JP2014001341A - Ultraviolet curable silicone resin composition and image display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet curable silicone resin composition which suppresses shrinkage on curing, is hardly discolored even at a high temperature, and can provides a cured product having a small fluctuation range of an elastic coefficient due to a temperature change.SOLUTION: An ultraviolet curable silicone resin composition comprises (A) a linear polyorganosiloxane represented by following formula, (B) a branched polyorganosiloxane represented by a specific formula, and (C) a photoinitiator. A sealant for an image display device comprises the composition. An image display device uses the sealant for an image display device to seal an image display part and a protection part.

Description

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

  In recent years, attention has been focused on flat panel image display devices such as liquid crystal, plasma, and organic EL. 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.

  In such an image display device, an ultraviolet curable resin composition is interposed between the protective part and the image display part in order to prevent deterioration in visibility (visibility) due to reflection of outdoor light or indoor lighting. A thin image display device is manufactured, and an ultraviolet curable acrylic resin composition is used as the ultraviolet curable resin composition used here (Patent Document 1).

JP 2008-282000 A

In manufacturing a thin image display device in which an ultraviolet curable resin composition is interposed between the protective part and the image display part, a conventional ultraviolet curable acrylic resin composition has an internal structure caused by shrinkage during curing. The image display unit (for example, a liquid crystal display panel) is deformed by the stress, and a display defect may occur due to disorder of the alignment of the liquid crystal material. This display defect has good visibility, high luminance, and high brightness. This is a cause of hindering contrast display. In addition, the problem of display failure due to display unevenness caused by external stress applied to the image display unit due to warpage of the protection unit due to shrinkage at the time of curing is a problem in recent years when image display devices are becoming brighter, higher definition and larger in size. It has become more obvious.
Furthermore, when the cured product of the conventional ultraviolet curable acrylic resin composition is exposed to a high temperature during use, there is a problem that such a decrease in transparency and yellowing are remarkable. Furthermore, the cured product has a problem that the elastic modulus fluctuates violently due to temperature change, and the protective part and the image display part are easily peeled off.

  The present invention relates to an ultraviolet curable silicone resin composition capable of providing a cured product in which shrinkage at the time of curing is suppressed and hardly discolored even at high temperatures, and further can provide a cured product having a small fluctuation range of elastic modulus due to a temperature change. It is an object to provide an image display device used.

  As a result of intensive studies in order to achieve the above object, the present inventors have found that a linear polyorganosiloxane having a specific (meth) acryloxy group and a branched polyorganoorganism having a specific (meth) acryloxy group. It has been found that the above problem can be solved by combining siloxane, and the present invention has been completed.

（式中、
Ｒは、独立して、Ｃ１〜Ｃ６アルキル基、Ｃ６〜Ｃ１２アリール基又は式（II）：

（ここで、Ｒ_ａは、独立して、水素原子又はメチル基であり、
Ｑ_１は、独立して、Ｃ１〜Ｃ５アルキレン基である）で示される基であるが、
少なくとも１個のＲは、式（II）で示される基であり、
ｎは、０〜６００である）
で示される直鎖状ポリオルガノシロキサン
（Ｂ）平均式（III）；

（式中、
Ｒ_ｂは、独立して、水素原子又はメチル基であり、
Ｑ_２は、独立して、Ｃ１〜Ｃ５アルキレン基であり、
Ｒ^１は、独立して、Ｃ１〜Ｃ６アルキル基又はＣ６〜Ｃ１２アリール基であり、
Ｒ^２は、独立して、Ｃ１〜Ｃ６アルキル基又はＣ６〜Ｃ１２アリール基であり、
Ｒ^３は、独立して、Ｃ１〜Ｃ６アルキル基又はＣ６〜Ｃ１２アリール基であり、
ｐは、１〜１０であり、
ｑは、０〜１０であり、
ｒは、０〜１００であり、
ｓは、０〜１０であり、
ｐ／（ｐ＋ｑ＋ｒ＋ｓ）≧０．０２である）
で示される分岐状ポリオルガノシロキサン、及び
（Ｃ）光開始剤
を含む、紫外線硬化型シリコーン樹脂組成物に関する。
本発明２は、成分（Ａ）１００重量部に対して、成分（Ｂ）５〜２５０重量部、成分（Ｃ）０．１〜５重量部を含む、本発明１の紫外線硬化型シリコーン樹脂組成物に関する。
本発明３は、成分（Ａ）が、両末端に、式（II）で示される基を有する直鎖状ポリオルガノシロキサンである、本発明１又は２の紫外線硬化型シリコーン樹脂組成物に関する。
本発明４は、さらに、（Ｄ）（メタ）アクリレートを含む、本発明１〜３のいずれかの紫外線硬化型シリコーン樹脂組成物に関する。
本発明５は、さらに、（Ｅ）（メタ）アクリロキシ基含有シランを含む、本発明１〜４のいずれかの紫外線硬化型シリコーン樹脂組成物に関する。
本発明６は、さらに、（Ｆ）シリコーン樹脂系接着向上剤（ただし、脂肪族不飽和基及びメルカプト基を含有しないこととする）を含む、本発明１〜５のいずれかの紫外線硬化型シリコーン樹脂組成物に関する。
本発明７は、さらに、（Ｇ）２３℃における粘度が５〜１００００ｃＰ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を含む、本発明１〜６のいずれかの紫外線硬化型シリコーン樹脂組成物に関する。
本発明８は、本発明１〜７のいずれかの紫外線硬化型シリコーン樹脂組成物からなる画像表示装置用シール剤に関する。
本発明９は、本発明８の画像表示装置用シール剤を用いて、画像表示部と保護部とが封止された画像表示装置に関する。 Invention 1 comprises (A) Formula (I):

(Where
R is independently a C1-C6 alkyl group, a C6-C12 aryl group or formula (II):

(Wherein R _a is independently a hydrogen atom or a methyl group;
Q ₁ is independently a group represented by a C1-C5 alkylene group,
At least one R is a group of formula (II);
n is 0-600)
A linear polyorganosiloxane represented by formula (B): average formula (III);

(Where
R _b is independently a hydrogen atom or a methyl group,
Q ₂ is independently a C1-C5 alkylene group,
R ¹ is independently a C1-C6 alkyl group or a C6-C12 aryl group,
R ² is independently a C1-C6 alkyl group or a C6-C12 aryl group,
R ³ is independently a C1-C6 alkyl group or a C6-C12 aryl group,
p is 1 to 10,
q is 0 to 10,
r is 0-100,
s is 0-10,
p / (p + q + r + s) ≧ 0.02)
And (C) an ultraviolet curable silicone resin composition comprising a photoinitiator.
The present invention 2 includes the ultraviolet curable silicone resin composition of the present invention 1 comprising 5 to 250 parts by weight of the component (B) and 0.1 to 5 parts by weight of the component (C) with respect to 100 parts by weight of the component (A). Related to things.
The present invention 3 relates to the ultraviolet curable silicone resin composition of the present invention 1 or 2, wherein the component (A) is a linear polyorganosiloxane having groups represented by the formula (II) at both ends.
The present invention 4 further relates to the ultraviolet curable silicone resin composition according to any one of the present inventions 1 to 3, further comprising (D) (meth) acrylate.
This invention 5 is further related with the ultraviolet curable silicone resin composition in any one of this invention 1-4 containing (E) (meth) acryloxy group containing silane.
The present invention 6 further includes (F) a silicone resin adhesion improver (provided that it does not contain an aliphatic unsaturated group and a mercapto group). The present invention relates to a resin composition.
Invention 7 further includes (G) a polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom and having a viscosity at 23 ° C. of 5 to 10000 cP. The present invention relates to a silicone resin composition.
This invention 8 relates to the sealing compound for image display apparatuses which consists of a ultraviolet curable silicone resin composition in any one of this invention 1-7.
The present invention 9 relates to an image display device in which an image display unit and a protection unit are sealed using the sealant for an image display device of the present invention 8.

  According to the ultraviolet curable silicone resin composition of the present invention, it is possible to obtain a cured product in which shrinkage at the time of curing is suppressed, discoloration is difficult even at high temperatures, and further, the fluctuation range of the elastic modulus due to temperature change is small. It is suitable for manufacturing.

（式中、
Ｒは、独立して、Ｃ１〜Ｃ６アルキル基（好ましくは、メチル基）、Ｃ６〜Ｃ１２アリール基（好ましくは、フェニル基）又は式（II）：

（ここで、Ｒ_ａは、独立して、水素原子又はメチル基であり、
Ｑ_１は、独立して、Ｃ１〜Ｃ５アルキレン基（好ましくは、トリメチレン基）である）で示される基であるが、
少なくとも１個のＲは、式（II）で示される基であり、
ｎは、０〜６００（好ましくは、０〜３００、より好ましくは、０〜１００）である）
で示される直鎖状ポリオルガノシロキサンを含む。 The composition of the present invention comprises (A) Formula (I):

(Where
R is independently a C1-C6 alkyl group (preferably a methyl group), a C6-C12 aryl group (preferably a phenyl group) or a compound represented by the formula (II):

(Wherein R _a is independently a hydrogen atom or a methyl group;
Q ₁ is independently a group represented by a C1-C5 alkylene group (preferably a trimethylene group),
At least one R is a group of formula (II);
n is 0 to 600 (preferably 0 to 300, more preferably 0 to 100).
The linear polyorganosiloxane shown by these is included.

  In the formula (I), R, which is a group represented by the formula (II), is preferably 1 to 10, more preferably 2 to 5, from the viewpoints of ease of synthesis, reactivity, and obtained properties. It is a piece.

  R, which is a group represented by the formula (II), may be bonded to any silicon atom in the formula (I), but is preferably bonded to a terminal silicon atom. From the viewpoint of the flexibility of the resulting cured product, it is more preferable that it is bonded to silicon atoms at both terminals, more preferably only bonded to silicon atoms at both terminals, particularly preferably silicon atoms at both terminals. Only in each case, R, which is a group represented by the formula (II), is bonded.

R _a is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of ease of synthesis and storage stability.

Q ₁ is a C1-C5 alkylene group, which may be linear or branched. Q ₁ preferably has a chain length of 3 or more carbon atoms from the viewpoint of the reactivity of the (meth) acryl functional group, and more preferably a trimethylene group from the viewpoint of durability and transparency of the resulting cured product. (— (CH ₂ ) ₃ —).

  In the formula (I), R other than the group represented by the formula (II) is a C1-C6 alkyl group (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, s-butyl group, tert group) -Butyl group or the like) or a C6-C12 aryl group (for example, a phenyl group, a tolyl group or the like). A methyl group is preferred from the viewpoint of ease of synthesis and economics, and a phenyl group is preferred from the viewpoint of optical viewpoint and high refractive index.

  n is 0 to 600, and preferably 0 to 300, more preferably 0 to 100, from the viewpoint of compatibility with other components.

  The linear polyorganosiloxane represented by the formula (I) preferably has a viscosity of 0.1 cP to 5000 cP, more preferably 1 to 1500 cP, and still more preferably 1 to 1000 cP. In this specification, the viscosity is No. using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.). A value measured at 23 ° C. at 60 rpm using 2 to 4 rotors.

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

（式中、
Ｒ_ｂは、独立して、水素原子又はメチル基であり、
Ｑ_２は、独立して、Ｃ１〜Ｃ５アルキレン基（好ましくは、トリメチレン基）であり、
Ｒ^１は、独立して、Ｃ１〜Ｃ６アルキル基（好ましくは、メチル基）又はＣ６〜Ｃ１２アリール基（好ましくは、フェニル基）であり、
Ｒ^２は、独立して、Ｃ１〜Ｃ６アルキル基（好ましくは、メチル基）又はＣ６〜Ｃ１２アリール基（好ましくは、フェニル基）であり、
Ｒ^３は、独立して、Ｃ１〜Ｃ６アルキル基（好ましくは、メチル基）又はＣ６〜Ｃ１２アリール基（好ましくは、フェニル基）であり、
ｐは、１〜１０（好ましくは、１〜８、さらに好ましくは、１〜５）であり、
ｑは、０〜１０（好ましくは、０〜８、さらに好ましくは、０〜５）であり、
ｒは、０〜１００（好ましくは、１〜８０、さらに好ましくは、２〜７０）であり、
ｓは、０〜１０(好ましくは、０〜８、さらに好ましくは、０〜６)であり、
ｐ／（ｐ＋ｑ＋ｒ＋ｓ）≧０．０２（好ましくは、≧０．０６、さらに好ましくは、≧０．１０）である）
で示される分岐状ポリオルガノシロキサンを含む。 The composition of the present invention comprises (B) an average formula (III);

(Where
R _b is independently a hydrogen atom or a methyl group,
Q ₂ is independently a C1-C5 alkylene group (preferably a trimethylene group),
R ¹ is independently a C1-C6 alkyl group (preferably a methyl group) or a C6-C12 aryl group (preferably a phenyl group);
R ² is independently a C1-C6 alkyl group (preferably a methyl group) or a C6-C12 aryl group (preferably a phenyl group);
R ³ is independently a C1-C6 alkyl group (preferably a methyl group) or a C6-C12 aryl group (preferably a phenyl group);
p is 1 to 10 (preferably 1 to 8, more preferably 1 to 5);
q is 0-10 (preferably 0-8, more preferably 0-5),
r is 0 to 100 (preferably 1 to 80, more preferably 2 to 70);
s is 0-10 (preferably 0-8, more preferably 0-6),
p / (p + q + r + s) ≧ 0.02 (preferably ≧ 0.06, more preferably ≧ 0.10)
The branched polyorganosiloxane shown by these is included.

R _b is a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of ease of synthesis and storage stability.

Q ₂ is a C1-C5 alkylene group, which may be linear or branched. Q ₂ preferably has a chain length of 3 or more carbon atoms from the viewpoint of the reactivity of the (meth) acryl functional group, and more preferably a trimethylene group from the viewpoint of durability and transparency of the resulting cured product. (— (CH ₂ ) ₃ —).

R ¹ is a C1-C6 alkyl group (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, etc.), or C6-C12 aryl group (for example, A phenyl group, a tolyl group, and the like. From the viewpoint of ease of synthesis and economy, a methyl group is preferable, and from the viewpoint of obtaining an optical viewpoint and a high refractive index, a phenyl group is preferable.

R ² is a C1-C6 alkyl group (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, etc.), or C6-C12 aryl group (for example, A phenyl group, a tolyl group, and the like. From the viewpoint of ease of synthesis and economy, a methyl group is preferable, and from the viewpoint of obtaining an optical viewpoint and a high refractive index, a phenyl group is preferable.

R ³ is a C1-C6 alkyl group (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, s-butyl group, tert-butyl group, etc.), or C6-C12 aryl group (for example, A phenyl group, a tolyl group, and the like. From the viewpoint of ease of synthesis and economy, a methyl group is preferable, and from the viewpoint of obtaining an optical viewpoint and a high refractive index, a phenyl group is preferable.

p is 1-10, More preferably, it is 1-8, More preferably, it is 1-5.
q is 0-10, More preferably, it is 0-8, More preferably, it is 0-5.
r is 0-100, More preferably, it is 1-80, More preferably, it is 2-70.
s is 0-10, More preferably, it is 0-8, More preferably, it is 0-6.

  From the viewpoint of obtaining good curability, p / (p + q + r + s) ≧ 0.02, preferably p / (p + q + r + s) ≧ 0.06, and more preferably p / (p + q + r + s) ≧ 0.10. is there.

Examples of (B) include branched polyorganosiloxanes represented by the following average formula. However, q, r, and s are not 0 when present in the average equation.
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {CH 3 SiO 3/2} q {(CH 3) 2 SiO} r {(CH ₃ ) ₃ SiO _1/2 } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {(CH 3) 2 SiO} r {(CH 3) 3 SiO 1/2} s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {CH 3 SiO 3/2} q {(CH 3) 3 SiO 1/2} s
{CH ₂ ═C (CH ₃ ) —C (═O) —O— (CH ₂ ) ₃ SiO _3/2 } p {CH ₃ SiO _3/2 } q {(CH ₃ ) ₂ SiO} r
{CH ₂ ═C (CH ₃ ) —C (═O) —O— (CH ₂ ) ₃ SiO _3/2 } p {(CH ₃ ) ₃ SiO _1/2 } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {CH 3 SiO 3/2} q
{CH ₂ ═C (CH ₃ ) —C (═O) —O— (CH ₂ ) ₃ SiO _3/2 } p {(CH ₃ ) ₂ SiO} r
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {Ph 3 SiO 3/2} q {(CH 3) 2 SiO} r {(CH ₃ ) ₃ SiO _1/2 } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {Ph 3 SiO 3/2} q {(CH 3) 2 SiO} r
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {Ph 3 SiO 3/2} q {(CH 3) 3 SiO 1/2} s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {Ph 3 SiO 3/2} q
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {CH 3 SiO 3/2} q {Ph 2 SiO} r {(CH 3) 3 SiO _1/2 } s
{CH ₂ ═C (CH ₃ ) —C (═O) —O— (CH ₂ ) ₃ SiO _3/2 } p {CH ₃ SiO _3/2 } q {Ph ₂ SiO} r
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {Ph 2 SiO} r {(CH 3) 3 SiO 1/2} s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {Ph 2 SiO} r
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {CH 3 SiO 3/2} q {(CH 3) 2 SiO} r {Ph 3 SiO _1/2 } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {CH 3 SiO 3/2} q {Ph 3 SiO 1/2} s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {(CH 3) 2 SiO} r {Ph 3 SiO 1/2} s
{CH ₂ ═C (CH ₃ ) —C (═O) —O— (CH ₂ ) ₃ SiO _3/2 } p {Ph ₃ SiO _1/2 } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {PhSiO 3/2} q {Ph 2 SiO} r {(CH 3) 3 SiO 1 _{/ 2} } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {PhSiO 3/2} q {Ph 2 SiO} r
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {PhSiO 3/2} q {(CH 3) 2 SiO} r {Ph 3 SiO 1 _{/ 2} } s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {PhSiO 3/2} q {Ph 3 SiO 1/2} s
_{{CH 2 = C (CH 3} ) -C (= O) -O- (CH 2) 3 SiO 3/2} p {PhSiO 3/2} q {Ph 2 SiO} r {Ph 3 SiO 1/2} s

  (B) has a preferable weight average molecular weight of 500-100000, More preferably, it is 1000-80000, More preferably, it is 1000-60000. Here, the weight average molecular weight is a value using polystyrene as a calibration curve by gel permeation chromatography (GPC).

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

  The composition of the present invention comprises (C) a photoinitiator. (C) is excited by receiving light and gives excitation energy to siloxane containing a (meth) acryloxy group to initiate a curing reaction by ultraviolet irradiation.

  (C) is an aromatic hydrocarbon, acetophenone and derivatives thereof, benzophenone and derivatives thereof, o-benzoylbenzoic acid ester, benzoin and benzoin ether and derivatives thereof, xanthone and derivatives thereof, disulfide compounds, quinone 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 (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: manufactured by BASF), 2-methyl-1- (4-methylthio) Benzyl) -2-morpholinopropan-1-one (IRGACURE 907: manufactured by BASF), 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -butanone-1 (IRGACURE 369: manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379: manufactured by BASF); 2,4,6- Trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN TPO: manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819: manufactured by BASF); 1,2-octanedione, 1 -[4- (phenylthio)-, 2- (O-benzoyloxime)] (IRGACURE OXE 01: manufactured by BASF), ethanone, 1- [9-ethyl-6- (2- Tylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02: manufactured by BASF); oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl Mixture of ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester (IRGACURE 754: manufactured by BASF), phenylglyoxylic acid methyl ester (DAROCUR MBF: manufactured by BASF), ethyl-4-dimethylaminobenzoate (DAROCUR EDB: manufactured by BASF), 2-ethylhexyl-4-dimethylaminobenzoate (DAROCUR EHA: manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide ( CGI 403 (manufactured by BASF), benzoyl peroxide, cumene peroxy De, and the like.

  From the viewpoint of compatibility and photoreactivity, acetophenone, propiophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651: manufactured by BASF Corporation) ), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR 1173: manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184: manufactured by BASF), 2-methyl- 1- (4-Methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907: manufactured by BASF), 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 : BASF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN TPO: BASF), bis (2,4 6- trimethyl benzoyl) - phenyl phosphine oxide (IRGACURE 819: manufactured by BASF) is preferable.

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

  The composition of the present invention can contain 5 to 250 parts by weight of (B) and 0.1 to 5 parts by weight of component (C) with respect to 100 parts by weight of (A). (B) is preferably 10 to 200 parts by weight, more preferably 15 to 180 parts by weight, from the viewpoint of curability (hardness expression) and the properties of the resulting cured product. (C) is preferably 0.2 to 3 parts by weight, more preferably 0.4 to 2 parts by weight, from the viewpoint of curability and optical properties after curing.

  The composition of this invention can contain (D) (meth) acrylate further from the point of an improvement of sclerosis | hardenability and fluidity | liquidity. The (meth) acrylate may be monofunctional or polyfunctional. In addition, (meth) acrylates include C1-C8 alkyl esters and C6-C20 aryl esters, which are substituted with substituents such as hydroxy, C1-C4 alkoxy, C6-C12 aryloxy, or C3-C10 cycloalkyl. And / or modified with polyoxyalkylene.

  The C1-C8 alkyl moiety may be linear or branched, for example, methyl, ethyl, propyl, n-butyl, isobutyl, s-butyl, tert-butyl. A methyl group and an ethyl group are preferable from the viewpoint of imparting compatibility and fluidity. Examples of the C6-C12 aryl moiety include a phenyl group and a tolyl group.

  Examples of the C1-C4 alkoxy group as a substituent include methoxy, ethoxy, and propoxy groups, and a methoxy group and an ethoxy group are preferable from the viewpoint of compatibility and fluidity.

  Examples of (meth) acrylates include (I) methyl acrylate, ethyl acrylate, acrylpropyl acid, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. Alkyl (meth) acrylate; 2-hydroxy-3-phenoxypropyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, alkyl (meth) acrylate having a substituent such as 2-oxycyclopentylmethyl acrylate; Phenol EO modified acrylate, nonylphenol PO modified acrylate, 2-D Polyoxyalkylene modified (meth) acrylates such as ruhexyl EO modified acrylate, o-phenylphenol EO modified acrylate, paracumylphenol EO modified acrylate; polypropylene glycol diacrylate, polyethylene glycol diacrylate, bisphenol F EO modified diacrylate, bisphenol A EO Bifunctional (meth) acrylates such as modified diacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified diacrylate; trimethylolprohan triacrylate, trimethylolpropane PO modified triacrylate, trimethylolpropane EO modified triacrylate, isocyanuric Acid EO-modified triacrylate, pentaerythritol tri- and tetraacrylate, ditrime Trimethylolpropane tetraacrylate include trifunctional or more (meth) acrylates such as dipentaerythritol penta and hexaacrylate. Methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, 2-oxycyclopentylmethyl acrylate, polypropylene glycol diacrylate, polyethylene in terms of compatibility and fluidity Glycol diacrylate, phenol EO modified acrylate, nonylphenol PO modified acrylate, 2-ethylhexyl EO modified acrylate, polypropylene glycol diacrylate and the like are preferable. Furthermore, from the point of low volatility, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, ethoxyethyl methacrylate, 2-oxycyclopentylmethyl acrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, phenol EO modified acrylate Nonylphenol PO-modified acrylate, 2-ethylhexyl EO-modified acrylate, polypropylene glycol diacrylate and the like are preferable.

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

  (D) can be 50 parts by weight or less with respect to 100 parts by weight of (A). 0.1-30 weight part is preferable from the point of suppressing a cure shrinkage rate, yellowing reduction, a heat resistant fall, and the provision of fluidity, More preferably, it is 0.5-25 weight part.

  The composition of the present invention further includes (E) a silane compound containing an aliphatic unsaturated group from the viewpoint of improving adhesion. (E) plays a role of improving the adhesion and adhesion of the cured product to the substrate. Aliphatic unsaturated groups include alkenyl groups such as C2-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.

  (E) includes 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltri Examples include ethoxysilane, preferably 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane.

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

  (E) can be 20 parts by weight or less with respect to (A) 100 parts by weight. From the viewpoint of providing fluidity and improving adhesion, 1 to 20 parts by weight is preferable, and 1 to 15 parts by weight is more preferable.

  The composition of the present invention may further contain (F) a silicone resin-based adhesion improver (however, (A), (B), and (E) are excluded) from the viewpoint of improving adhesiveness. . The silicone resin adhesion improver refers to a silicone resin having tackiness, and is blended as necessary to further strengthen and stabilize the adhesive property of the ultraviolet curable silicone resin composition of the present invention. In particular, when the adherend is a polarizing plate, a high improvement effect can be expected.

From the viewpoint of adhesiveness and economy, (F) includes at least one silicone resin selected from the group consisting of MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin and TQ resin. Adhesive adhesion improver (but not containing aliphatic unsaturated group and mercapto group) is preferable, and is selected from the group consisting of MQ resin, MDQ resin, MDT resin and MDTQ resin from the viewpoint of fluidity and ease of synthesis. One or more silicone resin-based adhesion improvers are more preferable, and one or more silicone resin-based adhesion improvers selected from the group consisting of MQ resin, MDQ resin and MDT resin are more preferable, and high tackiness and easy structure control are possible. From the viewpoint, MQ resin is more preferable.
As the MQ resin, the average structural formula is represented by the following formula _{{(CH 3) 3 SiO 1/2} } m {SiO 2} n
(Where m + n = 1, and m and n are non-zero numbers), and the MDQ resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _{1 / 2} m {SiO 2} n} {(CH 3) 2 SiO} l
(Where m + n + 1 is 1 and m, n, and 1 are non-zero numbers), and the MT resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _1/2 } _m {(CH ₃ ) SiO _3/2 } _o
(Where m + o = 1, m and o are non-zero numbers), and the MDT resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _{1 1 2} } _m {(CH ₃ ) ₂ SiO} _l {(CH ₃ ) SiO _3/2 } _o
(Where m + l + o = 1 and m, l and o are non-zero numbers), and the MDTQ resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _{1/2} m {SiO 2} n} {(CH 3) 2 SiO} l {(CH 3) SiO 3/2} o
(Where m + n + l + o = 1, and m, n, l and o are non-zero numbers). The DQ resin has an average structural formula represented by the following formula {SiO ₂ } _n {(CH ₃ ) ₂ SiO} _l
(Where n + 1 is 1 and n and l are non-zero numbers), and the DTQ resin has an average structural formula of the following formula {SiO ₂ } _n {(CH ₃ ) ₂ SiO} _l {(CH ₃ ) SiO _3/2 } _o
(Where n + l + o = 1 and n, l and o are non-zero numbers), and the TQ resin has an average structural formula represented by the following formula {SiO ₂ } _n {( CH ₃ ) SiO _3/2 } _o
(In the formula, n + o = 1, and m and o are non-zero numbers).

  As for the weight average molecular weight of (F), 2000-100000 are preferable, More preferably, it is 5000-80000, More preferably, it is 10000-60000. Here, the weight average molecular weight is a value obtained by using polystyrene as a calibration curve by gel permeation chromatographic analysis (GPC).

  (F) can be used at 120 parts by weight or less with respect to 100 parts by weight of (A), and is preferably 1 to 120 parts by weight, and 2 to 100 parts by weight from the viewpoint of improving the adhesion to the substrate. Part is more preferable, and 3 to 80 parts by weight is still more preferable.

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

  The composition of the present invention may further contain (G) a polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom and having a viscosity of 5 to 10000 cP at 23 ° C. from the viewpoint of improving curability.

  In (G), the number of mercaptoalkyl groups bonded to silicon atoms in 1 minute 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 and 10 or less are preferable, and more preferably 3 to 7.

  In (G), the alkyl portion of the mercaptoalkyl group bonded to the silicon atom can be a C1-C6 alkyl group. Examples of 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.

  In (G), the organic group other than the mercaptoalkyl group bonded to the silicon atom may be a substituted or unsubstituted monovalent hydrocarbon group (provided that it is not an aliphatic unsaturated group). . Specifically, an alkyl group, such as a C1-C6 alkyl group (for example, methyl, ethyl, propyl, etc.); a cycloalkyl group, such as a C3-C10 cycloalkyl group (for example, cyclohexyl, etc.); an aryl group, for example, C6-C12 Aryl (eg, phenyl, tolyl, xylyl, etc.); aralkyl group, eg, C7-C13 aralkyl group (eg, 2-phenylethyl, 2-phenylpropyl, etc.); substituted hydrocarbon group, eg, halogen-substituted hydrocarbon group (eg, Chloromethyl, chlorophenyl, 3,3,3-trifluoropropyl, etc.). An alkyl group is preferable from the viewpoint of easiness of synthesis and the like, and 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 (G) may be linear, branched or cyclic, and is preferably branched. For example, 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 (wherein R ″ is independently , Which represents an unsubstituted or substituted monovalent hydrocarbon group (which is not an aliphatic unsaturated group), and 2 or more and 20 or less R ″ per molecule is a mercaptoalkyl group And a branched organopolysiloxane containing a mercaptoalkyl group, and examples of the mercaptoalkyl group and the unsubstituted or substituted monovalent hydrocarbon group include the above-described groups. "in, R in any unit" may also be present as, preferably R exists as "R a SiO _3/2 units". mercaptoalkyl group and unsubstituted or monovalent substituted hydrocarbon 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 not containing a mercaptoalkyl group is 1: Although the thing of 60-1: 25 is preferable, it is not limited to this.

  In (G), the viscosity at 23 ° C. is 5 to 10,000 cP. From the viewpoint of workability and refractive index, for example, the viscosity can be 5 to 5000 cP. From the viewpoint of workability, the viscosity is preferably low, and the viscosity at 23 ° C. can be, for example, 5 to 1000 cP, and more preferably 5 to 400 cP.

The number of mercapto groups in (G) 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.

  (G) is preferably highly transparent. As an index of transparency, at 23 ° C., when (A) was filled in a container, and the transmittance at a 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 preparation method of (G) is not particularly limited. For example, 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.

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

  (G) is preferably an amount such that the mercapto group is 0.05 to 1, more preferably 0.1 to 1 with respect to the number of (meth) acrylic functional groups contained in (A) and (B). It is a certain amount.

  In the composition of the present invention, a silane coupling agent (excluding (E)), a polymerization inhibitor, an antioxidant, and an ultraviolet absorber that is a light-resistant stabilizer, as long as the effects of the present invention are not impaired. Additives such as light stabilizers can be blended.

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

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

  Antioxidants 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-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, 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- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenol-based 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), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4- Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5,5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium Diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5- Triazine-2-ylamino) phenol and the like although not limited thereto. The said antioxidant may be individual or may use 2 or more types together.

  The light stabilizer can be used to prevent photo-oxidative deterioration 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) -Yl) -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 the like triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. 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. As the light stabilizer, 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. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (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 preferably contains no inorganic filler from the viewpoint of obtaining a desired E hardness.

  From the viewpoint of workability when the composition of the present invention is applied between the image display part and the protective part, the viscosity at 23 ° C. is preferably 50 to 10,000 cP, and preferably 70 to 9000 cP. Is more preferable, and it is still more preferable that it is 100-7000 cP.

  The composition of the present invention can be obtained by blending (A) to (C) and optional components (D) to (G) and additives. Specifically, for example, in a room where foreign matter in the air is managed, such as a clean room, component A, component B, and component F, if necessary, are placed in a 5 L universal mixing stirrer equipped with a vacuum degassing device. (10 to 30 ° C.), uniformly mixed at low speed for 30 minutes, and thereafter, components C, D and E, which are a small amount of additives in a room from which ultraviolet rays such as yellow room are removed, polymerization inhibitors, etc. Under ice-cooling (10 ° C. or lower), uniformly mixed at low speed for 30 minutes at low pressure, defoamed, and then filtered using a membrane filter having fine pores of 10 μm or less. Can be prepared.

The composition of the present invention can be cured by irradiation with ultraviolet rays. Examples of the lamp in the wavelength range of the reactive range of (C) include, for example, a high pressure mercury lamp (UV-7000), metal halide lamp (MHL-250, MHL-450, MHL-150, MHL-) manufactured by USHIO INC. 70), Korea: JM tech metal halide lamp (JM-MTL 2KW), Mitsubishi Electric Corporation ultraviolet irradiation lamp (OSBL360), Nippon Battery Co., Ltd. ultraviolet irradiation machine (UD-20-2), stock Examples include fluorescent lamps (FL-20BLB) manufactured by Toshiba Corporation, H bulbs, H plus bulbs, D bulbs, Q bulbs, M bulbs, etc. manufactured by Fusion. Irradiation dose is preferably 100~12000mJ / cm ^2, more preferably 300~8000mJ / cm ^2, more preferably from 500~6000mJ / cm ^2.

The cured product of the composition of the present invention has the following suitable physical properties.
[Visible light transmittance after curing]
Since the visible light transmittance after curing at a cured thickness of 150 μm can be 95% or more, the composition of the present invention is preferable from the viewpoint of visibility. 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.

[Curing shrinkage]
Since 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.

[E hardness after curing]
Since the composition according to the present invention can have an E hardness after curing of 1 to 50, when applied to an image display device, it can easily moderate stress from the outside, and has a high temperature. It is preferable in that visibility can be ensured by preventing moisture penetration even under high humidity. The E hardness is preferably 1 to 40.

[Elongation after curing]
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.

[Storage modulus after curing]
The composition of the present invention has a ratio of storage elastic modulus MS (T) in a temperature range of −50 ° C. to 100 ° C. to storage elastic modulus G ′ (23) at 23 ° C. after curing (G ′ (T) / G ′ (23)) can be preferably 0.1 to 30, which is preferable in that the temperature change of the cured product is suppressed. The ratio (G ′ (T) / G ′ (23)) of the storage elastic modulus MS (T) is preferably 0.5 to 10.

[Loss modulus after curing]
The composition of the present invention has a ratio (G ″ (T) / G) of storage elastic modulus M ₁ (T) in a temperature range of −50 ° C. to 100 ° C. to loss elastic modulus G ″ (23) at 23 ° C. after curing. "(23)) can be 0.05 to 300, which is preferable in that the temperature change of the cured product is suppressed, and the penetration of moisture under high temperature and high humidity is suppressed. Storage elastic modulus M _l (T) The ratio (G ″ (T) / G ″ (23)) is preferably 0.1 to 150.

The composition of the present invention can be suitably used in an image display device, and is particularly preferable as a resin interposed between a protective portion and an image display portion of a flat panel type image display device.
Specifically, after applying the composition of the present invention on a protective panel constituting a transparent protective part formed of optical plastic or the like, the image display panel constituting the image display part is laminated and irradiated with ultraviolet rays. be able to. The protective panel may be provided with a step for preventing the composition of the present invention from flowing out at the outer peripheral edge.

  The composition of the present invention is liquid and excellent in coatability, does not cause display defects due to deformation of the image display portion, and does not deteriorate visibility, enabling display with high brightness and high contrast. An ultraviolet curable resin can be provided. 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, more preferably 7 to 80 inches, and still more preferably 10 to 60 inches. It is suitable for manufacturing an ultra-thin image display device having a thickness of preferably 10 to 500 μm, more preferably 20 to 450 μm, and even more preferably 50 to 400 μm.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise indicated, parts and% represent parts by weight and% by weight. The present invention is not limited by these examples. Curing of each composition prepared in Examples and Comparative Examples was performed at 120 w / cm ² using a high pressure mercury lamp: UVL-4001M manufactured by USHIO INC.

[Evaluation conditions for physical properties]
(1) E hardness after curing High-pressure mercury lamp manufactured by USHIO INC .: Using UVL-4001M, a sample with a thickness of 2 mm was prepared by irradiation with predetermined ultraviolet rays at 120 w / cm ² , in accordance with JIS K 6253 E. The E hardness of the cured product at 23 ° C. was measured with DUROMETER HARDNESS TYPE E (manufactured by ASKER).

(2) Tensile strength after curing USHIO INC. High-pressure mercury lamp: UVL-4001M was used to prepare a sample with a thickness of 2 mm by irradiation with predetermined ultraviolet rays at 120 w / cm ² , in accordance with JIS K 6301. The tensile strength of the sample at 23 ° C. was measured with an autograph (manufactured by Shimadzu Corporation).

(3) Elongation after curing High-pressure mercury lamp manufactured by USHIO INC .: Using UVL-4001M, a sample with a thickness of 200 μm was prepared by irradiating with a predetermined ultraviolet ray at 120 w / cm ² , in accordance with JIS K 6301, autograph The elongation of the cured product at 23 ° C. was measured (manufactured by Shimadzu Corporation).

(4) Viscosity Using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.), No. Using 4 rotors, the viscosity at 23 ° C. was measured at 60 rpm.

(5) Transmittance High pressure mercury lamp manufactured by Ushio Electric Co., Ltd .: Using UVL-4001M, a sample having a thickness of 200 μm was prepared by irradiation with predetermined ultraviolet rays at 120 w / cm ² and measured with the above spectrophotometer.

(6) Cloudiness High-pressure mercury lamp manufactured by Ushio Electric Co., Ltd .: Using a UVL-4001M, a sample having a thickness of 200 μm was prepared by irradiation with predetermined ultraviolet rays at 120 w / cm ² , and the sample was 500 at a temperature of 85 ° C. and a humidity of 85%. After being stored for a period of time, it was returned to a state of 23 ° C. and humidity 50% and measured with a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105.

(7) Curing Shrinkage The specific gravity before and after curing of the composition was measured with an electronic hydrometer (SD-120L manufactured by MIRAGE), and calculated from the difference in specific gravity of both from the following formula.
Curing shrinkage (%) = (volume before curing−volume after curing) / volume before curing × 100
Volume before curing = 1 / Specific gravity before curing Volume after curing = 1 / Specific gravity after curing

(8) Discoloration at high temperature After leaving the cured product for 500 hours in a constant temperature and humidity layer set to a high temperature and humidity condition of 85 ° C. and humidity 85% RH, using a spectrophotometer (CM-3500d manufactured by Minolta Co., Ltd.) Then, after returning to a temperature of 23 ° C. and a humidity of 50%, evaluation was performed using a yellow index which is an index of the degree of discoloration.

(9) Cohesive failure rate (9-1) vs. acrylic On each adherend (PMMA) having a width of 25 mm, the composition is applied to a thickness of 0.1 mm so that the thickness is 0.1 mm and the length is 10 mm or more. After a tempered glass plate having a thickness of 2 mm and a width of 25 mm was stacked so that the stacking width was 10 mm, the sample was cured at a predetermined ultraviolet energy irradiation amount to prepare a sample.
Immediately after sample preparation, 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.
Obtain the area Smm ² of the peeled portion of the ultraviolet curable resin composition on the adherend,
(100 × S) / (10 × 25)
Was calculated as the cohesive failure rate (%).
(9-2) Glass to glass The adherend was changed to glass, and the cohesive failure rate was determined in the same manner as in (9-1).
(9-3) Anti-polarizing plate As the polarizing plate, a polarizing film for liquid crystal having a width of 25 mm (product name: SEG1425DU, manufactured by Nitto Denko Corporation), an anti-glare-treated film (product name: AG 150, manufactured by Nitto Denko Corporation), and anti-reflection treatment were performed. A film (product name: ARS type manufactured by Nitto Denko Corporation) was prepared. 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. After that, the sample was cured by curing with a predetermined ultraviolet energy irradiation amount. About the sample immediately after sample preparation and 2 hours later, 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.
Obtain the area Smm ² of the peeled portion of the ultraviolet curable resin composition on the adherend,
(100 × S) / (10 × 25)
Was calculated as the cohesive failure rate (%).

(10) Curability A high pressure mercury lamp manufactured by Ushio Electric Co., Ltd .: A sample was prepared in the same manner as in (1) except that UVL-4001M was used and a predetermined ultraviolet irradiation amount was set at 120 w / cm ² . Hardness was measured.

(11) Point-push test A glass plate for a 3.5-inch display with a thickness of 0.6 mm (diagonal length of the image display portion is 3.5 inches) and 0.4 mm so that the thickness of the composition is 200 μm. A sample was prepared by coating between PMMA plates for a thick 3.5 inch display (diagonal length of the image display portion is 3.5 inches) and curing at a predetermined ultraviolet energy dose.
Twenty-four hours after the end of UV irradiation, a metal rod having a semicircular tip with a diameter of 10 mm at one central part with a PMMA (polymethyl methacrylate) plate side of the sample facing upward is 7.5 mm / min. The sample was pressurized with a pressure until the load reached 20 kgf / cm ² .
By this pressurization, when a fine crack enters the glass plate, PMMA plate or cured composition at the pressurization location, 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 cracks are confirmed on the appearance of the pressurized part,
△, if peeling is confirmed on the appearance of the pressurized part,
If there is no change in the appearance of the pressurized part, it is marked as ◯.

(12) Storage elastic modulus and loss elastic modulus after curing About the cured product having a thickness of 2 mm, the storage elastic modulus and loss elastic modulus were measured at a measurement frequency of 120 Hz using a viscoelasticity measuring device (RSA3 manufactured by TA Instruments).

(13) Crack resistance (13-1) Crack resistance under heat shock It was applied between a 1 mm thick glass plate and a 1 mm thick PMMA plate so that the thickness of the composition was 200 μm, and predetermined ultraviolet energy irradiation was performed. After being cured in an amount, an environmental test was performed in a temperature cycle from -50 ° C. to 125 ° C. (each temperature was kept for 30 minutes) (device name: TSA-71S-A manufactured by Espec Corp.).
Then, after returning to the state of 23 degreeC, the state of hardened | cured material, PMMA, and glass was observed with the optical microscope (10 time).
The cured product has a crack 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. If NG,
The case where these cracks, air layers, and damage were not recognized at all was determined to be OK.
(13-2) Crack resistance under high temperature and high humidity After leaving the cured product in a constant temperature and high humidity layer set at a high temperature and high humidity of 85 ° C. and humidity 85% RH, a spectrophotometer (Minolta Co., Ltd.) After returning to a temperature of 23 ° C. and a humidity of 50% by CM-3500d), the state of the cured product, PMMA, and glass was observed with an optical microscope (10 times) and evaluated in the same manner as (13-1).

Each component in Examples and Comparative Examples is as follows. The weight average molecular weight is a value obtained by using polystyrene as a calibration curve by gel permeation chromatography (GPC).
( ^A1 ) MD ^A ₃ D ^Ph D ₁₂ M
(A2) M ^A D ₇₀ M _A
( ^A3 ) M ^A D ₁₀ M _A
(A4) M ^A D ₄ M _A
(B1) T ^A ₂ T ^Ph D ₁₂ M Weight average molecular weight: 2220
(B2) T ^A D ^Ph D ₃₀ Weight average molecular weight: 2080
(B3) T ^A D ^Ph D ₁₀ Weight average molecular weight: 850
(B4) T ^A D ₁₀ M Weight average molecular weight: 750
_{^{(B5) T A T 2 D}} 10 M weight average molecular weight: 3080
(C-1) 2-hydroxy-2-methyl-1-phenyl-propan-1-one (c-2) 2,2-dimethoxy-1,2-diphenylethane-1-one (c-3) 2- Hydroxy-4-octoxybenzophenone (c-4) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (d-1) methoxyethyl acrylate (d-2) methoxyethyl methacrylate (e-1) γ-methacrylate Roxypropyltrimethoxysilane (e-2) γ-methacryloxypropylmethyldimethoxysilane (f1) MQ resin:
Average structural formula: {(CH ₃ ) ₃ SiO _1/2 } {SiO ₂ } _3.5
Weight average molecular weight: 52,000
Into a 3 L separable flask equipped with a cooling reflux tube and a three-one motor as a stirrer, 293 g of hydrochloric acid was charged, the temperature in the flask was adjusted to -5 ° C to 2 ° C, and 440 g of water was charged while stirring. 308 g of glass No. 3 (S40 sodium silicate No. 3) is dropped over 1 hour. Next, 316 g of isopropyl alcohol is charged into the flask to form a hydrosol. Thereafter, a mixture of 128 g of trimethylchlorosilane and 139 g of xylene was dropped within about 10 minutes, and the temperature in the flask was stirred at -5 ° C to 2 ° C for 1 hour. Next, the temperature was raised to about 80 ° C., and then heated to reflux at 80 ° C. for 2 hours. Next, after adding 24 g of xylene, the mixture was stirred for 30 minutes, allowed to stand for 30 minutes, and liquid separation was performed. Thereafter, dehydration and desorption were performed at 125 to 140 ° C., and the nonvolatile content was measured. The nonvolatile content was 58%. The MQ resin thus obtained was mixed with the components (a1) to (a4) used in each of the examples and comparative examples, and used after removing xylene.
(G1) Mercaptopropyl group-containing polymethylsiloxane:
{(CH ₃ ) ₃ SiO _1/2 } ・ {HS (CH ₂ ) ₃ SiO _3/2 } ₅・ {(CH ₃ ) ₂ SiO _2/2 } ₆₀
Viscosity: 230 cP
Number of mercapto groups per unit weight: 0.98 mmol / g
(G2) Mercaptopropyl group-containing polymethylsiloxane:
{(CH ₃ ) ₃ SiO _1/2 } ・ {HS (CH ₂ ) ₃ SiO _3/2 } ₅・ {(CH ₃ ) ₂ SiO _2/2 } ₆
Viscosity: 160 cP
Number of mercapto groups per unit weight: 4.3 mmol / g
Polymerization inhibitor 1: pt-butylcatechol polymerization inhibitor 2: p-methoxyphenol

Ｄ：（ＣＨ_３）_２ＳｉＯ
Ｄ^Ｐｈ：（Ｃ_６Ｈ_５）_２ＳｉＯ
Ｄ^Ａ

Ｔ：（ＣＨ_３）ＳｉＯ_３／２
Ｔ^Ａ：

Ｔ^Ｐｈ：（Ｃ_６Ｈ_５）ＳｉＯ_３／２ here,
M: (CH ₃ ) ₃ SiO _1/2
M ^A :

D: (CH ₃ ) ₂ SiO
D ^Ph : (C ₆ H ₅ ) ₂ SiO
D ^A

T: (CH ₃ ) SiO _3/2
T ^A :

T ^Ph : (C ₆ H ₅ ) SiO _3/2

Example 1:
Among the components shown in Table 1, the components except for (c1) were placed in a 5 L universal mixing stirrer (manufactured by Dalton) and mixed uniformly at room temperature (23 ° C.) for 30 minutes. After mixing uniformly, (c1) was further added, and the mixture was uniformly mixed under cooling with reduced pressure under cooling with ice water (8 ° C.) for 30 minutes. After removing foreign matters and the like from the obtained composition with a 10 μm membrane filter, a composition was obtained. Each characteristic was measured about the obtained composition.

  About each Example and the comparative example, the composition of Table 1 and 2 was mix | blended like Example 1, and the characteristic was measured about the obtained composition. However, the comparative example 2 is SVR1100 (Sony Chemical & Information Device Co., Ltd.) which is a commercially available ultraviolet curable acrylic resin. The measurement results of each characteristic are shown in Tables 3-8.

  In the examples, a cured product was obtained in which shrinkage during curing was suppressed, discoloration was difficult even at high temperatures, and the fluctuation range of the elastic modulus due to temperature change was small. Moreover, sclerosis | hardenability improved by mix | blending a mercaptoalkyl-group containing polyorganosiloxane.

  According to the ultraviolet curable silicone resin composition of the present invention, it is possible to obtain a cured product in which shrinkage at the time of curing is suppressed, discoloration is difficult even at high temperatures, and further, the fluctuation range of the elastic modulus due to temperature change is small. It is suitable for manufacturing.

Claims (9)

(A) Formula (I):

(Where
R is independently a C1-C6 alkyl group, a C6-C12 aryl group or formula (II):

(Wherein R _a is independently a hydrogen atom or a methyl group;
Q ₁ is independently a group represented by a C1-C5 alkylene group,
At least one R is a group of formula (II);
n is 0-600)
A linear polyorganosiloxane represented by
(B) Average formula (III);

(Where
R _b is independently a hydrogen atom or a methyl group,
Q ₂ is independently a C1-C5 alkylene group,
R ¹ is independently a C1-C6 alkyl group or a C6-C12 aryl group,
R ² is independently a C1-C6 alkyl group or a C6-C12 aryl group,
R ³ is independently a C1-C6 alkyl group or a C6-C12 aryl group,
p is 1 to 10,
q is 0 to 10,
r is 0-100,
s is 0-10,
p / (p + q + r + s) ≧ 0.02)
An ultraviolet curable silicone resin composition comprising: a branched polyorganosiloxane represented by: and (C) a photoinitiator.   The ultraviolet curable silicone resin composition according to claim 1, comprising 5 to 250 parts by weight of component (B) and 0.1 to 5 parts by weight of component (C) with respect to 100 parts by weight of component (A).   The ultraviolet curable silicone resin composition according to claim 1 or 2, wherein the component (A) is a linear polyorganosiloxane having groups represented by the formula (II) at both ends.   Furthermore, the ultraviolet curable silicone resin composition of any one of Claims 1-3 containing (D) (meth) acrylate.   Furthermore, the ultraviolet curable silicone resin composition of any one of Claims 1-4 containing (E) (meth) acryloxy group containing silane.   Furthermore, the ultraviolet curable silicone resin composition of any one of Claims 1-5 containing the (F) silicone resin type | system | group adhesive improvement agent (however, an aliphatic unsaturated group and a mercapto group shall not be included). object.   Furthermore, (G) UV curable silicone resin of any one of Claims 1-6 containing the polyorganosiloxane containing the mercaptoalkyl group couple | bonded with a silicon atom whose viscosity in 23 degreeC is 5-10000 cP. Composition.   The sealing compound for image display apparatuses which consists of an ultraviolet curable silicone resin composition in any one of Claims 1-7.   An image display device in which an image display unit and a protection unit are sealed using the sealant for an image display device according to claim 8.