜 (메타)아크릴레이트, 에톡시디에틸렌글리콜 (메타)아크릴레이트, 부톡시에틸 (메타)아크릴레이트, 부톡시트리에틸렌글리콜 (메타)아크릴레이트, 2-에틸헥실폴리에틸렌글리콜 (메타)아크릴레이트, 노닐페닐폴리프로필렌글리콜 (메타)아크릴레이트, 메톡시디프로필렌글리콜(메타)아크릴레이트, 글리시딜 (메타)아크릴레이트, 글리세롤 (메타)아크릴레이트, 폴리에틸렌글리콜 (메타)아크릴레이트, 폴리프로필렌글리콜 (메타)아크릴레이트, 에피클로로히드린(이하, ECH라고 약기) 변성 부틸 (메타)아크릴레이트, 에피클로로히드린(이하, ECH라고 약기) 변성 페녹시 (메타)아크릴레이트, 에틸렌옥사이드(이하, EO라고 약기) 변성 프탈산 (메타)아크릴레이트, EO 변성 호박산 (메타)아크릴레이트, 카프로락톤 변성 2-히드록시에틸 (메타)아크릴레이트, N,N-디메틸아미노에틸 (메타)아크릴레이트, N,N-디에틸아미노에틸 (메타)아크릴레이트, 모르폴리노 (메타)아크릴레이트, EO 변성 인산 (메타)아크릴레이트 등을 들 수 있다. 이미드 (메타)아크릴레이트(제품명: M-140, 토아합성사 제품)와 같은 이미드기를 갖는 (메타)아크릴레이트 등을 들 수 있다.As monofunctional (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl ( Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxyethyl ( Meta) acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth ) Acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydipropylene Glycol (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, epichlorohydrin (hereinafter, ECH) Modified butyl (meth) acrylate, epichlorohydrin (hereinafter abbreviated as ECH) modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (meth) acrylate, EO modified succinic acid ( Meta) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (Meth) acrylate, morpholino (meth) acrylate, EO modified phosphoric acid (meth) acrylate, etc. are mentioned. (Meth) acrylate etc. which have an imide group like imide (meth) acrylate (a brand name: M-140, the product made by Toa Synthetics) are mentioned.
다관능 (메타)아크릴레이트로서는 디(메타)아크릴화 이소시아누레이트, 트리(메타)아크릴화 이소시아누레이트, 1,3-디부틸렌글리콜 디(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올 디(메타)아크릴레이트, 1,9-노난디올 디(메타)아크릴레이트, EO(에틸렌옥사이드) 변성 비스페놀A 디(메타)아크릴레이트, 디에틸렌글리콜 디(메타)아크릴레이트, ECH(에피클로로히드린)변성 헥사히드로프탈산 디(메타)아크릴레이트, 네오펜틸글리콜 디(메타)아크릴레이트, EO 변성 네오펜틸글리콜디(메타)아크릴레이트, 카프로락톤 변성 히드록시피바린산 에스테르 네오펜틸글리콜 디(메타)아크릴레이트, 스테아린산 변성 펜타에리스리톨 디(메타)아크릴레이트, ECH 변성 프탈산 디아크릴레이트, 폴리(에틸렌글리콜-테트라메틸렌글리콜) 디(메타)아크릴레이트, 폴리에틸렌글리콜 디(메타)아크릴레이트, 폴리프로필렌글리콜 디(메타)아크릴레이트, ECH 변성 프로필렌글리콜 디(메타)아크릴레이트, 트리시클로데칸디메탄올(메타)아크릴레이트, 트리프로필렌글리콜 디(메타)아크릴레이트, 트리글리세롤 디(메타)아크릴레이트, ECH 변성글리세롤 트리(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, EO 변성 인산 트리(메타)아크릴레이트, 트리메티롤프로판 트리(메타)아크릴레이트, 카프로락톤 변성 트리메티롤프로판 트리(메타)아크릴레이트,EO 변성 트리메티롤프로판 트리(메타)아크릴레이트, P0 변성 트리메티롤프로판 트리(메타)아크릴레이트, 트리스((메타)아크릴록시에틸) 이소시아누레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 펜타에리스리톨에톡시 테트라(메타)아크릴레이트를 들 수 있다.As the polyfunctional (meth) acrylate, di (meth) acrylated isocyanurate, tri (meth) acrylated isocyanurate, 1,3-dibutylene glycol di (meth) acrylate, 1,4-butanedioldi ( Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO (ethylene oxide) modified bisphenol A di (meth) acrylate, diethylene glycol di (Meth) acrylate, ECH (epichlorohydrin) modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, caprolactone modified hydroxide Oxypibaric acid ester neopentylglycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid diacrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate , Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, tripropylene glycol di (meth) Acrylate, triglycerol di (meth) acrylate, ECH modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO modified phosphoric acid tri (meth) acrylate, trimetholpropane tri (meth) acrylic Latex, caprolactone modified trimetholpropane tri (meth) acrylate, EO modified trimetholpropane tri (meth) acrylate, P0 modified trimetholpropane tri (meth) acrylate, tris ((meth) acryloxyethyl Isocyanurate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerys The toll may be mentioned ethoxy tetra (meth) acrylate.
경화성 조성물은, 피착체에 대한 밀착력, 예를 들면, 유리에 대한 밀착력을 향상시키기 위하여 공지의 실란 커플링제를 추가로 포함할 수 있다. 또한, 경화성 조성물은, 공기에 접하고 있는 부분의 경화를 촉진하기 위하여 공지의 파라핀류를 추가로 포함할 수 있다. 또한, 경화성 조성물은, 저장 안정성을 유지하는 목적으로 중합 금지제를 포함하는 공지의 산화 방지제 등을 추가로 포함할 수 있다. 또한, 경화성 조성물은 이들 이외에도 목적하는 용도에 따라 엘라스토머, 가소제, 충전제, 착색제 또는 방정체 등의 공지의 첨가제를 추가로 포함할 수 있다. The curable composition may further include a known silane coupling agent in order to improve the adhesion to the adherend, for example, the adhesion to glass. Moreover, curable composition may further contain well-known paraffins in order to accelerate hardening of the part which contact | connects air. The curable composition may further include a known antioxidant including a polymerization inhibitor for the purpose of maintaining storage stability. In addition, the curable compositions may further include known additives such as elastomers, plasticizers, fillers, colorants, or crystals, depending on the intended use.
본 출원은, 또한, 경화체에 관한 것이다. 예시적인 경화체는 하기 수식 1의 관계를 만족할 수 있다. This application also relates to a cured product. Exemplary cured bodies may satisfy the relationship of Equation 1 below.
[수식 1][Equation 1]
수식 1에서 A는 경화체의 1 MHz에서의 유전상수이고, B는 경화체의 겔분율(%)이며, C는 경화체의 수축율(%)이고, D는 경화체의 저장 탄성률(Pa)이다. In Equation 1, A is the dielectric constant at 1 MHz of the cured product, B is the gel fraction (%) of the cured product, C is the shrinkage percentage (%) of the cured product, and D is the storage modulus (Pa) of the cured product.
예시적인 경화체는, 예를 들면, 상기 경화성 조성물을 경화된 상태로 포함할 수 있다, 본 명세서에서 「경화된 상태」란, 상기 조성물에 포함되는 성분들이 가교 반응 또는 중합 반응 등을 거쳐서 조성물이 하드(hard)한 상태로 전환된 경우를 의미할 수 있다. 상기 경화체의 수식 1에서 유전상수, 겔분율, 수축율 및 저장 탄성률에 대한 구체적인 내용은 상기 경화성 조성물의 항목에서 기술한 유전상수, 겔분율, 수축율 및 저장 탄성률에 대한 내용이 동일하게 적용될 수 있다. Exemplary cured bodies may include, for example, the curable composition in a cured state. In the present specification, the "cured state" means that the components contained in the composition undergo a crosslinking reaction, a polymerization reaction, or the like. This may mean a case where the state is converted into a hard state. Specific information on the dielectric constant, gel fraction, shrinkage and storage modulus in Equation 1 of the cured body may be equally applicable to the dielectric constant, gel fraction, shrinkage and storage modulus described in the item of the curable composition.
예시적인 경화체는 상기 경화성 조성물을 경화시켜 제조할 수 있다. 상기 경화 방법은 특별히 한정되지 않으며, 경화성 조성물의 항목에서 기술한 활성 에너지선 경화성 올리고머의 가교 반응이 진행될 수 있도록 적정 온도에서 조성물을 유지하는 방식이나 중합 반응이 진행될 수 있도록 적절한 활성 에너지선을 조사하는 공정을 통하여 경화시킬 수 있다. 적정 온도에서의 유지 및 활성 에너지선의 조사가 동시에 요구되는 경우, 상기 공정은 순차적 또는 동시에 진행될 수 있다. 상기에서 활성 에너지선의 조사는, 예를 들면, 고압수은 램프, 무전극 램프 또는 크세논 램프(xenon lamp) 등을 사용하여 수행할 수 있으며, 조사되는 활성 에너지선의 파장이나 광량 등의 조건은 상기 활성 에너지선 경화성 올리고머의 가교 또는 중합이 적절히 이루어질 수 있는 범위에서 선택될 수 있다.Exemplary cured bodies can be prepared by curing the curable composition. The curing method is not particularly limited, and a method of maintaining the composition at an appropriate temperature or irradiating an appropriate active energy ray such that the polymerization reaction may proceed so that the crosslinking reaction of the active energy ray curable oligomer described in the section of the curable composition may proceed. It can be hardened through the process. If the maintenance at the appropriate temperature and the irradiation of the active energy ray is required at the same time, the process can be carried out sequentially or simultaneously. The irradiation of the active energy ray may be performed using, for example, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like, and the conditions such as the wavelength and the amount of light of the active energy ray to be irradiated may be the active energy. The crosslinking or polymerization of the precurable oligomer may be selected within a range that can be appropriately made.
본 출원은, 또한, 상기 경화성 조성물 또는 경화체의 용도에 관한 것이다. 상기 경화성 조성물 또는 경화체는 저 유전율을 나타내면서도 접착 특성이 우수하므로 디스플레이 장치의 다양한 광학 부재의 접합을 위한 용도로 유용하게 사용될 수 있다. 예를 들면, 경화성 조성물 또는 경화체는 표시체와 광학 기능 재료를 접합하기 위하여 사용될 수 있다. 이러한 표시체는, 예를 들면, 유리에 대한 편광판이 부착되어 있는 LCD(Liquid Crystal Display), EL(Electroluminescence) 디스플레이 장치, EL 조명, 전자 페이퍼나 플라즈마 디스플레이 등의 표시 소자일 수 있다. 광학 기능 재료로는, 시인성 향상이나 외부 충격으로부터 표시 소자의 깨짐 방지를 목적으로 하는 아크릴판 (예를 들면, 일측면 또는 양면에 하드 코팅 처리나 반사 방지 코팅을 처리할 수 도 있음), PC(Polycarbonate) 판, PET(Polyethylene terephthalate) 판, PEN(Polyethylene naphthalate) 판 등의 투명 플라스틱 판, 강화 유리(예를 들면, 비산 방지 필름이 부착되어 있을 수도 있음) 또는 터치 패널 입력 센서 등을 예로 들 수 있다. This application also relates to the use of the curable composition or cured product. Since the curable composition or the cured product exhibits low dielectric constant and excellent adhesive properties, it may be usefully used for bonding various optical members of the display device. For example, the curable composition or cured body can be used to bond the indicator and the optically functional material. Such a display body may be, for example, a display element such as an LCD (Liquid Crystal Display), an EL (Electroluminescence) display device, an EL illumination, an electronic paper or a plasma display, to which a polarizing plate for glass is attached. As the optically functional material, an acrylic plate (for example, a hard coating or an antireflective coating may be applied to one or both surfaces) or a PC (for example, to improve visibility or to prevent cracking of a display element from external impact) Examples include a transparent plastic plate such as a polycarbonate (PET) plate, a polyethylene terephthalate (PET) plate, and a polyethylene naphthalate (PEN) plate, tempered glass (for example, a shatterproof film may be attached), or a touch panel input sensor. have.
상기 경화성 조성물 또는 경화체는, 또한, 예를 들면, 정전 용량식 터치 패널에서, 투명 전극이 형성되어 있는 투명 기판과 투명판을 접합하기 위한 용도로 유용하게 사용될 수 있다. 이러한 투명 기판의 재질은, 예를 들면, PC, PMMA(Polymethyl methacrylate), PC와 PMMA의 복합체, COC(Cyclo-Olefin Copolymer), COP(Cyclo-Olefin Polymer) 일 수 있다. 투명판의 재질은, 예를 들면, 유리, PC, PMMA, PC와 PMMA의 복합체 COC 또는 COP 등일 수 있다.The curable composition or cured product may also be usefully used for bonding a transparent substrate and a transparent plate on which a transparent electrode is formed, for example, in a capacitive touch panel. The material of the transparent substrate may be, for example, PC, polymethyl methacrylate (PMMA), a composite of PC and PMMA, cyclo-olefin copolymer (COC), cyclo-olefin polymer (COP). The material of the transparent plate may be, for example, glass, PC, PMMA, composite COC or COP of PC and PMMA.
상기 경화성 조성물 또는 경화체는, 또한, 예를 들면, 터치 패널과 상기 터치 패널 상의 시트 또는 판을 접합하기 위한 용도로 유용하게 사용할 수 있다. 이러한 시트로는, 예를 들면, 아이콘 시트, 보호 시트, 화장 시트 등일 수 있고, 시트의 재질은, 예를 들면, PET, PC, COC 또는 COP 등일 수 있다. 판으로는, 화장판 또는 보호판 등을 예로 들 수 있고, 판의 재질은, 예를 들면, PET 유리, PC, PMMA, PC와 PMMA의 복합체, COC 또는 COP 등일 수 있다. 이러한 시트 또는 판과 접합하는 터치 패널의 재질은, 예를 들면, 유리, PET, PC, PMMA, PC와 PMMA의 복합체, COC 또는 COP 등일 수 있다. The said curable composition or hardened | cured material can also be usefully used for the use for bonding a touch panel and the sheet | seat or plate on the said touch panel, for example. The sheet may be, for example, an icon sheet, a protective sheet, a makeup sheet, or the like, and the material of the sheet may be, for example, PET, PC, COC, or COP. Examples of the plate include a decorative plate or a protective plate, and the material of the plate may be, for example, PET glass, PC, PMMA, a composite of PC and PMMA, COC, or COP. The material of the touch panel bonded to the sheet or plate may be, for example, glass, PET, PC, PMMA, a composite of PC and PMMA, COC, or COP.
상기 경화성 조성물 또는 경화체는, 또한, 예를 들면, 디스플레이 장치의 터치 패널과 표시 패널의 접합(Direct Bonding)을 위한 용도로 유용하게 사용될 수 있다. 도 1 은 표시 패널(101) 및 터치 패널(102)을 포함하고 상기 표시 패널(101)과 터치 패널(102)이 상기 경화성 조성물 또는 경화체(103)에 의하여 접합되어 있는 디스플레이 장치를 예시적으로 나타낸다. The curable composition or the cured product may also be usefully used, for example, for direct bonding of a touch panel and a display panel of a display device. FIG. 1 exemplarily illustrates a display device including a display panel 101 and a touch panel 102, and the display panel 101 and the touch panel 102 are bonded by the curable composition or the cured body 103. .
상기 경화성 조성물 또는 경화체는, 또한, 예를 들면, 디스플레이 장치에 있어서 스페이서에 의해 이격되어 있는 광학 기능 재료와 표시 패널 사이의 이격된 공간을 충진하는 용도로도 유용하게 사용될 수 있다. 도 2는 상기 광학 기능 재료가 터치 패널인 디스플레이 장치를 예시적으로 나타낸다. 도 2를 참고하면, 디스플레이 장치는 표시 패널(201), 터치 패널(202) 및 상기 표시 패널과 터치 패널을 이격시키고 있는 스페이서(203) 를 포함할 수 있고, 이 경우에 상기 표시 패널과 터치 패널이 이격된 공간, 소위 에어갭의 공간을 상기 경화성 조성물 또는 경화체(204)가 충진하고 있는 구조를 가질 수 있다. The curable composition or the cured product may also be usefully used for filling a space spaced between the optical functional material spaced by a spacer and a display panel, for example, in a display device. 2 exemplarily shows a display device in which the optical functional material is a touch panel. Referring to FIG. 2, the display device may include a display panel 201, a touch panel 202, and a spacer 203 spaced apart from the display panel. In this case, the display panel and the touch panel may be disposed. This spaced space, a so-called air gap space may have a structure in which the curable composition or the cured body 204 is filled.
상기 디스플레이 장치에 경화성 조성물 또는 경화체가 적용될 경우에, 상기 장치를 구성하는 다른 부품이나 그 장치의 구성 방법은 특별히 제한되지 않고, 상기 경화성 조성물 또는 경화체가 사용되는 한, 해당 분야에서 공지되어 있는 임의의 재료나 방식이 모두 채용될 수 있다. When the curable composition or cured product is applied to the display device, other components constituting the device or a method of constituting the device are not particularly limited, and any known in the art may be used as long as the curable composition or cured product is used. Both materials and methods may be employed.
본 출원의 예시적인 경화성 조성물은 저 유전율을 나타내면서 접착 특성이 우수한 경화체를 제조할 수 있으므로, 디스플레이 장치의 다양한 광학 기능 부재의 접합, 예를 들면, 터치 패널과 표시 패널의 접합 (Directing Bonding)에 유용하게 사용될 수 있다. Exemplary curable compositions of the present application can produce a cured product exhibiting low dielectric constant and excellent adhesive properties, and thus are useful for bonding various optical functional members of a display device, for example, bonding a touch panel and a display panel. Can be used.
도 1 및 2는 본 출원의 예시적인 디스플레이장치의 모식도이다.1 and 2 are schematic views of an exemplary display device of the present application.
도 3은 배경기술과 관련된 디스플레이장치의 모식도이다. 3 is a schematic diagram of a display device related to the background art.
이하, 본 출원에 따른 실시예를 통하여 상기 경화성 조성물을 보다 구체적으로 설명하지만, 본 출원의 범위가 하기 제시된 실시예에 의해 제한되는 것은 아니다.Hereinafter, the curable composition will be described in more detail through Examples according to the present application, but the scope of the present application is not limited to the Examples given below.
실시예 및 비교예의 저장 탄성률, 수축율, 겔 분율 및 유전 상수는 하기 방법에 의하여 측정하였다. The storage modulus, shrinkage, gel fraction and dielectric constant of Examples and Comparative Examples were measured by the following method.
1. 저장 탄성률 측정1. Measurement of storage modulus
실시예 및 비교예에서 제조된 경화체를 직경 8 mm 및 두께 1 mm의 크기로 절단하여 원형 샘플을 제조한 후, ARES(Advanced Rheometrics Expansion System) 장치를 사용하여 Frequency Sweep mode로 1 Hz 주파수에서 저장 탄성률을 측정하였다. After the cured product prepared in Examples and Comparative Examples were cut to a size of 8 mm in diameter and 1 mm in thickness to prepare a circular sample, storage elastic modulus at 1 Hz frequency in Frequency Sweep mode using ARES (Advanced Rheometrics Expansion System) device. Was measured.
2. 2.
수축율Shrinkage
측정 Measure
실시예 및 비교예에서 제조된 경화체를 직경 2.5 mm 및 두께 1 mm의 크기로 절단하여 원형 샘플을 제조한 후, 경화 전후의 비중을 측정하여 하기 수식에 따라 수축율을 계산하였다.After the cured product prepared in Examples and Comparative Examples were cut to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, the specific gravity before and after curing was measured, and the shrinkage ratio was calculated according to the following formula.
3. 겔 분율 측정3. Gel fraction measurement
실시예 및 비교예에서 제조된 경화체를 직경 2.5 mm 및 두께 1 mm의 크기로 절단하여 원형 샘플을 제조한 후, 이를 과량의 에틸아세테이트(Ethyl acetate)에 침적시키고 24시간 동안 방치하여 경화되지 않은 부분을 녹여 거름망을 이용하여 거른 후, 분리된 불용해분을 약 150℃ 오븐에서 약 30분 내지 1시간 동안 건조하여 건조 전후 질량 변화를 측정한 값을 기초로 겔 분율을 계산하다.The cured product prepared in Examples and Comparative Examples was cut to a size of 2.5 mm in diameter and 1 mm in thickness to prepare a circular sample, which was then immersed in an excess of ethyl acetate and left for 24 hours to leave uncured portion. After dissolving and filtering using a strainer, the separated insoluble fraction was dried in an oven at about 150 ° C. for about 30 minutes to 1 hour to calculate a gel fraction based on the measured mass change before and after drying.
4. 유전 상수 측정4. Dielectric constant measurement
실시예 및 비교예에서 제조된 경화체를 이용하여, 2 cm x 2 cm (가로 x 세로)의 크기를 가지는 동판/경화체/동판 적층 구조의 규격 시편을 제작한 후, Agilent 4294A Precision impedance Analyzer를 사용하여 유전율을 측정하였고, 진공 상태에서의 상기 시편의 유전율에 대한 값을 계산하여 유전 상수를 측정하였다.Using the cured bodies prepared in Examples and Comparative Examples, a standard specimen of a copper / hardened body / copper laminated structure having a size of 2 cm × 2 cm (width × length) was fabricated, and then the Agilent 4294A Precision Impedance Analyzer was used. The dielectric constant was measured and the dielectric constant was measured by calculating the value for the dielectric constant of the specimen in vacuum.
실시예Example
1. One.
경화성 조성물의 제조Preparation of Curable Compositions
올리고머로서, 수산기를 가지는 폴리 부타디엔 러버를 포함하고 중량 평균 분자량이 15,000인 폴리 우레탄 아크릴레이트(이하, 올리고머 A) 18g 및 수산기를 가지는 폴리 부타디엔 러버를 포함하고 중량 평균 분자량이 10,000인 폴리 우레탄 아크릴레이트(이하, 올리고머 B) 2g, 러버 성분으로서, 수산기를 가지고 중량 평균 분자량이 2,000인 폴리 부타디엔 러버(이하, 러버 A) 60g, 모노머로서, Isobonyl acrylate 20 중량부 및 광중합 개시제로서, Darocur TPO 1g를 균일하게 혼합하여 경화성 조성물을 제조하였다.As the oligomer, a polyurethane acrylate comprising a polybutadiene rubber having a hydroxyl group and having a weight average molecular weight of 15,000 (hereinafter oligomer A) 18 g and a polybutadiene rubber having a hydroxyl group and having a weight average molecular weight of 10,000 ( Hereinafter, 2 g of oligomer B), 60 g of polybutadiene rubber (hereinafter referred to as rubber A) having a hydroxyl group as a rubber component and having a weight average molecular weight of 2,000, 20 parts by weight of isobonyl acrylate as a monomer, and 1 g of Darocur TPO as a photopolymerization initiator Mixing produced a curable composition.
경화체의Cured
제조 Produce
상기 제조된 경화성 조성물을 유리 기재 상에 약 0.2 mm로 도포한 후 약 365 nm 내지 400 nm의 장파장대의 UV를 LED 또는 metal-halide lamp를 이용하여 조사함으로써 측정 샘플에 따라 소정의 크기를 가지는 경화체를 제조하였다. After applying the prepared curable composition to about 0.2 mm on a glass substrate, the cured body having a predetermined size according to the measurement sample by irradiating UV of about 365 nm to 400 nm long wavelength using an LED or a metal-halide lamp Prepared.
실시예Example
2 내지 12 2 to 12
실시예 1에서 경화성 조성물의 조성을 하기 표 1과 같이 조절한 것을 제외하고는 실시예 1의 경우와 동일하게 경화체를 제조하였다.A cured product was prepared in the same manner as in Example 1, except that the composition of the curable composition in Example 1 was adjusted as shown in Table 1 below.
실시예Example | 올리고머Oligomer | 러버Rubber | 모노머Monomer | 기타Other | ||||
AA | BB | CC | AA | BB | IBOAIBOA | S.CS.C | 개시제Initiator | |
1One | 1818 | 22 | -- | 6060 | -- | 2020 | -- | 1One |
22 | 1616 | 44 | -- | 6060 | -- | 2020 | -- | 1One |
33 | 1414 | 66 | -- | 6060 | -- | 2020 | -- | 1One |
44 | 1818 | -- | 22 | 6060 | -- | 2020 | -- | 1One |
55 | 1616 | -- | 44 | 6060 | -- | 2020 | -- | 1One |
66 | 1414 | -- | 66 | 6060 | -- | 2020 | -- | 1One |
77 | 2020 | -- | -- | -- | 6060 | 2020 | 0.50.5 | 1One |
88 | 2020 | -- | -- | 6060 | -- | 2020 | 0.50.5 | 1One |
99 | 2222 | -- | -- | -- | 6060 | 1818 | 0.50.5 | 1One |
1010 | 2020 | -- | -- | -- | 6060 | 2020 | 0.250.25 | 1One |
1111 | 2020 | -- | -- | -- | 6060 | 2020 | 1One | 1One |
1212 | 2020 | -- | -- | -- | 6060 | 2020 | 22 | 1One |
함량 단위(g)-올리고머 A: 수산기를 가지는 폴리 부타디엔 러버를 포함하는 폴리 우레탄 아크릴레이트(중량평균분자량: 15,000)-올리고머 B: 수산기를 가지는 폴리 부타디엔 러버를 포함하는 폴리 우레탄 아크릴레이트 (중량평균분자량: 10,000)-올리고머 C: 수산기를 가지는 폴리부타디엔 러버를 포함하는 폴리 우레탄 아크릴레이트 (중량평균분자량: 10,000, 단, 올리고머 B에 비하여 아크릴레이트 함량이 10% 증가)-러버 A: 수산기를 가지는 폴리부타디엔 러버 (중량평균분자량: 2,000)-러버 B: 수산기를 가지는 폴리부타디엔 러버 (중량평균분자량: 3,000)-IBOA: Isobonyl acrylate-S.C(접착력 향상을 위한 실란커플링제): 3-(trimethoxysiyl)propyl methacrylate-개시제: Darocur TPOContent Unit (g)-Oligomer A: Polyurethane acrylate containing polybutadiene rubber having hydroxyl group (weight average molecular weight: 15,000)-Oligomer B: Polyurethane acrylate containing polybutadiene rubber having hydroxyl group (weight average molecular weight : 10,000)-oligomer C: Polyurethane acrylate containing a polybutadiene rubber having a hydroxyl group (weight average molecular weight: 10,000, except that the acrylate content is increased by 10% compared to oligomer B)-Rubber A: Polybutadiene having a hydroxyl group Rubber (weight average molecular weight: 2,000)-rubber B: polybutadiene rubber having a hydroxyl group (weight average molecular weight: 3,000) -IBOA: Isobonyl acrylate-SC (silane coupling agent for improving adhesion): 3- (trimethoxysiyl) propyl methacrylate- Initiator: Darocur TPO |
비교예Comparative example
1 내지 3 1 to 3
실시예 1에서 경화성 조성물의 조성을 하기 표 2와 같이 조절한 것을 제외하고는 실시예 1의 경우와 동일하게 경화체를 제조하였다A cured product was prepared in the same manner as in Example 1 except that the composition of the curable composition in Example 1 was adjusted as shown in Table 2 below.
비교예Comparative example | 올리고머Oligomer | 러버Rubber | 모노머Monomer | 기타Other | ||
DD | CC | IBOAIBOA | DADA | 가소제Plasticizer | 개시제Initiator | |
1One | 2020 | 6060 | 2020 | -- | -- | 1One |
22 | 2020 | -- | 2020 | -- | 6060 | 1One |
33 | 6060 | -- | -- | 4040 | -- | 1One |
함량 단위: 중량부(g)-올리고머 D: 수산기를 가지지 않는 폴리 우레탄 아크릴레이트 (중량평균분자량: 15,000)-러버 C: 이소프렌 러버-DA: Dodecyl acrylate-가소제: DINCH-개시제: Darocur TPOContent Unit: parts by weight (g) -oligomer D: polyurethane acrylate without hydroxyl group (weight average molecular weight: 15,000)-rubber C: isoprene rubber-DA: Dodecyl acrylate-plasticizer: DINCH-initiator: Darocur TPO |
실시예 1 내지 12 및 비교예 1 내지 3에 대하여 저장탄성률, 수축율, 겔 분율 및 유전상수를 측정한 후, 하기 수식 1에 따라 계산된 값 및 유리에 대한 박리력을 평가 결과를 표 3에 기재하였다. 박리력은 상온에서 300 mm/min의 박리속도 및 180° 박리각도로 TA-XT2plus 장치를 이용하여 측정하였다.After measuring the storage modulus, shrinkage rate, gel fraction and dielectric constant for Examples 1 to 12 and Comparative Examples 1 to 3, the values calculated according to the following Equation 1 and the peeling force on the glass are described in Table 3. It was. Peel force was measured using a TA-XT2plus device at 300 mm / min peel rate and 180 ° peel angle at room temperature.
[수식 1][Equation 1]
하기 표 3을 참고하면, 수식 1의 값이 30 이상인 실시예 1 내지 12은 저 유전율을 나타내면서, 동시에 수식 1의 값이 30 미만인 비교예 1 내지 3 에 비하여 박리력이 현저히 우수함을 확인할 수 있다. Referring to Table 3 below, Examples 1 to 12 having a value of Equation 1 or more exhibited a low dielectric constant, and at the same time, it was confirmed that the peeling force was remarkably superior to Comparative Examples 1 to 3 having a value of Equation 1 less than 30.
저장 탄성률(Pa)Storage modulus (Pa) | 수축율(%)Shrinkage (%) | 겔분율(%)Gel fraction (%) | 유전상수(1MHz)Dielectric Constant (1 MHz) | 수식 1의값Value of Equation 1 | 박리력(N/mm)Peel force (N / mm) | |
실시예 1Example 1 | 29652965 | 1.881.88 | 3232 | 2.452.45 | 4949 | 0.510.51 |
실시예 2Example 2 | 30263026 | 2.352.35 | 3434 | 2.682.68 | 7171 | 0.450.45 |
실시예 3Example 3 | 31853185 | 2.222.22 | 3737 | 2.712.71 | 7070 | 0.430.43 |
실시예 4Example 4 | 26842684 | 2.292.29 | 5757 | 2.782.78 | 135135 | 0.720.72 |
실시예 5Example 5 | 29622962 | 2.192.19 | 3333 | 2.722.72 | 6666 | 0.420.42 |
실시예 6Example 6 | 35993599 | 2.62.6 | 4848 | 2.912.91 | 101101 | 0.70.7 |
실시예 7Example 7 | 42514251 | 2.552.55 | 5050 | 2.82.8 | 8484 | 0.550.55 |
실시예 8Example 8 | 56145614 | 2.322.32 | 5353 | 2.832.83 | 6262 | 0.540.54 |
실시예 9Example 9 | 42184218 | 2.612.61 | 7676 | 2.432.43 | 114114 | 0.650.65 |
실시예 10Example 10 | 40764076 | 2.512.51 | 7474 | 2.482.48 | 113113 | 0.860.86 |
실시예 11Example 11 | 51115111 | 2.322.32 | 7575 | 2.602.60 | 8989 | 0.810.81 |
실시예 12Example 12 | 38943894 | 2.622.62 | 4646 | 2.762.76 | 8585 | 0.990.99 |
비교예 1Comparative Example 1 | 3100031000 | 1One | 5757 | 2.842.84 | 55 | 0.060.06 |
비교예 2Comparative Example 2 | 1500015000 | 2.112.11 | 5454 | 3.413.41 | 2626 | 0.260.26 |
비교예 3Comparative Example 3 | 7100071000 | 3.983.98 | 6868 | 4.244.24 | 1616 | 0.170.17 |
Claims (17)
- 하기 수식 1의 관계를 만족하는 경화성 조성물:Curable composition satisfying the relationship of the following formula 1:[수식 1][Equation 1]수식 1에서 A는 상기 조성물의 경화 후 1 MHz에서의 유전상수이고, B는 상기 조성물의 경화 후 겔분율(%)이며, C는 상기 조성물의 경화 후 수축율(%)이고, D는 상기 조성물의 경화 후 저장 탄성률(Pa)이다. In Formula 1, A is the dielectric constant at 1 MHz after curing of the composition, B is the gel fraction after curing of the composition (%), C is the shrinkage after curing of the composition (%), and D is Storage modulus after curing (Pa).
- 제 1 항에 있어서, The method of claim 1,경화 후 1 MHz에서의 유전상수가 3.5 이하인 경화성 조성물. A curable composition having a dielectric constant of 3.5 or less at 1 MHz after curing.
- 제 1 항에 있어서, The method of claim 1,경화 후 겔 분율이 30% 내지 80% 범위 내인 경화성 조성물. Curable composition having a gel fraction in the range of 30% to 80% after curing.
- 제 1 항에 있어서, The method of claim 1,경화 후 수축율이 1.5% 내지 3.0% 범위 내인 경화성 조성물. A curable composition having a shrinkage ratio after curing in the range of 1.5% to 3.0%.
- 제 1 항에 있어서, The method of claim 1,경화 후 저장 탄성률이 20,000 Pa 이하인 경화성 조성물. Curable composition whose storage modulus after hardening is 20,000 Pa or less.
- 제 1 항에 있어서, The method of claim 1,경화 후 상온에서 180°의 박리각도 및 300 mm/min의 박리속도로 측정된 유리에 대한 박리력이 0.3 N/m 이상인 경화성 조성물. Curable composition whose peeling force with respect to glass measured by the peeling angle of 180 degrees and the peeling rate of 300 mm / min at room temperature after hardening is 0.3 N / m or more.
- 제 1 항에 있어서, The method of claim 1,경화 후 가시광 영역의 투과율이 80% 이상인 경화성 조성물.Curable composition whose transmittance | permeability of visible region after hardening is 80% or more.
- 제 1 항에 있어서, The method of claim 1,활성 에너지선 경화성 올리고머를 포함하는 경화성 조성물. Curable composition containing an active energy ray curable oligomer.
- 제 8 항에 있어서,The method of claim 8,활성 에너지선 경화성 올리고머는 수산기를 가지는 폴리디엔 골격을 포함하는 경화성 조성물.A curable composition in which an active energy ray curable oligomer comprises a polydiene skeleton having a hydroxyl group.
- 제 8 항에 있어서, The method of claim 8,활성 에너지선 경화성 올리고머는 우레탄계 (메타)아크릴레이트 올리고머, 폴리에스테르계 (메타)아크릴레이트 올리고머, 폴리에테르계 (메타)아크릴레이트 올리고머, 에폭시계 (메타)아크릴레이트 올리고머, 디엔 중합체계 (메타)아크릴레이트 올리고머 및 디엔 중합체계 (메타)아크릴레이트의 수소 첨가물의 주쇄를 갖는 올리고머로 이루어진 군으로부터 선택되는 1종 이상인 경화성 조성물. Active energy ray-curable oligomers include urethane-based (meth) acrylate oligomers, polyester-based (meth) acrylate oligomers, polyether-based (meth) acrylate oligomers, epoxy-based (meth) acrylate oligomers, and diene polymer-based (meth) acryl Curable composition which is 1 or more types chosen from the group which consists of an oligomer which has a principal chain of the hydrogenated substance of a late oligomer and diene polymer type (meth) acrylate.
- 제 8 항에 있어서, The method of claim 8,러버(rubber) 성분을 더 포함하는 경화성 조성물. A curable composition further comprising a rubber component.
- 제 11 항에 있어서, The method of claim 11,러버 성분은 수산기를 가지는 폴리디엔인 경화성 조성물.The rubber component is a curable composition which is a polydiene having a hydroxyl group.
- 제 11 항에 있어서,The method of claim 11,러버 성분은 50% 내지 70중량% 범위 내의 비율로 포함되는 경화성 조성물.The rubber component comprises a ratio in the range of 50% to 70% by weight.
- 하기 수식 1의 관계를 만족하는 경화체:Hardening body which satisfies the relationship of following formula (1):[수식 1][Equation 1]수식 1에서 A는 경화체의 1 MHz에서의 유전상수이고, B는 경화체의 겔분율(%)이며, C는 경화체의 수축율(%)이고, D는 경화체의 저장 탄성률(Pa)이다. In Equation 1, A is the dielectric constant at 1 MHz of the cured product, B is the gel fraction (%) of the cured product, C is the shrinkage percentage (%) of the cured product, and D is the storage modulus (Pa) of the cured product.
- 제1항의 경화성 조성물로 접합된 표시체와 광학 기능 재료를 포함하는 표시 패널체.A display panel body comprising a display body bonded with the curable composition of claim 1 and an optically functional material.
- 제1항의 경화성 조성물로 접합된 터치 패널과 표시 패널을 포함하는 디스플레이 장치.A display device comprising a touch panel and a display panel bonded to the curable composition of claim 1.
- 광학 기능 재료, 표시 패널, 상기 광학 기능 재료와 표시 패널을 이격시키고 있는 스페이서 및 상기 광학 기능 재료와 표시 패널 사이의 이격된 공간을 충진하고 있는 제1항의 경화성 조성물 또는 제11항의 경화체를 포함하는 디스플레이 장치. A display comprising an optical functional material, a display panel, a spacer spaced apart from the optical functional material and the display panel, and a curable composition of claim 1 or a cured body of claim 11 filling a spaced space between the optical functional material and the display panel. Device.
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