WO2013084836A1 - シート状カバリング剤、カバリング方法又は電子デバイスの製造方法 - Google Patents

シート状カバリング剤、カバリング方法又は電子デバイスの製造方法 Download PDF

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WO2013084836A1
WO2013084836A1 PCT/JP2012/081247 JP2012081247W WO2013084836A1 WO 2013084836 A1 WO2013084836 A1 WO 2013084836A1 JP 2012081247 W JP2012081247 W JP 2012081247W WO 2013084836 A1 WO2013084836 A1 WO 2013084836A1
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polymer
covering agent
temperature
sheet
meth
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PCT/JP2012/081247
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English (en)
French (fr)
Japanese (ja)
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WO2013084836A4 (ja
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浩一 梅本
伊藤　久義
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株式会社ダイセル
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Priority to KR1020147018040A priority Critical patent/KR20140101829A/ko
Priority to CN201280069144.1A priority patent/CN104105748B/zh
Publication of WO2013084836A1 publication Critical patent/WO2013084836A1/ja
Publication of WO2013084836A4 publication Critical patent/WO2013084836A4/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention provides a sheet-like covering agent (or covering sheet, sealing sheet, etc.) useful for protecting an element (such as a semiconductor element) formed on a substrate and bonding optical members constituting a display device (such as a display device with a touch panel). And a covering method (or sealing method) or an electronic device manufacturing method using the same.
  • Functional elements such as semiconductor elements, organic electroluminescence (EL) elements, liquid crystal elements (liquid crystal cells), photoelectric conversion elements (solar cells, etc.), these functional element packages, the functional elements or printed boards on which the packages are mounted, etc.
  • These precision parts are usually sealed with a resin and protected from external influences (especially humidity).
  • a sealing method a method is known in which a precision part is placed in a mold cavity, and a thermosetting resin having low viscosity and high fluidity is injected and sealed.
  • additives such as a crosslinking agent are added to the thermosetting resin, not only the pot life is short, but a relatively long time is required for curing in the mold cavity. Productivity is low.
  • thermoplastic resin As a method with high productivity, it is also known to seal a precision part by injection molding a thermoplastic resin. However, in this method, since a high-temperature thermoplastic resin is injection-molded, the substrate and the electronic component mounted on the substrate are easily damaged by heat.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2008-282906 relates to a method of manufacturing a solar cell module in which a solar cell is sealed with a resin between a substrate and a film, and the substrate between the substrate and the solar cell. A first encapsulating resin sheet covering the entire surface of the substrate is disposed, and a second encapsulating resin sheet covering the entire surface of the substrate is disposed between the film and the solar battery cell to produce a laminated body. Are stacked, and a backing plate is arranged outside the film of the uppermost laminate, and air between the substrate and the film is discharged, heated to melt the resin, cooled, and sealed.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2009-99417
  • Patent Document 2 includes a barrier film for sealing an organic electronic device formed on a substrate, and a hot melt type member is provided between the organic electronic device and the barrier film.
  • Disposed organic electronic device sealing panels are disclosed.
  • these film-like encapsulants are inferior in conformity to the uneven portions of the device (or element), and thus effective in devices with few uneven portions, but tightly seal the details of devices with many uneven portions. Is difficult.
  • Temporarily it is possible to increase the sealing temperature to increase the fluidity of the resin and increase the followability to the uneven portion of the device. In this case, however, the possibility that the device is damaged by heat increases.
  • sealing at high temperatures increases the fluidity and adhesiveness of the resin, so the film-like sealant may flow out of the predetermined sealing site, reducing work efficiency, or preventing the designed sealing. There is also.
  • Patent Document 3 (A) epoxy (meth) acrylate having a non-flowability at 25 ° C. and a flowability in the range of 50 to 100 ° C. and (B) initiation of photopolymerization are disclosed.
  • a sheet-shaped encapsulant comprising a photocurable resin layer containing an agent and a light-transmitting film layer is bonded to a substrate having an organic EL element by crimping the sheet-form encapsulant with a heated pressure-bonding roll. It is described that a primary coating serving as a base of an inorganic film is formed by a step of combining and a step of curing a photocurable resin layer by light irradiation.
  • this method requires a crimping step, a photocuring step, and a peeling step of the transparent film layer using a laminated sheet provided with a photocurable resin layer, and the formation of the primary coating is complicated.
  • the photocurable resin contracts with photocuring, a contraction stress acts on the device, and the contraction stress remains in the primary film, which may adversely affect the device.
  • a photoinitiator and its decomposition product remain in a photocurable resin layer in a primary film, there is a possibility of adversely affecting the device.
  • an object of the present invention is to provide a sheet-like covering agent (a coating agent or a sealing agent) that can effectively cover (or seal) a portion to be processed (a portion to be sealed) of a member to be processed such as an electronic device at a relatively low temperature. Agent), a covering method (or sealing method) using the same, or a method of manufacturing an electronic device.
  • Another object of the present invention is a sheet-like covering agent (or sealing agent) that has fluidity (or followability to a stepped surface, etc.) at low temperatures and can effectively relieve residual stress, and a covering method ( Or providing a method of manufacturing an electronic device.
  • Still another object of the present invention is to use a sheet-like covering agent (or encapsulant) that can cover (or seal) an object to be processed such as an electronic device at a low temperature and whose fluidity is reduced at a high temperature.
  • the object is to provide a covering method (or sealing method) or a method for manufacturing an electronic device.
  • Another object of the present invention is to provide a sheet-like covering agent that can effectively protect the member to be treated even under high temperature and high humidity, and does not impair the visibility to the device, a covering method using the same, or a method for manufacturing an electronic device. is there.
  • Still another object of the present invention is to provide a transparent pressure-sensitive adhesive sheet that can achieve both step following ability and peelability (reworkability) after sticking, and a method for producing the same.
  • Another object of the present invention is to provide a transparent pressure-sensitive adhesive sheet that can adhere both adherends without gaps even when the gap between adherends is large, and a method for producing the same.
  • Still another object of the present invention is to provide a transparent pressure-sensitive adhesive sheet having excellent durability and capable of preventing bubbles from being generated at the interface with the adherend even under high temperature and high humidity, and a method for producing the same.
  • Another object of the present invention is to provide a transparent adhesive sheet excellent in punching workability and a method for producing the same.
  • Still another object of the present invention is to provide a transparent pressure-sensitive adhesive sheet which is excellent in optical isotropy and does not impair visibility even when used for bonding optical members constituting a display device, and a method for producing the same.
  • the present inventors have made a sheet of a polymer that softly crosslinks a polymer that softens at low temperatures, has a large molecular weight between crosslinking points, and has a predetermined storage modulus at low and high temperatures.
  • a sheet of a polymer that softly crosslinks a polymer that softens at low temperatures has a large molecular weight between crosslinking points, and has a predetermined storage modulus at low and high temperatures.
  • covering covering (sealing or sealing)
  • it has fluidity at low temperature (or followability to the surface of a step, etc.) and has high stress relaxation properties, which only relieves residual stress.
  • the present invention has been completed by finding that electronic components can be effectively covered (or sealed) at a relatively low temperature without flowing at a high temperature, and has heat resistance against deformation.
  • the covering agent (covering agent or sealing agent) of the present invention contains a polymer and has a sheet-like form.
  • the polymer has a storage elastic modulus at a temperature of 25 ° C. of 100 to 5000 MPa, a storage elastic modulus at 80 ° C. of 0.01 to 10 MPa, a molecular weight between crosslinking points of 8000 to 30000, and after 10 seconds to 20 seconds after stopping the strain.
  • the stress relaxation rate is 0.5 to 30% at a temperature of 80 ° C.
  • the polymer has a storage elastic modulus at 60 ° C. of about 0.05 to 100 MPa.
  • Such a polymer is formed of a loosely cross-linked polymer having a low-temperature softening property. Since the polymer having the above characteristics has a high storage elastic modulus at 25 ° C., it has a high mechanical strength at room temperature and a low storage elastic modulus at 60 ° C. and 80 ° C. Temperature) and shows high followability to the surface of the step. Therefore, even if the step is very small, it can be effectively covered or sealed. Moreover, since the molecular weight between cross-linking points is large, fluidity at low temperatures is not impaired, but at high temperatures (for example, temperatures exceeding 100 ° C.), flow and deformation are restricted by cross-linking and show heat resistance against deformation. Furthermore, since the molecular weight between cross-linking points is large and the stress relaxation rate is large, even if it shrinks as it solidifies, the residual stress is quickly relaxed and no strain remains.
  • the glass transition temperature of the polymer may be about 10 to 100 ° C.
  • the linear expansion coefficient of the polymer at 20 to 100 ° C. is about 500 to 5000 ppm / K.
  • the tensile stress of the polymer at 100% elongation at room temperature (for example, a temperature of 23 ° C.) may be about 15 to 100 MPa.
  • the total light transmittance of the polymer may be about 89 to 95%
  • the haze value may be about 0.1 to 1.5%
  • the in-plane retardation of the polymer at a wavelength of 590 nm is 10 nm. It may be the following.
  • the gas barrier property of the polymer is high.
  • the water vapor barrier property of the polymer at a thickness of 100 ⁇ m may be about 0.1 to 10 g / m 2 / day.
  • Such a polymer can be composed of polymers having various low-temperature softening properties, for example, non-crystalline olefin polymers (or non-crystalline olefin copolymers).
  • the covering agent of the present invention can be used to cover (or cover) various members in a sheet form, and is useful as, for example, a sheet-like sealant for sealing an electronic device (component).
  • the present invention includes a transparent pressure-sensitive adhesive sheet comprising a core film formed of the covering agent (or containing the polymer) and a pressure-sensitive adhesive layer formed on at least one surface of the core film.
  • the surface of the core material film may be subjected to corona treatment or plasma treatment.
  • the surface tension of the core film may be about 40 to 70 mN / m.
  • the thickness of the core film may be about 20 to 400 ⁇ m.
  • the core material film may be formed by extruding the polymer.
  • Such a transparent adhesive sheet can be suitably used for bonding two panels selected from a touch panel, a liquid crystal display panel, and a protective panel.
  • the present invention also includes a covering method (or sealing method). That is, in this method, the sheet-like covering agent (or sealant) is brought into contact with the site to be treated (or the site to be sealed), and the covering agent (or sealant) is heated (or the polymer). After being flowed), it is cooled, and the site to be treated is covered (covered or sealed) with a covering agent (or sealant).
  • the present invention also includes a method for manufacturing an electronic device. In this method, an electronic device is used as the adherend. That is, the sheet-like covering agent (or sealant) is brought into contact with the electronic device, the covering agent (or sealant) is heated (or the polymer is made to flow), and then cooled to cool the electronic device. An electronic device is manufactured by covering (covering or sealing) with a covering agent (or sealing agent). In these methods, the heating temperature may be, for example, a temperature not lower than the glass transition temperature of the polymer and not higher than 100 ° C.
  • a crosslinked polymer having a predetermined molecular weight between crosslinking points may be simply referred to as “polymer”.
  • Acrylic monomers and methacrylic monomers are collectively referred to as (meth) acrylic monomers.
  • Low temperature softening means softening at a temperature of about 30 to 80 ° C., and the elastic modulus after softening becomes 1/100 or less of that before softening.
  • sheet and “film” may be used synonymously.
  • the upper limit and the lower limit of the numerical range can be arbitrarily combined.
  • a portion to be treated (such as a portion to be sealed) of a member to be treated such as an electronic device is covered (covered or sealed) with a sheet-like covering agent (coating agent or sealant) containing a specific polymer. Therefore, it can be effectively covered (or sealed) at a relatively low temperature. In addition to high fluidity at low temperatures (or followability to the surface of a step, etc.), it has high stress relaxation properties and can effectively relieve residual stress. Therefore, it is effective and tight with a sheet-like covering agent (or sealant). Can be covered or sealed. In particular, even a minute step portion (uneven portion) can be accurately sealed.
  • a processing target member such as an electronic device at a low temperature
  • it has heat resistance against deformation at a high temperature and can regulate the flow of the polymer. Sealing).
  • the covering agent (or sealing agent) using a highly transparent polymer does not impair the visibility to the device, the covering or covering state can be easily confirmed, and the occurrence of defective products can be prevented.
  • a covering agent (or sealant) having a high gas barrier property is used, the member to be treated can be effectively protected even under high temperature and high humidity. Therefore, it is effective for covering (covering or sealing) various members, particularly precision parts (or electronic devices).
  • the transparent adhesive sheet of the present invention has an adhesive layer on at least one surface of a core film containing a specific polymer, it softens at the bonding processing temperature and follows the uneven surface shape of the adherend. In addition, it has a high elastic modulus at room temperature and does not break even when a large stress is applied during peeling, and therefore has excellent reworkability. Further, even if the thickness of the transparent pressure-sensitive adhesive sheet is large, the followability to the surface of the step is excellent, so that both adherends can be bonded without gap even if the gap between the adherends is large. Furthermore, it is excellent in durability and it is possible to effectively prevent bubbles from being generated at the interface with the adherend even under severe conditions (such as under high temperature and high humidity). Moreover, since it has a specific core material film, it is excellent in punching workability. Furthermore, it is excellent in optical isotropy, and does not impair the display performance of the display device even when used for bonding optical members constituting the display device.
  • FIG. 1 is a graph showing the relationship between the storage elastic modulus and temperature of the test pieces of Comparative Examples 1 and 2 and Example 3.
  • FIG. 2 is a stress relaxation graph showing the relationship between time and storage elastic modulus in the test piece of Comparative Example 2.
  • FIG. 3 is a stress relaxation graph showing the relationship between time and storage elastic modulus of the test piece of Example 3.
  • the covering agent (or sealant) of the present invention has a sheet-like form and contains a specific crosslinked polymer.
  • This crosslinked polymer has a structure in which a low-temperature softening polymer is loosely crosslinked, has a high storage elastic modulus at room temperature, and a low storage elastic modulus at processing temperature (covering or sealing temperature). Has a special color.
  • the storage elastic modulus of the polymer at a temperature of 25 ° C. can be selected from the range of 100 to 5000 MPa, for example, 100 to 4000 MPa, preferably 500 to 3000 MPa (for example, 750 to 2500 MPa), more preferably 1000 to 2000 MPa (for example, About 1200 to 1800 MPa), about 500 to 5000 MPa, preferably about 800 to 4000 MPa, and more preferably about 1000 to 3000 MPa.
  • the storage elastic modulus of the polymer at a temperature of 60 ° C. is, for example, about 0.05 to 100 MPa, preferably about 0.1 to 50 MPa, and more preferably about 0.5 to 30 MPa (eg, 1 to 10 MPa).
  • the storage elastic modulus of the polymer at a temperature of 80 ° C. is 0.01 to 10 MPa, preferably 0.1 to 8 MPa (eg 0.5 to 7.5 MPa), more preferably 1 to 7 MPa (eg 2 to 7 MPa).
  • a polymer having such characteristics has high mechanical strength near room temperature (about 20 to 25 ° C.), and can effectively protect the adherend, and can flow around the processing temperature (such as covering or sealing temperature).
  • the adherend can be coated or covered uniformly and tightly.
  • the storage elastic modulus at 25 ° C. with respect to the storage elastic modulus at 60 ° C. is, for example, 50-5 ⁇ 10 5 (for example, 60-1 ⁇ 10 4 ), preferably about 70 to 1000 (for example, 80 to 500), more preferably about 90 to 300 (for example, 100 to 280).
  • the storage elastic modulus at 80 ° C. is “1”
  • the storage elastic modulus of the polymer can be measured by the method described in Examples.
  • the crosslinked polymer has a feature that the molecular weight between crosslinking points is large.
  • the molecular weight between crosslink points of the polymer is about 8000 to 30000, preferably about 9000 to 25000 (for example, 9500 to 20000), more preferably about 10,000 to 18000 (for example, 10,000 to 16000).
  • Such a large molecular weight between cross-linking points indicates that the polymer has a loosely cross-linked structure with a low cross-linking density. For this reason, when heated, the polymer behaves and flows like a thermoplastic resin, but when the temperature rises above a predetermined temperature, the flow and deformation of the polymer are regulated by crosslinking, and unlike the thermoplastic resin, it has heat resistance.
  • the molecular weight between crosslinking points of the polymer can be determined by a conventional method, for example, a typical method using the rubber elasticity theory. In this method, the molecular weight between crosslinking points can be calculated by the following formula.
  • G ( ⁇ RT) / M X (Wherein, G is the shear modulus (unit Pa), [rho is the density (g / m 3), R is the gas constant (8.314J / K / mol), T is the absolute temperature (K), the M X cross (Indicates molecular weight between points (g / mol))
  • the shear elastic modulus G can be measured by a storage elastic modulus in a rubber-like flat region (for example, 140 ° C., angular frequency 0.1 Hz) (the storage elastic modulus is measured in the same manner as described above).
  • the density ⁇ can be measured by the Archimedes method, and the density of the polymer described in the book “Polymer Engineering and Science, MID-JULY, 1990, Vol. 30, No. 13, P753-761” can also be referred to.
  • the stress relaxation rate after 10 seconds to 20 seconds after strain stop (load removal) is about 0.5 to 30, preferably 1 to 25, more preferably about 1.5 to 22% at a temperature of 80 ° C. is there.
  • the stress relaxation rate can be calculated by measuring by the method described in the examples.
  • a polymer having a high elongation at room temperature is preferred.
  • the tensile stress of the polymer at 100% elongation at room temperature (temperature 15 to 25 ° C., for example 23 ° C.) is, for example, about 15 to 100 MPa, preferably 17 to 80 MPa, and more preferably about 20 to 60 MPa.
  • the tensile stress can be measured by the method described in the examples using JIS No. 2 dumbbell pieces (width 6 mm, thickness 100 ⁇ m).
  • the glass transition temperature Tg (or melting point Tm for crystalline polymers) of the polymer is, for example, 10 to 100 ° C. (eg 15 to 90 ° C.), preferably 20 to 80 ° C. (eg 25 to 75 ° C.), Preferably, it is about 25 to 70 ° C. (eg, 25 to 60 ° C., preferably 30 to 50 ° C.), and may be about 15 to 50 ° C. (eg, 20 to 40 ° C., preferably 25 to 35 ° C.). 25 to 50 ° C. (for example, more than 30 ° C. and 50 ° C.
  • the glass transition temperature Tg and the melting point Tm can be measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min.
  • the linear expansion coefficient (linear thermal expansion coefficient) of the polymer is, for example, 500 to 5000 ppm / K, preferably 1000 to 3500 ppm / K (for example, 1200 to 3000 ppm / K) in a temperature range of 20 to 100 ° C. Preferably, it is about 1700-2700 ppm / K (for example, 1500-2500 ppm / K).
  • the linear expansion coefficient is too small, the heat resistance is poor, and when the linear expansion coefficient is too large, the covering property is lowered.
  • the polymer has an appropriate linear thermal expansion coefficient, does not melt even at high temperatures, regulates melt flow, and has heat resistance against deformation.
  • the linear expansion coefficient of a polymer can be measured by the method as described in an Example.
  • the degree of crosslinking of the polymer can be indicated by the gel fraction.
  • the gel fraction of the polymer may be, for example, 5% by weight or more (for example, 10 to 99% by weight), 30 to 98% by weight, preferably 50 to 97% by weight, more preferably 80 to 95% by weight. % (For example, 85 to 93% by weight).
  • the cross-linked polymer is excellent in heat resistance and durability, and retains moderate flexibility.
  • the gel fraction of the polymer can be measured by the measuring method described in the examples.
  • the total light transmittance of the polymer may be about 80 to 99%, more preferably 85 to 98% (especially 90 to 95%) at a thickness of 100 ⁇ m, and usually 89 to 95%, preferably 90 to 90%. It is about 94%, more preferably about 91 to 93%.
  • the total light transmittance can be measured according to JIS K7105.
  • the haze value (cloudiness value) of the polymer is 5% or less (preferably 2% or less (for example, 0 to 2%)) at a thickness of 100 ⁇ m, and usually 1.5% or less, for example, 0.1 to 1.5%, preferably about 0.1 to 1% (for example, 0.2 to 0.7%), more preferably about 0.1 to 0.5% (for example, 0.2 to 0.4%) It is. Haze can be measured according to JIS K7105.
  • a polymer excellent in optical isotropy is preferable in order to prevent the display property from being impaired even if the optical member constituting the display device is covered or sealed.
  • the in-plane retardation of the polymer at a wavelength of 590 nm is, for example, 10 nm or less (for example, 0.1 to 5 nm), preferably 0.5 to 3 nm (for example, 1 to 3 nm), more preferably 1. It is about 5 to 2.5 nm. In-plane retardation can be measured using a conventional phase difference measuring device.
  • the polymer preferably has a high gas barrier property, particularly a water vapor barrier property.
  • the water vapor permeability (unit: g / m 2 / day) of the polymer is 0.1 to 10 (eg 0.2 to 8), preferably 0.5 to 5 (eg 0.7 to 4), more preferably about 1 to 3.
  • the water vapor transmission rate can be measured by the method described in the Examples, and can be obtained as a water vapor transmission rate per 1 m 2 for 24 hours.
  • the sheet-like covering agent (sealing agent) exhibits high fluidity even when the thickness is large, the sheet-like covering agent (sealing agent) has high followability to the surface shape, and can uniformly cover or cover the uneven portions and the step portions on the surface. Therefore, the thickness of the sheet covering agent (sealing agent) is not particularly limited as long as it can be covered or sealed, and is, for example, 20 to 400 ⁇ m, preferably 30 to 350 ⁇ m, more preferably 40 to 300 ⁇ m (for example, 50 To about 200 ⁇ m), 100 ⁇ m or more (for example, 100 to 400 ⁇ m), preferably about 150 ⁇ m or more (for example, 200 to 350 ⁇ m).
  • Such a polymer can be formed by crosslinking an uncrosslinked polymer.
  • the uncrosslinked polymer can be selected from polymers having a glass transition temperature (Tg) of about ⁇ 130 ° C. to 100 ° C. (eg, ⁇ 50 ° C. to 90 ° C.), for example, 10 to 90 ° C., preferably 20 to It may be about 80 ° C. (for example, 25 to 75 ° C.).
  • the glass transition temperature (Tg) of the uncrosslinked polymer is usually about 15 to 50 ° C. (eg, 20 to 40 ° C.), preferably (eg, about 25 to 35 ° C.).
  • Such an uncrosslinked polymer is often a polymer having a low temperature softening property, and the uncrosslinked polymer is a copolymer of a monomer having a low Tg and a monomer having a high Tg. Often combined.
  • the uncrosslinked polymer is characterized by a relatively large molecular weight.
  • the number average molecular weight of the uncrosslinked polymer is, for example, 3000 to 500,000 (for example, 5000 to 400,000), preferably 7,000 to 300,000 (for example, 10,000 to 200,000) in terms of polystyrene in gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • it is about 15000 to 100,000 (for example, 20000 to 90000).
  • a polymer having a low temperature softening property usually has a low glass transition temperature as described above and a low temperature fluidity, but has a low heat resistance, and it is difficult to achieve both low temperature fluidity and heat resistance.
  • moderate low-temperature softening properties and heat resistance can be achieved by crosslinking an uncrosslinked polymer having low-temperature softening properties (especially, loose crosslinking to achieve a predetermined molecular weight between crosslinking points).
  • the uncrosslinked polymer may be a polymer that can be crosslinked by a crosslinking agent, or a polymer that can be crosslinked by irradiation with active energy rays.
  • the latter polymer may be a polymer having an ⁇ , ⁇ -ethylenically unsaturated bond, and does not require an ⁇ , ⁇ -ethylenically unsaturated bond when a high energy beam is used.
  • a wide range of polymers can be used.
  • the type of the uncrosslinked polymer is not particularly limited.
  • a typical polymer that can be crosslinked by a crosslinking agent a polymer that forms a crosslinked structure using a reactive functional group.
  • examples include (meth) acrylic polymers, aliphatic polyester polymers, aliphatic polyamide polymers, unsaturated polyester polymers, and the like.
  • Representative examples of the polymer that can be cross-linked by irradiation with active energy rays include, for example, olefin polymers, polyurethane (meth) acrylate polymers, polyester (meth) acrylate polymers, and unsaturated polyesters. Examples thereof include a system polymer.
  • the (meth) acrylic polymer includes a polymer having a (meth) acrylic monomer as a polymerization component.
  • (Meth) acrylic monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid C 1-12 alkyl esters such as butyl, isobutyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid hydroxy C 2-6 alkyl esters such as 2-hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate; C 5-10 cycloalkyl
  • Preferred (meth) acrylic monomers include monomers that form a homopolymer having a glass transition temperature of about 20 to 105 ° C. (preferably 30 to 100 ° C.). That is, (meth) acrylic monomer, at least methacrylic monomers (e.g., methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid and methacrylic acid hexyl C 1- 10 alkyl esters, hydroxy C2-4 alkyl esters of methacrylic acid, glycidyl methacrylate, etc.). These methacrylic monomers can be used alone or in combination of two or more. Preferred methacrylic monomers contain methacrylic acid C 1-6 alkyl esters.
  • the methacrylic monomer is an acrylic monomer (acrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, Acrylic acid C 1-12 alkyl esters such as isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate; hydroxy C 2 -acrylate such as 2-hydroxyethyl acrylate 6 alkyl esters; glycidyl acrylate, etc.), organic acid vinyl esters (eg, C 2-6 alkane carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, etc.), chain olefins ( ⁇ -C 2 such as ethylene, propylene, etc.) -4 olefins, etc.) other, aromatic Vinyl monomers (styrene, etc.
  • Acrylic acid C 1-12 alkyl esters such as isopropyl
  • monomers can also be used alone or in combination of two or more.
  • Preferred monomers are the above acrylic monomers (particularly acrylic acid, acrylic acid C 1-8 alkyl ester, acrylic acid hydroxy C 2-4 alkyl ester, glycidyl acrylate, etc.) It is.
  • the (meth) acrylic polymer has a reactive functional group (for example, a side chain hydroxyl group, carboxyl group, glycidyl group, etc.) with a crosslinking agent by copolymerization with a monomer having a reactive functional group.
  • a reactive functional group for example, a side chain hydroxyl group, carboxyl group, glycidyl group, etc.
  • examples of the monomer having a reactive functional group include (meth) acrylic acid hydroxy C 2-6 alkyl ester, (meth) acrylic acid, glycidyl (meth) acrylate, and the like. Or it can be used in combination of two or more.
  • the use amount of the monomer having a reactive functional group can be selected from the range of about 0.1 to 100 mol% with respect to the whole monomer, and is usually 1 to 30 mol%, preferably 3 to 25 mol. %, More preferably about 5 to 20 mol%.
  • the (meth) acrylic polymer may be prepared by using a solution transfer method, a suspension polymerization method, a bulk polymerization method (bulk polymerization method), etc., if necessary, using a chain transfer agent such as mercaptans.
  • the molecular weight can be adjusted.
  • Aliphatic polyester polymers are produced by reaction of diol component and dicarboxylic acid component, reaction of hydroxycarboxylic acid component and / or lactone component, reaction of diol component and dicarboxylic acid component, and hydroxycarboxylic acid component and / or lactone component. Obtainable. Of these components, at least one of the aliphatic diol component and the aliphatic dicarboxylic acid component (particularly the dicarboxylic acid component) is often an aliphatic dicarboxylic acid component, and the aliphatic diol component and the aliphatic dicarboxylic acid component. And a lactone component are often used.
  • aliphatic dicarboxylic acid component examples include an alkane dicarboxylic acid component (eg, C 4-12 alkane dicarboxylic acid such as adipic acid, sebacic acid, decanedicarboxylic acid, etc.), cycloalkane dicarboxylic acid (eg, 1,4-cyclohexane dicarboxylic acid, etc.) C 5-10 cycloalkane-dicarboxylic acid such as acid), ester-forming derivatives thereof and the like.
  • alkane dicarboxylic acid component eg, C 4-12 alkane dicarboxylic acid such as adipic acid, sebacic acid, decanedicarboxylic acid, etc.
  • cycloalkane dicarboxylic acid eg, 1,4-cyclohexane dicarboxylic acid, etc.
  • C 5-10 cycloalkane-dicarboxylic acid such as acid
  • ester-forming derivatives thereof and the like
  • the aliphatic dicarboxylic acid component may be used in combination with an aromatic dicarboxylic acid component in order to adjust the glass transition temperature and the like.
  • aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid (for example, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid), biphenyldicarboxylic acid, and ester formation properties thereof. Derivatives and the like.
  • ester-forming derivative examples include C 1-4 alkyl esters (particularly C 1-2 alkyl esters) such as methyl esters and ethyl esters, acid halides (acid chlorides, etc.), acid anhydrides, and the like. .
  • the dicarboxylic acid component often contains at least C 6-12 alkanedicarboxylic acid in order to form a soft polyester resin.
  • the proportion of C 6-12 alkanedicarboxylic acid used may be about 50 to 100 mol%, preferably about 60 to 80 mol%, based on the entire dicarboxylic acid component.
  • aliphatic diol component examples include alkanediols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, C 2-10 alkanediol such as neopentyl glycol, preferably C 2-6 alkane diol), poly alkanediol (e.g., diethylene glycol And poly C 2-4 alkane diols such as dipropylene glycol, triethylene glycol, polytetramethylene ether glycol and the like) and cycloalkane diols (eg, cyclohexane diol, cyclohexane dimethanol and the like). These aliphatic diol components may be al
  • the aliphatic diol component may be used in combination with an aromatic diol component.
  • aromatic diol component examples include hydroquinone, resorcinol, 1,4-benzenedimethanol, biphenol, bisphenols (for example, bisphenol compounds such as bisphenol A and bisphenol fluorene, and alkylene oxides of this bisphenol compound).
  • the hydroxycarboxylic acid and / or lactone component can be used in place of the aliphatic dicarboxylic acid component and the aliphatic diol component or together with the aliphatic dicarboxylic acid component and the aliphatic diol component.
  • the lactone component include C 3-10 lactones such as ⁇ -butyrolactone (GBL), ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, enanthlactone (7-hydroxyheptanoic acid lactone), and the like. These lactone components can be used alone or in combination of two or more. Of these lactone components, C 4-8 lactones such as valerolactone and caprolactone are preferred.
  • the lactone component may be used as a diol component in the form of a polymer obtained by ring-opening polymerization of a lactone as an initiator.
  • the initiator include water, the aliphatic diol component [alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, polyethylene glycol (PEG), polypropylene glycol (PPG ), Polyalkylene glycols such as polytetramethylene ether glycol (PTMG)], aromatic diol components, diamines such as ethylenediamine, hexamethylenediamine, hydrazine, xylylenediamine, and isophoronediamine, and polyamines such as diethylenetriamine.
  • alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, polyethylene glycol (PEG), polypropy
  • alkylene glycol for example, C 2-6 alkylene glycol
  • polyalkylene glycol for example, polytetramethylene ether glycol
  • the diol component may contain an alkane polyol (eg, glycerin, trimethylolpropane, pentaerythritol, etc.), and the dicarboxylic acid component is a polycarboxylic acid (eg, trimellitic anhydride). And a compound such as pyromellitic anhydride).
  • a plurality of reactive functional groups may be introduced at the terminal by reaction between the terminal hydroxyl group and / or carboxyl group and the alkane polyol and / or polycarboxylic acid.
  • the polyester polymer can be prepared by a conventional method such as a solution polymerization method, a melt polymerization method, or an interfacial polymerization method.
  • Such a polyester-based polymer has a hydroxyl group and / or a carboxyl group at the terminal, and can form a crosslinked structure using such a reactive functional group.
  • the aliphatic polyamide-based polymer includes a polymer produced by a reaction between a dicarboxylic acid component and a diamine component.
  • the dicarboxylic acid component include the above aliphatic dicarboxylic acid components, and the dicarboxylic acid component usually contains at least one component selected from a long-chain alkane dicarboxylic acid (such as C 6-12 alkane carboxylic acid) and a dimer acid.
  • the diamine component include alkylene diamines (C 6-12 alkylene diamines such as hexamethylene diamine) and the like, and usually include polyether diamines (polytetramethylene ether diamines) and the like. Many.
  • the dicarboxylic acid component may contain a polycarboxylic acid (for example, a compound such as trimellitic anhydride or pyromellitic anhydride), and the diamine component is an alkane polyamine (for example, diethylenetriamine). , Triethylenetetramine, etc.).
  • a polycarboxylic acid for example, a compound such as trimellitic anhydride or pyromellitic anhydride
  • the diamine component is an alkane polyamine (for example, diethylenetriamine). , Triethylenetetramine, etc.).
  • the polyamide polymer can be prepared by a conventional method, for example, a solution polymerization method, a melt polymerization method, an interfacial polymerization method or the like.
  • Such a polyamide-based polymer has a carboxyl group and / or an amino group at the terminal, and can form a crosslinked structure using such a reactive functional group.
  • the unsaturated polyester polymer uses a polymerizable unsaturated dicarboxylic acid or an acid anhydride thereof (maleic anhydride, fumaric acid, etc.) as part of the dicarboxylic acid component of the aliphatic polyester resin, and is polymerizable in the main chain. It can be prepared by introducing unsaturated bonds.
  • the amount of polymerizable unsaturated dicarboxylic acid or its acid anhydride used is considerably smaller than the amount used in ordinary unsaturated polyester resins, for example, the entire dicarboxylic acid component The amount may be about 0.1 to 5 mol% (for example, 0.2 to 2.5%).
  • vinyl alcohol polymers polyvinyl alcohol (saponified polyvinyl acetate), ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer)] vinyl Examples include acetalized products of alcohol polymers (polyvinyl formal, polyvinyl butyral, etc.).
  • the uncrosslinked polymer is a hydroxyl group, a carboxyl group, or a soft polymer such as a (meth) acrylic polymer, an aliphatic polyester polymer, an aliphatic polyamide polymer, or an olefin polymer described below.
  • a monomer having a reactive functional group such as a polymerizable polyvalent carboxylic acid such as the (meth) acrylic monomer having a glycidyl group, maleic acid or an acid anhydride thereof, or fumaric acid. It may be.
  • the number average molecular weight of these uncrosslinked polymers usually corresponds to the molecular weight between the crosslinking points in many cases and is, for example, 5000 to 30000 (for example, 7500 to 27000) in terms of polystyrene in GPC, preferably It may be about 8000 to 25000 (for example, 9000 to 23000), more preferably about 10,000 to 20000 (for example, 12000 to 17000).
  • the uncrosslinked polymer having a reactive functional group can form a crosslinked structure by crosslinking with a crosslinking agent having a crosslinking reactive group reactive to the reactive functional group.
  • crosslinking agent for the polymer having a hydroxyl group examples include an isocyanate crosslinking agent, an acid anhydride crosslinking agent, a silane crosslinking agent, and a melamine crosslinking agent.
  • isocyanate-based crosslinking agent examples include aliphatic polyisocyanates (C 4-16 alkane diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate (HDI), C 6-20 alkane triisocyanates such as lysine ester triisocyanate), fats, and the like.
  • Cyclic polyisocyanates diisocyanates such as isophorone diisocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate), hydrogenated xylylene diisocyanate, norbornane diisocyanate, 1,3,5-trimethylisocyanatocyclohexane, 2- (3- Isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2.1] heptane, etc.), aromatic aliphatic polyiso Anates (diisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate, triisocyanates such as 1,3,5-triisocyanatomethylbenzene), aromatic polyisocyanates (phenylene diisocyanate, 1,5-naphthylene diene) Diisocyanates such as isocyanate (NDI), dipheny
  • Examples of the derivative include dimer, trimer (trimer having an isocyanurate ring), biuret, and allophanate of the polyisocyanate.
  • isocyanate-based crosslinking agents can be used alone or in combination of two or more.
  • aliphatic diisocyanates such as HDI
  • alicyclic diisocyanates such as IPDI and hydrogenated XDI
  • araliphatic diisocyanates such as XDI
  • aromatic diisocyanates such as TDI, MDI and NDI, etc.
  • acid anhydride crosslinking agents examples include aromatic dicarboxylic acid anhydrides (such as phthalic anhydride), alicyclic dicarboxylic acid anhydrides (such as tetrahydrophthalic anhydride, het acid anhydride, and hymic anhydride), and aliphatic dicarboxylic acid anhydrides.
  • aromatic dicarboxylic acid anhydrides such as phthalic anhydride
  • alicyclic dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, het acid anhydride, and hymic anhydride
  • aliphatic dicarboxylic acid anhydrides aliphatic dicarboxylic acid anhydrides.
  • Products succinic anhydride, maleic anhydride, etc.
  • polyvalent carboxylic acid anhydrides eg trimellitic anhydride, pyromellitic anhydride, etc.
  • silane-based crosslinking agents include dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and other alkoxysilanes.
  • examples of the melamine crosslinking agent include hexamethoxymethyl melamine.
  • crosslinking agent for the polymer having a carboxyl group examples include an epoxy crosslinking agent, an isocyanate crosslinking agent and a silane crosslinking agent similar to those described above.
  • epoxy-based crosslinking agent examples include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, novolak type epoxy resins, hydrogenated bisphenol A type epoxy resins, propylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl isocyanurate. Examples thereof include glycidyl ester type epoxy resins, alicyclic epoxy resins, glycidyl amine type epoxy resins, and long-chain aliphatic epoxy resins.
  • crosslinking agent for a polymer having a glycidyl group examples include a polyamine crosslinking agent and the same acid anhydride crosslinking agent as described above.
  • examples of the polyamine crosslinking agent include ethylenediamine, diethylenetriamine, triethylenediamine, and tetraethylenepentamine.
  • aliphatic polyamines such as hexamethylene diamine, isophorone diamine, alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, and aromatic polyamines such as xylene diamine.
  • crosslinking agent for the polymer having an amino group examples include the same isocyanate crosslinking agents and acid anhydride crosslinking agents as described above.
  • an isocyanate crosslinking agent hexamethylene diisocyanate, tolylene diisocyanate, etc.
  • a polymer having a hydroxyl group at a predetermined ratio
  • the mixture is heated and mixed to cause an addition reaction, thereby depending on the amount of the isocyanate crosslinking agent added.
  • a crosslinked product can be produced.
  • This crosslinking reaction may be carried out in a reaction solvent in order to increase the reaction efficiency.
  • crosslinking is performed even if the ratio of the crosslinking reactive group (isocyanate group, etc.) of the crosslinking agent is increased with respect to 1 mol of the reactive functional group.
  • the ratio of the cross-linking reactive group (isocyanate group, etc.) of the cross-linking agent is increased with respect to 1 mol of the reactive functional group.
  • the molecular weight of the polymer per reactive functional group may be a molecular weight corresponding to the molecular weight between the crosslinking points or less.
  • the amount of the crosslinking agent used can be selected according to the concentration of the reactive functional group of the polymer, and is usually 1 mol or less (for example, 0.01 to 0) of the crosslinking reactive group per 1 mol of the reactive functional group. 0.7 mol, preferably 0.05 to 0.5 mol).
  • the amount of the crosslinking agent used may be about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the polymer.
  • the crosslinked polymer includes a polymer having a hydroxyl group and / or a carboxyl group (or an acid anhydride group thereof) and a crosslinking agent that can be cured at a low temperature (eg, room temperature to 100 ° C., preferably about 30 to 70 ° C.). It is often prepared in combination with (isocyanate-based crosslinking agent and / or silane-based crosslinking agent, etc.). In particular, it is useful to crosslink a polymer having a hydroxyl group and / or a carboxyl group (for example, (meth) acrylic polymer, aliphatic polyester polymer, etc.) with an isocyanate crosslinking agent.
  • a polymer having a hydroxyl group and / or a carboxyl group for example, (meth) acrylic polymer, aliphatic polyester polymer, etc.
  • Examples of the olefin polymer include a chain olefin homopolymer or a copolymer, a copolymer of a chain olefin and a copolymerizable monomer, a copolymer of a chain olefin and a cyclic olefin, and the like.
  • Examples of the chain olefin include chain C such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. And 2-10 olefins.
  • chain olefins can be used alone or in combination of two or more.
  • ⁇ -C 2-8 olefins eg, ⁇ -C 2-4 olefins
  • ethylene is preferred.
  • chain olefin homopolymer or copolymer examples include polyethylene (low, medium or high density polyethylene, linear low density polyethylene, etc.), ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, ethylene Examples thereof include ethylene resins such as -butene-1 copolymer, propylene resins (propylene-ethylene copolymer, etc.), and the like.
  • the organic acid vinyl ester such as vinyl acetate
  • the (meth) acrylic monomer ((meth) acrylic acid; (meth) acrylic acid C such as methyl (meth) acrylate) 1-12 alkyl ester; (meth) acrylic acid hydroxy C 2-6 alkyl ester; (meth) acrylic acid glycidyl and the like.
  • These copolymerizable monomers can be used alone or in combination of two or more.
  • At least acrylic monomers for example, acrylic acid C 2-10 alkyl esters such as ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate
  • acrylic acid C 2-10 alkyl esters such as ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate
  • Examples of the copolymer of a chain olefin and a copolymerizable monomer include, for example, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid C 2-10 alkyl ester copolymer, and an ethylene-propylene-acrylic acid C 2. Examples thereof include a -10 alkyl ester copolymer.
  • the cyclic olefin may be any polymerizable cyclic olefin having an ethylenic double bond in the hydrocarbon ring, and may be a monocyclic olefin (for example, a cyclic C 4-12 cycloolefin such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, etc.
  • Polycyclic olefins (such as bicyclic to tetracyclic olefins) are preferable.
  • Representative polycyclic olefins include, for example, norbornene (2-norbornene), norbornene having a substituent, and a multimer of cyclopentadiene. (Dicyclopentadiene and the like), and cyclopentadiene multimers having a substituent.
  • the substituent include an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a cyano group, an amide group, and a halogen atom. These substituents may be used alone or in combination of two or more.
  • examples of the polycyclic olefin include 2-norbornene; 1-methyl-2-norbornene (2-bornene), 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5- Norbornenes having an alkyl group such as ethyl-2-norbornene, 5-butyl-2-norbornene, 7,7-dimethyl-2-norbornene; norbornenes having an alkenyl group such as 5-ethylidene-2-norbornene; Norbornenes having an alkoxycarbonyl group such as methoxycarbonyl-2-norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene; norbornenes having a cyano group such as 5-cyano-2-norbornene; 5-phenyl-2 -Norbornene, 5-phenyl-5-methyl-2-norbol Norbornenes having an aryl group such as benzene; dicyclopentad
  • cyclic olefins can be used alone or in combination of two or more.
  • polycyclic olefins such as norbornenes are preferred.
  • the chain olefin-cyclic olefin copolymer is preferably an ⁇ -C 2-4 olefin (particularly at least ethylene), and the cyclic olefin is a polycyclic olefin such as norbornene (norbornene, dicyclopentadiene, etc.) And a bicyclic olefin having about 7 to 10 carbon atoms in the hydrocarbon ring.
  • the ratio (molar ratio) of the cyclic olefin is 15 to 50 mol% (for example, 16 to 45 mol%), preferably based on the total of the chain olefin and the cyclic olefin. May be about 15 to 40 mol% (for example, 17 to 40 mol%, preferably 17 to 35 mol%). If the ratio of the cyclic olefin is too small, the crystallinity is increased, and the low temperature softening property is lowered by generating a melting point.
  • the ratio (molar ratio) of the cyclic olefin exceeds 15 mol% with respect to the total of the chain olefin and the cyclic olefin from the point of improving the crosslinkability (the point where active energy ray crosslinking can be performed without heating). And 40 mol% or less, for example, 16 to 35 mol% (for example, 16 to 30 mol%), preferably about 17 to 25 mol% (for example, 18 to 22 mol%).
  • the glass transition temperature is adjusted to a desired temperature, and by adjusting the crosslinking density, the melt fluidity is reduced, and the balance between flexibility at low temperature and heat resistance is excellent. A polymer is obtained.
  • the chain olefin-cyclic olefin copolymer includes other copolymerizable monomers such as the vinyl ester monomers exemplified above (for example, vinyl acetate), (meth) acrylic monomers (for example, A copolymer with (meth) acrylic acid, (meth) acrylic acid ester, etc.) may be used. These other copolymerizable monomers may be used alone or in combination of two or more. Content of a copolymerizable monomer is 5 mol% or less with respect to a copolymer, for example, Preferably it is 1 mol% or less.
  • the chain olefin-cyclic olefin copolymer may be an addition polymer or a ring-opening polymer (such as a ring-opening metathesis polymer).
  • the polymer obtained by ring-opening metathesis polymerization may be a hydrogenated hydrogenated resin.
  • conventional methods such as ring-opening metathesis polymerization using a metathesis polymerization catalyst, addition polymerization using a Ziegler type catalyst, addition polymerization using a metallocene catalyst (usually) , Ring-opening metathesis polymerization using a metathesis polymerization catalyst) can be used.
  • the chain olefin-cyclic olefin copolymer may be combined with other crosslinkable resin components.
  • the other resin component is usually a resin or elastomer that is compatible or cross-linked with the chain olefin-cyclic olefin copolymer, and may be a chain olefin resin and / or a cyclic olefin resin.
  • the crosslinking density can be adjusted to control flexibility and heat resistance.
  • chain olefin-based resin examples include, for example, the chain olefins exemplified above [for example, ⁇ -C 2-4 olefins such as ethylene and propylene (particularly ethylene) and the like] and, if necessary, copolymerizable monomers [for example, Examples thereof include polymers having a polymerization component such as the above exemplified vinyl ester monomers, diene monomers, (meth) acrylic monomers, and the like].
  • Typical chain olefin resins are polyethylene resins, polypropylene resins, and the like. These chain olefin resins can be used alone or in combination of two or more. Of these chain olefin resins, polyethylene resins such as low, medium or high density polyethylene, and linear low density polyethylene are preferred.
  • a copolymer having a large cyclic olefin ratio is a chain olefin (for example, , Ethylene) and cyclic olefins (for example, norbornenes) in a proportion exceeding 40 mol%, for example, 50 to 100 mol%, preferably about 60 to 90 mol% copolymer).
  • the glass transition temperature of the resin component can be selected from a range of about ⁇ 150 ° C. to 200 ° C., and the glass transition temperature is higher than that of a chain olefin-cyclic olefin copolymer.
  • Resin having a high glass temperature for example, a resin having a glass transition temperature exceeding 100 ° C., for example, a resin having a temperature of about 120 to 200 ° C.
  • a resin having a glass transition temperature lower than that of a chain olefin-cyclic olefin copolymer for example, glass A resin having a transition temperature of less than 10 ° C.
  • the resin having a low glass transition temperature may be a polyethylene resin, and the glass transition temperature of the resin component (polyethylene resin or the like) is ⁇ 150 ° C. to 10 ° C. (for example, ⁇ 110 to 0 ° C.), preferably ⁇ It may be about 80 to -5 ° C (eg, -50 to -10 ° C).
  • the number average molecular weight of other resin components is, for example, 5000 to 300,000, preferably 10,000 to 200,000 in terms of polystyrene in gel permeation chromatography (GPC). More preferably, it may be about 15000 to 150,000.
  • the ratio of other resin components is 0.01 to 100 parts by weight (for example, 0.05 to 50 parts by weight) with respect to 100 parts by weight of the chain olefin-cyclic olefin copolymer.
  • the amount may preferably be about 0.1 to 30 parts by weight, or 25 parts by weight or less (eg, about 0.01 to 20 parts by weight, preferably about 0.1 to 10 parts by weight).
  • the other resin component is a chain olefin resin, if the content is too large, the transparency is lowered.
  • the polyurethane (meth) acrylate polymer generates a polymer (prepolymer) having a terminal isocyanate group by the reaction of a polymer polyol and a polyisocyanate, and the reaction between the terminal isocyanate group and the (meth) acrylic acid hydroxyalkyl ester.
  • this polyurethane (meth) acrylate polymer By irradiating this polyurethane (meth) acrylate polymer with active energy rays, a polymer having a crosslinked structure having a predetermined molecular weight between crosslinking points can be obtained.
  • J Polym Sci Part B, Vol 37, No 9 and Page 919-937 J Polym Sci Part B, Vol 37, No 9 and Page 919-937 can be referred to.
  • the polymer polyol may be polyester polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, polyester amide polyol, acrylic polymer polyol, or the like.
  • the polymer polyol is usually a polymer diol in many cases.
  • the polyester polyol is, for example, a diol component (for example, an aliphatic diol component such as C 2-10 alkane diol) and a dicarboxylic acid component (for example, C 6-16 alkane dicarboxylic acid) as in the case of the aliphatic polyester resin.
  • a diol component for example, an aliphatic diol component such as C 2-10 alkane diol
  • a dicarboxylic acid component for example, C 6-16 alkane dicarboxylic acid
  • Reaction of aliphatic dicarboxylic acid component reaction of hydroxycarboxylic acid component and / or lactone component (eg, lactone component such as C 4-8 lactone), diol component and dicarboxylic acid component, and hydroxycarboxylic acid component and / or lactone It can be obtained by reaction with the components.
  • the polyester polyol is an aliphatic polyester having a terminal hydroxyl group (aliphatic polyester) prepared by using the same aliphatic component as described above, for example, the aliphatic diol component, the aliphatic dicarboxylic acid component and / or the lactone component. Diol etc.) in many cases.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Usually, polytetramethylene ether glycol is used.
  • polyether ester polyol examples include a polymer of the polyether polyol and the dicarboxylic acid component (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, etc.) or a reactive derivative thereof. Can be illustrated.
  • polycarbonate polyol examples include glycols (alkane diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol; diethylene glycol, dipropylene glycol).
  • (Poly) oxyalkylene glycols such as: 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and other alicyclic diols; bisphenols such as bisphenol A, alkylene oxide adducts of bisphenols, etc.
  • a terminal carboxyl group-containing polyester and a diamine for example, an aliphatic group having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine, etc. It can be prepared by reaction with a diamine or the like).
  • the acrylic polyol includes a polymerizable monomer having a hydroxyl group (for example, the (meth) acrylic acid hydroxy C 2-4 alkyl ester) and a (meth) acrylic monomer having no hydroxyl group (for example, (Meth) acrylic acid or its ester).
  • a polymerizable monomer having a hydroxyl group for example, the (meth) acrylic acid hydroxy C 2-4 alkyl ester
  • a (meth) acrylic monomer having no hydroxyl group for example, (Meth) acrylic acid or its ester
  • polyester polyols polyester polyols, polyether polyols, and polycarbonate polyols are preferable.
  • polymer diols aliphatic polyester diols such as polyethylene adipate, polybutylene adipate, and polybutylene sebacate, and polytetramethylene ether glycol
  • Ether diols are used.
  • alkanediol ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol etc.
  • triols glycol, trimethylolethane, trimethylolpropane, triethanolamine etc.
  • tetraols penentaerythritol etc.
  • polyisocyanate a compound corresponding to the isocyanate-based crosslinking agent can be used.
  • polyisocyanates aliphatic diisocyanates such as HDI, IPDI, alicyclic diisocyanates such as hydrogenated XDI, araliphatic diisocyanates such as XDI, aromatic diisocyanates such as TDI, MDI, and NDI are often used.
  • a non-yellowing type diisocyanate or a polyisocyanate derivative such as a trimer having an isocyanurate ring
  • These polyisocyanates may be used alone or in combination of two or more.
  • the polyisocyanate is usually a diisocyanate or a trimer having an isocyanurate ring (such as a trimer of an aliphatic diisocyanate).
  • triisocyanate tetraisocyanate, etc. may be used in combination.
  • the polymer having a terminal isocyanate group can be prepared by using an excess mole of polyisocyanate with respect to the hydroxyl group of the polymer polyol. Further, the reaction between the terminal isocyanate group and the (meth) acrylic acid hydroxyalkyl ester (such as (meth) acrylic acid hydroxy C 2-6 alkyl ester) can be easily carried out using a conventional urethanization reaction.
  • this polyurethane (meth) acrylate polymer By irradiating this polyurethane (meth) acrylate polymer with active energy rays, a polymer having a crosslinked structure having a predetermined molecular weight between crosslinking points can be obtained.
  • the polyester (meth) acrylate polymer introduces a (meth) acryloyl group by a reaction between the terminal hydroxyl group of the polyester polyol and (meth) acrylic acid or a reactive derivative thereof ((meth) acrylic acid chloride or the like). Can be prepared. Further, in the preparation of the aliphatic polyester-based resin, a polyester having a terminal carboxyl group is prepared by using an excessive amount of a dicarboxylic acid component relative to the diol component, and this terminal carboxyl group and hydroxy (meth) acrylate C 2- You may prepare by introduce
  • the same unsaturated polyester polymer as described above unsaturated polyester polymer in which the amount of polymerizable unsaturated dicarboxylic acid or its acid anhydride is small
  • unsaturated polyester polymer in which the amount of polymerizable unsaturated dicarboxylic acid or its acid anhydride is small
  • the number average molecular weight of the uncrosslinked polymer may correspond to the molecular weight between the crosslinking points, or may correspond to a molecular weight larger than the molecular weight between the crosslinking points.
  • the number average molecular weight of the uncrosslinked polymer is, for example, 3000 to 150,000 (for example, 5000 to 120,000), preferably 8000 to 100,000 (for example, 10,000 to 100,000), more preferably 20,000 to 90,000 (in terms of polystyrene) in GPC. For example, it may be about 25000 to 90000).
  • the uncrosslinked polymer may contain a polymerization initiator or may not contain a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator (a thermal radical generator such as a peroxide such as benzoyl peroxide), but is preferably a photopolymerization initiator (a photo radical generator).
  • photopolymerization initiator examples include benzoins (benzoin, benzoin alkyl ethers, etc.), phenyl ketones [eg, acetophenones (eg, acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one) Alkylphenyl ketones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone), 2-hydroxy-2-methylpropiophenone; -Cycloalkyl phenyl ketones such as hydroxycyclohexyl phenyl ketone], aminoacetophenones ⁇ 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1,2-benzyl-2-dimethyl Amino-1- (4- Ruphorinophenyl) -butanone-1 ⁇ , anthraquinones (anthraquinone,
  • photopolymerization initiators can be used alone or in combination of two or more.
  • the ratio of the polymerization initiator is about 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably about 0.1 to 2.5 parts by weight with respect to 100 parts by weight of the polymer. May be.
  • the photopolymerization initiator may be combined with a photosensitizer.
  • the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl.
  • Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenones such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone)], phosphines such as triphenylphosphine, N, N-dimethyl Toluidines such as toluidine, and anthracene such as 9,10-dimethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene.
  • the photosensitizers may be used alone or in combination of two or more.
  • the amount of the photosensitizer used may be, for example, about 0.1 to 100 parts by weight, preferably about 1 to 80 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.
  • An uncrosslinked polymer containing a photopolymerization initiator may be crosslinked by irradiation with active energy rays such as ultraviolet rays, and if necessary, active high energy rays such as radiation ( ⁇ rays, X rays, etc.) and electron beams. You may make it bridge
  • active energy rays such as ultraviolet rays
  • active high energy rays such as radiation ( ⁇ rays, X rays, etc.) and electron beams.
  • a Deep UV lamp a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), or the like can be used.
  • Irradiation light amount varies depending on the thickness of the sheet-like covering material, for example, 50 ⁇ 10000mJ / cm 2, preferably 70 ⁇ 7000mJ / cm 2, even more preferably from 100 ⁇ 5000mJ / cm 2 of about Good.
  • the crosslinked structure is formed without the need for an additive (or auxiliary agent) such as a polymerization initiator.
  • Active high energy rays that can be introduced [for example, active radiation such as radiation ( ⁇ rays, X-rays, etc.), electron beams, etc.], particularly electron beams, can be used.
  • active radiation such as radiation ( ⁇ rays, X-rays, etc.), electron beams, etc.
  • electron beams particularly electron beams
  • room temperature for example, a temperature of about 10 to 30 ° C.
  • the irradiation amount (dose) of a high energy beam can be selected according to the type of uncrosslinked polymer, and can be selected from a range of, for example, about 100 to 500 kGy (gray) (for example, 150 to 400 kGy). It may be about 150 to 500 kGy (for example, 170 to 450 kGy), preferably about 200 to 430 kGy (for example, 250 to 400 kGy).
  • the acceleration voltage of the high energy beam can be selected from a range of, for example, about 10 to 1000 kV (for example, 100 to 500 kV), and is about 150 kV or more (for example, 160 to 400 kV, preferably 170 to 300 kV, more preferably 180 to 250 kV). It may be.
  • the irradiation of active energy rays may be performed in the air, and may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas) atmosphere if necessary.
  • an inert gas for example, nitrogen gas, argon gas, helium gas
  • the uncrosslinked polymer may be crystalline, but is often non-crystalline.
  • Typical non-crystalline uncrosslinked polymers include, for example, non-crystalline olefin polymers (copolymers of chain olefins and cyclic olefins (such as copolymers of ethylene and norponenes)), (meta )
  • An acrylic polymer can be exemplified.
  • the degree of crystallinity of the amorphous polymer (a polymer such as a chain olefin-cyclic olefin copolymer) is usually 10% or less, for example, 0 to 10%, preferably 0 to 5%, more preferably 0. It is about 3% (especially 0-1%).
  • the crystallinity can be calculated by using an X-ray diffraction method, fitting a crystalline part (peak) and an amorphous part (halo), and substituting each integral intensity into the following equation.
  • X represents the crystalline scattering integrated intensity (scattering integrated intensity derived from the crystalline part)
  • Y represents the amorphous scattering integrated intensity (scattering integrated intensity derived from the amorphous part).
  • the refractive index of the uncrosslinked polymer is, for example, 1.45 to 1.6, preferably 1.48 to 1 at 23 ° C. and a wavelength of 589 nm. 58, more preferably about 1.5 to 1.56 (for example, 1.51 to 1.55). If the refractive index is in such a range, the difference in refractive index with an optical member (such as a glass plate) constituting the display device can be reduced. Therefore, even when used for covering or bonding the optical member, The reflection of the light can be effectively prevented, and the display performance of the display device is not impaired.
  • the sheet-like covering agent should just contain the said uncrosslinked polymer, and if necessary, contains the resin component, for example, the said olefin resin, acrylic resin, polyester resin, etc. May be.
  • the sheet-like covering agent (or sealant) may be a conventional additive, for example, a crosslinking agent, a crosslinking accelerator, a crosslinking aid, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, if necessary. And other stabilizers, plasticizers, antistatic agents, flame retardants, colorants and the like. These additives can be used alone or in combination of two or more.
  • the sheet covering agent substantially contains a crosslinking agent, a crosslinking accelerator, and a crosslinking assistant when a polymer crosslinked with an active energy ray (such as active radiation such as an electron beam) is used. It may not be necessary, and a component (such as an oligomer or a resin) having a crosslinkable group (for example, a group having an ethylenically unsaturated bond) may not be substantially contained.
  • the sheet-like covering agent is obtained by subjecting an uncrosslinked polymer (or a composition containing an uncrosslinked polymer and a crosslinking agent or a polymerization initiator) to a conventional molding method such as a casting method, an extrusion molding method, or a blow molding method. It can be obtained by forming a sheet with a predetermined thickness and then crosslinking.
  • Crosslinking may be performed by heating a sheet containing a crosslinking agent as described above (for example, heating at room temperature to 100 ° C., particularly about 30 to 70 ° C.), or may contain a polymerization initiator (In particular, it may be carried out by irradiating an active energy ray (radiation, electron beam, etc.) to a sheet that does not contain a crosslinking agent, a polymerization initiator or the like. Vulcanization by irradiation with active energy rays is effective for crosslinking an uncrosslinked polymer having a low glass transition temperature because the sheet molded body can be crosslinked without heating.
  • the sheet-like molded body may be subjected to a surface treatment such as a corona treatment or a plasma treatment before or after the crosslinking treatment, or may be uniaxially or biaxially stretched at a predetermined magnification.
  • a surface treatment such as a corona treatment or a plasma treatment before or after the crosslinking treatment, or may be uniaxially or biaxially stretched at a predetermined magnification.
  • FIG. 1 is a graph showing the relationship between the storage elastic modulus and temperature of the test pieces of Comparative Example 1, Comparative Example 2 and Example 3.
  • the storage elastic modulus starts to decrease (melt flow starts) at a predetermined temperature T1, and the temperature is higher than the temperature T1. Increases, the storage elastic modulus is greatly reduced to form a melt flow region.
  • an uncrosslinked polymer shows a tendency that the storage elastic modulus decreases as the temperature rises even at a temperature higher than the temperature T2.
  • a crosslinked polymer having a small molecular weight between crosslinking points exhibits a flat storage elastic modulus at a temperature lower than the temperature T2.
  • the sheet-like molded product of the present invention containing a polymer having a low glass transition temperature has high fluidity at a relatively low temperature (processing temperature such as covering or sealing temperature) and can follow the surface step even if the thickness is large. Even if the member to be processed has a minute stepped portion, it can be coated or sealed uniformly and tightly. Moreover, since the stress relaxation property is high, even if the covering agent is solidified, the residual strain is quickly released, and the residual stress does not act on the member to be processed. Moreover, at high temperatures, the melt fluidity is regulated by the cross-linked structure, and heat resistance is obtained. Therefore, the said sheet-like molded object is useful as a sheet-like covering agent (or sealing agent) of various to-be-processed members.
  • processing temperature such as covering or sealing temperature
  • the present invention also includes a covering method for covering or covering a member to be processed.
  • the treated site can be covered or covered with the covering agent by bringing the sheet-like covering agent into contact with the treated site, heating the covering agent to flow the polymer, and then cooling.
  • the member to be processed is a precision part (sealing part) such as an electronic device
  • the precision part can be sealed using a sheet-like covering agent as the sheet-like sealing agent.
  • the sheet-like covering agent may be in contact with at least a portion to be treated (point, line, or surface contact) of the member to be treated, and at least the portion to be treated (or the member to be treated) is often covered with the sheet-like covering agent.
  • at least a portion to be treated point, line, or surface contact
  • the heating temperature can be selected from the temperature of the flow region of the polymer. However, in order to avoid damage to the member to be treated due to heat, in precision parts such as electronic devices, the temperature is usually higher than the glass transition temperature of the polymer. However, it is often heated at a temperature of 100 ° C. or lower. A preferable heating temperature may be about 40 to 80 ° C. (for example, 45 to 75 ° C., particularly 45 to 65 ° C.). If necessary, it may be heated at normal pressure or under pressure.
  • a member in which at least a portion to be treated is coated (or covered) can be obtained by melting and flowing the polymer to coat (or cover) a predetermined portion of the member to be treated and then cooling to solidify the polymer. it can.
  • the sealing part by which the predetermined part was sealed with the polymer can be obtained. Therefore, this invention also includes the manufacturing method of the electronic device which seals or covers an electronic device with a covering agent.
  • the surface of the member to be processed may be flat, or may have a stepped portion such as an uneven portion (or mounted component). In the present invention, even a minute step portion (uneven portion) can be effectively covered or sealed, so the height of the step portion is not particularly limited.
  • the step of the minute step portion is 1 ⁇ m to 30 mm (for example, 2 ⁇ m to 25 mm), preferably about 3 ⁇ m to 20 mm (for example, 5 ⁇ m to 15 mm).
  • step-difference part (uneven part) is large, it can coat
  • the transparent pressure-sensitive adhesive sheet includes a core film containing the polymer (or formed with the covering agent) and a pressure-sensitive adhesive layer formed on at least one surface of the core film.
  • the adhesive sheet double-sided adhesive sheet which has an adhesive layer on both surfaces of a core film is useful as an OCA (Optical Clear Adhesive) tape.
  • the core material film only needs to contain the polymer. From the viewpoint of optical properties (low birefringence, transparency, etc.), heat resistance, etc., a crosslinked product of a chain olefin-cyclic olefin copolymer (for example, radiation Or a cross-linked electron beam).
  • the core film may be subjected to surface treatment (corona treatment, plasma treatment, etc.) from the viewpoint of effectively preventing the generation of bubbles and lifting off.
  • the surface energy (or surface tension) of the core film is, for example, 30 to 80 mN / m, preferably 35 to 75 mN / m, more preferably 40 to 70 mN / m (for example 45 to 45), in accordance with JIS K 768. 65 mN / m).
  • the adhesiveness with the pressure-sensitive adhesive layer is excellent.
  • the thickness of the core film can be selected from the same range as the thickness of the sheet covering agent (sealing agent), and may be, for example, about 20 to 400 ⁇ m, or 100 ⁇ m or more (for example, about 100 to 400 ⁇ m). May be. Even if the thickness of the core material film is large, the core film has an appropriate flexibility at the bonding processing temperature. Therefore, even if the gap between both adherends is large, the core film can be bonded without a gap.
  • the core film can be formed by a conventional film forming method such as a casting method, an extrusion method, or a blow molding method.
  • a conventional film forming method such as a casting method, an extrusion method, or a blow molding method.
  • the core film contains the chain olefin-cyclic olefin copolymer, high optical isotropy can be obtained even if the film is formed by an extrusion method.
  • the pressure-sensitive adhesive layer is not particularly limited as long as it has adhesiveness to an adherend (such as an optical member) and is transparent.
  • the pressure-sensitive adhesive layer contains a conventional pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive. These pressure-sensitive adhesives may be used alone or in combination of two or more. Of these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are widely used.
  • the polymer etc. which use a (meth) acrylic monomer as a polymerization component can be illustrated.
  • the (meth) acrylic monomer include monomers exemplified in the section of “polymer crosslinkable with a crosslinking agent”, for example, linear or branched C 1-12 alkyl (meth) acrylate, C And 5-10 cycloalkyl (meth) acrylate, bridged cyclic (meth) acrylate, C 6-10 aryl (meth) acrylate, and the like.
  • the (meth) acrylic monomer includes a (meth) acrylic monomer having a crosslinkable group. Examples of the crosslinkable group include a hydroxyl group, a carboxyl group, and an epoxy group.
  • Examples of (meth) acrylic monomers having a hydroxyl group include hydroxy C 2-6 alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; (poly) ethylene glycol mono (meth) acrylate and the like (poly ) C 2-4 alkylene glycol mono (meth) acrylate; glycerin di (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, dipenta Examples include erythritol di to penta (meth) acrylate.
  • Examples of the (meth) acrylic monomer having a carboxyl group include (meth) acrylic acid; a carboxy C 2-6 alkyl (meth) acrylate such as ⁇ -carboxyethyl (meth) acrylate; a dicarboxylic acid and a hydroxyl group ( Examples thereof include monoesters with (meth) acrylic monomers.
  • Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate.
  • acrylic monomers may be used alone or in combination of two or more.
  • Preferred (meth) acrylic monomers include at least acrylic monomers such as alkyl acrylates (eg, C 1-10 alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate).
  • alkyl acrylates eg, C 1-10 alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate.
  • an acrylic monomer having an alkyl acrylate and a crosslinkable group for example, an acrylic monomer having a hydroxyl group and / or an acrylic monomer having a carboxyl group
  • combinations with hydroxyl C 2-6 alkyl acrylates are preferred.
  • the ratio is about 5 / 0.5, more preferably about 90/10 to 99/1.
  • the (meth) acrylic monomer may be combined with other copolymerizable monomers.
  • copolymerizable monomers include organic acid vinyl esters (eg, C 2-6 alkanecarboxylic acid vinyl esters such as vinyl acetate and vinyl propionate), chain olefins ( ⁇ -C such as ethylene and propylene). 2-4 olefins), aromatic vinyl monomers (styrene, etc.), halogen-containing vinyl monomers (vinyl chloride, etc.) and the like.
  • organic acid vinyl esters eg, C 2-6 alkanecarboxylic acid vinyl esters such as vinyl acetate and vinyl propionate
  • chain olefins ⁇ -C such as ethylene and propylene
  • aromatic vinyl monomers styrene, etc.
  • halogen-containing vinyl monomers vinyl chloride, etc.
  • the glass transition temperature of the pressure-sensitive adhesive is, for example, about ⁇ 80 ° C. to 100 ° C., preferably ⁇ 70 ° C. to 50 ° C., more preferably about ⁇ 60 ° C. to 30 ° C. (eg, ⁇ 50 ° C. to 10 ° C.).
  • the pressure-sensitive adhesive layer may further contain a conventional additive such as a crosslinking agent, a tackifier, a stabilizer, a plasticizer, a flame retardant, and a silane coupling agent.
  • a conventional additive such as a crosslinking agent, a tackifier, a stabilizer, a plasticizer, a flame retardant, and a silane coupling agent.
  • crosslinking agents and tackifiers are widely used.
  • crosslinking agent examples include the crosslinking agents exemplified in the section “Polymer crosslinkable with crosslinking agent”, for example, an isocyanate crosslinking agent, an acid anhydride crosslinking agent, a silane crosslinking agent, and the like. These crosslinking agents can be used alone or in combination of two or more. Of these crosslinking agents, isocyanate-based crosslinking agents such as araliphatic polyisocyanates (xylylene diisocyanate modified with alkane polyols such as xylylene diisocyanate and trimethylol propane) are preferred.
  • araliphatic polyisocyanates xylylene diisocyanate modified with alkane polyols such as xylylene diisocyanate and trimethylol propane
  • the ratio of the crosslinking agent is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the pressure-sensitive adhesive (acrylic pressure-sensitive adhesive, etc.). Degree.
  • tackifier examples include rosin resins (such as tall rosin, gum rosin, and wood rosin), terpene resins (such as monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, and tetraterpenes), styrene resins (such as Polystyrene, a copolymer of styrene and acrylonitrile, etc.), methacrylic resins [methacrylic monomers (for example, C 1-10 such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, etc.) Examples thereof include alkyl methacrylate and the like) or a copolymer thereof. These tackifiers can be used alone or in combination of two or more.
  • terpene resins such
  • the ratio of the tackifier is, for example, about 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably about 5 to 30 parts by weight with respect to 100 parts by weight of the adhesive.
  • the thickness of the pressure-sensitive adhesive layer (when the pressure-sensitive adhesive layer is formed on both sides, the thickness of each layer) is, for example, about 5 to 100 ⁇ m, preferably 10 to 90 ⁇ m, more preferably 20 to 80 ⁇ m (for example, 30 to 70 ⁇ m). .
  • the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive and, if necessary, an additive and a solvent, to the peelable substrate or the core material film.
  • a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive and, if necessary, an additive and a solvent
  • examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating, and part coating.
  • coating it dries as needed, and when a crosslinking agent is included, it is bridge
  • the transparent pressure-sensitive adhesive sheet only needs to have a core film and a pressure-sensitive adhesive layer, and other arbitrary layers (functional layers) may be laminated.
  • the transparent pressure-sensitive adhesive sheet is a release sheet [for example, paper or paper that may be surface-treated with a release agent (such as a silicone resin) on the pressure-sensitive adhesive layer in order to prevent adhesion to members other than the adherend. Plastic sheets etc.] may be laminated.
  • the transparent adhesive sheet has a protective layer [glass plate, transparent plastic film (polyester resin film, acrylic resin film, etc.), hard coat film, etc.], optical layer [antiglare film ( AG film), antireflection film (AR film), polarizing film, retardation film, optical isotropic film, transparent conductive film (ITO film), electromagnetic prevention film (EMI film), viewing angle control film, etc.] You may laminate.
  • the transparent adhesive sheet may have two or more lamination units (repeating unit) comprised by the adhesive layer, the protective layer, and / or the optical layer.
  • the transparent adhesive sheet is excellent in transparency, adhesiveness, and reworkability, it is useful for bonding optical members.
  • a display device equipped with a touch panel 2 selected from a touch panel, a display panel, and a protective panel. It can be suitably used for bonding two panels.
  • the transparent adhesive sheet is also excellent in step followability, it can be suitably used for bonding members having convex portions on the surface (such as convex portions having side surfaces that rise substantially perpendicularly from a flat surface).
  • a member include an optical member (such as a protective panel) on which a printed layer (such as a black printed layer) is formed.
  • the present invention also includes an electronic device in which an optical member is bonded with a transparent adhesive sheet (double-sided adhesive sheet), for example, a display device provided with a touch panel (resistance film type, capacitance type, etc.).
  • a transparent adhesive sheet double-sided adhesive sheet
  • a display device provided with a touch panel (resistance film type, capacitance type, etc.).
  • a typical display device includes a first laminated unit having a hard coat layer / transparent adhesive sheet / hard coat layer / transparent conductive layer in this order, and a transparent conductive layer / hard coat layer / transparent adhesive sheet / transparent resin layer.
  • Examples include a laminate obtained by laminating / transparent adhesive sheet / second laminate unit having a display layer in this order with each transparent conductive layer facing each other.
  • a glass plate, a transparent conductive layer, a glass plate, and a display layer are usually bonded via a transparent adhesive sheet.
  • a laminate having a glass plate / transparent adhesive sheet / transparent conductive layer / glass plate / transparent adhesive sheet / transparent conductive layer / glass plate / transparent adhesive sheet / display layer in this order can be exemplified. .
  • the bonding temperature is not particularly limited as long as the pressure-sensitive adhesive layer can express the adhesive force, and is, for example, 40 to 60 ° C., preferably 45 to 55 ° C. Degree. Bonding is often performed under normal pressure or under pressure (for example, about 1.5 to 5 MPa, preferably about 2 to 4 MPa).
  • the density ⁇ (g / m 3 ) was 1.02.
  • Stress relaxation rate The stress relaxation rate was obtained by cutting a sample into a width of 5 mm and a length of 50 mm, and using a dynamic viscoelasticity measuring device (RSA-III, manufactured by TA Instruments Japan Co., Ltd.) at a temperature of 80 ° C. and between chucks.
  • the storage elastic modulus after 10 seconds and the storage elastic modulus after 20 seconds are measured immediately after the distance of 20 mm and 5% extension (strain stop), and can be calculated by the following formula.
  • A indicates the storage elastic modulus after 10 seconds of strain stop
  • B indicates the storage elastic modulus after 20 seconds of strain stop.
  • Total light transmittance About the test piece of an Example and a comparative example, the total light transmittance was measured based on JISK7105.
  • the linear expansion coefficient is calculated by using TMA (EXSTA TMA / SS7100, manufactured by SII Nanotechnology Co., Ltd.), with a temperature increase rate of 5 ° C / min, and an expansion coefficient per 1 ° C temperature increase from 20 ° C to 100 ° C. did.
  • TMA EXSTA TMA / SS7100, manufactured by SII Nanotechnology Co., Ltd.
  • a temperature increase rate of 5 ° C / min
  • an expansion coefficient per 1 ° C temperature increase from 20 ° C to 100 ° C. did.
  • the sample whose linear expansion coefficient is within 3000 ppm / K has high heat resistance (thermal deformation property), exceeds the measurement limit, and the sample subjected to melt fracture is inferior in heat resistance.
  • test piece of the example and the comparative example was pressed once and reciprocally with a 2 kg roller against a regular square flat glass plate (length and length 5 cm), and autoclaved (50 ° C., 3 Mpa). 30 minutes). When peeled from the glass plate in the direction of 150 ° at a speed of 500 mm / min, there was no adhesive residue. If it did not break, it passed ( ⁇ ).
  • an ultraviolet irradiation device (produced by Eye Graphics Co., Ltd.) in a nitrogen atmosphere (ECS-4011GX, high pressure mercury lamp) was irradiated with ultraviolet rays at a lamp output of 4 kW and a conveying speed of 4 m / min to obtain a cured product having a thickness of 76 ⁇ m.
  • ECS-4011GX high pressure mercury lamp
  • Example 1 The film obtained in Comparative Example 1 was subjected to electron beam irradiation at an acceleration voltage of 200 kV and a dose of 150 kGy using an electron beam irradiation apparatus (“TYPE: CB250 / 15 / 180L” manufactured by Iwasaki Electric Co., Ltd.) in a nitrogen atmosphere at room temperature. Were cross-linked to produce a film-like test piece having a thickness of 100 ⁇ m.
  • Example 2 The film obtained in Comparative Example 1 was irradiated with an electron beam at an accelerating voltage of 200 kV and a dose of 250 kGy using an electron beam irradiation apparatus (“TYPE: CB250 / 15 / 180L” manufactured by Iwasaki Electric Co., Ltd.) in a nitrogen atmosphere at room temperature. Were cross-linked to produce a film-like test piece having a thickness of 100 ⁇ m.
  • Example 3 The film obtained in Comparative Example 1 was irradiated with an electron beam at an acceleration voltage of 200 kV and a dose of 350 kGy using an EB irradiation apparatus (“TYPE; CB250 / 15 / 180L” manufactured by Iwasaki Electric Co., Ltd.) in a nitrogen atmosphere at room temperature. Then, a film-like test piece having a thickness of 100 ⁇ m was produced.
  • TYPE CB250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd.
  • Example 4 The resin used in Example 3 is a cyclic olefin resin (made by Topas Advanced Polymers GmbH, trade name “TOPAS9506”, number average molecular weight 66000, glass transition temperature 70 ° C., norbornene content 32 mol%), 40 parts by weight, cyclic olefin resin A film was produced in the same manner as in Example 3 except that a mixture of 60 parts by weight of resin (made by Topas Advanced Polymers GmbH, trade name “TOPAS 9903”, number average molecular weight 69000, glass transition temperature 33 ° C., norbornene content 20 mol%) was used. A test specimen was prepared.
  • Example 3 As is clear from Table 1, the examples showed higher step following ability and heat resistance than the comparative examples. As is clear from FIG. 1, the test piece of Example 3 exhibited a unique viscoelastic behavior compared to the test pieces of Comparative Example 1 and Comparative Example 2.
  • Example 5 Using the film obtained in Example 3 as a core material, the pressure-sensitive adhesive layer obtained in Preparation Example 1 was bonded to both surfaces of the core material to prepare a transparent pressure-sensitive adhesive sheet.
  • Example 6 Using a corona treatment device (manufactured by Kasuga Denki Co., Ltd.) whose electrodes were covered with ceramic on both surfaces of the film obtained in Example 3, discharge treatment was performed twice under the conditions of an output of 300 W and a conveyance speed of 5 m / min. Using the obtained film as a core material, the pressure-sensitive adhesive layer obtained in Preparation Example 1 was bonded to both surfaces of the core material to prepare a transparent pressure-sensitive adhesive sheet.
  • a corona treatment device manufactured by Kasuga Denki Co., Ltd.
  • Example 7 A film having a thickness of 200 ⁇ m was prepared in the same manner as in Comparative Example 1, cross-linked with an electron beam in the same manner as in Example 3, and discharged in the same manner as in Example 6. Using the obtained film as a core material, the pressure-sensitive adhesive layer obtained in Preparation Example 1 was bonded to both surfaces of the core material to prepare a transparent pressure-sensitive adhesive sheet.
  • the step absorbability and the reworkability can be achieved in the embodiment as compared with the comparative example.
  • floating and peeling can be prevented even under high temperature and high humidity, and the generation of bubbles is remarkably suppressed.
  • in-plane retardation is small and it is excellent in optical isotropy.
  • it has moderate surface energy and is excellent also in adhesiveness with an adhesive layer.
  • the present invention is effective for covering or covering various members to be processed.
  • various functional elements such as semiconductor elements, organic EL elements, liquid crystal elements (liquid crystal cells), photoelectric conversion elements (solar battery cells, etc.), piezoelectric elements, devices such as these functional element packages (semiconductor packages, etc.) (or This is effective for sealing (especially sealing at a low temperature) precision components such as electronic devices) and the functional elements or printed boards mounted with the packages.
  • the present invention is effective for bonding various members (for example, a member having a convex portion on the surface) because it is excellent in step following ability and reworkability.
  • the present invention is an optical member such as an optical glass, an optical lens, an optical film (a hard coat film, an antiglare film, an antireflection film, a polarizing film, a retardation film, an optical isotropic film, a transparent conductive film. , Anti-electromagnetic prevention film, viewing angle control film, etc.).
  • an electronic device including the optical member for example, a display device [for example, a display device having a flat panel display (liquid crystal display, plasma display, organic EL, etc.), a touch panel (optical method, ultrasonic method, capacitance method). It is useful as a constituent member of a display device provided with a resistive film method.
  • a display device for example, a display device having a flat panel display (liquid crystal display, plasma display, organic EL, etc.), a touch panel (optical method, ultrasonic method, capacitance method). It is useful as a constituent member of a display device provided with a resistive film method.

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PCT/JP2012/081247 2011-12-06 2012-12-03 シート状カバリング剤、カバリング方法又は電子デバイスの製造方法 WO2013084836A1 (ja)

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