WO2021039320A1 - Composition photodurcissable, corps durci associé, matériau d'étanchéité, matériau protecteur, structure étanche à l'eau et procédé de production de corps durci - Google Patents

Composition photodurcissable, corps durci associé, matériau d'étanchéité, matériau protecteur, structure étanche à l'eau et procédé de production de corps durci Download PDF

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WO2021039320A1
WO2021039320A1 PCT/JP2020/029924 JP2020029924W WO2021039320A1 WO 2021039320 A1 WO2021039320 A1 WO 2021039320A1 JP 2020029924 W JP2020029924 W JP 2020029924W WO 2021039320 A1 WO2021039320 A1 WO 2021039320A1
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photocurable composition
acrylic
curing
styrene
chromaticity
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PCT/JP2020/029924
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English (en)
Japanese (ja)
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優 花倉
眸 愛澤
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積水ポリマテック株式会社
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Priority to KR1020217038886A priority Critical patent/KR20220055451A/ko
Priority to CN202080044270.6A priority patent/CN113993912A/zh
Priority to JP2021542688A priority patent/JPWO2021039320A1/ja
Publication of WO2021039320A1 publication Critical patent/WO2021039320A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to a photocurable composition, a cured product thereof, and the like, and a method for producing the same.
  • a photocurable composition that is liquid before application and can be used as a gasket or the like after being photocured after application is used after being sufficiently cured after being applied to a desired site.
  • the uncured photocurable composition may come into contact with the contact body and become contaminated.
  • the product may be commercialized with insufficient curing, resulting in product defects due to a decrease in compression set.
  • the cured state of the photocurable composition does not necessarily correspond to the color change, and the color change indicates the end of curing. I could't say that. Further, if the dye concentration is high, it is difficult for light rays such as ultraviolet rays to reach the inside, and there is a concern that the curability is impaired.
  • the present invention has been made to solve such a problem. That is, there is provided a photocurable composition capable of obtaining a color change that can be distinguished from that before curing after completion of curing while coloring with a low concentration leuco dye.
  • the photocurable composition of the present invention and a cured product thereof that achieve the above object are as follows. That is, the present invention contains at least one acrylic compound selected from an acrylic monomer, an acrylic oligomer, and an acrylic polymer, a photoradical generator, and a leuco dye, and describes CIE1976 (L * , a *) described in JISZ8781-4.
  • a * 0 and b * 0 indicate chromaticity a * value and b * value in the L * a * b * color space before curing, and a * 50 and b * 50 are.
  • the chromaticity a * value and b * value in the L * a * b * color space at a curing rate of 50% are shown, and a * 100 and b * 100 are the chromaticity a in the L * a * b * color space after curing.
  • * Value and b * value are shown.
  • the present invention contains at least one acrylic compound selected from an acrylic monomer, an acrylic oligomer, and an acrylic polymer, a photoradical generator, and a leuco dye, the acrylic monomer, acrylic oligomer, and acrylic can be irradiated with light. At least one acrylic compound selected from the polymers can be cured, and the chromaticity can be changed before and after curing.
  • a * 0 and b * 0 indicate chromaticity a * value and b * value in the L * a * b * color space before curing, and a * 50 and b * 50 are.
  • the chromaticity a * value and b * value in the L * a * b * color space at a curing rate of 50% are shown, and a * 100 and b * 100 are the chromaticity a in the L * a * b * color space after curing.
  • * Value and b * value are shown.
  • the chromaticity change parameter represented by the above formula (1) is in the range of 0 to 2.0, the distance (color change) in the latter half of the reaction is at least half or more larger than that in the first half of the reaction, so that curing due to color change It is possible to prevent misunderstanding of the state.
  • the chromaticity difference and the chromaticity change parameter in the present invention are values measured and calculated by the method described in Examples.
  • the present invention can be a photocurable composition that does not contain an acid generator.
  • the photocurable composition containing no acid generator does not cause an early color change to the leuco dye, and it is easy to make the curing of the acrylic monomer, the acrylic oligomer, and the acrylic polymer correspond to the reaction by the leuco dye.
  • the acrylic compound can be a photocurable composition in which the acrylic compound is at least one of a monofunctional acrylic monomer, a bifunctional or higher acrylic oligomer, and a bifunctional or higher acrylic polymer.
  • a photocurable composition in which the acrylic compound is at least one of a monofunctional acrylic monomer, a bifunctional or higher acrylic oligomer, and a bifunctional or higher acrylic polymer, the cured product obtained by curing the photocurable composition is an electronic element. It can be used as a suitable sealing material, protective material, etc. because it adheres to the substrate and exhibits waterproofness and the like.
  • the acrylic compound can be a photocurable composition containing at least a monofunctional acrylic monomer and further containing a styrene-based elastomer.
  • a photocurable composition in which the acrylic compound contains at least a monofunctional acrylic monomer and further contains a styrene-based elastomer can reduce the transparency of the cured product and impart rubber elasticity while increasing its mechanical strength. it can.
  • the styrene-based elastomer is at least one of a high-molecular-weight styrene-based elastomer having a weight average molecular weight of 200,000 or more, an epoxy-modified styrene-based elastomer, and a styrene-based elastomer having an unsaturated bond in a soft segment. It can be a curable composition.
  • a high-molecular-weight styrene-based elastomer having a weight average molecular weight of 200,000 or more an epoxy-modified styrene-based elastomer
  • a styrene-based elastomer having an unsaturated bond in a soft segment can reduce the compression set when it is made into a cured product, and can be suitably used as a sealing material, a protective material, and the like.
  • the styrene-based elastomer can be a photocurable composition which is a styrene-isobutylene-styrene block polymer.
  • the photocurable composition in which the styrene-based elastomer is a styrene-isobutylene-styrene block polymer can reduce the transparency of the cured product and impart rubber elasticity while increasing its mechanical strength.
  • the present invention can be a photocurable composition further containing an inorganic powder.
  • a photocurable composition further containing an inorganic powder imparts thixotropy to the photocurable composition and has shape stability after coating, and thus serves as a protective material such as a sealing material and a sealing material, and a masking material. It can be preferably used.
  • the present invention can be a cured product of any of the above photocurable compositions in which ⁇ E changes by 20 or more when immersed in 1N hydrochloric acid at 70 ° C. for 120 hours.
  • the cured product obtained by curing any of the above photocurable compositions in which ⁇ E changes by 20 or more when immersed in 1N hydrochloric acid at 70 ° C. for 120 hours does not contain an acid generator.
  • Such a cured product is preferable because there is little concern that the residual acid will corrode the substrate, wiring, electronic elements, housing, and other adherends.
  • the present invention can be a cured product having a Martens hardness of 0.005 to 50 N / mm 2 as measured by a nanoindentation test.
  • a cured product having a Martens hardness of 0.005 to 50 N / mm 2 measured in a nanoindentation test has an excellent balance of flexibility, extensibility, and compressibility, and protects sealing materials, encapsulants, etc. It can be suitably used as a material and a masking material.
  • the present invention can be a cured product of any of the above photocurable compositions or the cured product, and can be a sealing material having a compression set of 50% or less. Since the cured product of any of the above photocurable compositions or the cured product has a compression set of 50% or less, it can be used as a sealing material such as a gasket having excellent sealing properties.
  • the present invention can be a cured product of any of the above photocurable compositions or a cured product of any of the above, and can be used as a protective material for covering an electronic element or wiring on a substrate.
  • the cured product of any of the photocurable compositions or the cured product of any of the above, and the protective material covering the electronic element or wiring on the substrate is excellent with predetermined flexibility and flexibility. It is a protective material.
  • the present invention includes a case having an opening, a lid that closes the opening, and the sealing material provided on at least one of the case or the lid, and by fitting the case and the lid.
  • the sealing material can be compressed and deformed to form a waterproof structure that tightly seals the opening.
  • the present invention includes a case having an opening, a lid that closes the opening, and the sealing material provided on at least one of the case or the lid, and by fitting the case and the lid. Since the sealing material is compressed and deformed to form a waterproof structure that tightly seals the opening, the waterproof structure has excellent sealing properties.
  • the present invention is selected from a sealing material, a protective material, a masking material, an adhesive, and a vibration-proof material, which comprises at least a step of applying any of the above-mentioned photocurable compositions and a step of irradiating with activation energy rays. It can be a method for producing at least one cured product.
  • the present invention is selected from a sealing material, a protective material, a masking material, an adhesive, and an anti-vibration material, which comprises at least a step of applying any of the above photocurable compositions and a step of irradiating with activation energy rays. Since the method for producing at least one cured product is used, the production of these cured products is easy.
  • the photocurable composition of the present invention has a color change that can be distinguished from that before curing after the completion of photocuring. Further, the cured product of the photocurable composition of the present invention can be used for various purposes such as an adhesive, a masking material, a gasket, a sealing material, and a sealing material.
  • the photocurable composition of the present invention comprises at least one acrylic compound selected from an acrylic monomer, an acrylic oligomer, and an acrylic polymer, a photoradical generator, and a leuco dye, and comprises JISZ8781-4.
  • the chromaticity difference ⁇ E from * 100 , b * 100 ) is 10 or more, and the chromaticity change parameter represented by the following equation (1) is in the range of 0 to 2.0.
  • a * 0 and b * 0 indicate chromaticity a * value and b * value in the L * a * b * color space before curing, and a * 50 and b * 50 are.
  • the chromaticity a * value and b * value in the L * a * b * color space at a curing rate of 50% are shown, and a * 100 and b * 100 are the chromaticity a in the L * a * b * color space after curing.
  • * Value and b * value are shown.
  • the "before curing" of the photocurable composition means a state before the photocuring reaction such as irradiation with ultraviolet rays is performed in a state where the components forming the photocurable cured product are mixed, and the "after curing” means.
  • "after curing” is defined as a state of being cured by irradiating light for curing under the condition of an integrated light amount of 15,000 mJ / cm 2.
  • the change in peak height when the infrared absorption spectrum is measured by the FT-IR method described later is shown in a substantially saturated state.
  • the photocurable composition is cured with an uncured color value (L * 0 , a * 0 , b * 0 ) defined in the CIE1976 (L * , a * , b *) color space described in JISZ8781-4. Since the chromaticity difference ⁇ E from the later color values (L * 100 , a * 100 , b * 100 ) is 10 or more, the color change between the uncured state and the cured state is clear, and the difference can be seen. Can be recognized. When ⁇ E is 20 or more, the color change is larger, and when ⁇ E is 30 or more, the color change in the latter half of the reaction is large even when the chromaticity change parameter is large, which is particularly preferable. On the other hand, if ⁇ E is less than 10, the color change before and after curing is small, and it may be difficult to determine whether or not curing is completed.
  • the molecules of the above formula (1) are based on the coordinates of the uncured chromaticity (a * 0 , b * 0 ) on the a * , b * plane, and the coordinates of the chromaticity in the cured state with a curing rate of 50% (a *).
  • the distance to 50 , b * 50 ) is shown, and the denominator of equation (1) is the coordinates of the chromaticity of the cured state with a curing rate of 50% on the a * , b * plane (a * 50 , b * 50 ). It shows the distance from to the coordinates (a * 100 , b * 100 ) of the chromaticity in the cured state after curing (curing rate 100%).
  • the formula (1) is expressed when the curing rate of the photocurable composition is 50% to 100% with respect to the distance (color change) when the curing rate is 0% to 50% (first half of the reaction).
  • the ratio of the distance (color change) of (the latter half of the reaction) is shown. This is used as a chromaticity change parameter. Since the value of this equation (1), that is, the chromaticity change parameter is in the range of 0 to 2.0, the color change in the latter half of the reaction is the smallest when the value is 2.0, and the closer to 0, the latter half of the reaction.
  • the color change is large (or the color change in the first half of the reaction is small), and the distance (color change) in the latter half of the reaction is at least half or more larger than that in the first half of the reaction.
  • the chromaticity change parameter is preferably 0 to 1.0, and particularly preferably 0 to 0.5.
  • the photocurable composition of the present invention comprises at least an acrylic compound of at least one of an acrylic monomer, an acrylic oligomer, and an acrylic polymer, a photoradical generator, and a leuco dye, but the acrylic monomer and acrylic.
  • acrylic monomer is synonymous with (meth) acrylic monomer and is used to include not only acrylic acid ester monomer but also methacrylic acid ester monomer.
  • acrylic oligomer is synonymous with (meth) acrylic oligomer and includes methacrylic acid ester oligomer in addition to acrylic acid ester oligomer
  • acrylic polymer is synonymous with (meth) acrylic polymer and is acrylic. It is used in the sense that it includes a methacrylate ester polymer in addition to the acid ester polymer.
  • all of the acrylic monomer, the acrylic oligomer, and the acrylic polymer are compounds having a radically polymerizable group, and those after the radical polymerization reaction are distinguished by notation as "cured product".
  • This photocurable composition can be made into a cured product by photocuring an acrylic monomer, an acrylic oligomer and an acrylic polymer.
  • the monofunctional acrylic monomer is a component that is cured by a photoradical polymerization initiator, and is a low-viscosity liquid before curing. If a styrene-based thermoplastic elastomer is included in the photocurable composition, the monofunctional acrylic monomer dissolves the styrene-based thermoplastic elastomer. The cured product of the monofunctional acrylic monomer adheres to an electronic element or a substrate and exhibits waterproofness and the like.
  • the monofunctional acrylic monomer contains a monofunctional high-polarity monomer such as a monofunctional (meth) acrylamide-based monomer in addition to the monofunctional (meth) acrylic acid ester monomer. More specifically, aliphatic (meth) acrylic acid ester monomer, alicyclic (meth) acrylic acid ester monomer, ether-based (meth) acrylic acid ester monomer, cyclic ether-based (meth) acrylic acid ester acrylic monomer, fragrance.
  • a monofunctional high-polarity monomer such as a monofunctional (meth) acrylamide-based monomer in addition to the monofunctional (meth) acrylic acid ester monomer. More specifically, aliphatic (meth) acrylic acid ester monomer, alicyclic (meth) acrylic acid ester monomer, ether-based (meth) acrylic acid ester monomer, cyclic ether-based (meth) acrylic acid ester acrylic monomer, fragrance.
  • the monofunctional aliphatic (meth) acrylic acid ester monomer include aliphatic carbides such as butyl acrylate, lauryl acrylate, stearyl acrylate, isostearyl acrylate, decyl acrylate, isodecyl acrylate, isononyl acrylate, and n-octyl acrylate.
  • aliphatic carbides such as butyl acrylate, lauryl acrylate, stearyl acrylate, isostearyl acrylate, decyl acrylate, isodecyl acrylate, isononyl acrylate, and n-octyl acrylate.
  • Examples thereof include hydrogen-based (meth) acrylic acid ester monomers.
  • Lauryl acrylate is preferable when used in combination with a styrene-based elastomer because it is extremely excellent in solubility of the styrene-based elastomer and also excellent
  • the styrene-based thermoplastic elastomer By blending a monofunctional aliphatic (meth) acrylic acid ester monomer, the styrene-based thermoplastic elastomer is dissolved when blended, and the flexibility of the cured product obtained after curing of the photocurable composition is increased. It can be increased, the Martens hardness and Young's modulus can be lowered, and the elongation at the time of cutting can be greatly improved.
  • monofunctional alicyclic (meth) acrylic acid ester monomer examples include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 4 -Tert-Butylcyclohexylacrylate and the like can be mentioned.
  • a monofunctional alicyclic (meth) acrylic acid ester monomer By blending a monofunctional alicyclic (meth) acrylic acid ester monomer, when a styrene-based thermoplastic elastomer is contained, it can be dissolved.
  • the monofunctional alicyclic (meth) acrylic acid ester monomer enhances the adhesive strength of the cured product (for example, a sealing material) after curing of the photocurable composition, and when the cured product is peeled off from the adherend. It is possible to reduce the adhesive residue. It also has the effect of making the cured product tough and increasing Young's modulus. In addition, increasing the proportion of this component can enhance moisture resistance and transparency.
  • the acrylic acid ester monomer For the monofunctional aliphatic (meth) acrylic acid ester monomer and the alicyclic (meth) acrylic acid ester monomer, it is preferable to use the acrylic acid ester monomer, respectively. This is because many acrylic acid ester monomers are superior in photocurability as compared with methacrylic acid ester monomers, and in addition to being able to be cured with a relatively low integrated amount of light, the cured product tends to be flexible.
  • a monofunctional aliphatic (meth) acrylic acid ester monomer and a monofunctional alicyclic (meth) acrylic acid ester monomer are used, they can be used as an adhesive because they have adhesive strength derived from these components. .. It is also preferable as a sealing material because it adheres to the adherend and can prevent foreign matter and moisture from entering.
  • the alicyclic (meth) acrylic acid ester monomer and the aliphatic (meth) acrylic acid ester monomer in combination.
  • the aliphatic (meth) acrylic acid ester monomer can increase the flexibility of the cured product and greatly improve the elongation at the time of cutting, while the alicyclic (meth) acrylic acid ester monomer makes the cured product tough. It has the effect of increasing the tensile strength. Therefore, by using both of them in combination, it is possible to achieve both appropriate flexibility and hardness.
  • ether-based (meth) acrylic acid ester monomer examples include 2-butoxyethyl acrylate, ethoxydiethylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and nonylphenolethylene oxide-modified acrylate.
  • cyclic ether-based acrylic acid ester monomer examples include tetrahydrofurfuryl acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methyl acrylate, and (3-ethyl-3-oxetanyl) methyl acrylate. Can be mentioned.
  • aromatic acrylic acid ester monomer examples include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, nonylphenol ethylene oxide-modified acrylate, and benzyl acrylate.
  • hydroxyl group-containing acrylic acid ester monomer examples include 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxyethyl acrylate.
  • carboxyl group-containing acrylic acid ester monomer examples include ⁇ -carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and the like. it can.
  • acrylamide-based monomer examples include acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, hydroxyethylacrylamide, acroylmorpholin and the like.
  • tertiary amino group-containing (meth) acrylic acid ester monomer examples include 2- (dimethylamino) ethyl methacrylate (DMAEMA) and the like.
  • imide-based (meth) acrylic acid ester monomer examples include N-acryloyloxyethyl hexahydrophthalimide and N-acryloyloxyethyl tetrahydrophthalimide.
  • glycidyl group-containing (meth) acrylic acid ester monomer examples include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like.
  • Examples of the phosphoric acid group-containing (meth) acrylic acid ester monomer include 2-metacloyloxyethyl acid phosphate and the like.
  • an aliphatic acrylic acid ester monomer and an alicyclic acrylic acid ester can be obtained from the viewpoint that a photocurable composition having almost no adverse effect on color change and having excellent distinguishability of color change due to curing can be obtained.
  • Monomers, aromatic acrylic acid ester monomers, and acrylamide-based monomers are preferable.
  • a monofunctional highly polar monomer and among the monofunctional highly polar monomers, an acrylamide-based monomer and a tertiary amino group are contained.
  • Nitrogen-containing monomers such as (meth) acrylic acid ester monomer and imide-based (meth) acrylic acid ester monomer are preferable.
  • an imide-based (meth) acrylic acid ester monomer is preferable from the viewpoint of enhancing the adhesion to the polyimide film.
  • a phosphoric acid group-containing (meth) acrylic acid ester monomer, a hydroxyl group-containing acrylic acid ester monomer, and a carboxyl group-containing acrylic acid ester monomer are preferable.
  • the alicyclic (meth) acrylic acid ester monomer and the aliphatic (meth) acrylic acid ester monomer are contained, the alicyclic (meth) acrylic acid ester monomer and the aliphatic (meth) acrylic acid ester monomer The mass ratio is preferably 4: 1 to 1: 4.
  • Polyfunctional acrylic monomer is also a component that is cured by the photoradical polymerization initiator.
  • the cured product of the photocurable composition is used as a gasket, a sealing material, a sealing material, etc., it can be blended in a small amount for the purpose of adjusting the hardness and reducing the surface tack, but only this is an essential component. It is difficult to do so, and it can be added as an auxiliary component of the monofunctional acrylic monomer.
  • Examples of such a polyfunctional acrylic monomer include a polyfunctional aliphatic (meth) acrylic acid ester monomer, a polyfunctional highly polar monomer, and a cyclized polymerizable (meth) acrylic monomer.
  • polyfunctional aliphatic (meth) acrylic acid ester monomer examples include a bifunctional aliphatic (meth) acrylic acid ester monomer, and specific examples of the bifunctional aliphatic (meth) acrylic acid ester monomer include ethylene glycol di. (Meta) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecanedimethanol di.
  • a styrene-based thermoplastic elastomer is added, since the compatibility with the soft segment is relatively high, a bifunctional aliphatic hydrocarbon-based di (meth) acrylic acid ester monomer having reactive groups at both ends is used. It is preferable to use it.
  • the polyfunctional high-polarity monomer includes a (meth) acrylic acid ester monomer having a polar group and bismaleimide.
  • Specific examples of the (meth) acrylic acid ester monomer having a polar group include di / tri (meth) acrylate ethoxylated isocyanurate, ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, and 2-methacryoxy. Examples thereof include ethyl acid phosphate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, and bisphenol A diglycidyl ether acrylic acid adduct. From the viewpoint of improving adhesion, a tris (2-hydroxyethyl) isocyanurate-based (meth) acrylic acid ester monomer is preferable.
  • bismaleimide examples include 4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, and bis.
  • examples thereof include (3-ethyl-5-methyl-4-maleimidephenyl) methane, 1,6-bis (maleimide) hexane, and 1,6'-bismaleimide- (2,2,4-trimethyl) hexane.
  • 1,6-bis (maleimide) hexane and 1,6'-bismaleimide- (2,2,4-trimethyl) hexane are difficult to inhibit the compatibility and photocurability of the photocurable composition.
  • Such as aliphatic bismaleimide is preferable.
  • examples of the cyclized polymerizable (meth) acrylic monomer include ⁇ -allyloxymethyl acrylate (AOMA) and ⁇ -hydroxymethyl acrylate dimer (RHMA-D). Since these have a low viscosity, they can be used for adjusting the viscosity of a photocurable composition, and since the three-dimensional crosslink density is not excessively increased by curing, they have hardness and heat resistance while maintaining appropriate flexibility. , Can increase toughness.
  • ⁇ -allyloxymethyl acrylate is preferable from the viewpoint of improving coatability, heat resistance, and adhesiveness of glass and the like.
  • a cured product of a photocurable composition When a cured product of a photocurable composition is used as a gasket, a sealing material, a sealing material, etc. and a bifunctional or higher acrylic monomer is blended, 5% by mass or less is contained in the photocurable composition or the cured product thereof. It is preferably contained so as to be, and more preferably 1% by mass or less. This is because if a large amount is added, there is a concern that the hardness will increase and the adhesiveness to the adherend will decrease.
  • the acrylic oligomer is a compound having a (meth) acrylic group mainly having a weight average molecular weight in the range of 1,000 to 50,000.
  • the acrylic oligomer includes an oligomer obtained by polymerizing the acrylic monomer to a predetermined molecular weight, and an oligomer having a (meth) acrylic group at the end or side chain of a main chain other than acrylic.
  • polybutadiene-based acrylic oligomer acrylamide-based oligomer, polyisoprene-based acrylic oligomer, polyurethane-based acrylic oligomer, polyester-based acrylic oligomer, polyether-based acrylic oligomer, epoxy ester-based acrylic oligomer, bisphenol-based acrylic oligomer, novolak-type acrylic oligomer, etc.
  • acrylamide-based oligomer polyisoprene-based acrylic oligomer
  • polyurethane-based acrylic oligomer polyester-based acrylic oligomer
  • polyether-based acrylic oligomer polyether-based acrylic oligomer
  • epoxy ester-based acrylic oligomer bisphenol-based acrylic oligomer
  • novolak-type acrylic oligomer etc.
  • Acrylic polymers are compounds having (meth) acrylic groups with a weight average molecular weight of 50,000 to 5 million.
  • Acrylic polymers include polymers obtained by polymerizing the acrylic monomer or acrylic oligomer to a predetermined molecular weight, and polymers in which a (meth) acrylic group is added to a compound other than the acrylic compound.
  • the former includes a homopolymer obtained by polymerizing butyl acrylate.
  • Examples of the latter include compounds having a (meth) acrylic group added to a compound having a polybutadiene, acrylamide, polyisoprene, polyurethane, polyester, polyether, epoxy skeleton and the like, and specifically, a polybutadiene-based acrylic polymer and an acrylamide-based acrylic.
  • Examples thereof include polymers, polyisoprene-based acrylic polymers, polyurethane-based acrylic polymers, polyester-based acrylic polymers, polyether-based acrylic polymers, epoxy ester-based acrylic polymers, bisphenol-based acrylic polymers, and novolak-type acrylic polymers.
  • the total amount of the acrylic monomer, the acrylic oligomer, and the acrylic polymer is preferably 50% by mass to 99% by mass with respect to the mass of the photocurable composition.
  • the blending amount of the monofunctional acrylic monomer is preferably 10% by mass to 94% by mass with respect to the total mass of the acrylic monomer, the acrylic oligomer, the acrylic polymer, and the thermoplastic elastomer described later.
  • Styrene-based thermoplastic elastomer Styrene-based thermoplastic elastomers (also referred to as styrene-based elastomers) are not essential components. However, the styrene-based elastomer can be dissolved in an acrylic monomer or an acrylic oligomer in the photocurable composition, and the transparency can be lowered due to the hard segment thereof. Therefore, the color change can be easily recognized as compared with the case where the photocurable composition is transparent. Further, the styrene-based elastomer can increase the mechanical strength of the cured product after the acrylic monomer or the acrylic oligomer is cured and can impart rubber elasticity (flexibility). Then, the compression set can be reduced, and in addition, the moisture permeability can be reduced.
  • styrene-based elastomer examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and the like.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SEPS Styrene-ethylene-propylene-styrene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • SEEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
  • epoxy-modified styrene-based Examples thereof include these modified products such as styrene.
  • soft products such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene / isoprene copolymer-styrene block copolymer.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SIS styrene-butadiene / isoprene copolymer-styrene block copolymer
  • the sealing property can be maintained for a long period of time.
  • the tack on the surface of the cured product can be reduced, and the compression set can be made less likely to deteriorate when the inorganic powder is added.
  • the styrene-based elastomer having an unsaturated bond in the epoxy-modified styrene-based elastomer or the soft segment is used among the above-mentioned styrene-based elastomers.
  • the styrene-based elastomer having an unsaturated bond in the epoxy-modified styrene-based elastomer or the soft segment is used.
  • the compression set of the cured product obtained after curing can be reduced, and the sealing property during long-term use is improved.
  • the tack on the surface of the cured product can be reduced, and the compression set deteriorates even if an inorganic powder is added. It can be difficult to do.
  • the styrene-based elastomer preferably contains a high molecular weight styrene-based elastomer.
  • the high molecular weight styrene-based elastomer means an elastomer having a weight average molecular weight of 200,000 or more.
  • the weight average molecular weight of this high molecular weight styrene elastomer is preferably 250,000 or more, and more preferably 400,000 or more. There is no particular upper limit, but it can be, for example, 1 million or less.
  • the weight average molecular weight can be measured by using the GPC method (Gel Permeation Chromatography) and based on the calibration curve (calibration curve) measured by standard polystyrene.
  • the compression set can be reduced as compared with the case of using the low molecular weight styrene elastomer having a weight average molecular weight of less than 200,000, and the cured product can be sealed with a gasket, a sealing material or a sealant.
  • the sealing property can be maintained for a long period of time.
  • the bleed-out of the plasticizer can be suppressed by containing the high molecular weight styrene-based elastomer, a cured product having high flexibility can be obtained by adding a large amount of the plasticizer.
  • the amount added is preferably 1 to 60% by mass, more preferably 2 to 45% by mass in the photocurable composition. If the content of the styrene-based elastomer is less than 1% by mass, the mechanical strength may be lowered when the cured product is used as a gasket, a sealing material, a sealing material, or the like. On the other hand, if it exceeds 60% by mass, the viscosity of the photocurable composition tends to increase. If it is 35% by mass or less, the fluidity is suitable and it is easy to apply.
  • the amount added is preferably 1 to 7% by mass, more preferably 2 to 5% by mass in the photocurable composition. If the content of the high molecular weight styrene elastomer is less than 1% by mass, the mechanical strength may be lowered. On the other hand, if it exceeds 10% by mass, the viscosity of the photocurable composition tends to increase.
  • a high molecular weight styrene elastomer having a predetermined branched chain typically a branched chain extending radially from the core
  • a star polymer typically a branched chain extending radially from the core
  • the high molecular weight styrene elastomer having such a predetermined branched chain can suppress the entanglement of the main chains as compared with the linear high molecular weight styrene elastomer, and even if it is blended in a relatively high concentration. It is possible to suppress an increase in the viscosity of the photocurable composition.
  • this high molecular weight styrene-based elastomer can be blended in the photocurable composition at a concentration of about 5 to 20% by mass.
  • the photoradical generator is one that generates radicals and cures an acrylic monomer, an acrylic oligomer, and an acrylic polymer by a photoradical polymerization reaction.
  • the photoradical generator includes a photoradical polymerization initiator.
  • photoradical polymerization initiator examples include benzophenone-based, thioxanthone-based, acetophenone-based, acylphosphine-based, oxime ester-based, alkylphenone-based, and intramolecular hydrogen abstraction-type photopolymerization initiators.
  • alkylphenone system 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-2-methyl-methylpropanol, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-Hydroxy-methylpropanone, 2-hydroxy-1-(4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one, 2-methyl- 1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -4'-morpholinobutylphenone, 2-dimethylamino-2- (4-) Examples thereof include methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one.
  • acylphosphine type examples include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like.
  • intramolecular hydrogen abstraction type examples include a mixture of methyl benzoylate, oxyphenylacetic acid-2-oxo-2-phenylacetoxyethoxyethyl ester and oxyphenylacetic acid-2-hydroxyethoxyethyl ester.
  • the amount of the photoradical polymerization initiator added is preferably 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, based on 100 parts by mass of the total amount of all acrylic monomers and acrylic oligomers including monofunctional and bifunctional or higher.
  • the part is more preferable. This is because if it is less than 0.1 part by mass, the polymerization may be insufficient and the curing may not be completed, and even if it is added in excess of 10 parts by mass, the effect of increasing the degree of polymerization does not increase so much.
  • Leuco dye is a compound that generally develops color upon contact with an acid, and in the present invention, it has a function of developing color after curing of the photocurable composition to confirm the completion of curing of the photocurable composition.
  • Specific examples of leuco dyes include indrill phthalides, diphenylmethane phthalides, monovinyl phthalides, divinyl phthalides, diphenylmethane azaphthalides, phthalides including phenyl indolyl azaphthalides, fluorans, and the like. Types such as thiazines, stylinoquinolins, lactones, lactams, and triphenylmethanes can be mentioned.
  • Phthalides include 3,3 bis [4- (dimethylamino) phenyl] phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3. -(1-Ethyl-2-methylindole-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3,3-bis (1-butyl-2-methyl-1H-) Indole-3-yl) phthalide, etc. can be mentioned.
  • Fluolans include 2'-methyl-6'-(Np-tolyl-N ethylamino) spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one, 1,3.
  • thiazines examples include benzoyl leucomethylene blue.
  • lactams examples include rhodamine-B-anilinolactam, rhodamine- (p-nitroanilino) lactam, rhodamine- (o-chloroanilino) lactam, and rhodamine- (o-nitroanilino) lactam.
  • triphenylmethanes examples include leuco crystal violet (LCV).
  • lactones examples include crystal violet lactone (CVL), which is a lactone derivative of crystal violet, and a diazarhodamine lactone derivative.
  • CVL crystal violet lactone
  • various lactones, phthalides, and fluorans having a lactone ring structure are preferable from the viewpoint that the color does not easily change after curing and the presence or absence of curing is excellent in distinguishability even after a lapse of a predetermined time.
  • the amount of the leuco dye added can be 0.001 to 2 parts by mass with respect to 100 parts by mass of the acrylic monomer, the acrylic oligomer, and the acrylic polymer, and is preferably 0.005 to 1 part by mass. If it is 0.001 to 0.1 parts by mass, it is possible to enhance the distinctiveness of the presence or absence of curing when curing with a thickness of 0.5 mm or more. Further, when the content is 0.1 to 2 parts by mass, the mechanical properties of the cured product of the photocurable composition can be enhanced. It is considered that the effect of enhancing the mechanical properties is observed in the region where the amount of the leuco dye added is slightly high, because the leuco dye promotes the radical reaction.
  • Plasticizer It is preferable to add a plasticizer to the photocurable composition if necessary. High flexibility can be imparted to the cured product by adding a plasticizer, which is suitable when used as a gasket or a sealing material. When a styrene-based elastomer is added, the plasticizer is preferably one that is compatible with the soft segment thereof. Specific examples of the plasticizer include paraffin-based oil, olefin-based oil, naphthen-based oil, and ester-based plasticizer, and specific examples of the ester-based plasticizer include phthalic acid ester, adipic acid ester, and trimellitic acid ester.
  • Polyester phosphoric acid ester, citric acid ester, epoxidized vegetable oil, sebacic acid ester, azelacinic acid ester, maleic acid ester, benzoic acid ester and the like.
  • paraffin-based oil is preferable among these, and if paraffin-based oil is used, the effect of improving the extensibility by physical cross-linking of the hard segment of the styrene-based elastomer is small, and the cured product is cured. Contributes to the improvement of flexibility and compression set.
  • the amount of the plasticizer is preferably 30 parts by mass or less with respect to 100 parts by mass of the acrylic monomer and the acrylic oligomer. If it exceeds 30 parts by mass, the risk of the plasticizer bleeding out from the cured product increases.
  • Thixotropy-imparting agent It is preferable to add a thixotropic agent to the photocurable composition. By increasing the thixotropic property, the shape retention of the applied photocurable composition is improved. Therefore, it is possible to suppress dripping during application of the photocurable composition and improve the shape retention of the applied photocurable composition.
  • the photocurable composition when the photocurable composition is formed into a three-dimensional object using a dispenser, it can be cured in the form in which the photocurable composition is applied, so that the cured product is used as a gasket material or a sealing material. Suitable for cases.
  • the thixotropy-imparting agent examples include an inorganic thixotropy-imparting agent consisting of inorganic powders such as silica, aluminum oxide, and titanium oxide; Agents and the like can be mentioned, but inorganic powder is preferable, and silica is preferable among them.
  • inorganic powder is preferable, and silica is preferable among them.
  • the reason is that it is easy to control the hydrogen ion index (pH) of the photocurable composition by performing a predetermined surface treatment on the inorganic powder, and it is easy to obtain such a surface-treated silica among the inorganic powders. Because.
  • the amount added is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the acrylic monomer, the acrylic oligomer, and the acrylic polymer (including the plasticizer when the plasticizer is contained). If it is less than 2 parts by mass, the effect of addition is difficult to obtain, and if it exceeds 10 parts by mass, the viscosity of the photocurable composition may increase too much, or the hardness of the cured product may become too hard.
  • the surface-treated inorganic powder it is preferable to use an inorganic powder having a hydrogen ion index of 3.0 to 11.0.
  • the leuco dye undergoes a predetermined color change due to curing, so that it is excellent in distinguishability of the presence or absence of curing.
  • the hydrogen ion index is more preferably 3.6 to 5.5. This is because the distinguishability of the presence or absence of curing is enhanced.
  • the hydrogen ion index is a hydrogen ion index measured for a dispersion liquid in which an inorganic powder having a concentration of 4% by mass is dispersed in pure water.
  • a white inorganic filler can also be added to the photocurable composition in order to make the color change clearer. By using a white inorganic filler, small color changes can be made clearer and visually distinguishable. Further, when the photocurable composition is applied to a coating target having a low lightness, the discriminability of the presence or absence of curing is enhanced.
  • the colorant include inorganic compounds such as aluminum oxide, titanium oxide, magnesium oxide, calcium carbonate, talc, bennite, and montmorolinite.
  • aluminum oxide is particularly preferable because it not only enhances the distinctiveness of the presence or absence of curing, but also has the effect of enhancing the coatability by imparting appropriate thixotropy.
  • the hydrogen ion index of the colorant is preferably 3.0 to 11.0, and more preferably 3.6 to 5.5. This is because within this range, the effect of imparting thixotropy can be obtained in the same manner as when the thixotropic agent is added, and the synergistic effect of imparting thixotropy can be expected.
  • additives can be appropriately blended in the photocurable composition as long as the gist of the present invention is not deviated.
  • plasticizers and thixophilicity-imparting agents for example, silane coupling agents, polymerization inhibitors, defoamers, light stabilizers, antioxidants, antistatic agents, thermal conductive fillers, and other functional fillers. And so on.
  • the viscosity of the photocurable composition is preferably 10 to 1000 Pa ⁇ s at 25 ° C., more preferably 20 to 300 Pa ⁇ s. If it is less than 10 Pa ⁇ s, dripping is likely to occur when applying to an electronic element or the like with a dispenser. On the other hand, if it exceeds 1000 Pa ⁇ s, it becomes difficult to apply with a dispenser. Further, when it is set to 20 Pa ⁇ s or more, the shape retention from application to curing is enhanced, and when it is set to 200 Pa ⁇ s or less, fine dispensing using a finer needle becomes possible.
  • the viscosity can be a value measured using a B-type rotational viscometer at a rotational speed of 10 rpm and a measurement temperature of 25 ° C.
  • the thixotropy of the photocurable composition is preferably 2 or more at 25 ° C., and more preferably 4 or more.
  • the thixotropy is preferably 2 or more at 25 ° C., and more preferably 4 or more.
  • the thixotropy is a value calculated as a ratio (viscosity (1 rpm) / viscosity (10 rpm)) obtained by measuring viscosity at rotational speeds of 1 rpm and 10 rpm at a measurement temperature of 25 ° C. using a B-type rotational viscometer.
  • the upper limit of the thixotropy ratio is not limited, but is preferably about 20 or less.
  • the photocurable composition can be cured by a photocuring reaction and used for various purposes such as an adhesive, a masking material, a gasket, a sealing material, and a sealing material.
  • a photocuring reaction for various purposes such as an adhesive, a masking material, a gasket, a sealing material, and a sealing material.
  • the seal can be used. It can be used as a material.
  • ultraviolet rays As active energy rays, energy rays that activate (meth) acryloyl groups such as visible light or electron rays, and energy rays that generate radicals in a photoradical polymerization initiator can be used.
  • the light source that irradiates ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, and an ultraviolet LED.
  • the hardness thereof is preferably 60 degrees or less, more preferably 40 degrees or less, still more preferably 20 degrees or less in terms of A hardness according to JIS K6253-3: 2012 from the viewpoint of imparting rubber elasticity. It is even more preferable if the temperature is 5 degrees or less. If the temperature is 5 degrees or less, it can be used as a sealing material that requires an extremely low load. Further, the compression set of the cured product is preferably 50% or less. This is because the long-term sealing property can be guaranteed.
  • the maltens hardness measured in the nanoindentation test is preferably in the range of 0.005 to 30 N / mm 2.
  • the Martens hardness is in this range, it has predetermined flexibility and flexibility, and is suitable for applications such as sealing materials such as gaskets, masking materials, protective materials such as sealing materials, adhesives, and anti-vibration materials. It becomes.
  • the method for measuring the Martens hardness can be specifically the method described in Examples.
  • the encapsulant preferably has flexibility that can be applied to a flexible substrate and strength that has repairability that can be removed after being used for encapsulating electronic components.
  • storage elastic modulus E' it is preferably in the range of 0.4 to 4.1 MPa.
  • the storage elastic modulus E' is 0.4 MPa or more, the cured product of the photocurable composition is hard to be torn and easily repaired, and when it is 4.1 MPa or less, the seal arranged on the flexible substrate is sealed. It becomes easy to peel off from the part to be stopped.
  • the storage elastic modulus E' is preferably in the range of 4.1 to 250 MPa. Within this range, the cured product of the photocurable composition is less likely to be peeled off from the adherend due to the increased toughness, and the appropriate rigidity is provided to prevent the wiring from being broken due to bending. be able to.
  • the mechanical strength such as Young's modulus and Martens hardness of the cured product of the photocurable composition is the strength appropriately required for the application. Is preferable.
  • Sample 1 to Sample 29 Acrylic monomer, acrylic oligomer, acrylic polymer, leuco dye, and styrene-based elastomer required depending on the sample are mixed, and after these are sufficiently mixed, an additive and a photoradical polymerization initiator are mixed to sample 1 to 1.
  • a photocurable composition of Sample 29 was prepared. These photocurable compositions were irradiated with ultraviolet rays (LED light source having a wavelength of 365 nm) under the conditions of an illuminance of 250 mW / cm 2 and an integrated light intensity of 15,000 mJ / cm 2 to obtain cured products of Samples 1 to 29.
  • LED light source having a wavelength of 365 nm
  • acrylic monomer lauryl acrylate as the aliphatic acrylate, isobornyl acrylate as the alicyclic acrylate, phenoxyethyl acrylate as the aromatic acrylate, 2-hydroxyethyl acrylate as the hydroxyl group-containing acrylate, and carboxyl.
  • ⁇ -carboxy-polycaprolactone monoacrylate as the group-containing acrylate
  • 2-methacryloxyethyl acid phosphate as the phosphate-containing acrylate
  • acroylmorpholine as the amide group-containing acrylate
  • 2-methacrylate as the amino group-containing acrylate
  • Dimethylamino ethyl was used, and 1,9-nonanediol diacrylate was used as the bifunctional aliphatic acrylate.
  • acrylic polymer an acrylic polymer having an acrylic skeleton ("RC500 (XX067C)" (trade name), manufactured by Kaneka Corporation) was used.
  • 2-hydroxy-2-methyl-methylpropanol was used as an alkylphenone-based initiator, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide was used as an acylphosphine oxide-based agent.
  • [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] esterone-1- (O-acetooxym) was used, respectively.
  • Leuco dyes include 2'-methyl-6'-(N-p-tolyl-N ethylamino) spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one as fluorans.
  • "RED520" (trade name), manufactured by Fukui Yamada Chemical Industry Co., Ltd., 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide ("Crystal Violet lactone (CVL)", Fukui as phthalides Yamada Chemical Industry Co., Ltd.) and "Leuco Crystal Violet” ((trade name), manufactured by Tokyo Ohka Kogyo Co., Ltd.) were used as triphenylmethanes.
  • styrene-based thermoplastic elastomer a styrene-isobutylene-styrene triblock copolymer (“SIBSTAR 102T” (trade name), manufactured by Kaneka Co., Ltd.) was used.
  • SIBSTAR 102T styrene-isobutylene-styrene triblock copolymer
  • a photoacid generator (“CPI-210S” (trade name), manufactured by San-Apro Co., Ltd.) is used, and silica (“Aerosil 200" (trade name), Nippon Aerosil Co., Ltd.) is used as a viscosity modifier and a nitrogen-imparting agent.
  • Hydrophilic fumed silica with a specific surface area of about 200 m 2 / g manufactured by the company) and aluminum oxide (“Alu C” (trade name), manufactured by Nippon Aerosil Co., Ltd., fumed aluminum oxide) were used as colorants. ..
  • Calculation of curing rate when transitioning from a photocurable composition to a cured product How much curing is achieved when the photocurable composition is in an intermediate state from an uncured state, that is, a state in which the curing rate is 0% to a completely cured state, that is, a state in which the curing rate is 100%. Whether it was progressing, that is, what percentage the curing rate was, was measured by the FT-IR method.
  • the vertical axis to record an infrared absorption spectrum is the absorbance for the cured finished product with uncured material, 780 cm -1 from fluctuations peak (820 cm -1 attributable to the chemical bonds decreases with the curing reaction ) And the area of the internal standard peak (1730 cm -1 ) are read from each spectrum, and the curing rate of the sample whose curing rate is undecided is calculated based on the values of the uncured body and the cured product.
  • the area of the fluctuation peak of the measured sample is A
  • the area of the internal standard peak is B
  • the R value of the uncured product is Ru
  • the R value of the cured product cured product produced by irradiating ultraviolet rays under the condition of an integrated light amount of 15,000 mJ / cm 2
  • the rate Dc (%) that is, the rate of decrease in the R value of the cured product can be calculated by the following formula (2).
  • the reduction rate D (%) of this R value with respect to the Ru value can be obtained by the following equation (3).
  • the curing rate C (%) of the sample for which the curing rate is to be obtained can be obtained by comparing the D value of this sample with the Dc value. That is, it can be obtained by the following equation (4).
  • the chromaticity was measured as follows. Explaining with reference to the schematic view shown in FIG. 1, first, as shown in FIG. 1A, two 1 mm-thick transparent glass plates 11 are prepared, and one side of the two transparent glass plates 11 is subjected to 0.1 mm peeling treatment (PET). HSPX) is pasted (not shown). A shim ring (spacer) 12 having a thickness of 1 mm and having a circular through hole 13 having a diameter of 10 mm is arranged on the glass plate 11 to which the PET is not attached, and the other glass plate is placed so that the PET faces the shim ring. The shim ring is sandwiched between two glass plates.
  • PET 0.1 mm peeling treatment
  • the chromaticity of the reference white plate for calibration is measured. (Measurement of blank, FIG. 1B). Subsequently, the photocurable composition of each sample is applied to the through hole 13 of the shim ring 12, and the chromaticity of the photocurable composition before curing that has entered the through hole is measured as shown in FIG. 1C. .. At this time, a white calibration plate (not shown) is placed under the lower glass plate 11. The reason why the photocurable composition is sealed with two glass plates is to prevent the influence of oxygen in the air. Then, as shown in FIG.
  • the photocurable composition 15 is irradiated with ultraviolet rays for a predetermined time with a UV lamp (“Aice UJ30” manufactured by Panasonic Corporation, wavelength 365 nm, illuminance 250 mW / cm 2) 16.
  • a UV lamp (“Aice UJ30” manufactured by Panasonic Corporation, wavelength 365 nm, illuminance 250 mW / cm 2) 16.
  • the chromaticity of the cured product of the photocurable photocurable composition is measured with a spectrophotometer (“Handy spectrophotometer JX777” manufactured by Color Techno System Co., Ltd.) 14.
  • the ultraviolet irradiation time at which the curing rate becomes 50% was determined in advance for each sample, and the chromaticity was determined for the sample after being irradiated with the ultraviolet rays for that time.
  • the value of the formula (1) which is a chromaticity change parameter, was calculated from the chromaticity of each sample at uncured, cured rate of 50%, and cured (curing
  • the sample used in the measurement of the chromaticity is placed on a white plate for calibration, and the chromaticity of each sample is measured by a spectrocolorimeter to obtain a second chromaticity difference ⁇ E.
  • the term "chromaticity difference ⁇ E" indicates the chromaticity difference based on the color of the color chip, and the latter indicates the "second chromaticity difference ⁇ E 2 ".
  • the above-mentioned chromaticity difference ⁇ E is a value that faithfully reflects the color change visually observed. Therefore, if the chromaticity difference ⁇ E is large and the above-mentioned chromaticity change parameter is within a predetermined range, it means that it is easy to visually distinguish between before curing and after photocuring.
  • the second chromaticity difference ⁇ E 2 is preferably 10 or more. , 20 or more is more preferable. In this case, replacing the chromaticity difference Delta] E in the second chromaticity difference Delta] E 2, only the second chromaticity difference Delta] E 2 may be 10 or more. Further, both the chromaticity difference ⁇ E and the second chromaticity difference ⁇ E 2 are preferably 10 or more, and more preferably 20 or more.
  • Martens hardness (N / mm 2 ): A nanoindentation test of the cured product of each sample was carried out using a nanoindenter (manufactured by ELIONIX, ENT-2100). The test piece was prepared by applying a photocurable composition to a glass plate having a thickness of 1 mm so as to have a thickness of 200 ⁇ m, using an LED having a wavelength of 365 nm, under the conditions of an illuminance of 250 mW / cm 2 and an integrated light amount of 15000 mJ / cm 2. A cured product prepared by curing by irradiating with ultraviolet rays was used. Then, with the nano indenter, the Martens hardness of the cured product was measured under the conditions of a maximum pushing load of 0.1 mN and a pushing speed of 0.01 mN / sec.
  • Immersion test with 1 specified hydrochloric acid Each of the above samples was irradiated with ultraviolet rays having an integrated light intensity of 15,000 mJ / cm 2 and cured to a thickness of 1 mm to obtain a cured product of each sample. Subsequently, 0.2 g of a test piece was cut out from this cured product, immersed in 10 g of 1N hydrochloric acid, and allowed to stand in an environment of 70 ° C. for 120 hours. Then, after 120 hours, the test piece was taken out and the water on the surface was lightly wiped off.
  • the post-test test piece thus obtained was visually compared with the color chip of the color sample "PANTONE uncoated chips" (manufactured by PANTONE), and the closest color number was recorded. Subsequently, the chromaticity of each color chip is measured with the spectrocolorimeter, and the chromaticity difference is calculated from the chromaticity of the test piece after the test of each sample and the chromaticity of the test piece before the test. The results are shown in the item of chromaticity difference ⁇ E 3 after the immersion test in each table.
  • the chromaticity difference ⁇ E is a sufficiently large value exceeding 30, but the chromaticity change parameter is 2.0 or less but a large value exceeding 1.0, so that the color change in the latter half of the reaction is a large value. It seems that it was a little difficult to understand.
  • Samples 1 to 3 and 7 all had a second chromaticity difference of 20 or more. Therefore, it was found that the use of aliphatic, alicyclic, aromatic, and acrylamide-based monomers enhances not only visual discrimination but also spectrophotometric discrimination.
  • Sample 7 had a slightly higher maltens hardness than Samples 1 to 6. It is presumed that the acrylamide-based monomer promotes the curing reaction. From this, it was found that it is preferable to use an acrylic monomer excluding the acrylamide-based monomer when seeking flexibility, and to add an acrylamide-based monomer when increasing the hardness and seeking rigidity.
  • the chromaticity difference tended to become smaller as the addition amount of the leuco dyes decreased.
  • the reason why the difference in chromaticity is small seems to be that the density of the dye is low.
  • the chromaticity difference ⁇ E exceeds 30, but the value is smaller than that of the sample 15 which is 0.001 part by mass. The reason seems to be that when the amount of the leuco dye added is larger than the predetermined amount, the initial chromaticity becomes slightly yellowish, and the color approaches the color after curing.
  • the amount of the leuco dye added is preferably in the range of 0.005 to 1 part by mass.
  • sample 12 has the largest second chromaticity difference ⁇ E 2. Therefore, it was found that the addition amount exceeding 1 part by mass is preferable when the curing is judged by the spectrocolorimeter.
  • the chromaticity change parameter of Sample 2 exceeded 0.1 in Samples 19 to 23 containing a colorant as compared with Sample 2 not containing a colorant. In each case, the chromaticity change parameter is 0.1 or less. From this, it was found that the visibility of the color was enhanced by including aluminum oxide, which is a white powder, as the colorant.
  • the amount of the colorant added is the total amount of the resin components in order to improve the distinctiveness by the spectrocolorimeter. It was found that 0.1 to 1.5 parts by mass is preferable with respect to (100 parts by mass).
  • the initial color of Sample 22 and Sample 23 was reddish. This is because the pH of silica used in the present invention is 4.0 to 4.5 and the pH of aluminum oxide is 4.5 to 5.5. Therefore, a large amount is added to make the photocurable composition acidic. It seems that this is because the degree has increased. From this, it was found that the addition amount of such an additive is preferably about 5 parts by mass or less with respect to 100 parts by mass of the total amount of the resin components.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition photodurcissable capable de changer de couleur après la fin du durcissement, de façon à pouvoir être distingué d'avant le durcissement. La composition photodurcissable comprend un leuco-colorant, un agent de génération de photoradicaux, et au moins un composé acrylique sélectionné parmi les monomères acryliques, les oligomères acryliques et les polymères acryliques. La différence de couleur ΔE entre La valeur de couleur non durcie (L* 0, a* 0, b* 0) et la valeur de couleur post-durcissement (L* 100, a* 100, b* 100), telle que définie dans l'espace chromatique (L*, a*, b*) CIE 1976 décrit dans JIS Z8781-4, est supérieure ou égale à 10. Le paramètre de changement de couleur représenté par la formule (1) se situe dans la plage de 0 à 2,0. Dans la formule (1), a* 0 et b* 0 représentent respectivement la valeur de couleur a* et la valeur de couleur b* dans l'espace chromatique L*a*b* pré-durcissement, a* 50 et b* 50 représentent respectivement la valeur de couleur a* et la valeur de couleur b* dans un espace chromatique L*a*b* avec un taux de durcissement de 50 %, et a* 100 et b* 100 représentent respectivement la valeur de couleur a* et la valeur de couleur b* dans l'espace chromatique L*a*b* post-durcissement.
PCT/JP2020/029924 2019-08-29 2020-08-05 Composition photodurcissable, corps durci associé, matériau d'étanchéité, matériau protecteur, structure étanche à l'eau et procédé de production de corps durci WO2021039320A1 (fr)

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KR1020217038886A KR20220055451A (ko) 2019-08-29 2020-08-05 광경화성 조성물 및 그의 경화체, 실링재, 보호재, 방수 구조 및 경화체의 제조 방법
CN202080044270.6A CN113993912A (zh) 2019-08-29 2020-08-05 光固化性组合物及其固化体、密封材、保护材、防水构造以及固化体的制造方法
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JPS59178448A (ja) * 1983-03-30 1984-10-09 Sekisui Chem Co Ltd 光重合可能な画像形成用組成物
JP2006243018A (ja) * 2005-02-28 2006-09-14 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料、及び、液晶表示素子
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JP2018199796A (ja) * 2017-05-29 2018-12-20 積水ポリマテック株式会社 封止材組成物および封止材
WO2019124452A1 (fr) * 2017-12-20 2019-06-27 旭化成株式会社 Stratifié de résine photosensible

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