HK1185369B

HK1185369B - Ultraviolet-curable silicone resin composition and image display device using same

Info

Publication number: HK1185369B
Application number: HK13112653.8A
Authority: HK
Inventors: 小野�和久; 大皷弘二
Original assignee: 迈图高新材料日本合同公司
Priority date: 2010-12-22
Filing date: 2011-12-06
Publication date: 2015-11-20

Description

Ultraviolet-curable silicone resin composition and image display device using same

Technical Field

The present invention relates to an ultraviolet-curable silicone resin composition that can be suitably used in an image display device, and an image display device using the same.

Background

In recent years, flat-type image display devices such as liquid crystal, plasma, and organic EL have attracted attention. A flat-panel type image display device generally has a display region (image display portion) in which a plurality of pixels including a semiconductor layer, a phosphor layer, or a light-emitting layer constituting an active element are arranged in a matrix between a pair of substrates at least one of which has light permeability such as glass. In general, the display region (image display portion) and the periphery of the protective portion made of optical plastic such as glass or acrylic are hermetically sealed with an adhesive.

In such an image display device, in order to prevent a reduction in visibility (visibility) due to reflection of outdoor light or indoor illumination, a thin image display device in which an ultraviolet curable resin composition is interposed between a protective portion and an image display portion is manufactured, and an ultraviolet curable acrylic resin or an ultraviolet curable silicone resin composition is used as the ultraviolet curable resin composition used herein (patent documents 1 and 2).

On the other hand, an ultraviolet-curable silicone resin composition comprising a polyorganosiloxane containing a mercaptoalkyl group and a polyorganosiloxane containing an aliphatic unsaturated group has been proposed (patent documents 3 and 4).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2008-282000

Patent document 2: japanese laid-open patent publication No. 7-134538

Patent document 3: japanese laid-open patent publication No. 2-245060

Patent document 4: japanese laid-open patent publication No. 3-064389

Disclosure of Invention

Problems to be solved by the invention

In the case of manufacturing the above-described thin image display device in which the ultraviolet curable resin composition is interposed between the protective portion and the image display portion, the image display portion (for example, a liquid crystal display panel) is deformed due to internal stress caused by shrinkage of the conventional ultraviolet curable acrylic resin composition or ultraviolet curable silicone resin composition during curing, and thus, there is a case where a display defect is caused due to disturbance of the orientation of the liquid crystal material, which causes a problem in that display with high brightness and high contrast is prevented while having good visibility. Further, display unevenness occurs due to external stress applied to the image display portion due to warpage of the protective portion caused by shrinkage at the time of curing, and the problem of display failure due to the display unevenness has become more apparent in recent years in which the image display device has been increasingly high in luminance, high in definition, and large in size.

Further, the ultraviolet-curable silicone resin compositions disclosed in patent documents 3 and 4 have not yet been thin as in the prior art in image display devices at the time of their application, and therefore cannot cope with the above-mentioned problem of display defects.

An object of the present invention is to provide an ultraviolet-curable silicone resin composition which is liquid and excellent in coatability, does not cause display defects (hereinafter, also referred to as deformation resistance) due to deformation of an image display unit, does not reduce visibility, and can realize high-brightness and high-contrast display, in the case of manufacturing a thin or large image display device in which a resin is interposed between a protective unit and the image display unit, and an image display device using the ultraviolet-curable silicone resin composition.

Means for solving the problems

The present invention provides an ultraviolet-curable silicone resin composition comprising:

(A) a polyorganosiloxane having a viscosity of 20 to 25000cP at 23 ℃ and containing a mercapto alkyl group bonded to a silicon atom;

(B) an aliphatic unsaturated group-containing organopolysiloxane that contains (B1) and (B2) (wherein the amount of (B2) is such that the proportion of the number of aliphatic unsaturated groups in (B2) to the total number of aliphatic unsaturated groups in (B) is 50% or less),

(B1) is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by the formula (I),

(in the formula (I), R¹Independently is an aliphatic unsaturated group, R independently is a C1-C6 alkyl group or a C6-C12 aryl group, 1-60% of R is a C6-C12 aryl group, n is a number for making the viscosity at 23 ℃ reach 100-25000 cP,

(B2) is a branched organopolysiloxane comprising SiO_4/2Unit, R'₃SiO_1/2Unit and R'₂SiO_2/2Units, and optionally also R' SiO_3/2A unit (wherein, R 'each independently represents a C1-C6 alkyl group or an aliphatic unsaturated group), and at least 3R's per 1 molecule are aliphatic unsaturated groups;

(C) a photoreaction initiator; and

(D) a silane compound containing an aliphatic unsaturated group,

here, the first and second liquid crystal display panels are,

(A) the ratio of the number of mercaptoalkyl groups in (B) to the total number of aliphatic unsaturated groups in (D) is 0.5 to 1.05,

(A) the ratio of the number of mercaptoalkyl groups in (B) to the number of aliphatic unsaturated groups in (B) is 0.95 to 3, and

(A) the ratio of the number of mercaptoalkyl groups in (D) to the number of aliphatic unsaturated groups in (D) is 1.5 to 3.

The second invention provides the ultraviolet-curable silicone resin composition according to the first invention, wherein the content of (C) is 0.05 to 50 parts by weight relative to 100 parts by weight of (B).

The present invention provides the ultraviolet-curable silicone resin composition according to one or two of the present invention, further comprising (E) 1 or more silicone resin-based adhesion promoters selected from MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin, and TQ resin.

The present invention provides the ultraviolet curable silicone resin composition according to any one of the first to third aspects of the present invention, wherein (D) is at least one aliphatic unsaturated group-containing silane compound selected from the group consisting of 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

The present invention provides the ultraviolet-curable silicone resin composition according to any one of the first to fourth aspects of the present invention, wherein the visible light transmittance after curing is 95% or more.

The present invention provides the ultraviolet-curable silicone resin composition according to any one of the first to fifth inventions, wherein the cure shrinkage is 1.0% or less.

The seventh invention provides the ultraviolet-curable silicone resin composition according to any one of the first to sixth inventions, wherein the E hardness after curing is 5 to 40.

The eighth invention provides the ultraviolet-curable silicone resin composition according to any one of the first to seventh inventions, wherein a ratio (G '(T)/G' (23)) of a storage elastic modulus G '(T) in a temperature range of 50 to 100 ℃ to a storage elastic modulus G' (23) at 23 ℃ after curing is 0.1 to 30.

The present invention further provides the ultraviolet-curable silicone resin composition according to any one of the first to eighth aspects of the present invention, wherein a ratio (G "(T)/G" (23)) of a loss elastic modulus G "(T) to a loss elastic modulus G" (23) at 23 ℃ in a temperature range of-50 ℃ to 100 ℃ after curing is 0.1 to 300.

The present invention also provides a sealing agent for an image display device, which comprises the ultraviolet-curable silicone resin composition according to any one of the first to ninth aspects of the present invention.

The eleventh aspect of the invention provides an image display device in which the image display portion and the protective portion are sealed with the sealant for an image display device according to the tenth aspect of the invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, in the case of manufacturing a thin or large-sized image display device in which a resin is interposed between a protective portion and an image display portion, it is possible to provide an ultraviolet-curable silicone resin composition which is liquid and excellent in coatability, does not cause display defects due to deformation of the image display portion, does not reduce visibility, and can realize high-brightness and high-contrast display.

Drawings

FIG. 1 is a graph showing the results of NMR measurement of vinyl-terminated polymethylphenylsiloxane of example (b-2).

Detailed Description

The ultraviolet-curable silicone resin composition of the present invention contains:

(in the formula (I), R¹Independently an aliphatic unsaturated group, R independently is a C1-C6 alkyl group or a C6-C12 aryl group, 1-60 mol% of R is a C6-C12 aryl group, n is a value such that the viscosity at 23 ℃ reaches 100-25000 cP),

(B2) is a branched organopolysiloxane comprising SiO_4/2Unit, R'₃SiO_1/2Unit and R'₂SiO_2/2Units, and optionally also R' SiO_3/2A unit (wherein R 'independently represents a C1-C6 alkyl group or an aliphatic unsaturated group), and at least 3R's per 1 molecule are aliphatic unsaturated groups;

(C) a photoreaction initiator; and

(D) a silane compound containing an aliphatic unsaturated group.

The composition of the present invention comprises (A) a polyorganosiloxane having a viscosity of 20 to 25000cP at 23 ℃ and containing a mercapto alkyl group bonded to a silicon atom.

(A) In the above (1) molecule, the number of mercaptoalkyl groups bonded to silicon atoms may be 2 or more and 20 or less on average, from the viewpoint of suppressing excessive curing shrinkage while ensuring a stable structure by the crosslinking reaction. Among them, the number of them is preferably more than 2 and 10 or less, and more preferably 3 to 7.

(A) In (3), the alkyl moiety of the mercaptoalkyl group bonded to the silicon atom may be a C1-C6 alkyl group. Examples of the mercaptoalkyl group include a mercaptomethyl group, a 2-mercaptoethyl group, a 3-mercaptopropyl group, a 4-mercaptobutyl group, and a 6-mercaptohexyl group, but from the viewpoint of ease of synthesis, the mercaptomethyl group and the 3-mercaptopropyl group are preferable, and the 3-mercaptopropyl group is more preferable.

(A) In (2), the organic group other than the mercaptoalkyl group bonded to the silicon atom may be a substituted or unsubstituted 1-valent hydrocarbon group (however, not an aliphatic unsaturated group). Specific examples thereof include alkyl groups such as C1-C6 alkyl groups (e.g., methyl, ethyl, propyl, etc.); cycloalkyl groups such as C3 to C10 cycloalkyl groups (e.g., cyclohexyl and the like); aryl groups such as C6 to C12 aryl groups (e.g., phenyl, tolyl, xylyl, etc.); aralkyl groups such as C7 to C13 aralkyl groups (e.g., 2-phenylethyl group, 2-phenylpropyl group, etc.); substituted hydrocarbon groups such as halogen-substituted hydrocarbon groups (e.g., chloromethyl, chlorophenyl, 3, 3, 3-trifluoropropyl, etc.). In view of ease of synthesis and the like, preferred are alkyl groups, and among them, methyl, ethyl and propyl groups are preferred, and methyl groups are more preferred. In order to adjust the refractive index, aryl groups may be used in combination, and among them, phenyl groups are preferable in view of ease of synthesis and the like.

(A) The main chain structure of (b) may be linear, branched or cyclic, and is preferably branched. Examples thereof include branched organopolysiloxanes containing mercaptoalkyl groups, said organopolysiloxanes containing R' SiO_3/2Unit, R ″)₃SiO_1/2Units and R ″)₂SiO_2/2A unit cell, and optionally SiO_4/2A unit wherein each of R 'independently represents an unsubstituted or substituted 1-valent hydrocarbon group (but not an aliphatic unsaturated group), and 2 or more and 20 or less of R' per 1 molecule is a mercaptoalkyl group. Examples of the mercaptoalkyl group and the unsubstituted or substituted 1-valent hydrocarbon group include those mentioned above. R ' as mercaptoalkyl may be present as R ' of any of the units, but is preferably R ' SiO_3/2R' of the unit is present. As the mercaptoalkyl group and the unsubstituted or substituted hydrocarbon group having a valence of 1, the above-mentioned groups can be used. The ratio of the number of the mercapto alkyl group-containing siloxane units to the number of the mercapto alkyl group-free siloxane units is preferably 1: 60 to 1: 25 from the viewpoints of handling properties and crosslinking reactivity, but is not limited thereto.

(A) And a viscosity at 23 ℃ of 20 to 25000 cP. For example, the viscosity can be set to 30 to 23000cP from the viewpoints of workability and refractive index. The viscosity is preferably low from the viewpoint of handling properties, and the viscosity at 23 ℃ may be, for example, 20 to 2000cP, more preferably 50 to 500 cP.

In the present specification, the viscosity is a value measured at 23 ℃ by a rotational viscometer (Vismetron VDA-L) (manufactured by Zhipu System Co., Ltd.) using spindle Nos. 2 to 4 at 30 to 60 rpm.

(A) The number of thiol groups in (a) can be determined by colorimetric titration with iodine. It utilizes the following formula:

2RSH+I₂→RSSR+2HI

the method of the reaction (2) utilizes that a titration solution becomes pale yellow due to a trace amount of excess iodine in the titration.

(A) The transparent substance is preferably high. As an index of transparency, there can be mentioned an index in which the transmittance of (A) at a wavelength in the visible light region (360 to 780nm) is measured by a spectrocolorimeter at a thickness of 10mm by filling the container with (A) at 23 ℃ and the transmittance is 80% or more. The transmittance is preferably 90% or more in view of stably maintaining the transparency of the cured product of the composition of the present invention.

(A) The production method of (a) is not particularly limited, and for example, it can be produced by hydrolyzing, polycondensing and rebalancing alkylchlorosilanes such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethylmethoxysilane and mercaptopropyldimethylethoxysilane, mercaptoalkylalkoxysilanes and desired alkylchlorosilanes, alkylalkoxysilanes and silanol-containing siloxanes.

(A) These may be used alone or in combination of two or more.

The composition of the present invention contains (B) an aliphatic unsaturated group-containing organopolysiloxane containing (B1) and (B2) (wherein the amount of (B2) is such that the proportion of the number of aliphatic unsaturated groups in (B2) to the total number of aliphatic unsaturated groups in (B) is 50% or less),

(in the formula (I), R¹Independently an aliphatic unsaturated group, R independently is a C1-C6 alkyl group or a C6-C12 aryl group, 1-60 mol% of R is a C6-C12 aryl group, n is a number for attaining a viscosity of 100-25000 cP at 23 ℃,

(B2) is a branched organopolysiloxane comprising SiO_4/2Unit, R'₃SiO_1/2Unit and R'₂SiO_2/2Units, and optionally also R' SiO_3/2A unit (wherein R 'each independently represents a C1-C6 alkyl group or an aliphatic unsaturated group), and at least 3R's per 1 molecule are aliphatic unsaturated groups.

(B) In (B2), the number of aliphatic unsaturated groups in (B2) is preferably 50% or less, more preferably 30% or less, based on the total number of aliphatic unsaturated groups in (B). By using (B2) in combination, the E hardness of the cured product can be adjusted. From the viewpoint of effectively adjusting the E hardness, the amount is preferably 8% or more, and more preferably 10% or more. Further, by using (B2) in combination, the adhesiveness can be improved, and particularly in the case where the adherend is a polarizing plate, a high improvement effect can be expected.

In formula (I) for (B1), R¹Is an aliphatic unsaturated group. R at both ends¹May be the same or different, but preferably are the same.

Examples of the aliphatic unsaturated group include alkenyl groups such as C2 to C6 alkenyl groups (e.g., vinyl, propenyl, butenyl, hexenyl, etc.). The terminal unsaturated alkenyl group is more preferable, and the vinyl group is preferable in view of ease of synthesis.

In the formula (I), R is C1-C6 alkyl (such as methyl, ethyl, propyl, etc.) or C6-C12 aryl (such as phenyl, tolyl, xylyl, etc.). R may be the same or different.

In terms of adjusting the refractive index, 1 to 60 mol% of R is preferably C6 to C12 aryl, and in terms of viscosity and thixotropy, 1 to 50 mol% of R is preferably C6 to C12 aryl, and more preferably 1 to 35 mol%.

From the viewpoint of ease of synthesis, the alkyl group having 1 to 6 is preferably a methyl group, and the aryl group having 6 to 12 is preferably a phenyl group.

In the formula (I), as (B1), 1 to 60 mol% of R is preferably phenyl and the remainder is methyl, more preferably 1 to 50 mol% of R is phenyl and the remainder is methyl, and still more preferably 1 to 35 mol% of R is phenyl and the remainder is methyl.

From the viewpoint of handling of the composition, the viscosity at 23 ℃ of (B1) is 100 to 25000cP, more preferably 200 to 10000cP, and still more preferably 300 to 5000 cP.

(B1) The number of aliphatic unsaturated groups in (2) can be determined from the average structural formula by NMR, the molecular weight calculated, and the molecular weight obtained.

(B1) The production method of (a) is not particularly limited, and for example, it can be obtained by polycondensation and reequilibration of chlorosilanes necessary for a desired structure, such as dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, and dimethylvinylchlorosilane, or by cohydrolysis, polycondensation, and reequilibration of alkoxysilanes necessary for a desired structure, such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, and dimethylvinylmethoxy (silane). Further, it can be obtained by ring-opening polymerization and rebalancing of siloxanes necessary for a desired structure, such as 1, 1, 3, 3, 5, 5, 5, 7, 7 octaphenylcyclotetrasiloxane, 1, 3, 3-tetramethyl-1, 3-divinyldisiloxane, in the presence of an alkali catalyst (alkali metal hydroxide, alkali metal silanolate, ammonium hydroxide salt, etc.) or an acid catalyst (sulfuric acid, silanolate sulfate, trifluoromethanesulfonic acid).

(B1) These may be used alone or in combination of two or more.

(B2) Is a branched organopolysiloxane comprising SiO_4/2Unit, R'₃SiO_1/2Unit and R'₂SiO_2/2Units, and optionally also R' SiO_3/2Units (wherein R 'each independently represents a C1-C6 alkyl group or an aliphatic unsaturated group), and at least 3 of R's per 1 molecule are aliphatic unsaturated groups.

(B2) is R'₂SiO_2/21 mol of the unit has SiO in a ratio of 6 to 10 mol_4/2Unit, having R 'in a ratio of 4 to 8 mol'₃SiO_1/2A branched organopolysiloxane of unit. (B2) The material is preferably a resin-like or liquid material which is solid or viscous semisolid at normal temperature. Examples thereof include those having a weight average molecular weight of 1,000 to 400,000, preferably 2,000 to 200,000. The weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a calibration curve (calbration curve).

Examples of the aliphatic unsaturated group related to R' include those listed as the aliphatic unsaturated group in (B1), and specifically, an alkenyl group such as a C2 to C6 alkenyl group (for example, a vinyl group, a propenyl group, a butenyl group, a hexenyl group, etc.) may be mentioned. The terminal unsaturated alkenyl group is more preferable, and the vinyl group is preferable in view of ease of synthesis. R ' as the aliphatic unsaturated group may be present as R ' of an arbitrary unit, but is preferably R '₂R' of the SiO unit.

R' other than the aliphatic unsaturated group is a C1-C6 alkyl group (e.g., methyl, ethyl, propyl, etc.), and in view of heat resistance, methyl is preferred.

When (B2) is used, two or more kinds may be used alone or in combination.

The composition of the present invention contains (C) a photoinitiator. (C) Is a component that functions as a radical initiator or a sensitizer when the components (A) and (B) are photocrosslinked. From the viewpoint of reactivity, the (C) may be an aromatic hydrocarbon, acetophenone and its derivatives, benzophenone and its derivatives, benzoylbenzoate, benzoin and benzoin ether and its derivatives, xanthone and its derivatives, a disulfide compound, a quinone compound, a halogenated hydrocarbon and amine, or an organic peroxide. From the viewpoint of compatibility with silicone and stability, a compound containing a substituted or unsubstituted benzoyl group or an organic peroxide is more preferable.

Examples of (C) include acetophenone, phenylethyl ketone, 2-hydroxy-2-methylphenylethyl ketone, 2 dimethoxy-1, 2-diphenylethan-1-one (IRGACURE 651: 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 (IRGACURE 2959: manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one (IRGACURE 127: BASF), 2-methyl-1- (4-methylphenylsulfanyl) -2-morpholinopropan-1-one (IRGACURE 907: BASF), 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -butanone-1 (IRGACURE 369: BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (IRGACURE 379: BASF); 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN TPO: BASF corporation), bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide (IRGACURE 819: BASF corporation); 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ] (IRGACURE OXE 01: manufactured by BASF Co., Ltd.), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (IRGACURE OXE 02: manufactured by BASF Co., Ltd.); p-hydroxyphenylacetic acid (oxyphenyl acetic acid), a mixture of 2- [ 2-oxo-2-phenylacetoxyethoxy ] ethyl ester and p-hydroxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester (IRGACURE 754: manufactured by BASF corporation), methyl benzoylformate (DAROCUR MBF: manufactured by BASF corporation), ethyl-4-dimethylaminobenzoate (DAROCUR EDB: manufactured by BASF corporation), 2-ethylhexyl-4-dimethylaminobenzoate (DAROCUR EHA: manufactured by BASF corporation), bis (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphine oxide (403: manufactured by BASF corporation), benzoyl peroxide, cumene peroxide CGI, etc.

(C) These may be used alone or in combination of two or more.

The composition of the present invention comprises (D) a silane compound having an aliphatic unsaturated group. (D) The adhesion between the cured product and the base material and the adhesiveness are improved. Examples of the aliphatic unsaturated group include those listed as the aliphatic unsaturated group in (B1), and specific examples thereof include alkenyl groups such as C2 to C6 alkenyl groups (e.g., vinyl, propenyl, butenyl, hexenyl, etc.). The terminal unsaturated alkenyl group is more preferable, and the vinyl group is preferable in view of ease of synthesis.

Examples of (D) include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, and 3-methacryloxypropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferable.

(D) These may be used alone or in combination of two or more.

When the number of mercaptoalkyl groups bonded to silicon atoms in (A) is HS, the number of aliphatic unsaturated groups in (B) is ViB, and the number of aliphatic unsaturated groups in (D) is ViD, the ratio of HS to ViB + ViD (HS/(ViB + ViD)) is 0.5 to 1.05, preferably 0.55 to 1.0, and more preferably 0.6 to 0.9, from the viewpoint of imparting appropriate hardness and elasticity to the cured product. When (B) is used alone, (B1) is the same as the number of aliphatic unsaturated groups ViB1 in (B1), and when (B1) and (B2) are used in combination, (B) is the total of the number of aliphatic unsaturated groups ViB1 in (B1) and the number of aliphatic unsaturated groups ViB2 in (B2).

The ratio of HS to ViB (HS/ViB) is 0.95 to 3, preferably 1 to 2, from the viewpoint of imparting good adhesiveness and suppressing the temperature change of the cured product.

The ratio of HS to ViD (HS/ViD) is 1.5 to 3, preferably 1.8 to 2.5, from the viewpoint of good adhesiveness and further improvement in suppression of temperature change of a cured product.

From the viewpoints of photoreaction initiation, heat resistance during curing, and visibility (high transmittance and low haze), the amount of (C) is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 40 parts by weight, based on 100 parts by weight of (B).

From the viewpoint of deformation resistance and visibility, the total amount of (a) to (D) is preferably 55% by weight or more, more preferably 75% by weight or more, and still more preferably 90% by weight or more of the composition.

The composition of the present invention preferably further contains (E) a silicone resin-based adhesion promoter (however, excluding (a), (B) and (D)). The silicone resin-based adhesion promoter is a silicone resin having adhesive properties, and may be blended as necessary in order to further enhance and stabilize the adhesive properties of the ultraviolet-curable silicone resin composition of the present invention. Particularly in the case where the adherend is a polarizing plate, a high improvement effect can be expected.

From the viewpoint of adhesion and economy, the silicone resin-based adhesion promoter (E) is preferably 1 or more selected from MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin, and TQ resin (but does not contain an aliphatic unsaturated group and a mercapto group), more preferably 1 or more selected from MQ resin, MDQ resin, MDT resin, and MDTQ resin, even more preferably 1 or more selected from MQ resin, MDQ resin, and MDT resin, and even more preferably MQ resin from the viewpoint of strength of adhesion and easy structural control, from the viewpoint of fluidity and ease of synthesis.

Further, as the MQ resin, there can be mentioned a silicone resin having an average structural formula represented by the following formula,

{(CH₃)₃SiO_1/2}_m{SiO₂}_n

(wherein m + n is 1, and m and n are numbers other than 0),

as the MDQ resin, there may be mentioned a silicone resin having an average structural formula represented by the following formula,

{(CH₃)₃SiO_1/2}_m{SiO₂}_n{(CH₃)₂SiO}₁

(wherein m + n + l is 1, and m, n and l are numbers other than 0),

as the MT resin, there may be mentioned a silicone resin having an average structural formula represented by the following formula,

{(CH₃)₃SiO_1/2}_m{(CH₃)SiO_3/2}_o

(wherein m + o is 1, and m and o are numbers other than 0),

as the MDT resin, there may be mentioned a silicone resin having an average structural formula represented by the following formula,

{(CH₃)₃SiO_1/2}_m{(CH₃)₂SiO}₁{(CH₃)SiO_3/2}_o

(wherein m + l + o is 1, and m, l and o are numbers other than 0),

examples of the MDTQ resin include silicone resins having an average structural formula represented by the following formula,

{(CH₃)₃SiO_1/2}_m{SiO₂}_n{(CH₃)₂SiO}₁{(CH₃)SiO_3/2}_o

(wherein m + n + l + o is 1, and m, n, l and o are not numbers of 0),

as the DQ resin, there can be mentioned a silicone resin having an average structural formula represented by the following formula,

{SiO₂}_n{(CH₃)₂SiO}₁

(wherein n + l is 1 and n and l are not 0),

examples of the DTQ resin include silicone resins having an average structural formula represented by the following formula,

{SiO₂}_n{(CH₃)₂SiO}₁{(CH₃)SiO_3/2}_o

(wherein n + l + o is 1, and n, l and o are numbers other than 0),

the TQ resin may be a silicone resin having an average structural formula represented by the following formula,

{SiO₂}_n{(CH₃)SiO_3/2}_o

(in the formula, n + o is 1, and m and o are numbers other than 0).

(E) The weight average molecular weight of (A) is preferably 2,000 to 100,000, more preferably 5,000 to 80,000, and still more preferably 10,000 to 60,000. Here, the weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a calibration curve.

(E) The amount of (E) is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and still more preferably 15 to 100 parts by weight, in view of improving adhesion to the substrate, although it may be 150 parts by weight or less based on 100 parts by weight of (B).

Additives such as a silane coupling agent (but not including (D)), a polymerization inhibitor, an antioxidant, an ultraviolet absorber as a light resistance stabilizer, and a light stabilizer may be blended in the composition of the present invention within a range not to impair the effects of the present invention. The composition of the present invention may contain a polyorganosiloxane containing an aliphatic unsaturated group other than (B) (for example, a branched polyorganosiloxane containing an aliphatic unsaturated group) within a range not impairing the effect of the present invention, but preferably does not contain it.

Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, trimethoxysilylpropyldiallylisocyanurate, bis (trimethoxysilylpropyl) allylisocyanurate, tris (trimethoxysilylpropyl) isocyanurate, triethoxysilylpropyldiallylisocyanurate, bis (triethoxysilylpropyl) allylisocyanurate and tris (triethoxysilylpropyl) isocyanurate.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine, and the like.

In order to prevent oxidation of the cured product of the composition and improve weather resistance, an antioxidant may be used, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine-based antioxidant include N, N '-tetrakis- (4, 6-bis (butyl- (N-methyl-2, 2, 6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4, 7-diazepane-1, 10-diamine, a polycondensate of dibutylamine/1, 3, 5-triazine/N, N' -bis- (2, 2, 6, 6-tetramethyl-4-piperidyl-1, 6-hexanediamine/N- (2, 2, 6, 6-tetramethyl-4-piperidyl) butylamine, poly [ {6- (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl } { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino } hexamethylene { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino } ], a polymer of dimethyl succinate and 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidylethanol, [ bis (2, 2, 6, 6-tetramethyl-1 (octyloxy) -4-piperidyl) sebacate, a reaction product of 1, 1-dimethylethylhydroperoxide and octane (70%) ] -polypropylene (30%), bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] butylmalonate, a salt thereof, a polymer thereof, and a polymer thereof, Methyl 1, 2, 2, 6, 6-pentamethyl-4-piperidyl sebacate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] ethyl ] -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2, 2, 6, 6-tetramethylpiperidine, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, etc., but is not limited thereto. Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], thiodiethylene-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), N' -hexane-1, 6-diylbis [3- (3, 5-di-t-butyl-4-hydroxyphenyl propionamide ], phenylpropanoic acid 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyC 7-C9 side chain alkyl ester, 2, 4-dimethyl-6- (1-methylpentadecyl) phenol, and mixtures thereof, Diethyl [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] phosphonate, 3 ', 5, 5 ' -hexane-tert-butyl-4-a, a ' - (mesitylene-2, 4, 6-tolyl) tri-p-cresol, diethyl bis [ [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] phosphonate ] calcium salt, 4, 6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], (methyl-ethyl-4-hydroxy-methyl) propionate), 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione, the reaction product of N-phenylaniline and 2, 4, 4-trimethylpentene, 2, 6-di-tert-butyl-4- (4, 6-bis (octylthio) -1, 3, 5-triazin-2-ylamino) phenol, and the like, but is not limited thereto. The antioxidant may be used alone or in combination of two or more.

Light stabilizers can be used to prevent photooxidative deterioration of the cured product, and examples thereof include benzotriazole compounds, hindered amine compounds, and benzoate compounds. Ultraviolet absorbers as light resistance stabilizers are used for preventing light deterioration and improving weather resistance, and examples thereof include ultraviolet absorbers such as benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ones. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2, 4-di-t-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4, 6-di-t-amylphenol, 2- (2H-benzotriazol-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol, reaction products of methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate/polyethylene glycol 300, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, and the like, Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, benzophenone-based ultraviolet absorbers such as octophenone, and benzoate-based ultraviolet absorbers such as 2, 4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate. The ultraviolet absorbers may be used alone or in combination of two or more. The light stabilizer is preferably a hindered amine type. Among these, the use of a hindered amine light stabilizer containing a tertiary amine is preferable because the storage stability of the composition can be improved. Examples of the hindered amine light stabilizer containing a tertiary amine include TINUVIN622LD, TINUVIN144, CHIMASSORB119FL (both of which are manufactured by BASF); MARK LA-57, LA-62, LA-67, LA-63 (all of them are manufactured by Asahi Denka Co., Ltd.); and light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114 and LS-744 (all of which are available from Sanko Co., Ltd.).

The composition of the present invention preferably does not contain an inorganic filler from the viewpoint of obtaining a desired E hardness.

The viscosity of the composition of the present invention at 23 ℃ is preferably 50 to 10000cP, more preferably 70 to 9000cP, and still more preferably 100 to 7000cP, from the viewpoint of workability when applying the composition between an image display part and a protective part.

The composition of the present invention can be obtained by blending (a) to (D), and optionally (E) and additives. In the production, it is preferable to mix (C) and (D) and an optional polymerization inhibitor in the absence of ultraviolet rays after mixing (A), (B) and optionally (E). Specifically, for example, in a room such as a clean room where air foreign matter management is performed, a 5L universal mixer equipped with a vacuum degassing apparatus is charged with component a and component B, and if necessary, component E, and uniformly mixed at room temperature (10 to 30 ℃) for 30 minutes at a low speed, then, in a room such as a yellow room where ultraviolet rays are removed, a small amount of component C, component D, and a polymerization inhibitor are charged, and uniformly mixed at a low speed under cooling and reduced pressure with ice water (10 ℃ or less), and after degassing for 30 minutes, the mixture is filtered by using a membrane filter or the like having fine pores of 10 μm or less, whereby an ultraviolet-curable silicone resin composition can be obtained.

The composition of the present invention can be cured by irradiation with ultraviolet rays. Examples of the lamp of the wavelength region in the range in which the reaction is possible in (C) include a high-pressure mercury lamp (UV-7000) manufactured by Ushio Motor Co., Ltd, a metal halide lamp (MHL-250, MHL-450, MHL-150, MHL-70), Korea: a metal halide lamp (JM-MTL 2KW) manufactured by JM tech, an ultraviolet irradiation lamp (OSBL360) manufactured by Mitsubishi Motor corporation, an ultraviolet irradiation machine (UD-20-2) manufactured by Nippon battery corporation, a fluorescent lamp (FL-20BLB) manufactured by Toshiba corporation, an H-type lamp tube, an H Plus lamp tube, a D-type lamp tube, a Q-type lamp tube, an M-type lamp tube, and the like manufactured by Fusion corporation. The irradiation dose is preferably 100 to 10000mJ/cm²More preferably 300 to 5000mJ/cm²More preferably 500 to 3500mJ/cm²。

The cured product of the composition of the present invention has suitable physical properties as shown below.

[ visible light transmittance after curing ]

The composition of the present invention is preferable from the viewpoint of visibility because the visible light transmittance after curing can be 95% or more when the cured thickness is 150 μm. The visible light transmittance is more preferably 96% or more, and still more preferably 98% or more. From the viewpoint of visible light transmittance, it is preferable to suppress the amount of (C) used. In addition, after the components (A) and (B) are separately or uniformly mixed, the visible light transmittance after curing can be improved by performing a heat treatment at 80 to 180 ℃. From the viewpoint of stability over time, it is also preferable to perform heat treatment.

[ curing shrinkage ]

The composition of the present invention can be used to reduce the curing shrinkage to 1.0% or less, and therefore, when it is used in an image display device, it is preferable in that it can easily prevent distortion and ensure visibility. The curing shrinkage is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less.

[ E hardness after curing ]

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 is preferable in that it can easily moderate stress from the outside, and can suppress the penetration of moisture even under high temperature and high humidity, thereby ensuring visibility. The E hardness is preferably 5 to 35, and more preferably 10 to 30.

[ elongation after curing ]

The composition of the present invention is preferable in that the elongation after curing can be 50% or more, and therefore, the composition 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.

[ storage elastic modulus after curing ]

The composition of the present invention is preferably such that the ratio (G ' (T)/G ' (23)) of the storage elastic modulus MS (T) in the temperature range of-50 ℃ to 100 ℃ to the storage elastic modulus G ' (23) at 23 ℃ after curing is 0.1 to 30, and the temperature change of the cured product can be suppressed. The ratio (G '(T)/G' (23)) of the storage modulus of elasticity MS (T) is preferably 0.5 to 10.

[ loss elastic modulus after curing ]

The compositions of the invention can have a loss modulus of elasticity M in the temperature range from-50 ℃ to 100 ℃₁The ratio (G ' (T)/G ' (23)) of the loss elastic modulus G ' (23) at 23 ℃ after curing is preferably 0.1 to 300, and the temperature change of the cured product can be suppressed, and the penetration of moisture under high temperature and high humidity can be suppressed. Loss modulus of elasticity M₁The ratio (G '(T)/G' (23)) of (T) is preferably 0.5 to 100.

The composition of the present invention can be suitably used for an image display device, and is particularly preferably used as a resin interposed between a protective portion and an image display portion of a flat-panel type image display device.

Specifically, the composition of the present invention is applied to a protective panel constituting a transparent protective portion made of an optical plastic or the like, and then the image display panel constituting the image display portion is stuck thereto and irradiated with ultraviolet rays. In the protective panel, a step for preventing the composition of the present invention from flowing out may be provided at the outer peripheral edge portion.

The composition of the present invention can provide an ultraviolet curable resin which is liquid and excellent in coatability, does not cause display defects due to deformation of an image display portion, does not reduce visibility, and can realize high-brightness and high-contrast display. The composition of the present invention is suitable for manufacturing a large-screen image display device having an image display panel of 5 to 100 inches, preferably 7 to 80 inches, and more preferably 10 to 60 inches, or for manufacturing an ultra-thin image display device having an image display device of preferably 10 to 500 μm, more preferably 20 to 450 μm, and even more preferably 50 to 400 μm.

[ examples ]

The present invention will be described in more detail below using examples and comparative examples. Parts and% are parts by weight and% by weight unless otherwise specified. The present invention is not limited to these examples. Each of the compositions prepared in examples and comparative examples was cured using a high-pressure mercury lamp UVL-4001M manufactured by Ushio Motor Co., Ltd at 120w/cm²Hereinafter, unless otherwise specified, the concentration is 2000mJ/cm²(measured by a light meter UIT-250, Ushio electric Co., Ltd.) was measured. In examples 26 to 29, MHL-250 was used as a metal halide lamp manufactured by Ushio Motor Co., Ltd at 250w/cm during curing²Hereinafter, unless otherwise specified, the concentration is 2000mJ/cm²(measured by a light meter UIT-250, Ushio electric Co., Ltd.) was measured.

[ evaluation conditions for physical Properties ]

(1) Viscosity of the oil

The viscosity at 23 ℃ was measured at 60rpm using a rotational viscometer (Vismetron VDA-L) (manufactured by Zhipu System Co., Ltd.) using a No.2 spindle at a range of 400cP or less, a No.3 spindle at a range of 400 to 1500cP, and a No.4 spindle at a range of 1500 cP.

(2) Determination of the number of mercapto groups

As an iodine source, 1/10 normal iodine solution (special grade reagent) was used, and the number of thiol groups per unit weight was determined by colorimetric titration.

The calculation method comprises the following steps: SH content (mmol/g) ═ a × P × 0.1)/(W × C)

A: required iodine solution dropping amount before color change

P: correction coefficient for iodine solution (correction coefficient described in reagent): in case of need of correction

W: sample weight (g)

C: non-volatile components of the sample

The amount of iodine solution was determined by preliminary measurement, and thereafter the measurement was performed 3 times with good accuracy, and the average value of the 3 times was determined.

(3) Determination of the number of aliphatic unsaturated groups

Si-CH in NMR measurements₃(around 0.1 ppm), Si-Ph (around 7.3-7.7 ppm) and CH₃Si-CH＝CH₂Peaks (around 5.7 to 6.3 ppm) respectively correspond to (CH)₃)₂SiO Unit, Ph₂-SiO unit and (CH)₃)₂Si-CH＝CH₂O_1/2And units, wherein the number of units is determined from the ratio of the respective peak intensities to obtain an average structural formula, and the molecular weight is determined from the average structural formula to calculate the number of unsaturated groups.

(4) Visible light transmittance

The liquid material was filled in a quartz cuvette to a thickness of 10mm, and the cured material was 150 μm, and the transmittance at a wavelength of the visible light region (360 to 780nm) at 23 ℃ was measured by a spectrophotometer (CM-3500 d manufactured by Minolta, Ltd.).

(5) Curing shrinkage

The specific gravities of the composition before and after curing were measured by an electron densitometer (SD-120L manufactured by MIRAGE corporation), and calculated from the difference between the specific gravities by the following equation.

Cure shrinkage (%) (specific gravity after curing before specific gravity curing)/specific gravity after curing) × 100

(6) E hardness after curing

The E hardness of a cured product at 23 ℃ was measured according to JIS K6253E using DUROMETER HARDNESS TYPE E (manufactured by ASKER).

(7) Elongation after curing

The elongation of the cured product at 23 ℃ was measured by a Shopper tensile tester (manufactured by Toyo Seiki Seisaku-Sho Ltd.) in accordance with JIS K6301.

(8) Point pressure test

The composition was coated between a 3.5-inch glass plate for a display (the length of the diagonal line of the image display part was 3.5 inches) having a thickness of 0.6mm and a 3.5-inch PMMA plate for a display (the length of the diagonal line of the image display part was 3.5 inches) having a thickness of 0.4mm so that the thickness of the composition became 200 μm, and the coating was carried out at 2000mJ/cm²The sample was prepared by curing the sample with the ultraviolet energy irradiation amount of (1).

24 hours after the completion of the ultraviolet irradiation, the sample was pressurized at a rate of 7.5 mm/min with a metal rod having a head end portion of a semicircular shape with a diameter of 10mm at the central portion 1 part with the PMMA (polymethyl methacrylate) plate side of the sample being the upper side until the load reached 20kgf/cm²Until now.

When fine cracks are formed in the glass plate, the PMMA plate, or the cured composition at the pressed portion by the pressing, the appearance of the pressed portion is changed from that of the non-pressed portion due to the existence of the cracks or the white color. The change in the appearance was confirmed by visual observation,

if a change in the appearance of the pressurized part is confirmed, it is set to X,

if no change in the appearance of the pressurized portion was observed, it was determined as ∘.

(9) Storage modulus of elasticity and loss modulus of elasticity after curing

The storage modulus and the loss modulus of elasticity of a cured product having a thickness of 2mm were measured at a measurement frequency of 120Hz using a viscoelasticity measuring apparatus (RSA 3, TA Instruments).

(10) Crack resistance and discoloration resistance

(10-1) thermal shock

Between a 1mm thick glass plate and a 1mm thick PMMA plate, the coating was made in such a manner that the thickness of the composition became 200. mu.m, and the coating was made at 3000mJ/cm²After curing, an environmental test was carried out by cycling the temperature from-50 ℃ to 125 ℃ (each temperature was maintained for 30 minutes) (machine name: TSA-71S-A, Espec Co., Ltd.).

Thereafter, the temperature was returned to 23 ℃, and then the state of the cured product, PMMA, and glass was observed with an optical microscope (10 × magnification).

NG is defined as a case where cracks of 0.02mm or more occur in one direction in a cured product, or an air layer of 0.02mm or more occurs in one direction, or a case where damage of 0.02mm or more occurs in one direction in either PMMA or glass,

the case where the cracks, air layers, and damages were not observed at all was regarded as OK.

(10-2) high temperature and humidity

The cured product was left to stand in a constant temperature and humidity layer set to high temperature and humidity conditions of 85 ℃ and 85% RH for 500 hours, and then returned to a state of 23 ℃ and humidity 50% by a spectrophotometer (CM-3500 d manufactured by Minolta), and then evaluated for a Yellow Index (Yellow Index) as an Index of the degree of discoloration.

NG when the yellow index is 1.0% or more,

the yellow index was set to OK when it was less than 1.0%.

(11) Failure rate of agglomeration

(11-1) relative to acrylic, relative to glass

On each adherend (P) having a width of 25mmMMA, polycarbonate, glass), a reinforced glass plate having a width of 25mm and a length of 10mm or more was coated so that the thickness of the composition became 0.1mm, a reinforced glass plate having a thickness of 2mm and a width of 25mm was laminated so that the width of the laminate became 10mm, and then the thickness was 2000mJ/cm²The sample was prepared by curing the sample with the ultraviolet energy irradiation amount of (1).

The samples immediately after the preparation, 1 day after and 3 days after the preparation were subjected to a shear adhesion test in which the adherend and the glass plate were peeled off by drawing at a drawing speed of 10 mm/min using a universal testing machine (autograph) manufactured by Shimadzu corporation.

Determining the area Smm of the peeled portion of the ultraviolet-curable resin composition on the adherend²The ratio of (100 XS)/(10X 25) was calculated as the agglomeration destruction rate (%).

(11-2) polarizing plate

As the polarizer films, a polarizing film for liquid crystal (brand: SEG1425DU Nissan electric corporation), a glare-resistant treated film (brand: AG150 Nissan electric corporation), and an antireflection treated film (brand: ARS Type Nissan electric corporation) each having a width of 25mm were prepared. Each polarizing film was coated with a tempered glass plate having a width of 25mm and a length of 60mm or more so that the thickness of the composition became 0.1mm, and a tempered glass plate having a thickness of 2mm and a width of 25mm was laminated so that the width of the laminate of the compositions became 10mm, and then the laminated polarizing film was used at 2000mJ/cm²The sample was prepared by curing the sample with the ultraviolet energy irradiation amount of (1). Immediately after the sample was produced and 2 hours after the sample was subjected to a 180 ° peel adhesion test from a polarizing film and a glass plate as an adherend by stretching the sample at a measuring speed of 10 mm/min using a universal testing machine manufactured by Shimadzu corporation.

(12) Turbidity of water

The cured product was stored at 85 ℃ and 85% humidity for 500 hours, and then returned to 23 ℃ and 50% humidity, according to JIS K7105, measured by a haze meter NDH5000 (manufactured by Nippon Denshoku industries Co., Ltd.).

(13) Discoloration at elevated temperatures

After the cured product was stored at 85 ℃ and 85% humidity for 500 hours, the temperature was returned to 23 ℃ and 50% humidity, and the yellow index as an index of the degree of discoloration was evaluated by a spectrophotometer (CM-3500 d, Minolta).

(14) Coating Properties (wettability with Member)

The time for spreading the composition to the edge of the glass was evaluated by dropping 2g of the composition from a 10ml container onto the center of a 5cm square glass plate washed with a neutral detergent and dried. The evaluation was carried out at a temperature of 23 ℃ and a humidity of 50%.

The glass reached the end within 60 seconds and was rated as o,

a value is defined as Δ when the end of the glass is reached within 120 seconds after exceeding 60 seconds,

the time required for reaching the end of the glass for more than 120 seconds was set to x.

[ Synthesis example ]

The examples and comparative examples (a) are as follows.

Synthesis of (a-1)

To a 5L separable flask equipped with a reflux tube for cooling, a dropping funnel, and a Three-One Motor as a stirring device, 1549.2g (12mol) of dimethyldichlorosilane, 21.7g (0.2mol) of trimethylchlorosilane, 196.4g (1.0mol) of 3-mercaptopropyltrimethoxysilane, and 1500g of toluene were added dropwise a mixture of 1000g of water and 500g of toluene from the dropping funnel over about 1 hour. Hydrolysis was carried out while heating and stirring at 70 ℃ for 2 hours. After the reaction, the aqueous phase is separated, washed with water, and then dehydrated by heating at 100 to 125 ℃. After the dehydration, 1.5g of a 50% potassium hydroxide aqueous solution was added, and the mixture was heated and stirred at 115 to 125 ℃ for 5 hours to effect a condensation reaction. After neutralization with 2-chloroethanol, 1200 to 1300g of toluene was desolventized, filtered with SUPER CELITE FLOSS in a filter aid, and then the remaining toluene was removed under constant pressure and reduced pressure to obtain 928g of mercaptopropyl-containing polymethylsiloxane.

Average structural formula: { (CH)₃)₃SiO_1/2}{HS(CH₂)₃SiO_3/2}₅{(CH₃)₂SiO_2/2}₆₀

Viscosity: 294cP

Transmittance at 10mm thickness: 92.3 percent of

Number of mercapto groups per unit weight: 0.98mmol/g

The following (a-2) to (a-3) were obtained.

(a-2) mercaptopropyl-containing methicone

Average structural formula: { (CH)₃)₃SiO_1/2}{HS(CH₂)₃SiO_3/2}₅{(CH₃)₂SiO_2/2}₆

Viscosity: 110cP

Transmittance at 10mm thickness: 91.6 percent

Number of mercapto groups per unit weight: 4.29mmol/g

(a-3) mercaptopropyl-containing methicone

Average structural formula: { (CH)₃)₃SiO_1/2}{HS(CH₂)₃SiO_3/2}_2.5{(CH₃)₂SiO_2/2}₆₀

Viscosity: 220cP

Transmittance at 10mm thickness: 93.3 percent

Number of mercapto groups per unit weight: 0.52mmol/g

(a-4) mercaptopropyl-containing methicone

Viscosity: 330cP

Transmittance at 10mm thickness: 93.1 percent

Number of mercapto groups per unit weight: 0.97mmol/g

(a-6) mercaptopropyl-containing methicone

Average structural formula: { (CH)₃)₃SiO_1/2}₅{HS(CH₂)₃SiO_3/2}₅

Viscosity: 60cP

Transmittance at 10mm thickness: 92.8 percent

Number of mercapto groups per unit weight: 4.60mmol/g

(a-5) is as follows.

Synthesis of (a-5)

To a 5L separable flask equipped with a reflux tube for cooling, a dropping funnel, and a Three-One Motor as a stirring device, 253.2g (1.0mol) of diphenyldichlorosilane, 141.5g (0.48mol) of triphenylchlorosilane, 406.7g (3.15mol) of dimethyldichlorosilane, 98.2g (0.5mol) of 3-mercaptopropyltrimethoxysilane, and 1000g of toluene were added dropwise a mixture of 1000g of water and 700g of toluene from the dropping funnel over about 1 hour. Hydrolysis was carried out while heating and stirring at 70 ℃ for 2 hours. After the reaction, the aqueous phase was separated and washed with water, and then dehydrated by heating at 100 to 125 ℃. After the dehydration, 0.5g of 50% potassium hydroxide aqueous solution was added, and the mixture was heated and stirred at 115 to 125 ℃ for 5 hours to perform a condensation reaction. After neutralization with 2-chloroethanol, 1300-1500 g of toluene was desolventized, filtered using SUPER CELITE FLOSS in a filter aid, and then the remaining toluene was removed under constant pressure and reduced pressure to obtain 511g of mercaptopropyl-containing polymethylsiloxane.

Average structural formula: { (C)₆H₅)₃SiO_1/2}{(C₆H₅)₂SiO_2/2}₂{HS(CH₂)₃SiO_3/2}{(CH₃)₂SiO_2/2}₆

Viscosity: 23000cP

Transmittance at 10mm thickness: 82.1 percent

Number of mercapto groups per unit weight: 0.82mmol/g

The (B1) of the examples and comparative examples are as follows.

Synthesis of (b1-1)

1800g of 1, 1, 3, 3, 5, 7, 7-octamethylcyclotetrasiloxane, 260g of 1, 1, 3, 3, 5, 5, 7-octamethylcyclotetrasiloxane and 37.5g of 1, 1, 3, 3-tetramethyl-1, 3-divinyldisiloxane were placed in a 3L separable flask equipped with a reflux tube for cooling and a Three-One Motor as a stirring device, and then 0.5Nm of the mixture was added thereto at 150 to 160 ℃³The reaction mixture was stirred under heating for 3 hours under nitrogen for dehydration, and then 0.1g of potassium hydroxide was added thereto under stirring under heating. Heating and stirring were continued until potassium hydroxide dissolved and became homogeneous in the flask and thickened to a viscosity of 2000cP to 2500 cP. Then neutralizing the reaction mixture with 10g of 2-chloroethanol at 100 ℃, filtering the neutralized reaction mixture with SUPER CELITE FLOSS as a filter aid, and removing low-boiling components under reduced pressure of 170-180 ℃ and 2mmHg to obtain a dimethylvinylsiloxy group having a terminal group1867g of vinyl-terminated polymethylphenylsiloxane having 5 mol% of diphenylsiloxy units and the balance of dimethylsiloxy units.

Viscosity: 3200cP

Average number of aliphatic unsaturated groups in1 molecule: 2

Average structural formula determined by NMR:

CH₂＝CH-Si(CH₃)₂-O-{Si(CH₃)₂O}₂₅₀-{SiPh₂O}₁₃-Si(CH₃)₂-CH＝CH₂

molecular weight: 21030

(b1-2) vinyl-terminated polymethylphenylsiloxane

Vinyl-terminated polymethylphenylsiloxane having terminal end blocked with dimethylvinylsiloxy group, 5 mol% of diphenylsiloxy unit and the balance of dimethylsiloxy unit

Average number of aliphatic unsaturated groups in1 molecule: 2

Average structural formula determined by NMR:

CH₂＝CH-Si(CH₃)₂-O-{Si(CH₃)₂O}₁₆₅-{SiPh₂O}_8.3-Si(CH₃)₂-CH＝CH₂

viscosity: 1020cP

Molecular weight: 13910

Fig. 1 shows a graph of NMR measurement.

(b1-3) vinyl-terminated polymethylphenylsiloxane

Average number of aliphatic unsaturated groups in1 molecule: 2

Average structural formula determined by NMR:

CH₂＝CH-Si(CH₃)₂-O-{Si(CH₃)₂O}₃₈₉-{SiPh₂O}₁₉-Si(CH₃)₂-CH＝CH₂

viscosity: 9020cP

Molecular weight: 32660

(b1-4) vinyl-terminated polymethylphenylsiloxane

Average number of aliphatic unsaturated groups in1 molecule: 2

Average structural formula determined by NMR:

CH₂＝CH-Si(CH₃)₂-O-{Si(CH₃)₂O}₅₈₀-{SiPh₂O}₂₉-Si(CH₃)₂-CH＝CH₂

viscosity: 18900cP

Molecular weight: 48720

(b1-5) vinyl-terminated polymethylphenylsiloxane

Average number of aliphatic unsaturated groups in1 molecule: 2

Average structural formula determined by NMR:

CH₂＝CH-Si(CH₃)₂-O-{Si(CH₃)₂O}₆₀₀-{SiPh₂O}₃₀-Si(CH₃)₂-CH＝CH₂

viscosity: 20450cP

Molecular weight: 50394

(b1-6) vinyl-terminated polymethylphenylsiloxane

Vinyl-terminated polymethylphenylsiloxane having its terminal end blocked with dimethylvinylsiloxy group, 33 mol% of diphenylsiloxy units and the balance of dimethylsiloxy units

Average number of aliphatic unsaturated groups in1 molecule: 2

Average structural formula determined by NMR:

CH₂＝CH-Si(CH₃)₂-O-{Si(CH₃)₂O}₁₀-{SiPh₂O}₂₇-Si(CH₃)₂-CH＝CH₂

viscosity: 2070cP

Molecular weight: 4030

The (B2) of the examples and comparative examples are as follows.

(b2-1) is represented by the average formula { (CH)₃)₃-SiO_1/2}₆{SiO₂}₈{(CH₂＝CH)(CH₃) M of-SiO₆D^vQ₈Resin composition

Weight average molecular weight: 22000

The weight molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a calibration curve.

The following (C) was used in the examples and comparative examples.

(c-1) 2-hydroxy-2-methylphenylethyl ketone

(c-2)2, 2-dimethoxy-1, 2-diphenylethan-1-one

(c-3) 1-hydroxy-cyclohexyl-phenyl-ketones

(c-4) 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one

(c-5) 2-benzyl-2-dimethylamino- (4-morpholinophenyl) butanone-1

The following shows (D) of examples and comparative examples.

(d-1) 3-methacryloxypropyltrimethoxysilane

Examples and comparative examples (E) are as follows.

(e-1) MQ resin

Average structural formula: { (CH)₃)₃SiO_1/2}{SiO₂}_3.5MQ resin of

Weight average molecular weight: 52000

The MQ resin can be obtained by using the cohydrolysis and polycondensation reaction of tetraalkoxysilane or tetrachlorosilane and trialkylsilane. Further, water glass may be used as a raw material of the Q unit. Specifically, materials prepared as shown below were used. 293g of hydrochloric acid was added to a 3L separable flask equipped with a Three-One Motor as a stirring device and a reflux tube for cooling, the temperature in the flask was adjusted to-5 ℃ to 2 ℃, 440g of water was added while stirring, and 308g of water glass No.3 (S40 sodium silicate No. 3) was added dropwise over 1 hour. Then, 316g of isopropyl alcohol was added to the flask, and water-gelation was performed. Thereafter, a mixture of 128g of trimethylchlorosilane and 139g of xylene was added dropwise over about 10 minutes, and the mixture was stirred for 1 hour while the temperature in the flask was maintained at-5 ℃ to 2 ℃. Then, the temperature was raised to about 80 ℃ and thereafter, heating reflux was carried out at 80 ℃ for 2 hours. Then, 24g of xylene was added, and the mixture was stirred for 30 minutes, left standing for 30 minutes, and subjected to liquid separation. Thereafter, dehydration and desolventization were carried out at 125-140 ℃ to measure the nonvolatile components. The nonvolatile content was 58%. The MQ resin thus obtained was mixed with the vinyl-terminated polymethylphenylsiloxane used in each example and comparative example, and used after xylene was removed.

Examples and comparative examples (F) are shown below.

(f-1) para-tert-butylcatechol (polymerization inhibitor)

(f-2) p-methoxyphenol (polymerization inhibitor)

[ example 1 ]

10.5 parts by weight (105g) of the mercaptopropyl-containing methicone (a-1) of synthesis example and 87.9 parts by weight (879g) of the vinyl-terminated polymethylphenylsiloxane (b1-1) of synthesis example were charged in a 5L universal mixer-blender (manufactured by Dulton), and uniformly mixed at room temperature (22 ℃) for 30 minutes under rotation of a low-speed stirring bar. After uniformly mixing, a dissolved mixture of 0.009 parts by weight (0.09g) of p-tert-butylcatechol (f-1) and 0.26 parts by weight (2.6g) of 2-hydroxy-2-methylphenylethyl ketone (c-1) and 1.29 parts by weight (12.9g) of 3-methacryloxypropyltrimethoxysilane (d-1) were added, and the mixture was uniformly mixed under cooling with ice water (8 ℃ C.) under reduced pressure by cooling with the aid of a low-speed stirring rod for 30 minutes. Thereafter, foreign matter and the like were removed by a 10 μm membrane filter to obtain a composition.

Example 2 and comparative examples 1 to 3 were prepared in the same manner with the compounding amounts shown in table 1, and physical properties were evaluated. Further, examples 3 to 6 and comparative examples 4 to 6 were prepared by the same procedure with the compounding amounts shown in Table 3, and physical properties were evaluated.

[ comparative example 7 ]

For comparison, SVR 1100(Sony Chemical & Information Device Co., Ltd.) as a commercially available ultraviolet-curable acrylic resin was evaluated.

The results of evaluating physical properties of examples 1 to 2 and comparative examples 1 to 3 are shown in Table 2. In addition, the physical property evaluation results of examples 3 to 6 and comparative examples 4 to 7 are shown in Table 4.

TABLE 1

TABLE 2

In the table, the states are indicated by 1 to 5.

*1: micro cracks were generated at 5. *2: micro cracks were generated at 1. *3: cracks are widely generated.

*4: turbidity occurred over the whole surface. *5: fine cracks occur in the seal portion, and peeling occurs at the end face.

As is clear from tables 1 and 2, examples 1 and 2 were liquid and had excellent coatability and excellent permeability of the cured product. Further, it is found that the shrinkage rate at the time of curing is suppressed, the hardness and elongation of the cured product are suitable, the temperature change with respect to the elastic modulus of the cured product is suppressed, and the adhesiveness is also good.

On the other hand, it is understood that comparative example 1 in which HS/ViD is out of the range of the present invention is inferior to the examples in terms of adhesiveness, and that comparative examples 2 and 3 in which HS/(ViB + ViD) is out of the range of the present invention have a larger cure shrinkage ratio than the examples, and the cured product has a larger E hardness and a smaller elongation. It is understood that the effect of suppressing the temperature change in the elastic modulus of the cured product is also shown by the value of G '(100)/G' (23), which is inferior to the examples.

As is clear from tables 3 and 4, even in the combination of mercaptopropyl-containing polymethylsiloxane and vinyl-terminated polymethylphenylsiloxane which have different viscosities, if HS/(ViB + ViD) and HS/ViB are within the range of the present invention, as shown in examples 3 to 6, the liquid-state silicone composition is liquid and excellent in coatability, and is excellent in permeability of the cured product. Further, it is found that the shrinkage rate at the time of curing is suppressed, the hardness and the elongation of the cured product are both suitable, and the temperature change with respect to the elastic modulus of the cured product is suppressed, and the adhesiveness is also excellent.

On the other hand, comparative example 4, in which HS/ViB is out of the range of the present invention, is inferior in adhesiveness. It is also found that, in comparative examples 5 to 6 in which HS/(ViB + ViD), HS/ViD and HS/ViB are out of the range of the present invention, the cured product has a higher E hardness and a lower elongation. Further, it was found that cracks and peeling were generated by thermal shock, and the adhesiveness was also poor.

It is clear that the evaluation of physical properties of comparative example 7, which is a commercially available ultraviolet-curable acrylic resin, is significantly inferior to those of the examples.

[ example 7 ]

11.8 parts by weight (118g) of mercaptopropyl-containing polymethylsiloxane (a-3), 44.1 parts by weight (441g) of synthetic example vinyl-terminated polymethylphenylsiloxane (b1-2), and 42.4 parts by weight (424g) of MQ resin (e-1) were charged into a 5L universal mixer (manufactured by Dulton) and uniformly mixed at room temperature (22 ℃) for 30 minutes under rotation of a low-speed stirring rod. After uniformly mixing, a dissolved mixture of 0.0042 part by weight (0.042g) of p-tert-butylcatechol (f-1) and 0.21 part by weight (2.1g) of 2-hydroxy-2-methylphenylethyl ketone (c-1) and 0.21 part by weight (2.1g) of 2, 2-dimethoxy-1, 2-diphenylethan-1-one (c-2), 1.00 part by weight (10.00g) of 3-methacryloxypropyltrimethoxysilane (d-1) were added, and uniformly mixed under cooling with ice water (8 ℃ C.) under reduced pressure by cooling under rotation with a low-speed stirring bar for 30 minutes. Thereafter, foreign matter and the like were removed by a 10 μm membrane filter to obtain a composition.

In the same manner as in example 7, examples 8 to 10 and comparative examples 8 to 10 were prepared in the formulation shown in Table 5, and the physical properties were evaluated. The results are shown in table 6.

It is understood that examples 7 to 10 and comparative examples 8 to 10 in tables 5 and 6 are compositions obtained by blending MQ resin for adjusting the hardness of the cured product, and examples 7 to 10 are liquid and excellent in coatability and in permeability of the cured product. Furthermore, it was found that the shrinkage rate during curing was suppressed, the elongation of the cured product was satisfactory, the temperature change in the elastic modulus of the cured product was also suppressed, and the adhesiveness was also good. Further, the adhesion to a polarizing plate or the like is also improved by blending the MQ resin.

On the other hand, it is found that comparative examples 8 to 10, in which at least one of HS/(ViB + ViD), HS/ViD and HS/ViB is out of the range of the present invention, are inferior to examples in elongation of the cured product, and cause haze on the whole surface under high temperature and humidity.

[ example 11 ]

10.2 parts by weight (102g) of mercaptopropyl-containing methicone (a-4), 44.1 parts by weight (441g) of vinyl-terminated polymethylphenylsiloxane (b1-2) of synthetic example, 3.7 parts by weight (37g) of vinyl-terminated polymethylphenylsiloxane (b1-4), and M₆D^vQ₈2.4 parts by weight (24g) of resin (b2-1) and 40.6 parts by weight (406g) of MQ resin (e-1) were charged in a 5-liter universal mixer (manufactured by Dulton Co.) and uniformly mixed at room temperature (22 ℃ C.) for 30 minutes under rotation by means of a low-speed stirring bar. After uniformly mixing, a dissolved mixture of 0.0042 part by weight (0.042g) of p-tert-butylcatechol (f-1) and 0.21 part by weight (2.1g) of 2-hydroxy-2-methylphenylethyl ketone (c-1) and 0.21 part by weight (2.1g) of 2, 2-dimethoxy-1, 2-diphenylethan-1-one (c-2), 1.27 parts by weight (12.7g) of 3-methacryloxypropyltrimethoxysilane (d-1) were added, and uniformly mixed under ice water cooling (8 ℃) under reduced pressure by cooling under rotation with a low-speed stirring bar for 30 minutes. Thereafter, foreign matter and the like were removed by a 10 μm membrane filter to obtain a composition.

In the same manner as in example 11, examples 12 to 14 and comparative example 11 were prepared in the formulation shown in Table 7, and the physical properties were evaluated. The results are shown in table 8.

Examples 11 to 14 and comparative example 11 in tables 7 and 8 are compositions in which a branched polyorganosiloxane having an aliphatic unsaturated group is used in combination and an MQ resin is blended, but examples 11 to 14 are excellent in coatability, permeability of a cured product, shrinkage/elongation at curing, and temperature change in elastic modulus of the cured product, and can achieve further improvement in adhesiveness.

On the other hand, comparative example 11 in which HS/(ViB + ViD) and HS/ViD were outside the range of the present invention exhibited cracks under high temperature and high humidity conditions, and the improvement of adhesion was inferior to that of the examples.

[ example 15 ]

9.5 parts by weight (95g) of mercaptopropyl-containing methicone (a-4), 66.12 parts by weight (661.2g) of vinyl-terminated polymethylphenylsiloxane (b1-1) of synthetic example, 21.7 parts by weight (217g) of vinyl-terminated polymethylphenylsiloxane (b1-4), and M₆D^vQ₈0.8 part by weight (8g) of the resin (b2-1) was charged in a 5L universal mixer (manufactured by Dulton Co.) and uniformly mixed at room temperature (22 ℃ C.) for 30 minutes by rotating a low-speed stirring bar. After uniformly mixing, a dissolved mixture of 0.04 parts by weight (0.4g) of p-tert-butylcatechol (f-1), 0.22 parts by weight (2.2g) of 2-hydroxy-2-methylphenylethyl ketone (c-1), 0.22 parts by weight (2.2g) of 2, 2-dimethoxy-1, 2-diphenylethan-1-one (c-2), and 1.3 parts by weight (13g) of 3-methacryloxypropyltrimethoxysilane (d-1) were uniformly mixed under ice water cooling (8 ℃) for 30 minutes under reduced pressure by cooling with the aid of a low-speed stirring bar under rotation. Thereafter, foreign matter and the like were removed by a 10 μm membrane filter to obtain a composition.

In the same manner as in example 15, examples 16 to 18 and comparative examples 12 and 13 were prepared in the formulation shown in Table 9, and the physical properties were evaluated. The results are shown in table 10.

Examples 15 to 18 and comparative examples 12 and 13 in tables 9 and 10 are compositions using a branched polyorganosiloxane having an aliphatic unsaturated group in combination, but examples 15 to 18 are excellent in coatability, permeability of a cured product, shrinkage/elongation at curing, and temperature change in terms of elastic modulus of the cured product, and can achieve further improvement in adhesiveness.

On the other hand, in comparative examples 12 and 13 in which HS/ViD was outside the range of the present invention, the cured products had high E hardness.

Compositions were prepared in the same manner as in example 1 with the formulation shown in example 19 of table 11, in the same manner as in example 2 with the formulations shown in examples 20 to 22, and in the same manner as in example 7 with the formulations shown in examples 23 to 25, and physical properties were evaluated. The results are shown in table 12.

As shown in examples 19 to 25 in table 12, it is understood that the composition of the present invention is excellent in coatability, permeability of a cured product, shrinkage/elongation at curing, temperature change with respect to elastic modulus of a cured product, and adhesiveness in combination with various photoinitiators.

Compositions were prepared in the same manner as in example 2 and with the formulations shown in examples 26 and 27 of table 13, in the same manner as in example 7 and with the formulation shown in example 28, and in the same manner as in example 11 and with the formulation shown in example 29, and physical properties were evaluated. Among the light sources, a metal halide lamp (MHL250) is used. The results are shown in table 14.

Watch 13

	Example 26	Example 27	Example 28	Example 29
					(a1-1) mercaptopropyl-containing methicone (294cP)	10.5	10.5
(a1-2) mercaptopropyl-containing methicone (110cP)
					(a1-3) mercaptopropyl-containing methicone (220cP)			11.8
(a1-4) mercaptopropyl-containing methicone (330cP)				9.3
					(a1-5) mercaptopropyl-containing methicone (23000cP)
(a1-6) mercaptopropyl-containing methicone (60cP)
					(b1-1) vinyl terminated polymethylphenylsiloxane (3200cP)	87.8	87.8
(b1-2) vinyl terminated polymethylphenylsiloxane (1020cP)			44.1	41.42
					(b1-3) vinyl terminated polymethylphenylsiloxane (9020cP)
(b1-4) vinyl terminated polymethylphenylsiloxane (18900cP)				3.7
					(b1-5) vinyl terminated polymethylphenylsiloxane (20450cP)
(b1-6) vinyl terminated polymethylphenylsiloxane (2070cP)
					(b2-1) M6Q8Dvi resin				2.47
(c-1) 2-hydroxy-2-methylphenylethyl ketone	0.22	0.20	0.21	0.21
					(c-2) 2, 2-dimethoxy-1, 2-diphenylethan-1-one	0.22	0.30	0.21	0.21
(d-1) 3-Methacryloxypropyltrimethoxysilane	1.27	1.27	1.00	1.27
					(e-1) MQ resin			42.4	42.4
(f-1) para-tert-butylcatechol	0.0042	0.0042	0.0042	0.0042
					(f-2) p-methoxyphenol			0.0084	0.0084
Total up to	100.0	100.1	99.7	101.0
					HS: (A) number mmol of SH groups in (1)	10.3	10.3	6.1	9.0
ViB 1: (B1) number mmol of vinyl group of methane	8.3	8.3	6.3	6.1
					ViB 2: (B2) number mmol of vinyl group of methane	0.0	0.0	0.0	2.5
ViB: (B1) number mmol of vinyl groups in (A) and (B2)	8.3	8.3	6.3	8.6
					(B2) The ratio (%) of the vinyl group in (B) to the vinyl group in (B)	0.0	0.0	0.0	28.9
ViD: (D) number mmol of vinyl group in (1)	5.1	5.1	4.0	5.1
					ViB + ViD: (B) number mmol of vinyl groups in (A) and (D)	13.5	13.5	10.4	13.7
HS/(ViB+ViD)	0.76	0.76	0.59	0.66
					HS/ViD	2.01	2.01	1.52	1.76
HS/ViB	1.23	1.23	0.97	1.05
					HS/ViB1	1.23	1.23	0.97	1.48

TABLE 14

In the table, the states are indicated by 1 to 5.

As shown in examples 26 to 29 in table 14, it is understood that the composition of the present invention is excellent in coatability, permeability of the cured product, shrinkage/elongation at curing, temperature change with respect to the elastic modulus of the cured product, and adhesiveness even when a metal halide lamp is used.

From the results of the above examples, it is understood that in the method for producing an image display device using the specific ultraviolet-curable silicone resin composition of the present invention and the ultraviolet-curable silicone resin composition, compared with the prior ultraviolet curing resin composition, the coating performance is excellent, the curing shrinkage is less, since the visibility can be ensured without causing discoloration or clouding in each durability test, in a general small-sized image display device, as compared with the conventional bonding of the thin image display unit and the protective unit, deformation resistance and visibility can be ensured, and particularly, in a large-sized image display device, deformation resistance and visibility can be ensured under smooth resin application, it is extremely preferable in terms of the quality and productivity of the adhesion between the image display portion and the protective portion.

Industrial applicability

According to the present invention, in the case of manufacturing a thin or large-sized image display device in which a resin is interposed between a protective portion and an image display portion, it is possible to provide an ultraviolet-curable silicone resin composition which is liquid and excellent in coatability, does not cause display defects due to deformation of the image display portion, does not reduce visibility, and can realize high-luminance and high-contrast display.

Claims

1. An ultraviolet-curable silicone resin composition comprising

A: a polyorganosiloxane having a viscosity of 20 to 25000cP at 23 ℃ and containing a mercapto alkyl group bonded to a silicon atom;

b: an aliphatic unsaturated group-containing organopolysiloxane that contains B1 and B2, wherein the amount of B2 is such that the proportion of the number of aliphatic unsaturated groups in B2 to the total number of aliphatic unsaturated groups in B becomes 50% or less,

wherein the content of the first and second substances,

b1 is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by the formula (I),

in the formula (I), R¹Independently an aliphatic unsaturated group, R independently is a C1-C6 alkyl group or a C6-C12 aryl group, 1-60 mol% of R is a C6-C12 aryl group, n is a value such that the viscosity at 23 ℃ reaches 100-25000 cP,

b2 is a branched organopolysiloxane containing SiO_4/2Unit, R'₃SiO_1/2Unit and R'₂SiO_2/2Units, and optionally also R' SiO_3/2A unit, and at least 3R's per 1 molecule are aliphatic unsaturated groups, wherein R's each independently represents a C1-C6 alkyl group or an aliphatic unsaturated group;

c: a photoreaction initiator; and

d: 1 or more silane compounds containing an aliphatic unsaturated group selected from the group consisting of 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane;

in this case, the amount of the solvent to be used,

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, and

the ratio of the number of mercaptoalkyl groups in A to the number of aliphatic unsaturated groups in D is 1.5 to 3.

2. The ultraviolet-curable silicone resin composition according to claim 1,

the content of C is 0.05-50 parts by weight relative to 100 parts by weight of B.

3. The ultraviolet-curable silicone resin composition according to claim 1, further comprising E: 1 or more silicone resin adhesion promoters selected from MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin and TQ resin.

4. The ultraviolet-curable silicone resin composition according to claim 2, further comprising E: 1 or more silicone resin adhesion promoters selected from MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin and TQ resin.

5. The ultraviolet-curable silicone resin composition according to any one of claims 1 to 4,

the visible light transmittance after curing is 95% or more.

6. The ultraviolet-curable silicone resin composition according to any one of claims 1 to 4,

the curing shrinkage is 1.0% or less.

7. The ultraviolet-curable silicone resin composition according to any one of claims 1 to 4,

the E hardness after curing is 5-40.

8. The ultraviolet-curable silicone resin composition according to any one of claims 1 to 4,

the ratio of the storage elastic modulus G '(T) at-50 to 100 ℃ after curing to the storage elastic modulus G' (23) at 23 ℃, that is, G '(T)/G' (23), is 0.1 to 30.

9. The ultraviolet-curable silicone resin composition according to any one of claims 1 to 4,

the ratio of the loss elastic modulus G '(T) at-50 to 100 ℃ after curing to the loss elastic modulus G' (23) at 23 ℃, i.e., G '(T)/G' (23), is 0.1 to 300.

10. A sealing agent for an image display device, comprising the ultraviolet-curable silicone resin composition according to any one of claims 1 to 9.

11. An image display device obtained by sealing an image display portion and a protective portion with the use of the sealant for an image display device according to claim 10.