WO2014181610A1 - 画像表示装置用のダム材組成物、及びそれを用いた画像表示装置 - Google Patents
画像表示装置用のダム材組成物、及びそれを用いた画像表示装置 Download PDFInfo
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- WO2014181610A1 WO2014181610A1 PCT/JP2014/059358 JP2014059358W WO2014181610A1 WO 2014181610 A1 WO2014181610 A1 WO 2014181610A1 JP 2014059358 W JP2014059358 W JP 2014059358W WO 2014181610 A1 WO2014181610 A1 WO 2014181610A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- 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
-
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- the present invention relates to a dam material composition for an image display device and an image display device using the same.
- a flat panel type image display device usually has a large number of pixels composed of a semiconductor layer, a phosphor layer, or a light emitting layer constituting an active element between a pair of light-transmitting substrates such as glass. It has a display area (image display portion) arranged in a matrix. Generally, the periphery of this display area (image display portion) and a protective portion formed of optical plastic such as glass or acrylic resin is sealed secretly with an adhesive.
- a sealant is interposed between the protection unit and the image display unit in order to prevent a reduction in visibility (visibility) due to reflection of outdoor light or indoor lighting.
- an ultraviolet curable silicone resin composition is used as the sealant (Patent Document 1), and the use of a thermosetting silicone resin composition has also been proposed (Patent Document 2).
- an epoxy resin composition may be used for the sealant (Patent Document 3).
- the above ultraviolet curable resin composition when used as an encapsulant in an image display part (for example, a liquid crystal display panel), the composition may protrude from the display part or on the back side of the display part due to its fluidity. Problems such as enveloping may occur, and in recent years when the display portion has become larger, it has become more apparent.
- a method of preventing a protrusion or the like by forming a frame using a dam material composition in advance on the display unit or the protection unit and applying the composition therein is known. ing.
- Patent Document 3 discloses that a dam material is obtained by adding fine silica to an epoxy resin composition as a sealant. However, Patent Document 3 does not describe the hardness and adhesiveness of the cured product of the dam material. Further, Patent Document 3 describes nothing about applying other resin-based sealants as dam materials. Although the dam material is used in the Example of patent document 2, the detail of the composition is not clear. Moreover, although it hardens
- An object of the present invention is to provide a dam material composition whose cured product has appropriate hardness and adhesion to an adherend as a dam material, and an image display device using the dam material composition. More preferably, in addition to this, a clear seam is generated between the frame of the dam material and the sealant therein, and the problem that visibility as an image display device may be reduced, It is an object of the present invention to provide a dam material composition and an image display device using the dam material composition that make it difficult to distinguish a joint.
- the present invention 1 relates to (A) a polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom and having a viscosity of 20 to 25,000 cP at 23 ° C .; (B) (B1) Formula (I): (Where R 1 is independently an aliphatic unsaturated group; R is independently a C1-C6 alkyl group or a C6-C12 aryl group, and 1-60 mol% of R is a C6-C12 aryl group, n is a number with a viscosity at 23 ° C.
- R ' are each independently, C1 ⁇ C6 alkyl group Or a branched polyorganosiloxane having at least three R's each of which is an aliphatic unsaturated group, and a polyorgano having an aliphatic unsaturated group.
- the amount of siloxane (wherein (B2) is such that the ratio of the number of aliphatic unsaturated groups in (B2) to the total number of aliphatic unsaturated groups in (B) is more than 50% and not more than 95%. Amount)); (C) a photoinitiator; (D) a silane compound; and (E) an MQ resin having a weight average molecular weight of 2,000 to 2,500,000 and / or an MDQ resin having a weight average molecular weight of 2,000 to 1,000,000, Where, where The ratio of the number of mercaptoalkyl groups in (A) to the number of aliphatic unsaturated groups in (B) is 0.5 to 3.0, and (E) is 100 parts by weight of (B) Is 30 to 200 parts by weight, and the viscosity at 23 ° C. is 20,000 to 150,000 cP.
- the present invention relates to a dam material composition for an image display device.
- the composition of the present invention has a viscosity as high as 20,000 cP or more and generally has a low wettability and is inferior in the adhesiveness of the cured product. Exhibits good adhesion and has a suitable hardness as a dam material. More preferably, in addition to this, a clear seam is generated between the frame of the dam material and the sealant therein, and the problem that visibility as an image display device may be reduced, It becomes possible to make the discrimination of the seam difficult.
- the present invention 2 uses a B-type rotational viscometer for a dam material composition, and the viscosity (cP) measured at 23 ° C. and 6 rpm is V 6 rpm and 23 ° C. and 12 rpm .
- the present invention relates to a dam material composition for an image display device of the present invention 1, wherein (cP) is V 12 rpm , and the value of the thixotropy ratio determined by the formula: V 6 rpm / V 12 rpm is 1.02 to 1.9.
- the present invention 3 relates to the dam agent composition for an image display device of the present invention 1 or 2, wherein (E) comprises an MQ resin having a weight average molecular weight of 1,000,000 to 2,500,000.
- the present invention 4 relates to the dam agent composition for an image display device of the present invention 3, wherein (E) further comprises an MDQ resin having a weight average molecular weight of 2,000 to 1,000,000.
- the present invention 5 is the dam material composition for an image display device according to any one of the present invention 1 to 4, wherein the content of (C) is 0.05 to 50 parts by weight with respect to 100 parts by weight of (B) Related to things.
- (D) is one or more aliphatic non-crystalline groups selected from the group consisting of 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.
- the present invention relates to a dam material composition for an image display device according to any one of the present inventions 1 to 5, which is a silane compound containing a saturated group.
- the present invention 7 relates to an image display device comprising the dam material composition for an image display device according to any one of the present inventions 1 to 6 for sealing the image display portion and the protection portion.
- the present invention is a dam material composition, and when an image display device is produced using the dam material composition, the frame formed from the dam material composition has an appropriate hardness and adhesion to an adherend. is there. More preferably, it is difficult to distinguish a seam between the frame of the dam material and the sealant therein, and an image display device having good visibility can be provided.
- the dam material composition for the image display device of the present invention is (A) a polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom, having a viscosity at 23 ° C. of 20 to 25,000 cP; (B) (B1) Formula (I):
- R 1 is independently an aliphatic unsaturated group; R is independently a C1-C6 alkyl group or a C6-C12 aryl group, and 1-60 mol% of R is a C6-C12 aryl group, n is a number with a viscosity at 23 ° C. of 10,000 to 1,000,000 cP) and a linear polyorganosiloxane containing an aliphatic unsaturated group, and (B2) SiO 4/2 Units, R ′ 3 SiO 1/2 units and R ′ 2 SiO 2/2 units, and optionally further R′SiO 3/2 units wherein R ′ is independently a C1-C6 alkyl group.
- the amount of siloxane (wherein (B2) is such that the ratio of the number of aliphatic unsaturated groups in (B2) to the total number of aliphatic unsaturated groups in (B) is more than 50% and not more than 95%. Amount)); (C) a photoinitiator; (D) a silane compound; and (E) an MQ resin having a weight average molecular weight of 2,000 to 2,500,000 and / or an MDQ resin having a weight average molecular weight of 2,000 to 1,000,000.
- composition of the present invention comprises (A) a polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom and having a viscosity of 20 to 25,000 cP at 23 ° C.
- the number of mercaptoalkyl groups bonded to silicon atoms in one molecule is, on average, 2 or more and 20 from the viewpoint of suppressing excessive curing shrinkage while ensuring a stable structure by a crosslinking reaction. It can be as follows. Among these, more than 2, preferably 10 or less, more preferably 3-7.
- the alkyl portion of the mercaptoalkyl group bonded to the silicon atom can be a C1-C6 alkyl group.
- the mercaptoalkyl group include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 4-mercaptobutyl, 6-mercaptohexyl and the like. From the viewpoint of ease of synthesis, mercaptomethyl, 3-mercaptopropyl, etc. Is preferred, and 3-mercaptopropyl is more preferred.
- the organic group other than the mercaptoalkyl group bonded to the silicon atom can be a substituted or unsubstituted monovalent hydrocarbon group (provided not to be an aliphatic unsaturated group).
- an alkyl group such as a C1-C6 alkyl group (eg, methyl, ethyl, propyl, etc.); a cycloalkyl group, eg, a C3-C10 cycloalkyl group (eg, cyclohexyl, etc.); Aryl groups (eg, phenyl, tolyl, xylyl, etc.); aralkyl groups, eg, C7-C13 aralkyl groups (eg, 2-phenylethyl, 2-phenylpropyl, etc.); substituted hydrocarbon groups, eg, halogen-substituted hydrocarbon groups (eg, Chloromethyl, chlorophenyl, 3,3,
- An alkyl group is preferable from the viewpoint of easiness of synthesis, etc. Among them, methyl, ethyl and propyl are preferable, and methyl is more preferable. In order to adjust the refractive index, an aryl group can be used in combination, and among them, phenyl is preferable from the viewpoint of ease of synthesis.
- the structure of the main chain of (A) may be linear, branched or cyclic, and is preferably branched.
- R ′′ SiO 3/2 units, R ′′ 3 SiO 1/2 units and R ′′ 2 SiO 2/2 units, and optionally further SiO 4/2 units (where R ′′ is Each independently composed of an unsubstituted or substituted monovalent hydrocarbon group (provided not to be an aliphatic unsaturated group), 2 or more and 20 or less R ′ per molecule
- Examples thereof include branched polyorganosiloxanes containing mercaptoalkyl groups, wherein 'is a mercaptoalkyl group.
- Examples of the mercaptoalkyl group and the unsubstituted or substituted monovalent hydrocarbon group include the groups described above.
- R ′′ which is a mercaptoalkyl group may be present as R ′′ of any unit, but is preferably present as R ′′ of R ′′ SiO 3/2 unit.
- the mercaptoalkyl group and the unsubstituted or substituted monovalent hydrocarbon group the above groups can be applied. From the viewpoint of workability and crosslinking reactivity, the ratio of the number of siloxane units containing a mercaptoalkyl group to the number of siloxane units containing no mercaptoalkyl group is preferably 1:60 to 1: 5, but is not limited thereto. .
- the viscosity at 23 ° C. is 20 to 25,000 cP. From the viewpoint of dam formation, it is preferable that the viscosity is high as long as the compatibility with the component (B) is not significantly impaired. Also, those having a low viscosity of 20 to 2,000 cP at 23 ° C. can be used, for example, those having a viscosity of 50 to 500 cP can be used.
- the viscosity is measured with a B-type rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.). Use values 2 to 4, and use the values measured at 30 to 60 rpm and 23 ° C. (However, if there is a separate description regarding the number of revolutions, follow it).
- the number of mercapto groups in (A) can be measured by colorimetric titration with iodine. This is the following formula: 2RSH + I 2 ⁇ RSSR + 2HI This method utilizes the fact that the titration solution becomes slightly yellow with a small amount of excess iodine during titration.
- (A) is preferably highly transparent.
- As an index of transparency at 23 ° C., when (A) was filled in a container, and the transmittance in the visible light region wavelength (360 to 780 nm) was measured with a spectrophotometer for a thickness of 10 mm, It is mentioned that the transmittance is 80% or more.
- the transmittance is preferably 90% or more from the viewpoint that the transparency of the cured product of the composition of the present invention can be stably maintained.
- the method for preparing (A) is not particularly limited.
- mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethylmethoxysilane, mercaptopropyldimethylethoxy It can be produced by hydrolyzing, polycondensing, and re-equilibrating an alkylchlorosilane such as silane, mercaptoalkylalkoxysilane, and a desired alkylchlorosilane, alkylalkoxysilane, or silanol-containing siloxane.
- (A) may be used alone or in combination of two or more.
- composition of the present invention comprises (B) (B1) formula (I):
- R 1 is independently an aliphatic unsaturated group; R is independently a C1-C6 alkyl group or a C6-C12 aryl group, and 1-60 mol% of R is a C6-C12 aryl group, n is a number with a viscosity at 23 ° C. of 10,000 to 1,000,000 cP) and a linear polyorganosiloxane containing an aliphatic unsaturated group, and (B2) SiO 4/2 Units, R ′ 3 SiO 1/2 units and R ′ 2 SiO 2/2 units, and optionally further R′SiO 3/2 units wherein R ′ is independently a C1-C6 alkyl group.
- Containing siloxane (wherein the amount of (B2) is such that the ratio of the number of aliphatic unsaturated groups in (B2) to the total number of aliphatic unsaturated groups in (B) exceeds 50%; %).
- (B2) is blended for the purpose of adjusting the hardness and elongation of the cured product, and by further using (B2), the adhesion is improved particularly when the adherend is a polarizing plate.
- (B2) can be used in such an amount that the ratio of the number of aliphatic unsaturated groups in (B2) to the total number of aliphatic unsaturated groups in (B) is 50 to 95%. From the viewpoint of the property and followability, it is preferably 55 to 85%.
- R 1 is an aliphatic unsaturated group.
- R 1 at both ends may be the same or different, but is preferably the same.
- Examples of the aliphatic unsaturated group include alkenyl groups such as C2 to C6 alkenyl groups (eg, vinyl, propenyl, butenyl, hexenyl, etc.).
- alkenyl groups such as C2 to C6 alkenyl groups (eg, vinyl, propenyl, butenyl, hexenyl, etc.).
- An alkenyl group having an unsaturated terminal is more preferable, and a vinyl group is preferable from the viewpoint of ease of synthesis.
- R is a C1-C6 alkyl group (for example, methyl, ethyl, propyl, etc.) or a C6-C12 aryl group (for example, phenyl, tolyl, xylyl, etc.). R may be the same or different.
- 1 to 60 mol% of R is a C6 to C12 aryl group
- 1 to 50 mol% of R is a C6 to C12 aryl group. It is preferably 1 to 35 mol%.
- the C1-C6 alkyl group is preferably methyl, and the C6-C12 aryl group is preferably phenyl.
- 1 to 60 mol% of R is preferably a phenyl group and the remainder is a methyl group, and more preferably 1 to 50 mol% of R.
- (B1) has a viscosity at 23 ° C. of 10,000 to 1,000,000 cP, preferably 15,000 to 1,000,000 cP, from the viewpoint of workability (sagging) of the composition.
- the number of aliphatic unsaturated groups in (B1) can be determined from the molecular weight obtained by calculating the average structural formula by NMR, calculating the molecular weight.
- the method for preparing (B1) is not particularly limited, and for example, polycondensation and re-equilibration of chlorosilanes necessary for a desired structure such as dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, dimethylvinylchlorosilane, and the like is performed. Alternatively, it can be obtained by cohydrolyzing alkoxysilanes necessary for a desired structure such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, dimethylvinylmethoxy, etc., and performing polycondensation and re-equilibration reactions.
- 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane, 1,1,3,3,5,5,7,7-octaphenylcyclotetrasiloxane, 1,1,3 Siloxanes necessary for a desired structure such as 3,3-tetramethyl-1,3-divinyldisiloxane are converted to alkali catalysts (alkali metal hydroxides, alkali metal silanolates, ammonium hydroxides, etc.) or acid catalysts (sulfuric acid). , Silanolate sulfate, trifluoromethanesulfonic acid) in the presence of ring-opening polymerization and re-equilibration.
- (B1) may be used alone or in combination of two or more.
- (B2) is SiO 4/2 unit, R ′ 3 SiO 1/2 unit and R ′ 2 SiO 2/2 unit, and optionally further R′SiO 3/2 unit (wherein R ′ is It is a branched polyorganosiloxane consisting of a C1-C6 alkyl group or an aliphatic unsaturated group and having at least 3 R's per molecule as an aliphatic unsaturated group.
- (B2) is a branched structure having a ratio of 6 to 10 moles of SiO 4/2 units and 4 to 8 moles of R ′ 3 SiO 1/2 units to 1 mole of R ′ 2 SiO 2/2 units.
- Polyorganosiloxane is mentioned.
- (B2) is preferably a solid or viscous semi-solid resinous or liquid at room temperature. Examples include those having a weight average molecular weight of 1,000 to 400,000, and preferably 2,000 to 200,000. The weight average molecular weight is a value obtained by using polystyrene as a calibration curve by gel permeation chromatography (GPC).
- Examples of the aliphatic unsaturated group relating to R ′ include the groups listed as the aliphatic unsaturated group in (B1), and specifically include alkenyl groups such as C2 to C6 alkenyl groups (eg, vinyl, propenyl, butenyl). Hexenyl, etc.). An alkenyl group having an unsaturated terminal is more preferable, and a vinyl group is preferable from the viewpoint of ease of synthesis.
- R ′ which is an aliphatic unsaturated group may be present as R ′ of any unit, but is preferably present as R ′ of the R ′ 2 SiO unit.
- R ′ other than the aliphatic unsaturated group is a C1-C6 alkyl group (for example, methyl, ethyl, propyl, etc.), and a methyl group is preferable in consideration of heat resistance.
- (B2) may be used alone or in combination of two or more.
- the composition of the present invention includes (C) a photoreaction initiator.
- C) is a component that functions as a radical initiator or a sensitizer when photocrosslinking (A) and (B).
- C) is an aromatic hydrocarbon, acetophenone and derivatives thereof, benzophenone and derivatives thereof, o-benzoylbenzoic acid ester, benzoin and benzoin ethers and derivatives thereof, xanthone and derivatives thereof, disulfide compounds, quinones.
- Examples include compounds, halogenated hydrocarbons and amines, and organic peroxides. From the viewpoint of compatibility with silicone and stability, a compound or an organic peroxide containing a substituted or unsubstituted benzoyl group is more preferable.
- Examples of (C) include acetophenone, propiophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACUREC651: manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR 1173: manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184: manufactured by BASF), 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACUREGA2959, manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one (IRGACURE® 127: manufactured by BASF), 2-methyl-1- (4-methyl Thiophenyl) -2-morpholinopropan-1-one (IRGACURE 907: manufactured by
- (C) may be used alone or in combination of two or more.
- composition of the present invention contains (D) a silane compound.
- (D) plays the role which improves the adhesiveness and adhesiveness to the base material of hardened
- a silane compound having an aliphatic unsaturated group can be used. It can be expected that the silane compound having an aliphatic unsaturated group reacts during UV curing and is incorporated into a matrix of a cured product to control physical properties and the like.
- the aliphatic unsaturated group include the groups listed as the aliphatic unsaturated group in (B1), specifically, alkenyl groups such as C2 to C6 alkenyl groups (for example, vinyl, propenyl, butenyl, hexenyl, etc.) ).
- An alkenyl group having an unsaturated terminal is more preferable, and a vinyl group is preferable from the viewpoint of ease of synthesis.
- silane compound having an aliphatic unsaturated group examples include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and bis (trimethoxysilylpropyl) allyl isocyanurate. And trimethoxysilylpropyl diallyl isocyanurate, preferably 3-methacryloxypropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane.
- silane compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tris (trimethoxysilylpropyl) isocyanurate can be used.
- (D) may be used alone or in combination of two or more.
- the composition of the present invention comprises (E) an MQ resin having a weight average molecular weight of 2,000 to 2,500,000 (hereinafter also simply referred to as “MQ resin”) and / or a weight average molecular weight of 2,000 to 1,000,000.
- MDQ resin a viscosity suitable for dam formation
- MDQ resin a viscosity suitable for dam formation
- adhesiveness thixotropic properties
- the composition of the present invention has a high viscosity of 20,000 cP or more, and generally there is a concern that the wettability is lowered and the adhesiveness of the cured product is poor. Nevertheless, the cured product of the composition of the present invention exhibits good adhesiveness, but it is understood that the formulation of (E) contributes to this.
- the MQ resin is a (R a ) 3 SiO 1/2 unit (wherein R a is an alkyl group or an aryl group, and is an alkyl group from the viewpoint of availability, ease of synthesis, and economy. And a resin composed of SiO 2 units, and a resin composed of (CH 3 ) 3 SiO 1/2 units and SiO 2 units, for example. .
- the ratio of the number of units of (R a ) 3 SiO 1/2 units to SiO 2 units is preferably 1:99 to 70:30, more preferably 5:95 to 50:50 It is.
- the weight average molecular weight of the MQ resin (E) is 2,000 to 2,500,000.
- the weight average molecular weight is a value using polystyrene as a calibration curve by gel permeation chromatography (GPC).
- the MQ resin is preferably used after being diluted with an organic solvent from the viewpoint of workability, and examples of the organic solvent include aromatic organic solvents such as toluene and xylene.
- the MQ resin preferably has a viscosity of a solution diluted with 40% by weight of xylene or toluene (for example, a xylene solution or a toluene solution having a nonvolatile content of 55 to 65% by mass) of 10 cP or more, more preferably 15 cP or more. .
- the upper limit of the viscosity of a solution can be set suitably, for example, can be 100 cP.
- the viscosity was measured using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.) No. This is a value measured at 60 rpm using one rotor.
- MQ resins having a weight average molecular weight of 1,000,000 to 2,500,000 are preferred, and a weight average molecular weight of 1,500,000 to 2 is preferred from the viewpoint of extensibility (elongation of cured product) and thixotropy. 500,000 MQ resin is more preferred.
- MQ resins having a weight average molecular weight of 2,000 or more and less than 1,000,000 are preferable, and MQ resins having a weight average molecular weight of 2,000 to 200,000 are more preferable. preferable.
- MDQ resin is (R a ) 3 SiO 1/2 unit (wherein R a includes an alkyl group and an aryl group, and an alkyl group is preferable from the viewpoint of availability, ease of synthesis, and economy, Among them, a methyl group is preferable from the viewpoint of tackiness), (R b ) 2 SiO unit (where R b includes an alkyl group and an aryl group, and is easy to obtain, synthesize, and economical)
- the alkyl group is preferable, and the methyl group is particularly preferable
- a resin composed of SiO 2 units for example, composed of (CH 3 ) 3 SiO 1/2 units, (CH 3 ) 2 SiO units and SiO 2 units. Resin.
- the ratio of (R a ) 3 SiO 1/2 units, (R b ) 2 SiO units, and SiO 2 units can be adjusted as appropriate depending on the desired refractive index.
- the weight average molecular weight of the MDQ resin (E) is 2,000 to 1,000,000.
- MDQ resin having a weight average molecular weight of 5,000 to 1,000,000 is preferable from the refractive index adjustment point, and MDQ resin having a weight average molecular weight of 10,000 to 1,000,000 is preferable. More preferred.
- MQ resin and MDQ resin may be used alone or in combination of two or more.
- MQ resin is preferable from the viewpoint of tackiness and thixotropy, and among (E), 20% by weight or more is preferably MQ resin, more preferably 30% by weight or more, and further preferably 40% by weight. 100% by weight may be MQ resin.
- (E) is an MQ having a weight average molecular weight of 1,000,000 to 2,500,000 (preferably 1,500,000 to 2,500,000). It is preferably a resin, more preferably 30% by weight or more, still more preferably 40% by weight, and 100% by weight may be such MQ resin.
- an MQ resin having a weight average molecular weight of 1,000,000 to 2,500,000 has a weight average molecular weight of 2,000 or more, MQ resin of less than 1,000,000 (preferably 2,000 to 200,000) can be blended, and 5 to 50% by weight of (E) is effective in achieving discharge efficiency.
- MQ resin is preferable, and more preferably 10 to 50% by weight.
- MQ resin and MDQ resin can be used in combination from the standpoint of adjusting the refractive index.
- the weight ratio of MQ resin to MDQ resin can be 80:20 to 5:95, preferably 80:20 to 20:80.
- the ratio can be appropriately changed depending on each refractive index and the refractive index of the component (A).
- the cured product has appropriate hardness and elasticity.
- the ratio of HS to ViB is 0.5 to 3.0, preferably 0.5 to 2.50, and more preferably 0.5 to 2.0.
- the number of aliphatic unsaturated groups in (B) is equal to the number of aliphatic unsaturated groups ViB1 in (B1), while (B1) and When (B2) is used in combination, the number of aliphatic unsaturated groups in (B) is the number of aliphatic unsaturated groups ViB1 in (B1) and the number of aliphatic unsaturated groups in (B2) ViB2. It becomes the sum of.
- the ratio of HS to ViD is 0.80 to 3, preferably 1.0 to 2.5.
- the ratio of HS to the sum of ViB and VID is 0.5 to 1.0. preferable.
- (C) is preferably 0.05 to 50 parts by weight with respect to (B) 100 parts by weight. More preferably, it is 0.1 to 40 parts by weight.
- (E) can be used in an amount of 5 to 400 parts by weight with respect to 100 parts by weight of (B). From the viewpoint of improving viscosity, thixotropy and adhesion to a substrate, (E) is 10 Is preferably 300 to 300 parts by weight, more preferably 20 to 250 parts by weight, and even more preferably 30 to 200 parts by weight.
- the total amount of (A) to (E) is preferably 55% by weight or more, more preferably 75% by weight or more, and still more preferably 90% in the composition. % By weight or more.
- a silane coupling agent excluding (D)
- a silicone resin adhesion improver excluding (E)
- polymerization prohibition as long as the effects of the present invention are not impaired.
- Additives such as an ultraviolet absorber, a light stabilizer, an inorganic filler, and the like can be blended.
- the composition of the present invention is a polyorganosiloxane containing an aliphatic unsaturated group other than (B) within a range not impairing the effects of the present invention (for example, a branched polyorganosiloxane containing an aliphatic unsaturated group). Can be included, but preferably is not included.
- silane coupling agents include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.
- trimethoxysilylpropyldiallyl isocyanurate bis (trimethoxysilylpropyl) allyl isocyanurate, tris (trimethoxysilylpropyl) isocyanurate, triethoxysilylpropyldiallyl isocyanurate, bis ( Examples include triethoxysilylpropyl) allyl isocyanurate and tris (triethoxysilylpropyl) isocyanurate.
- polymerization inhibitor examples include hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine and the like.
- the antioxidant can be used to prevent oxidation of the cured product of the composition and improve weather resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants.
- examples of the hindered amine antioxidant include N, N ′, N ′′, N ′′ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine ⁇ N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [ ⁇ 6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-
- hindered phenol antioxidants include penta Erythritol-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), N, N′-hexane-1,6-diylbis [3- ( 3,5-di-tert-butyl-4-hydroxyphenylpropioamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxyC7-C9 side chain alkyl ester of benzenepropanoic acid, 2,4- Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-
- the light stabilizer can be used to prevent photooxidative degradation of the cured product, and examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds.
- UV absorbers that are light-resistant stabilizers can be used to prevent light deterioration and improve weather resistance, for example, UV absorbers such as benzotriazole, triazine, benzophenone, and benzoate Etc.
- Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Il) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(he Sil) oxy] -phenol and other triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as
- Examples include, but are not limited to, benzoate ultraviolet absorbers.
- the said ultraviolet absorber may be individual, or may use 2 or more types together.
- a hindered amine system is preferable. Among them, it is preferable to use a tertiary amine-containing hindered amine light stabilizer for improving the storage stability of the composition.
- Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144, CHIMASSORB119FL (all of which are manufactured by BASF); MARK LA-57, LA-62, LA-67, LA-63 (all of which are Asahi) Light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Co., Ltd.).
- the composition of the present invention has a viscosity at 23 ° C. of 20,000 to 150,000 cP from the viewpoint of securing the shape at the time of discharge in dam formation.
- the viscosity is a value measured at a rotational speed of 6 rpm.
- the lower limit is preferably 23,000 cP, more preferably 25,000 cP, and from the viewpoint of workability and dischargeability, the upper limit is preferably 130,000 cP, more preferably. Is 100,000 cP.
- compositions of the present invention at 23 ° C., viscosity measured at a rotation speed 6rpm the (cP) at V 6rpm, 23 ° C., viscosity measured at a rotation speed 12rpm a (cP) and V 12rpm, with V 6rpm / V 12rpm
- the obtained thixotropy ratio is preferably 1.02 to 1.9.
- the thixotropy ratio is more preferably 1.03 to 1.7, and still more preferably 1.04 to 1.5.
- the composition of the present invention can be prepared by blending (A) to (E) and additives.
- preparation after blending (A), (B) and (E), it is preferable to blend (C) and (D) and an arbitrary polymerization inhibitor in the absence of ultraviolet rays.
- (B) and (E) are put in a universal mixing stirrer, and uniformly mixed at room temperature (10 to 30 ° C.) and at a low speed, and then uniformly mixed and cooled at 130 ° C. under reduced pressure.
- composition Component, heated to about 90-130 ° C., uniformly mixed under reduced pressure, cooled, and then added (C), (D) and a polymerization inhibitor in the absence of ultraviolet light, and cooled with ice water (
- the composition can be obtained by mixing uniformly at a low speed and cooling under reduced pressure at low speed, defoaming, and then filtering as desired.
- the composition of the present invention can be cured by irradiation with ultraviolet rays.
- the lamp in the wavelength range of the reactive range (C) include, for example, a high pressure mercury lamp (UV-7000), metal halide lamp (MHL-250, MHL-450, MHL-150, MHL-) manufactured by Ushio Electric Co., Ltd. 70), Korea: Metal halide lamp (JM-MTL 2KW) manufactured by JM tech, UV irradiation lamp (OSBL360) manufactured by Mitsubishi Electric Corporation, UV irradiation machine (UD-20-2) manufactured by Nippon Battery Co., Ltd.
- Irradiation dose is preferably 100 ⁇ 10000mJ / cm 2, more preferably 300 ⁇ 5000mJ / cm 2, more preferably from 500 ⁇ 3500mJ / cm 2.
- the cured product of the composition of the present invention has the following suitable physical properties.
- the visible light transmittance is more preferably 96% or more, and still more preferably 98% or more. From the viewpoint of visible transmittance, it is preferable to suppress the amount of (C) used. Further, after each of the components (A) and (B) is mixed uniformly or after heat treatment at 80 to 180 ° C., the visible light transmittance after curing can be improved. Heat treatment is preferable from the viewpoint of stability over time.
- the composition of the present invention can have a curing shrinkage rate of 1.0% or less, when applied to an image display device, distortion can be easily prevented and visibility can be ensured. Is preferable.
- the cure shrinkage is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less.
- the composition of the present invention can have an E hardness after curing of 5 to 40, and therefore, when applied to an image display device, it can easily moderate the stress from the outside, and has a high temperature. It is preferable in that visibility can be ensured by suppressing moisture penetration even under high humidity.
- the E hardness is preferably 5 to 35, more preferably 10 to 30.
- the composition of the present invention is preferable in that the elongation after curing can be 50% or more, which is excellent in stress relaxation from the outside and can secure deformation resistance.
- the elongation after curing is preferably 80% or more, more preferably 100% or more, and further preferably 200% or more.
- the composition of the present invention is a dam material composition in an image display device.
- the dam material composition is used to form a frame on the display unit or the protection unit of the image display device.
- the sealant protrudes from the display unit or the like.
- the composition is trimmed on a liquid crystal panel with a dispensing nozzle of a dispensing machine (for example, 23G can be selected as appropriate according to the ejection amount), and then a material as a filler is applied and pasted onto the cover panel.
- a material as a filler is applied and pasted onto the cover panel.
- the composition of this invention has favorable adhesiveness, and can be applied suitably to both a display part or a protection part.
- composition of the present invention is suitable for producing a large screen image display device having an image display panel of 5 to 100 inches, more preferably 7 to 80 inches, and further preferably 10 to 60 inches.
- the composition of the present invention is preferred when the sealant interposed between the protective part and the image display part in the image display device is an ultraviolet curable resin composition, more preferably an ultraviolet curable silicone resin composition.
- an ultraviolet curable silicone resin composition used as the sealant, the composition described in WO2012 / 086402 can be used. Specifically, (A ′) the viscosity at 23 ° C. is 20 to 25000 cP.
- R ′′ is independently C1 to C6 alkyl group or an aliphatic unsaturated group
- R ′′ are aliphatic unsaturated groups per molecule.
- Polyorganosiloxane containing a saturated group (however, the amount of (B2 ′) is the ratio of the number of aliphatic unsaturated groups in (B2 ′) to the total number of aliphatic unsaturated groups in (B ′).
- the ratio of the number of mercaptoalkyl groups present in (A ′) to the total number of aliphatic unsaturated groups in (B ′) and (D ′) is 0.5 to 1.05,
- the ratio of the number of mercaptoalkyl groups in (A ′) to the number of aliphatic unsaturated groups in (B ′) is 0.95 to 3
- the aliphatic unsaturated groups in (D ′) An ultraviolet curable silicone resin composition in which the ratio of the number of mercaptoalkyl groups in (A ′) to the number of is 1.5 to 3 is mentioned.
- Viscosity and thixotropy Using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.), the range of 400 cP or less is No. 2 rotors are used, and the range of more than 400 to 1500 cP is No. 3 rotors are used, and the range over 1500 cP is No. Using 4 rotors, the viscosity at 23 ° C. was measured at a predetermined rotational speed.
- composition is discharged for 10 seconds using a double thread plastic needle (Musashi Engineering Co., Ltd .: needle length 12.7 mm, gauge: 20 G (inner diameter 0.58 mm, outer diameter 0.91 mm)). It is the weight (g) at the time.
- Visible light transmittance The liquid material is filled in a quartz cell to a thickness of 10 mm, and the cured product is set to a thickness of 150 ⁇ m, and the spectrophotometer (CM-3500d manufactured by Minolta Co., Ltd.) is used at 23 ° C. The transmittance at a visible light wavelength (360 to 780 nm) was measured.
- CM-3500d manufactured by Minolta Co., Ltd.
- Curing shrinkage (%) (specific gravity after curing ⁇ specific gravity before curing) / specific gravity after curing) ⁇ 100
- E Hardness after Curing Based on JIS K 6253 E, the energy hardness was changed by DUROMETER HARDNESS TYPE E (manufactured by ASKER), and the E hardness of the cured product at 23 ° C. was measured. E hardness after hardening is E hardness of the hardened
- the sample was pressurized with a pressure until the load reached a predetermined value.
- a pressure reached a predetermined value.
- the appearance of the pressurization location is compared with the non-pressurization location by the presence of cracks or white discoloration. Change. Check this change in appearance visually, -If there is a change in the appearance of the pressurized part, -When there is no change in the appearance of the pressurized part ⁇ It was.
- the cured product has cracks of 0.02 mm or more in one direction and / or an air layer of 0.02 mm or more in one direction, and / or damage of 0.02 mm or more in one direction in either PMMA or glass. NG if there is, -If these cracks, air layer, and damage are not recognized at all, it is OK. It was. (10-2) High-temperature and high-humidity After the cured product is left in a constant-temperature and constant-humidity layer set to a high-temperature and high-humidity condition of 85 ° C.
- CM-3500d manufactured by Minolta Co., Ltd.
- a yellow index which is an index of the degree of discoloration. -If the yellow index is 1.0% or more, NG, -OK when the yellow index is less than 1.0% It was.
- Cohesive failure rate (11-1) vs. acrylic, vs. glass
- the composition On each adherend (PMMA, glass) having a width of 25 mm, the composition has a thickness of 0.1 mm and a length of 10 mm or more.
- a sample was prepared by coating and overlaying a tempered glass plate having a thickness of 2 mm and a width of 25 mm so that the composition had a stacking width of 10 mm, followed by curing at an ultraviolet energy dose of 3000 mJ / cm 2 .
- samples 1 day and 3 days later were subjected to a shear adhesion test using an autograph manufactured by Shimadzu Corporation with a measurement speed of 10 mm / min to peel off the adherend and glass plate. It was.
- Each polarizing film is applied with a width of 25 mm and a length of 60 mm or more so that the thickness of the composition is 0.1 mm, and a tempered glass plate with a thickness of 2 mm and a width of 25 mm is laminated so that the overlapping width of the composition is 10 mm.
- it was cured at an ultraviolet energy irradiation amount of 3000 mJ / cm 2 to prepare a sample.
- the sample was pulled at a tensile rate of 10 mm / min using an autograph manufactured by Shimadzu Corporation, and peeled 180 ° from the polarizing film and glass plate as the adherend. A peel adhesion test was conducted.
- samples 1 day and 3 days later were subjected to a shear adhesion test using an autograph manufactured by Shimadzu Corporation with a measurement speed of 10 mm / min to peel off the adherend and glass plate. It was. Measuring the area Smm 2 of the release portion of the composition on the adherend was calculated cohesive failure rate ratio of the coating area.
- the filling material was prepared as follows. The contents of (a-1), (c-1), (c-2), (d-1) and (e-1) are as described later.
- (A-1) 8.5 parts by weight, vinyl-terminated polymethylphenyl siloxane (viscosity 3000 cP) 79.76 weights whose end is blocked with a dimethylvinylsiloxy group, 5% by mole of diphenylsiloxy units and the remainder is dimethylsiloxy units Parts and (e-1) 10 parts by weight, (c-1) 0.22 parts by weight, (c-2) 0.22 parts by weight, (d-1) 1.3 parts by weight And mixed until uniform to obtain a filling material.
- (Synthesis example) (A) in an Example and a comparative example is as follows. Synthesis of (a-1) 1549.2 g (12 mol) of dimethyldichlorosilane and 21.7 g (0.2 mol) of trimethylchlorosilane in a 5 L separable flask equipped with a cooling reflux tube, a dropping funnel and a three-one motor as a stirring device. ), 3-mercaptopropyltrimethoxysilane (196.4 g, 1.0 mol) and toluene (1500 g), a mixture of water (1000 g) and toluene (500 g) was dropped from the dropping funnel over about 1 hour. Hydrolysis was performed with heating and stirring at 70 ° C. for 2 hours.
- the aqueous phase was separated, washed with water, and then dehydrated by heating at 100 ° C. to 125 ° C. After completion of dehydration, 1.5 g of a 50% aqueous potassium hydroxide solution was added, and a condensation reaction was performed by heating and stirring at 115 to 125 ° C. for 5 hours. After neutralization with ethylene chlorohydrin, 1200 to 1300 g of toluene was dissolved, and filtration was performed using super celite floss as a filter aid, and then the remaining toluene was removed under constant pressure and reduced pressure to remove mercaptopropyl groups. 928 g of polymethylsiloxane contained was obtained.
- Hydrolysis was performed with heating and stirring at 70 ° C. for 2 hours. After completion of the reaction, the aqueous phase was separated, washed with water, and then dehydrated by heating at 100 ° C. to 125 ° C. After completion of the dehydration, 0.5 g of a 50% potassium hydroxide aqueous solution was added, and a condensation reaction was performed by heating and stirring at 115 to 125 ° C. for 5 hours. After neutralization with ethylene chlorohydrin, 1300-1500 g of toluene was dissolved and filtered using super celite floss as a filter aid, and then the remaining toluene was removed under constant pressure and reduced pressure to remove mercaptopropyl groups.
- (B1) in Examples and Comparative Examples is as follows. Synthesis of (b1-1) 1800 g of 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane was added to a 3 L separable flask equipped with a cooling reflux tube and a three-one motor as a stirring device. 1,1,3,3,5,5,7,7-octaphenylcyclotetrasiloxane (260 g) and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (7.6 g) at 150 to 160 ° C.
- dehydration was performed by heating and stirring with nitrogen gas at 0.5 Nm 3 / h for 3 hours, and then 0.1 g of potassium hydroxide was added and stirring was performed. The heating and stirring was continued until the potassium hydroxide dissolved and became uniform in the flask, and the viscosity increased to 15000 cP to 18000 cP. Then, after neutralizing with 10 g of ethylene chlorohydrin at 100 ° C. and filtering using super celite floss as a filter aid, the low boiling point content is removed under reduced pressure of 170 to 180 ° C. and 2 mmHg.
- Viscosity 19200 cP Average number of aliphatic unsaturated groups in one molecule: 2 Average structural formula by NMR measurement: CH 2 ⁇ CH—Si (CH 3 ) 2 —O— ⁇ Si (CH 3 ) 2 O ⁇ 593 — ⁇ SiPh 2 O ⁇ 31 —Si (CH 3 ) 2 —CH ⁇ CH 2 Molecular weight: 49320
- (B1-3) Vinyl-terminated polymethylphenylsiloxane Vinyl-terminated polymethylphenylsiloxane whose end is blocked with a dimethylvinylsiloxy group, 5 mol% of diphenylsiloxy units, and the remainder is dimethylsiloxy units.
- (B2) in Examples and Comparative Examples is as follows.
- (B2-1) has an average structural formula of ⁇ (CH 3 ) 3 —SiO 1/2 ⁇ 6 ⁇ SiO 2 ⁇ 8 ⁇ (CH 2 ⁇ CH) (CH 3 ) —SiO ⁇ M 6 D v Q 8 Resin weight average molecular weight: 22000
- the weight molecular weight is a value using polystyrene as a calibration curve by gel permeation chromatography (GPC).
- C in Examples and Comparative Examples is as follows.
- (E) in Examples and Comparative Examples is as follows.
- (E-1) MQ resin Average structural formula: ⁇ (CH 3 ) 3 SiO 1/2 ⁇ ⁇ SiO 2 ⁇ 3.5
- MQ resin Weight average molecular weight 26200
- the weight molecular weight is a value using polystyrene as a calibration curve by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- Example 1 Mercaptopropyl group-containing polymethylsiloxane (a-2) 8.0 parts by weight (80 g), vinyl-terminated polymethylphenylsiloxane (b1-2) 46.5 parts by weight (465 g) and MQ resin (e-1) 40. 0 parts by weight (400 g) was placed in a 5 L universal mixing stirrer (manufactured by Dalton Co.) and mixed uniformly for 30 minutes at room temperature (22 ° C.) and rotating conditions with a low speed lever.
- compositions of Examples and Comparative Examples were prepared with the formulations shown in Table 1, and physical properties were evaluated. The results are shown in Tables 2-4.
- a cured product having physical properties such as hardness and adhesiveness suitable for use in an image display device can be obtained, and it is difficult to distinguish a seam between the cured product and the sealant. Therefore, it is also preferable from the viewpoint of visibility. From Examples 1 and 2, it can be seen that the curability is improved by blending a high molecular weight MQ resin. Also, from Examples 1 to 3 and Examples 4 to 5, it can be seen that by blending MDQ resin, the refractive index can be controlled and the joining performance can be further improved.
- Comparative Examples 1 to 3 which do not contain a branched polyorganosiloxane having an aliphatic unsaturated group are inferior in terms of ejection performance and curability as compared with Examples 1, 2 and 4, and temperature cycle adhesion test However, it is difficult to avoid the occurrence of peeling and cracks, and it is understood that the followability is inferior. Furthermore, it turns out that the comparative examples 4 and 5 which do not contain MQ resin and MDQ resin are inferior in sclerosis
- the present invention is a dam material composition, and when an image display device is produced using the dam material composition, a composition in which a frame formed from the dam material composition has appropriate hardness and adhesion to an adherend. Provided. More preferably, it is difficult to distinguish the joint between the frame of the dam material and the sealant applied therein, and an image display device having good visibility can be provided.
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Abstract
Description
(B)(B1)式(I):
R1は、独立して、脂肪族不飽和基であり、
Rは、独立して、C1~C6アルキル基又はC6~C12アリール基であって、Rのうち、1~60モル%はC6~C12アリール基であり、
nは、23℃における粘度を10,000~1,000,000cPとする数である)で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、(B2)SiO4/2単位、R'3SiO1/2単位及びR'2SiO2/2単位、並びに場合によってはさらにR'SiO3/2単位(式中、R'は、それぞれ独立して、C1~C6アルキル基又は脂肪族不飽和基を表す)からなり、1分子当たり、少なくとも3個のR'が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサン(ここで、(B2)の量は、(B)中の脂肪族不飽和基の全個数に占める(B2)中の脂肪族不飽和基の個数の割合が50%超、95%以下となる量とする);
(C)光反応開始剤;
(D)シラン化合物;並びに
(E)重量平均分子量2,000~2,500,000のMQ樹脂及び/又は重量平均分子量2,000~1,000,000のMDQ樹脂、
を含み、ここで、
(B)中の脂肪族不飽和基の個数に対する、(A)中のメルカプトアルキル基の個数の比が、0.5~3.0であり、かつ
(E)が、(B)100重量部に対して、30~200重量部であり、かつ
23℃における粘度が、20,000~150,000cPである、
画像表示装置用のダム材組成物に関する。
本発明3は、(E)が、重量平均分子量1,000,000~2,500,000のMQ樹脂を含む、本発明1又は2の画像表示装置用のダム剤組成物に関する。
本発明4は、(E)が、さらに、重量平均分子量2,000~1,000,000のMDQ樹脂を含む、本発明3の画像表示装置用のダム剤組成物に関する。
本発明5は、(C)の含有量が、(B)100重量部に対して、0.05~50重量部である、本発明1~4のいずれかの画像表示装置用のダム材組成物に関する。
本発明6は、(D)が、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン及びビニルトリエトキシシランからなる群より選ばれる1種以上の脂肪族不飽和基を含有するシラン化合物である、本発明1~5のいずれかの画像表示装置用のダム材組成物に関する。
本発明7は、画像表示部と保護部との封止に、本発明1~6のいずれかの画像表示装置用のダム材組成物を用いてなる、画像表示装置に関する。
(A)23℃における粘度が20~25,000cPである、ケイ素原子に結合するメルカプトアルキル基を含有するポリオルガノシロキサン;
(B)(B1)式(I):
R1は、独立して、脂肪族不飽和基であり、
Rは、独立して、C1~C6アルキル基又はC6~C12アリール基であって、Rのうち、1~60モル%はC6~C12アリール基であり、
nは、23℃における粘度を10,000~1,000,000cPとする数である)で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、(B2)SiO4/2単位、R'3SiO1/2単位及びR'2SiO2/2単位、並びに場合によってはさらにR'SiO3/2単位(式中、R'は、それぞれ独立して、C1~C6アルキル基又は脂肪族不飽和基を表す)からなり、1分子当たり、少なくとも3個のR'が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサン(ここで、(B2)の量は、(B)中の脂肪族不飽和基の全個数に占める(B2)中の脂肪族不飽和基の個数の割合が50%超、95%以下となる量とする);
(C)光反応開始剤;
(D)シラン化合物;並びに
(E)重量平均分子量2,000~2,500,000のMQ樹脂及び/又は重量平均分子量2,000~1,000,000のMDQ樹脂
を含む。
2RSH + I2 → RSSR + 2HI
の反応を利用した方法であり、滴定中、微量の過剰ヨウ素で滴定液が微黄色になることを利用する。
R1は、独立して、脂肪族不飽和基であり、
Rは、独立して、C1~C6アルキル基又はC6~C12アリール基であって、Rのうち、1~60モル%はC6~C12アリール基であり、
nは、23℃における粘度を10,000~1,000,000cPとする数である)で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、(B2)SiO4/2単位、R'3SiO1/2単位及びR'2SiO2/2単位、並びに場合によってはさらにR'SiO3/2単位(式中、R'は、それぞれ独立して、C1~C6アルキル基又は脂肪族不飽和基を表す)からなり、1分子当たり、少なくとも3個のR'が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサンを含有する(ここで、(B2)の量は、(B)中の脂肪族不飽和基の全個数に占める(B2)中の脂肪族不飽和基の個数の割合が50%超、95%以下となる量とする)。
〔硬化後の可視光透過率〕
本発明の組成物は、硬化厚み150μmにおける硬化後の可視光透過率を、95%以上とすることができるため、視認性の点から好ましい。可視光透過率は、より好ましくは96%以上、さらに好ましくは98%以上である。可視透過率の点からは、(C)の使用量を抑制することが好ましい。また、(A)、(B)の各成分を、それぞれ、又は均一に混合した後、80~180℃にて加熱処理することにより、硬化後の可視光透過率を向上させることができる。加熱処理は、経時的安定性の点からも好ましい。
本発明の組成物は、硬化収縮率を、1.0%以下とすることができるため、画像表示装置に適用した場合に、容易に、歪みが防止され、視認性を確保することができる点で好ましい。硬化収縮率は、好ましくは0.5%以下、より好ましくは0.3%以下、さらに好ましくは0.2%以下である。
本発明の組成物は、硬化後のE硬度を5~40とすることができるため、画像表示装置に適用した場合に、容易に、外部からの応力を適度に緩和することができ、かつ高温高湿下でも水分の浸透を抑止して、視認性を確保することができる点で好ましい。E硬度は、好ましくは5~35であり、より好ましくは10~30である。
本発明の組成物は、硬化後の伸びを50%以上とすることができるため、外部からの応力緩和に優れ、耐変形性を確保することができる点で好ましい。硬化後の伸びは、好ましくは80%以上であり、100%以上がより好ましく、200%以上がさらに好ましい。
(B’)(B1’)式(I’):
R1’は、独立して、脂肪族不飽和基であり、
R'は、独立して、C1~C6アルキル基又はC6~C12アリール基であって、R'のうち、1~60モル%はC6~C12アリール基であり、
n'は、23℃における粘度を100~25000cP、好ましくは100~8000cPとする数である)で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、(B2’)SiO4/2単位、R''3SiO1/2単位及びR''2SiO2/2単位、並びに場合によってはさらにR''SiO3/2単位(式中、R''は、それぞれ独立して、C1~C6アルキル基又は脂肪族不飽和基を表す)からなり、1分子当たり、少なくとも3個のR''が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサン(ただし、(B2’)の量は、(B’)中の脂肪族不飽和基の全個数に占める(B2’)中の脂肪族不飽和基の個数の割合が50%以下となる量とする);
(C’)光反応開始剤;及び
(D’)脂肪族不飽和基を含有するシラン化合物
を含み、ここで、
(B’)及び(D’)中の脂肪族不飽和基の合計個数に対する、(A’)に存在するメルカプトアルキル基の個数の比が、0.5~1.05であり、
(B’)中の脂肪族不飽和基の個数に対する、(A’)中のメルカプトアルキル基の個数の比が、0.95~3であり、かつ
(D’)中の脂肪族不飽和基の個数に対する、(A’)中のメルカプトアルキル基の個数の比が、1.5~3である、紫外線硬化型シリコーン樹脂組成物が挙げられる。
(1)メルカプト基の個数の測定
ヨウ素源として、1/10規定ヨウ素溶液(特級試薬)を使用し、比色滴定により、単位重量当りのメルカプト基数を定量した。
計算方法: SH含有量(mmol/g) = (A×P×0.1)/(W×C)
A:変色するまでに要したヨウ素溶液滴下量
P:ヨウ素溶液の補正係数(試薬に記載されている補正係数):補正が必要な場合に記載
W:サンプル重量(g)
C:サンプルの不揮発分
予備測定を行ないヨウ素溶液量を求め、その後精度よく3回測定し、3回の平均値を求めた。
NMR測定における、Si-CH3(0.1ppm付近)、Si-Ph(7.3-7.7ppm付近)及びCH3Si-CH=CH2(5.7-6.3ppm付近)のピークが、それぞれ、(CH3)2SiO単位、Ph2-SiO単位及び(CH3)2Si-CH=CH2O1/2単位に対応するものとして、それぞれのピーク強度の比より単位数を求め、平均構造式を得て、そこから分子量を求め、不飽和基の個数を算出した。
回転粘度計(ビスメトロン VDA-L)(芝浦システム株式会社製)を使用して、400cP以下の範囲は、No.2ローターを使用し、400超~1500cPの範囲は、No.3ローターを使用し、1500cP超の範囲は、No.4ローターを使用し、所定の回転数で、23℃における粘度を測定した。チキソ性は、回転数12rpmにおける粘度:V12rpm、回転数6rpmにおける粘度:V6rpmを測定し、式:V6rpm/V12rpmにより求めた値である。
2条ネジプラスチックニードル(武蔵エンジアリング株式会社製:針長12.7mm、ゲージ:20G(内径0.58mm、外径0.91mm))を用いて、組成物を10秒間吐出した際の重量(g)である。
液状物については、石英セルに充填して厚さ10mmについて、硬化物については厚さ150μmにして、分光測式計((株)ミノルタ製CM-3500d)によって23℃における可視光領域波長(360~780nm)における透過率を測定した。
組成物の硬化前と硬化後の比重を電子比重計(MIRAGE社製SD-120L)により測定し、下記式より双方の比重差から算出した。
硬化収縮率(%)=(硬化後の比重-硬化前の比重)/ 硬化後の比重)×100
JIS K 6253 Eに準拠し、DUROMETER HARDNESS TYPE E(ASKER製)にて、エネルギー照射量を変化させて、23℃における硬化物のE硬度を測定した。硬化後のE硬度は、最大のエネルギー照射量で硬化させた硬化物のE硬度である。
JIS K 6301に準拠し、ショッパー引張り試験機(株式会社東洋精機製作所 製)にて23℃における最大のエネルギー照射量で硬化させた硬化物の伸びを測定した。
組成物の厚みが200μmとなるように、0.6mm厚の3.5インチディスプレイ用(画像表示部の対角線の長さが3.5インチ)ガラス板と、0.4mm厚の3.5インチディスプレイ用(画像表示部の対角線の長さが3.5インチ)PMMA板の間に塗布し、5000mJ/cm2の紫外線エネルギー照射量にて硬化させて、試料を作製した。
紫外線照射終了後24時間後に、試料のPMMA(ポリメチルメタクリレート)板側を上側にして、中央部1箇所を、直径10mmの半円状の先端部を持つ金属棒を7.5mm/分の速度にて試料を加圧し、荷重が所定の値に到達するまで加圧した。
この加圧により、加圧箇所のガラス板、PMMA板又は硬化組成物に微細なクラックが入ると、クラックの存在又は白く変色することで、加圧箇所の外観が、非加圧箇所に比べて変化する。この外観の変化を目視で確認し、
-加圧箇所の外観の変化が確認された場合を×、
-加圧箇所の外観の変化が確認されない場合を○
とした。
(10-1)ヒートショック
組成物の厚みが200μmとなるように、1mm厚のガラス板全面に塗布し、1mm厚のPMMA板で挟み、5000mJ/cm2の紫外線エネルギー照射量にて硬化させた後、-50℃から125℃までの温度サイクル(各温度30分間保持)にて環境試験を行なった(機器名:エスペック株式会社製TSA-71S-A)。
その後、23℃の状態に戻した後、硬化物及びPMMA、ガラスの状態を光学顕微鏡(10倍)で観察した。
-硬化物に、一方向で0.02mm以上のクラック及び/若しくは一方向で0.02mm以上の空気層が生じる、並びに/又はPMMAとガラスのいずれかに一方向で0.02mm以上の損傷がある場合をNG、
-これらのクラック、空気層、損傷が全く認められない場合をOK
とした。
(10-2)高温多湿下
硬化物を温度85℃、湿度85%RHの高温多湿条件に設定した恒温恒湿層に500時間放置後、分光測式計((株)ミノルタ製CM-3500d)により、温度23℃、湿度50%の状態に戻した後に変色の度合いの指標であるイエローインデックスにて評価を行なった。
-イエローインデックスが1.0%以上の場合をNG、
-イエローインデックスが1.0%未満の場合をOK
とした。
(11-1)対アクリル、対ガラス
幅25mmの各被着体(PMMA、ガラス)上に、組成物を厚み0.1mmとなるように、幅25mmで長さ10mm以上塗布し、組成物を重ね幅が10mmとなるように厚さ2mm、幅25mmの強化ガラス板を重ねた後、3000mJ/cm2の紫外線エネルギー照射量にて、硬化させて、試料を作製した。
試料作成直後、1日後及び3日後の試料について、島津製作所(株)社製オートグラフを用い、測定速度10mm/分の引張り速度で引っ張り、被着体とガラス板を剥離させる剪断接着試験を行なった。
被着体上の組成物の剥離部分の面積Smm2を求め、
(100×S)/(10×25)
を計算して凝集破壊率(%)とした。
(11-2)対偏光板
偏光板フィルムとして、幅25mmの液晶用偏光フィルム(品名:SEG1425DU 日東電工社製)、アンチグレア処理したフィルム(品名:AG150日東電工社製)、及びアンチリフレクション処理されたフィルム(品名:ARSタイプ日東電工社製)を用意した。各偏光フィルムに、組成物の厚みが0.1mmとなるように幅25mmで長さ60mm以上塗布し、組成物の重ね幅が10mmとなるように厚さ2mm、幅25mmの強化ガラス板を重ねた後、3000mJ/cm2となる紫外線エネルギー照射量にて硬化させて、試料を作製した。試料作成直後及び2時間後の試料について、島津製作所(株)社製オートグラフを用い、試料を測定速度10mm/分の引張り速度で引っ張り、被着体である偏光フィルムとガラス板から180°剥離させる、ピール接着試験を行なった。
被着体上の組成物の剥離部分の面積Smm2を求め、
(100×S)/(10×25)
を計算して凝集破壊率(%)とした。
(11-3)対アルミニウム、対ステンレス
幅25mmの各被着体(アルミニウム、ステンレス(SUS304))上に、組成物を厚み0.1mmとなるように、幅25mmで長さ10mm以上塗布し、組成物を重ね幅が10mmとなるように厚さ2mm、幅25mmの強化ガラス板を重ねた後、ガラス側から3000mJ/cm2の紫外線エネルギー照射量にて、硬化させて、試料を作製した。
試料作成直後、1日後及び3日後の試料について、島津製作所(株)社製オートグラフを用い、測定速度10mm/分の引張り速度で引っ張り、被着体とガラス板を剥離させる剪断接着試験を行なった。
被着体上の組成物の剥離部分の面積Smm2を求め、塗布面積との比率で凝集破壊率を算出した。
硬化物を、温度85℃、湿度85%の条件下で500時間保管した後、23℃、湿度50%の状態に戻し、JIS K 7105に準拠し、ヘーズメータNDH5000(日本電色工業株式会社製)にて測定した。
松浪ガラス社製スライドガラス(S1112)上に、組成物(ダム材)を200μm厚みとなるように、幅0.3mmで、75mm×25mmの枠状に塗布し、2000mJ/cm2となる紫外線エネルギー照射量にて硬化させた後、充填用材料(フィル材)をその中に塗布し、松浪ガラス社製スライドガラス(S1112)を貼り合わせ、同様に3000mJ/cm2となる紫外線エネルギー照射量にて硬化させた。打ち継ぎ部分を目視で観察して、その視認性を評価した。
◎:目視では見分けられない
○:目視では容易には見分けられない
○-△:目視で簡単には見分けられない
△:目視で見分けられる
△-X:簡単に見分けられる
X:容易に見分けられる
ここで、充填用材料は、以下のようにして調製した。(a-1)、(c-1)、(c-2)、(d-1)及び(e-1)の内容は、後述のとおりである。
(a-1)8.5重量部、末端がジメチルビニルシロキシ基で閉塞され、ジフェニルシロキシ単位が5モル%、残余がジメチルシロキシ単位であるビニル末端ポリメチルフェニルシロキサン(粘度3000cP)79.76重量部及び(e-1)10重量部を、均一に混合した後、(c-1)0.22重量部、(c-2)0.22重量部、(d-1)1.3重量部を加え、さらに均一になるまで混合して、充填用材料とした。
ガラス板(1mm厚、137mm×102mm)の表面に、組成物(ダム材)を2条ネジプラスチックニードル(武蔵エンジアリング株式会社製:針長12.7mm、ゲージ:23G(内径0.33mm、外径0.64mm))を用いて、厚みが200μmになるように、幅0.3mmで、135mm×100mmの枠状に塗布し、充填用材料(フィル材)をサンエイテック社製ディスペンサー(2300N改)を用いて、その中に塗布し、PMMA板(1mm厚、157mm×110mm)と貼り合合わせ、5000mJ/cm2の紫外線エネルギー照射量にて硬化させた後、23℃で1時間放置、次いで85℃に加熱し、その温度で6時間放置した後、23℃の状態に戻すことを1サイクルとして、3サイクル繰り返した(機器名:エスペック株式会社製小型環境試験機 SU-661)。
各サイクル後、23℃の状態に戻した状態における硬化物及びPMMA、ガラスの状態を光学顕微鏡(10倍)で観察した。
-硬化物とPPMA及びガラスのいずれもが接着した状態ではあるが、硬化物にクラックが発生している場合を「クラック」、
-硬化物とPMMA及びガラスの少なくともいずれかとの間で剥離が生じている場合を「剥離」
とした。
デジタルノギス(ミツトヨ社製、NTD12)を用いて、5cm角ガラスの中央に所定量の組成物を供給し、所定時間後に広がりを観察した。
2条ネジプラスチックニードル(武蔵エンジアリング株式会社製:針長12.7mm、ゲージ:14G(内径1.52mm、外径0.91mm)、ゲージ:20G(内径0.58mm、外径0.91mm)、)を用いて、組成物を供給し、直後及び1分後の直径を電子顕微鏡を用いて観察した。
実施例及び比較例における(A)は、以下のとおりである。
(a-1)の合成
冷却用還流管、滴下ロート、攪拌装置としてスリーワンモーターを装備した5Lのセパルブルフラスコ中の、ジメチルジクロロシラン1549.2g(12mol)、トリメチルクロロシラン21.7g(0.2mol)、3-メルカプトプロピルトリメトキシシラン196.4g(1.0mol)及びトルエン1500gに、水1000gとトルエン500gの混合物を、滴下ロートから約1時間かけて滴下した。70℃で2時間加熱攪拌しながら加水分解を行なった。反応終了後、水相を分離し、水洗し、次いで100℃~125℃にて加熱により脱水を行なった。脱水終了後、50%水酸化カリウム水溶液1.5gを加え、115~125℃で5時間加熱攪拌することにより縮合反応を行った。エチレンクロロヒドリンにて中和後、トルエンを1200~1300g脱溶し、スーパーセライトフロスを濾過助剤に用いて濾過し、その後残存するトルエンを定圧及び減圧下にて除去し、メルカプトプロピル基を含有するポリメチルシロキサン928gを得た。
平均構造式:{(CH3)3SiO1/2}{HS(CH2)3SiO3/2}5{(CH3)2SiO2/2}60
粘度:286cP
10mm厚みにおける透過率:93.8%
単位重量当りのメルカプト基数:0.98mmol/g
平均構造式:{(CH3)3SiO1/2}{HS(CH2)3SiO3/2}5{(CH3)2SiO2/2}60
粘度:330cP
10mm厚みにおける透過率:93.1%
単位重量当りのメルカプト基数:0.97mmol/g
冷却用還流管、滴下ロート、攪拌装置としてスリーワンモーターを装備した5Lのセパルブルフラスコ中の、ジフェニルジクロロシラン253.2g(1.0mol)、トリフェニルクロロシラン141.5g(0.48mol)、ジメチルジクロロシラン406.7g(3.15mol)、3-メルカプトプロピルトリメトキシシラン98.2g(0.5mol)及びトルエン1000gに、水1000gとトルエン700gの混合物を、滴下ロートから約1時間かけて滴下した。70℃で2時間加熱攪拌しながら加水分解を行なった。反応終了後、水相を分離し、水洗し、次いで100℃~125℃にて加熱により脱水を行なった。脱水終了後、50%水酸化カリウム水溶液0.5gを加え、115~125℃で5時間加熱攪拌することにより縮合反応を行った。エチレンクロロヒドリンにて中和後、トルエンを1300~1500g脱溶し、スーパーセライトフロスを濾過助剤に用いて濾過し、その後残存するトルエンを定圧及び減圧下にて除去し、メルカプトプロピル基を含有するポリメチルシロキサン511gを得た。
平均構造式:{(C6H5)3SiO1/2}{(C6H5)2SiO2/2}2{HS(CH2)3SiO3/2}{(CH3)2SiO2/2}6
粘度:23000cP
10mm厚みにおける透過率:82.1%
単位重量当りのメルカプト基数:0.82mmol/g
(b1-1)の合成
冷却用還流管、攪拌装置としてスリーワンモーターを装備した3Lのセパルブルフラスコに、1,1,3,3,5,5,7,7-オクタメチルシクロテトラシロキサン1800g、1,1,3,3,5,5,7,7-オクタフェニルシクロテトラシロキサン260g、1,1,3,3-テトラメチル-1,3-ジビニルジシロキサン7.6gを150~160℃にて窒素ガス0.5Nm3/hにて3時間加熱攪拌することにより脱水を行い、その後水酸化カリウム0.1gを加えて加熱攪拌を行った。加熱撹拌は、フラスコ内で水酸化カリウムが溶解し均一になり、かつ粘度が15000cP~18000cPに増粘するまで継続した。その後、エチレンクロロヒドリン 10gにて100℃にて中和後、スーパーセライトフロスを濾過助剤に用いて濾過した後、170~180℃、2mmHgの減圧下にて低沸分を除去することにより、末端がジメチルビニルシロキシ基で閉塞され、ジフェニルシロキシ単位が5モル%、残余がジメチルシロキシ単位であるビニル末端ポリメチルフェニルシロキサン1832gを得た。
粘度:20450cP
1分子中の脂肪族不飽和基の平均個数:2
NMR測定による平均構造式:
CH2=CH-Si(CH3)2-O-{Si(CH3)2O}595-{SiPh2O}31-Si(CH3)2-CH=CH2
分子量:50130
冷却用還流管、攪拌装置としてスリーワンモーターを装備した3Lのセパルブルフラスコに、1,1,3,3,5,5,7,7-オクタメチルシクロテトラシロキサン1800g、1,1,3,3,5,5,7,7-オクタフェニルシクロテトラシロキサン260g、1,1,3,3-テトラメチル-1,3-ジビニルジシロキサン7.6gを150~160℃にて窒素ガス0.5Nm3/hにて3時間加熱攪拌することにより脱水を行い、その後水酸化カリウム0.1gを加えて加熱攪拌を行った。加熱撹拌は、フラスコ内で水酸化カリウムが溶解し均一になり、かつ粘度が15000~18000cPに増粘するまで継続した。その後、エチレンクロロヒドリン10gにて100℃にて中和後、スーパーセライトフロスを濾過助剤に用いて濾過した後、170~180℃、2mmHgの減圧下にて低沸分を除去することにより、末端がジメチルビニルシロキシ基で閉塞され、ジフェニルシロキシ単位が5モル%、残余がジメチルシロキシ単位であるビニル末端ポリメチルフェニルシロキサン1867gを得た。
粘度:19200cP
1分子中の脂肪族不飽和基の平均個数:2
NMR測定による平均構造式:
CH2=CH-Si(CH3)2-O-{Si(CH3)2O}593-{SiPh2O}31-Si(CH3)2-CH=CH2
分子量:49320
末端がジメチルビニルシロキシ基で閉塞され、ジフェニルシロキシ単位が5モル%、残余がジメチルシロキシ単位であるビニル末端ポリメチルフェニルシロキサン
1分子中の脂肪族不飽和基の平均個数:2
NMR測定による平均構造式:
CH2=CH-Si(CH3)2-O-{Si(CH3)2O}1165-{SiPh2O}61-Si(CH3)2-CH=CH2
粘度:98600cP
分子量:98540
(b2-1)は、平均構造式が{(CH3)3-SiO1/2}6{SiO2}8{(CH2=CH)(CH3)-SiO}のM6DvQ8樹脂
重量平均分子量:22000
重量分子量は、ゲル浸透クロマトグラフ分析(GPC)により、ポリスチレンを検量線とした値である。
(c-1)2-ヒドロキシ-2-メチルプロピオフェノン
(c-2)2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン
(c-3)ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド
(c-4)エチル(2,4,6-トリメチルベンゾイル)フェニルフォスフィナーと
(d-1)3-メタクリロキシプロピルトリメトキシシラン
(e-1)MQ樹脂
平均構造式:{(CH3)3SiO1/2}{SiO2}3.5のMQ樹脂
重量平均分子量:26200
重量分子量は、ゲル浸透クロマトグラフ分析(GPC)により、ポリスチレンを検量線とした値である。
冷却用還流管、攪拌装置としてスリーワンモーターを装備した3Lのセパルブルフラスコに、塩酸293gを仕込み、フラスコ内の温度を-5℃~2℃に調整し、攪拌をしながら水440gを仕込み、水ガラス3号(S40ケイ酸ソーダ3号)308gを1時間かけて滴下する。次いで、イソプロピルアルコール316gをフラスコ内へ仕込み、ヒドロゾル化を行なう。その後、トリメチルクロロシラン128gとキシレン139gの混合物を10分程度内で滴下を行ない、フラスコ内の温度を-5℃~2℃にて攪拌を1時間行なった。次いで、約80℃まで昇温し、その後、80℃にて2時間加熱還流を行なった。次いで、キシレン24gを加えた後、30分間攪拌を行ない、30分間静置、分液を行なった。その後、脱水、脱溶を125-140℃で行ない、不揮発分を測定した。不揮発分量は58質量%であった(粘度18cP、測定条件:回転粘度計:No.1、60rpm)。このようにして得られたMQ樹脂は、各実施例・比較例において使用されるビニル末端ポリメチルフェニルシロキサンと混合し、キシレンを除去して使用した。
(e-2)
平均構造式:{(CH3)3SiO1/2}{SiO2}3のMQ樹脂
重量平均分子量:1,990,000
60質量%キシレン溶液の粘度:27cP(測定条件:回転粘度計:No.1、60rpm)
(e-3)
平均構造式:{(CH3)3SiO1/2}{(CH3)2SiO}1.2{SiO2}3のMDQ樹脂
重量平均分子量:52120
60質量%キシレン溶液の粘度:17cP(測定条件:回転粘度計:No.1、60rpm)
(f-1)p-t-ブチルカテコール(重合禁止剤)
(f-2)p-メトキシフェノール(重合禁止剤)
メルカプトプロピル基含有ポリメチルシロキサン(a-2)8.0重量部(80g)、ビニル末端ポリメチルフェニルシロキサン(b1-2)46.5重量部(465g)及びMQ樹脂(e-1)40.0重量部(400g)を、5Lの万能混合攪拌機(ダルトン社製)に入れ、室温(22℃)、低速レバーによる回転条件で30分間、均一に混合した。均一に混合した後、さらに、p-t-ブチルカテコール(f-1)0.004重量部(0.04g)、2-ヒドロキシ-2-メチルプロピオフェノン(c-1)0.21重量部(2.1g)、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(c-2)0.21重量部(2.1g)の溶解混合物、3-メタクリロキシプロピルトリメトキシシラン(d-1)1.0重量部(10g)を加え、氷水冷却下(8℃)、低速レバーによる回転条件で30分間、冷却減圧にて均一に混合した。その後、10μmのメンブレンフィルターにて異物等を除去し、組成物を得た。
実施例1と実施例2から、高分子量のMQ樹脂を配合することにより硬化性が改善することがわかる。
また、実施例1~3と実施例4~5から、MDQ樹脂を配合することにより、屈折率を制御し、打継性能を一層改善できることがわかる。
一方、脂肪族不飽和基を有する分岐状ポリオルガノシロキサンを含まない比較例1~3については、実施例1、2及び4と比べて、吐出性能や硬化性の点で劣り、温度サイクル接着試験でも剥離やクラックの発生を回避しにくく、追従性の点でも劣ることがわかる。
さらに、MQ樹脂やMDQ樹脂を含まない比較例4及び5は、硬化性に劣り、偏光板に対する接着性にも乏しいことがわかる。
Claims (7)
- (A)23℃における粘度が20~25000cPである、ケイ素原子に結合するメルカプトアルキル基を含有するポリオルガノシロキサン;
(B)(B1)式(I):
R1は、独立して、脂肪族不飽和基であり、
Rは、独立して、C1~C6アルキル基又はC6~C12アリール基であって、Rのうち、1~60モル%はC6~C12アリール基であり、
nは、23℃における粘度を10,000~1,000,000cPとする数である)で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、(B2)SiO4/2単位、R'3SiO1/2単位及びR'2SiO2/2単位、並びに場合によってはさらにR'SiO3/2単位(式中、R'は、それぞれ独立して、C1~C6アルキル基又は脂肪族不飽和基を表す)からなり、1分子当たり、少なくとも3個のR'が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサン(ここで、(B2)の量は、(B)中の脂肪族不飽和基の全個数に占める(B2)中の脂肪族不飽和基の個数の割合が50%超、95%以下となる量とする);
(C)光反応開始剤;
(D)シラン化合物;並びに
(E)重量平均分子量2,000~2,500,000のMQ樹脂及び/又は重量平均分子量2,000~1,000,000のMDQ樹脂、
を含み、ここで、
(B)中の脂肪族不飽和基の個数に対する、(A)中のメルカプトアルキル基の個数の比が、0.5~3.0であり、かつ
(E)が、(B)100重量部に対して、30~200重量部であり、かつ
23℃における粘度が、20,000~150,000cPである、
画像表示装置用のダム材組成物。 - ダム材組成物について、B型回転粘度計を使用して、23℃で、回転数6rpmで測定した粘度(cP)をV6rpm、23℃で、回転数12rpmで測定した粘度(cP)をV12rpmとし、式:V6rpmm/V12rpmにより求めたチキソトロピー比の値が、1.02~1.9である、請求項1記載の画像表示装置用のダム材組成物。
- (E)が、重量平均分子量1,000,000~2,500,000のMQ樹脂を含む、請求項1又は2記載の画像表示装置用のダム剤組成物。
- (E)が、さらに、重量平均分子量2,000~1,000,000のMDQ樹脂を含む、請求項3記載の画像表示装置用のダム剤組成物。
- (C)の含有量が、(B)100重量部に対して、0.05~50重量部である、請求項1~4のいずれか1項記載の画像表示装置用のダム材組成物。
- (D)が、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン及びビニルトリエトキシシランからなる群より選ばれる1種以上の脂肪族不飽和基を含有するシラン化合物である、請求項1~5のいずれか記載の画像表示装置用のダム材組成物。
- 画像表示部と保護部との封止に、請求項1~6のいずれか記載の画像表示装置用のダム材組成物を用いてなる、画像表示装置。
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- 2014-03-28 CN CN201480002551.XA patent/CN104704058B/zh active Active
- 2014-03-28 KR KR1020157014038A patent/KR20160006657A/ko not_active Application Discontinuation
- 2014-03-28 WO PCT/JP2014/059358 patent/WO2014181610A1/ja active Application Filing
- 2014-04-10 TW TW103113168A patent/TWI618748B/zh active
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Also Published As
Publication number | Publication date |
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KR20160006657A (ko) | 2016-01-19 |
US9340711B2 (en) | 2016-05-17 |
EP2860222A4 (en) | 2015-08-19 |
JP5587520B1 (ja) | 2014-09-10 |
JP2014237808A (ja) | 2014-12-18 |
EP2860222A1 (en) | 2015-04-15 |
EP2860222B8 (en) | 2016-10-12 |
US20150218427A1 (en) | 2015-08-06 |
JP2014237834A (ja) | 2014-12-18 |
EP2860222B1 (en) | 2016-09-07 |
CN104704058A (zh) | 2015-06-10 |
TWI618748B (zh) | 2018-03-21 |
CN104704058B (zh) | 2017-09-22 |
TW201446882A (zh) | 2014-12-16 |
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