Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/28—Treatment by wave energy or particle radiation
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5397—Phosphine oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints

Definitions

• the present invention relates to a photocurable silicone composition and a cured product thereof.
• a curable silicone composition having good optical transparency and high elongation property is utilized as an adhesive or pressure sensitive adhesive.
• a photocurable silicone composition enabling relatively low curing temperature such as less than 40 °C is mainly used for an optical display because thermally instable components like liquid crystalline, OLED, touch panel, and cover lens are needed to use the image display unit.
• Patent Document 1 proposes an ultraviolet radiation-curable silicone composition comprising: a straight-chain organopolysiloxane having an aliphatic unsaturated group; an organopolysiloxane having a silicon atom-bonded mercaptoalkyl group; an acylphosphine oxide-based photoreaction initiator; and acetophenone and/or propiophenone.
• Patent Document 2 proposes a photocurable silicone composition comprising: an organopolysiloxane having at least one aryl group having from 6 to 12 carbons and at least one alkenyl group having from 2 to 12 carbons in a molecule, an organic compound having at least two ether bonds and at least one aliphatic carbon-carbon double bond in a molecule, a compound having at least two thiol groups in a molecule, a photoradical initiator having a phosphorus atom, and a hindered phenol compound.
• the photocurable silicone composition cures by irradiation with an active energy ray to form a cured product that suppresses reduction in transmittance due to coloring and haze even when being left in high temperature/high humidity
• such a photocurable silicone composition has a problem that, exhibiting excellent resistance to light, and poor curability by LED lamp with wide UV-Visible range (365 - 405 nm) as well as metal-halide lamp.
• Patent Document 1 Japanese Unexamined Patent Application Publication No. 2013- 253179 A
• Patent Document 2 International Publication No. WO 2017/155919 A1
• the photocurable silicone composition of the present invention comprises: (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula:
• R 1 a R 2 b SiO (4-a-b)/2 wherein, is an alkenyl group having from 2 to 12 carbons, R 2 is an alkyl group having from 1 to 12 carbons, an aryl group having from 6 to 12 carbons, or an aralkyl group having from 7 to 12 carbons; provided that, at least 30 mol% of R 2 in a molecule are the aryl groups or the aralkyl groups; and "a" and "b" are positive numbers satisfying: 1 ⁇ a + b ⁇ 2.5 and 0.001 ⁇ a/(a + b) ⁇ 0.2;
• R 4 is a linear or branched alkyl group having from 6 to 12 carbons or a group represented by the following general formula:
• R 2 is a linear or branched alkyl group having from 6 to 20 carbons.
• R 31 , R 34 and R 32 in component (D) are hydrogen atoms and R 32 , R 33 , R 32 and R 37 in component (D) are hydrogen atoms or alkyl groups having from 1 to 12 carbons.
• R 4 in component (D) is a group represented by the following general formula:
• R 2 is a linear or branched alkyl group having from 6 to 20 carbons.
• component (D) is an hydroxyphenyl triazine compound selected from a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula:
• component (D) may comprise just one, or two or more of the aforementioned compounds.
• the cured product of the present invention is obtained by irradiating the photocurable silicone composition described above with light.
• the cured product is laminated between same or different substrates, and especially, between same or different substrates in an optical device.
• the photocurable silicone composition of the present invention exhibits excellent curability by LED lamp with wide UV-Visible range as well as metal-halide lamp, and cures to form a cure product exhibiting excellent resistance to light. Furthermore, the cured product of the present invention exhibits excellent resistance to light.
• Such minor variations may be in the order of ⁇ 0-25, ⁇ 0-10, ⁇ 0-5, or ⁇ 0- 2.5, % of the numerical values. Further, the term “about” applies to both numerical values when associated with a range of values. Moreover, the term “about” may apply to numerical values even when not explicitly stated.
• a hyphen or dash in a range of values is “to” or “through”; a “>” is “above” or “greater-than”; a “ ⁇ ” is “at least” or “greater-than or equal to”; a “ ⁇ ” is “below” or “less-than”; and a “ ⁇ ” is “at most” or “less-than or equal to.”
• a hyphen or dash in a range of values is “to” or “through”; a “>” is “above” or “greater-than”; a “ ⁇ ” is “at least” or “greater-than or equal to”; a “ ⁇ ” is “below” or “less-than”; and a “ ⁇ ” is “at most” or “less-than or equal to.”
• a range “of from 0.1 to 0.9” may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
• a range such as “at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
• a range of “at least 10” inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
• an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
• a range “of from 1 to 9” includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
• Component (A) is a base compound of the present composition and is an organopolysiloxane represented by the average composition formula:
• R 1 is an alkenyl group having from 2 to 12 carbons, and examples thereof include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, and dodecenyl group. Among these, vinyl group and hexenyl group are preferred.
• R 2 is an alkyl group having from 1 to 12 carbons, an aryl group having from 6 to 12 carbons, or an aralkyl group having from 7 to 12 carbons.
• alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
• methyl group is preferred.
• the aryl group include phenyl group, tolyl group, naphthyl group, and biphenyl group.
• phenyl group is preferred.
• examples of the aralkyl group include phenylmethyl group, 1-phenylethyl group, 2- phenylethyl group, and 2-phenylpropyl group. Among these, 2-phenylethyl group and 2- phenylpropyl group are preferred.
• component (A) at least 30 mol% of R 2 in a molecule are the aryl groups or the aralkyl groups.
• a and "b” are positive numbers satisfying: 1 ⁇ a + b ⁇ 2.5, and preferably 1.5 ⁇ a + b ⁇ 2.2, and satisfying: 0.001 ⁇ a/(a + b) ⁇ 0.2, and preferably 0.005 ⁇ a/(a + b) ⁇ 0.1.
• the state of component (A) at 25°C is not limited and is preferably a liquid.
• the viscosity at 25°C of component (A) is not limited; however, the viscosity is preferably in a range of 100 to 1 ,000,000 mPa . s. Note that in the present specification, viscosity is the value measured using a type B viscometer according to ASTM D 1084 at 23 ⁇ 2 °C.
• Component (A) may be one type of organopolysiloxane that satisfies the average composition formula above or may be a mixture of at least two types of organopolysiloxanes that satisfy the average composition formula above.
• Examples of such component (A) include organopolysiloxanes represented by the following "average composition formulas: average formulas". Note that, in the formulas, "Me”, “Vi”, “Hex”, “Ph”, “Phe”, and “Php” respectively indicate methyl group, vinyl group, hexenyl group, phenyl group, 2-phenylethyl group, and 2- phenylpropyl group.
• Component (B) is a curing agent of the present composition and is a compound having at least two thiol groups in a molecule. Component (B) is not limited as long as the component has sufficient solubility in component (A). [0028] Examples of such component (B) include o-, m-, or p-xylenedithiol, ethyleneglycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, ethyleneglycol bis(3- thiopropionate), butanediol bis(3-thiopropionate), trimethylolpropane tris(3-thiopropionate), pentaerythritol tetrakis(3-thiopropionate), trihydroxyethyl triisocyanuric acid tris(3- thiopropionate), and organopolysiloxanes substituted with a
• the content of component (B) is an amount such that the amount of the thiol groups provided by the present component is in a range of from 0.2 to 2.0 mol, or optionally in a range of 0.3 to 1.6 mol, per 1 mol of the total alkenyl groups in component (A). This is because, when the content of component (B) is within the range described above, mechanical strength of the resulting cured product increases.
• Component (C) is a component to initiate photocuring reaction of the present composition, and is a photoradical initiator containing a phosphorus atom.
• component (C) include diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (trade name: TPO, manufactured by BASF), ethyl(2,4,6-trimethylbenzoyl) phenyl phosphonate (trade name: TPO- L, manufactured by BASF), and bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide (trade name: IRGACURE 819, manufactured by BASF).
• the content of component (C) is in a range of from 0.01 to 5 parts by mass, optionally in a range of from 0.05 to 2 parts by mass, or optionally in a range of from 0.1 to 1.5 parts by mass, per 100 parts by mass of component (A). This is because, when the content of component (C) is within the range described above, curing efficiently proceeds to form a cured product having excellent heat resistance and light resistance.
• Component (D) is a hydroxyphenyl triazine compound represented by the following general formula:
• R 31 , R 32 , R 33 , R 34 , R 32 , R 36 and R 37 are the same or different, and are groups selected from hydrogen atoms, hydroxy groups or alkyl groups having from 1 to 12 carbons.
• alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
• methyl group is preferred.
• R 31 , R 34 and R 32 are preferably hydrogen atoms and R 32 , R 33 , R 36 and R 37 are preferably hydrogen atoms or alkyl groups having from 1 to 12 carbons.
• R 4 is a linear or branched alkyl group having from 6 to 12 carbons or a group represented by the following general formula:
• R 4 is preferably the group represented by the following general formula:
• Examples of the alkyl group for R 4 include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
• R 5 is a linear or branched alkyl group having from 6 to 20 carbons. Examples of the alkyl group for include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
• Examples of such component (D) include a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: a hydroxyphenyl triazine compound represented by the following formula: and mixtures thereof.
• the content of component (D) is in a range of from 0.001 to 2 parts by mass, optionally in a range of from 0.01 to 1.5 parts by mass, or optionally in a range of from in a range of from 0.05 to 1.5 parts by mass, per 100 parts by mass of component (A). This is because, when the content of component (D) is within the range described above, curability of the composition by LED lamp increases.
• the present composition comprises component (A) to component (D) described above; however, to impart heat resistance to a cured product of the present composition, (E) a hindered phenol compound is preferably contained.
• component (E) include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[ ⁇ 3,5-bis(1 ,1-di- tert-butyl-4-hydroxyphenyl)methyl ⁇ phosphonate, 3 3',3",5,5',5"-hexane-tert-but
• the content of component (E) is not limited; however, the content is preferably in a range of 0.001 to 1 part by mass, and preferably in a range of 0.003 to 0.5 parts by mass, per 100 parts by mass of component (A). This is because, when the content of component (E) is within the range described above, change in viscosity of the composition prior to the photocuring is small and a cured product having excellent heat resistance and light resistance is obtained.
• the present composition may further contain, as an optional component, to enhance storage stability in a light-shielded condition of the present composition, (F) a radical scavenger other than component (E) is preferably contained.
• component (F) include hindered amines, such as N,N',N",N'"-tetrakis(4,6-bis(butyl-(N-methyl-2, 2,6,6- tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1 ,10-diamine, bis(1 , 2, 2,6,6- pentamethyl-4-piperidyl)[[3,5-bis(1 ,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, methyl-1 ,2,2,6,6-pentamethyl-4-piperidylsebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)
• the content of component (F) is not limited; however, the content is preferably in a range of 0.0001 to 1 part by mass, optionally 0.0001 to 0.1 parts by mass, or optionally 0.0001 to 0.05 parts by mass, per 100 parts by mass of component (A). This is because, when the content of component (F) is within the range described above, a cured product having excellent heat resistance and light resistance is obtained.
• the present composition may further contain, as an optional component, (G) an organic compound having at least two ether bonds and at least one aliphatic carbon-carbon double bond in a molecule.
• the group having an aliphatic carbon-carbon double bond in component (G) is not limited, and examples thereof include an alkenyl group, an acryloyl group, and a methacryloyl group. Among these, an acryloyl group or a methacryloyl group is preferred.
• the state of component (G) at 25°C is not limited and is preferably a liquid.
• the viscosity at 25°C of component (G) is not limited; however, the viscosity is preferably in a range of 1 to 10000 mPa-s.
• Examples of such component (G) include phenoxy diethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, methoxy triethylene glycol acrylate, methoxy nonaethylene glycol acrylate, methoxy polyethylene glycol acrylate, ethoxy diethylene glycol acrylate, ethoxyethoxyethyl acrylate, nonylphenoxy tetraethylene glycol acrylate, nonylphenoxy octaethylene glycol acrylate, nonylphenoxy dipropylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, polyethylene glycol methacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, bisphenol diethylene glycol diacrylate, bisphenol A triethylene glycol diacrylate, tetraethylene glycol diacrylate,
• the content of component (G) is not limited, however, it is preferably in a range of 3 to 30 parts by mass, or optionally in a range of 5 to 20 parts by mass, per 100 parts by mass of component (A). This is because, when the content of component (G) is greater than or equal to the lower limit of the range described above, reduction in transmittance of the cured product at a high temperature/high humidity becomes small. On the other hand, when the content is less than or equal to the upper limit of the range described above, change in hardness of the cured product at a high temperature is made small and coloring is reduced.
• the present composition may further contain, as an optional component, (H) an organic compound having at least one aliphatic carbon-carbon double bond in a molecule other than component (A) and component (G) described above; an adhesion-imparting agent; an inorganic filler, such as silica, titanium oxide, glass, alumina, or zinc oxide; an organic resin fine powder of polymethacrylate resin, silicone resin, or the like; as well as a pigment or a fluorescent substance, as long as the object of the present invention is not impaired.
• an organic compound having at least one aliphatic carbon-carbon double bond in a molecule other than component (A) and component (G) described above an adhesion-imparting agent
• an inorganic filler such as silica, titanium oxide, glass, alumina, or zinc oxide
• an organic resin fine powder of polymethacrylate resin, silicone resin, or the like as well as a pigment or a fluorescent substance, as long as the object of the present invention is not impaired.
• Component (H) is not limited as long as a component is an organic compound having at least one aliphatic carbon-carbon double bond in a molecule and is preferably a liquid at 25°C.
• the viscosity at 25°C of component (H) is not limited; however, the viscosity is preferably in a range of 1 to 500 mPa-s.
• Examples of such component (H) include methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isodecyl acrylate, triacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, phenoxyethyl acrylate, tetrahydrofuran acrylate, benzyl acrylate, o-phenylphenol ethoxyethyl acrylate, 2-ethylhexyl acrylate, hexane diol diacrylate, nonane diol diacrylate, 2-propenoic acid octahydro-4,7- methano-1 H-inden-5-
• the adhesion-imparting agent include silane compounds, such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3- methacryloxy propyltrimethoxysilane; siloxane compounds having at least one of silicon atom- bonded alkenyl groups and/or silicon atom-bonded hydrogen atoms, and at least one silicon atom-bonded alkoxy group in a molecule; mixtures of a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group and a siloxane compound having at least one silicon atom-bonded hydroxy group and at least one silicon atom-bonded alkenyl group in a molecule; methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate.
• the content of the adhesion-imparting agent is not limited; however, the content
• the viscosity at 25°C of the present composition is not limited; however, the viscosity is preferably in a range of 100 to 100,000 mPa-s, or optionally in a range of 500 to 10,000 mPa-s. This is because, when the viscosity of the present composition is greater than or equal to the lower limit of the range described above, a cured product having high mechanical strength can be obtained. On the other hand, when the viscosity is less than or equal to the upper limit of the range described above, excellent coatability/workability of the resulting composition is achieved and formation of a void in the cured product is avoided.
• the cured product of the present invention is obtained by irradiating the photocurable silicone composition described above with light.
• the light used to cure the present composition include ultraviolet light and visible light; however, the light with a wavelength in a range of 250 to 500 nm is preferred. This is because excellent curability is achieved, and the cured product is not decomposed by the light.
• the cured product is typically optically transparent. This is because when the cured product is preferably used for an optical device or an image display, optical transparency is desired for high performance.
• the form of the cured product is not limited and may be in a sheet, film, or block form.
• the cured product may be combined with various substrates.
• the cured product is typically laminated between same or different substrates, and especially, between same or different substrates in an optical device.
• the state of the cured product is not limited, but it is preferably an elastomer or gel.
• the hardness is preferably in a range of 0 to 80, or optionally in a range of 10 to 70, in Shore OO Hardness. This is because when the cure product is within the range described above, good cohesive strength against deformation and good flexibility against material fracture are obtained.
• Shore 00 Hardness is the value measured using a type 00 hardness according to ASTM D 2240 at 23 ⁇ 2 °C. ⁇ Method of producing the cured product>
• a method of producing the cured product is not limited, but it is exemplified by a method comprising the following steps: i-1 ) laminating the photocurable silicone composition of the present invention between same or different substrates providing that at least one of the substrates is transparent; and i-2) exposing the photocurable silicone composition to light through the transparent substrate.
• the photocurable silicone composition is applied on the surface of substrates blocking the light (for example, a black-color substrate).
• a coating method include a slit coating, a roll coating, a spin coating, a screen printing, or the like.
• a thickness of the photocurable silicone composition is not limited, but it is preferably in a range of from 50 to 1 ,000 pm, optionally in a range of from 50 to 500 pm, or optionally in a range of from 100 to 350 pm.
• the transparent substrate having the light shielding portion is laminated on the surface of the photocurable silicone composition as prepared above.
• Laminating can be carried out either in the air or in vacuum. In order to prevent air bubbles generated during the laminating, it is preferable to laminate in vacuum. Also, laminating can be carried out under pressure, by a press or the like.
• the ultraviolet-curing is conducted by ultraviolet irradiation.
• ultraviolet irradiation for example, low pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or an electrodeless lamp is useful as an UV lamp.
• Irradiation dose is preferably in a range of from 5 to 6,000 mJ/cm 2 , or optionally in a range of from 10 to 4,000 mJ/cm 2 .
• UV LED light emitting diode
• Typical wavelengths of UV LED lamp are 365, 385, 395 and 405 nm.
• 365 nm and 395 nm are generally used.
• Irradiance is preferably in a range of from 50 to 2,000 mJ/cm 2 , or optionally in a range of from 100 to 1 ,000 mJ/cm 2 .
• the irradiation time is preferably in a range of from 1 to 120 seconds, or optionally in a range of from 15 to 60 seconds.
• uncured denote the state where there is flowable under 25°C environment.
• Another method of producing the cured product may comprise the following steps: ii-1 ) applying the photocurable silicone composition of the present invention on a transparent or intransparent (or opaque) substrate; ii-2) exposing the photocurable silicone composition to light to form a silicone product in half-cure state; ii-3) laminating the silicone product with another transparent or intransparent substrate; and ii-4) exposing the silicone product to light through the transparent substrate.
• the photocurable silicone composition is applied on the surface of substrate.
• coating methods include the method mentioned above.
• a thickness of the photocurable silicone composition is not limited, but it is preferably in a range of from 50 to 1 ,000 pm, optionally in a range of from 50 to 500 pm, or optionally in a range of from 100 to 350 pm.
• the applied photocurable silicone composition is partially cured by UV LED lamp to form unflowable and less-cured layer.
• the term “less-cured” denotes the state where there is no flowable at 25 °C, but not fully crosslinked network (the state having middle physical properties between liquid and fully cured products).
• the ultraviolet-curing is conducted by ultraviolet irradiation, ultraviolet to does not matter source if the lamp for irradiating light rays near ultraviolet.
• UV LED lamp is generally used.
• Typical wavelengths of UV LED lamp are 365, 385, 395 and 405 nm.
• 365 nm and 395 nm are generally used.
• Irradiation dose is preferably in a range of from 5 to 1 ,000 mJ/cm 2 , or optionally in a range of from 10 to 500 mJ/cm 2 .
• the irradiation of ultraviolet rays is usually in the air, the upper surface of the coating side (usually the atmosphere preferably irradiated from the surface). If need to prevent surface oxygen inhibition, the photocurable silicone composition may be irradiated with ultraviolet rays in an environment of a gas which does not cause curing inhibition such as nitrogen and carbon dioxide.
• the transparent substrate with the light shielding portion is applied on the surface of the coated photocurable silicone composition as prepared in above.
• Laminating can be carried out either in the air and in vacuum. In order to prevent air bubbles generated during the laminating, it is preferable to laminate in vacuum. Also, laminating can be carried out under pressure, by a press or the like.
• the ultraviolet-curing is conducted by ultraviolet irradiation.
• Irradiation dose is preferably in a range of from 5 to 6,000 mJ/cm 2 , or optionally in a range of from 10 to 4,000 mJ/cm 2 .
• UV LED light emitting diode
• Typical wavelengths of UV LED lamp are 365, 385, 395 and 405 nm.
• 365 nm and 395 nm are generally used.
• Irradiance is preferably in a range of from 50 to 2,000 mJ/cm 2 , or optionally in a range of from 100 to 1 ,000 mJ/cm 2 .
• the irradiation time is preferably in a range of from 1 to 120 seconds, or optionally in a range of from 15 to 60 seconds.
• uncured denote the state where there is flowable under 25°C environment.
• the cured product is useful as laminates in an optical device or an image display.
• the optical device is, for example, an optical semiconductor device.
• the optical semiconductor device include a light emitting diode (LED), a photocoupler, and a CCD.
• a light emitting diode (LED) element and a solid-state image sensor are illustrated as an optical semiconductor element.
• the photocurable silicone composition of the present invention can be suitably used.
• the refractive index of the cured product may be adjusted as desired by selecting the type of functional group such as the content of aryl group.
• the photocurable silicone composition of the present invention is excellent in heat resistance and moisture resistance, it is hard to cause a decrease in transparency and hardly causes turbidity. Therefore, there is an advantage that the light extraction efficiency of the optical semiconductor device including the Micro LED can be maintained well.
• Viscosity at 23 ⁇ 2 °C was measured by using a type B viscometer (Brookfield LVF Type Rotational Viscometer with using Spindle #2 at 60 rpm) according to ASTM D 1084 “Standard Test Methods for Viscosity of Adhesive”.
• the photocurable silicone composition was poured into a mold having a depression of a predetermined shape, and ultraviolet rays were irradiated from the upper liquid surface with a high pressure mercury lamp so that the cumulative irradiation amount was 4,000 mJ/cm 2 .
• the hardness of the obtained cured product was measured by a type 00 durometer hardness tester according to the method specified by ASTM D 2240-00. cTransmittance and Yellow Index (Yl)>
• the resistance to light fatigue was determined by means of a QUV Accelerated Weathering Tester (Q-Panel Co., Cleveland, Ohio) equipped with UVA-340 lamps calibrated to
• the plate-like cured product having a thickness of 500 pm cured as described above was irradiated in the QUV Accelerated Weathering Tester for a series of 12 hours per a cycle consisting of 8 hours of irradiation at the temperature of 60°C and 4 hours of darkness (condensation) at a temperature of 50°C. Subsequently, the plate-like cured product was held for 48 cycles (24 days) and the yellow index (Yl) were measured in the same manner as above.
• the photocurable silicone composition was poured into a mold composed of two black plates with a thickness of 2 cm, wherein the plates were separated by a spacer with a thickness of 500 pm.
• Ultraviolet light at a UV illuminance of 1000 mW/cm 2 was irradiated for 30 and 60 seconds from the upper liquid surface with a 365 nm LED lamp (FIREJETTM FJ100).
• ultraviolet light at a UV illuminance of 200 mW/cm 2 was irradiated for 30 and 60 seconds from the upper liquid surface with a 395 nm LED lamp (FIREJETTM FJ100).
• the specimen was disassembled and the length (cm) of the portion losing fluidity by curing was measured.
• Photocurable silicone compositions were prepared by a planetary centrifugal vacuum mixer (Thinky mixer) from the following components using the composition (parts by mass) shown in Table 1. Note that the photocurable silicone compositions of Practical Examples 1-2 and Comparative Examples 1-4 were prepared to provide 0.8 moles of thiol groups in component (b1) with regard to 1 mole of total aliphatic carbon-carbon double bonds in components (a1) and (a2). The properties of this photocurable silicone compositions and cured product thereof are shown in Table 1.
• ViMe 2 SiO(MePhSiO) 92 SiMe 2 Vi (the average composition formula: Vi 0.02 Me 1.02 Ph 0.98 SiO 0.99 )
• ViMe 2 SiO(MePhSiO) 23 SiMe 2 Vi (the average composition formula: Vi 0.08 Me 1.08 Ph 0.92 SiO 0.96 )
• Photocurable silicone compositions were prepared by a planetary centrifugal vacuum mixer (Thinky mixer) from the above components using the composition (parts by mass) shown in Table 2. Note that the photocurable silicone compositions of Practical Examples 3-6 and Comparative Examples 5-8 were prepared to provide 0.8 moles of thiol groups in component (b1) with regard to 1 mole of total aliphatic carbon-carbon double bonds in components (a1) and (a2). The properties of this photocurable silicone compositions and cured product thereof are shown in Table 2.
• Photocurable silicone compositions were prepared by a planetary centrifugal vacuum mixer (Thinky mixer) from the above components and the following components using the composition (parts by mass) shown in Table 3. Note that the photocurable silicone compositions of Practical Examples 7-12 and Comparative Examples 9-13 were prepared to provide 0.8 moles of thiol groups in component (b1) with regard to 1 mole of total aliphatic carbon-carbon double bonds in components (a1) and (a2). The properties of this photocurable silicone compositions and cured product thereof are shown in Table 3.
• Photocurable silicone compositions were prepared by a planetary centrifugal vacuum mixer (Thinky mixer) from the above components and the following components using the composition (parts by mass) shown in Table 4. Note that the photocurable silicone compositions of Comparative Examples 14-24 were prepared to provide 0.8 moles of thiol groups in component (b1) with regard to 1 mole of total aliphatic carbon-carbon double bonds in components (a1) and (a2). The properties of this photocurable silicone compositions and cured product thereof are shown in Table 4.
• the present composition is cured easily by irradiation with a high energy ray, such as ultraviolet light and visible light, provides transparent cured products, and has excellent deep curability. Therefore, the present composition is useful as various potting agents, sealing agents, and adhesive agents.
• the present cured product has high optical transparency, and excellent adhesion property. Therefore, the present cured product is useful as laminates such as for optical devices and image displays.

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