JP2021116347A - Radical curable composition and cured product - Google Patents

Abstract

To provide a radical curable composition which can be cured at a low temperature.SOLUTION: There is provided a radical curable composition which comprises (A) a (meth)acrylic group-containing compound having a skeleton composed of an addition reaction product of (a) an Si-H group-containing compound represented by the following formula (1) and (b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule and a (meth)acrylic group at one or both molecular terminals and (B) a polymerization initiator. (wherein, R1 each independently represents a substituted or non-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms containing no addition-reactive carbon-carbon double bond or an alkoxy group having 1 to 6 carbon atoms, R2 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)SELECTED DRAWING: None

Description

The present invention relates to radically curable compositions and cured products.

Light emitting diodes (LEDs) are characterized by low power consumption, long life, design, etc. against the background of remarkable improvement in luminous efficiency, and are not limited to in-vehicle fields such as liquid crystal display (LCD) backlights and car headlights. The market is expanding rapidly even for general lighting. Such an LED light has a configuration in which an LED element mounted on a substrate is sealed with a sealing material made of a transparent resin. As a sealing material for sealing this LED, an addition-curing silicone composition is widely used because it has excellent heat resistance (Patent Document 1). However, since the sealing material made of the silicone composition has a low gas barrier property, the silver electrode may be discolored due to the intrusion of corrosive gas from the outside, and the brightness of the LED may be lowered.

Therefore, a sealing material for an optical element using an organically modified addition-curable silicone composition having a polycyclic hydrocarbon skeleton has been proposed. Since the sealing material obtained from such a composition has a high gas barrier property, it is possible to prevent the invasion of corrosive gas from the outside and suppress the discoloration of the silver electrode (Patent Documents 2 and 3).

In recent years, as a wavelength conversion material, quantum dots having excellent wavelength conversion efficiency have been attracting attention. Since quantum dots are sensitive to moisture, they must be sealed with a material with high gas barrier properties. On the other hand, quantum dots often contain a catalytic poison of an addition reaction, and when an addition-curing composition is used as a binder material for the quantum dots, curing defects may occur. Further, since quantum dots have low heat resistance, it is difficult to withstand the curing conditions of an addition-curable material.

Japanese Unexamined Patent Publication No. 2004-292714 Japanese Unexamined Patent Publication No. 2008-069210 Japanese Unexamined Patent Publication No. 2012-046604

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a radical-curable composition that can be cured at a low temperature.

（式中、Ｒ^１は、それぞれ独立に、付加反応性炭素−炭素二重結合を含まない、置換または非置換の炭素原子数１〜１２の１価炭化水素基、または炭素原子数１〜６のアルコキシ基であり、Ｒ^２は、置換または非置換の炭素原子数１〜１２の２価炭化水素基を表す。）
（Ｂ）重合開始剤
を含有するものであることを特徴とするラジカル硬化型組成物を提供する。 In order to solve the above problems, in the present invention, one molecule of (A) (a) a Si—H group-containing compound represented by the following formula (1) and (b) an addition-reactive carbon-carbon double bond A (meth) acrylic group-containing compound having a skeleton consisting of an addition reaction product with two polycyclic hydrocarbons contained therein and having a (meth) acrylic group at the end of one or both molecules, and a compound containing a (meth) acrylic group.

(In the formula, R ¹ is an independently substituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or 1 to 6 carbon atoms, which does not contain an addition-reactive carbon-carbon double bond. an alkoxy group, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(B) Provided is a radical curable composition characterized by containing a polymerization initiator.

The radically curable composition of the present invention can be cured at a low temperature.

（式中、Ｒ^１は、上記と同じ意味を表し、Ｒ^３は、水素原子またはメチル基のいずれかであり、Ｒ^４は、置換または非置換の炭素原子数１〜８の二価炭化水素基である。） The radical-curable composition of the present invention comprises a silicon-containing addition reaction product in which the component (A) has two addition-reactive carbon-carbon double bonds in one molecule, and (c) the following formula (2). A (meth) acrylic radical-containing compound which is an addition reaction product with a siloxane compound represented by.
It is preferable that the silicon-containing addition reaction product is (a) an addition reaction product of the Si—H group-containing compound and (b) the polycyclic hydrocarbon.

(In the formula, R ¹ has the same meaning as above, R ³ is either a hydrogen atom or a methyl group, and R ⁴ is a substituted or unsubstituted divalent hydrocarbon having 1 to 8 carbon atoms. It is a group.)

Such a radical curable composition is more excellent in curability.

In the radical curable composition of the present invention, the polycyclic hydrocarbons are 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2. -Any of the en, or a combination thereof, is more preferable.

With such a radical curable composition, a cured product having excellent hardness, crack resistance, heat resistance, and gas barrier property can be obtained.

（式中、Ｒ^３は、水素原子またはメチル基のいずれかであり、ｎ＝０〜１０である。） In the radical curable composition of the present invention, it is more preferable that the component (A) is a compound represented by the following formula (3).

(In the formula, R ³ is either a hydrogen atom or a methyl group, and n = 0 to 10.)

With such a radical curable composition, a cured product having more excellent hardness, crack resistance, heat resistance, and gas barrier property can be obtained.

In the radical curable composition of the present invention, it is preferable that the polymerization initiator is an organic peroxide or a photopolymerization initiator.

Such a polymerization initiator can cure the composition of the present invention more effectively.

In this case, it is more preferable that the organic peroxide has a 10-hour half-life temperature of 50 to 150 ° C.

Such an organic peroxide is excellent in storage stability and curability controllability of the composition.

The present invention also provides a cured product of the radical curable composition.

Since the cured product of the present invention has excellent transparency and good hardness, it is useful for applications such as encapsulants and filters for optical elements.

Since the radical-curable silicone composition of the present invention can be cured at a low temperature by radical curing, it is useful as a binder material for quantum dots, and is a cured product obtained by curing the radical-curable composition of the present invention. Has excellent transparency and good hardness, and is therefore useful for applications such as encapsulants for LED elements and wavelength conversion filters.

As a result of diligent studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved if the radical-curable composition containing the components (A) and (B) described later is used, and the present invention is completed. I let you.

（式中、Ｒ^１は、それぞれ独立に、付加反応性炭素−炭素二重結合を含まない、置換または非置換の炭素原子数１〜１２の１価炭化水素基、または炭素原子数１〜６のアルコキシ基であり、Ｒ^２は、置換または非置換の炭素原子数１〜１２の２価炭化水素基を表す。）
（Ｂ）重合開始剤
を含有するものであることを特徴とするラジカル硬化型組成物である。 That is, the present invention
(A) (a) A Si—H group-containing compound represented by the following formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule. A (meth) acrylic group-containing compound having a skeleton consisting of an addition reaction product and having a (meth) acrylic group at one or both molecular ends, and

(In the formula, R ¹ is an independently substituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or 1 to 6 carbon atoms, which does not contain an addition-reactive carbon-carbon double bond. an alkoxy group, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(B) A radical-curable composition characterized by containing a polymerization initiator.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[Radical curable composition]
The radically curable composition of the present invention contains the components (A) and (B) described later as essential components. This composition may further contain any component other than the essential component, if necessary.

Hereinafter, each component will be described in detail.

（式中、Ｒ^１は、それぞれ独立に、付加反応性炭素−炭素二重結合を含まない、置換または非置換の炭素原子数１〜１２の１価炭化水素基、または炭素原子数１〜６のアルコキシ基であり、Ｒ^２は、置換または非置換の炭素原子数１〜１２の２価炭化水素基を表す。） [(A) component]
The component (A) is a polycyclic hydrocarbon having (a) a Si—H group-containing compound represented by the following formula (1) and (b) two addition-reactive carbon-carbon double bonds in one molecule. It is a (meth) acrylic group-containing compound having a molecular chain composed of an addition reaction product with hydrogen and having a (meth) acrylic group at one end or both ends of the molecular chain. Such a (meth) acrylic group-containing compound has a skeleton composed of (a) an addition reaction product of the Si—H group-containing compound and (b) the polycyclic hydrocarbon, and (meth). ) It has an acrylic group at the end of one or both molecules.
In the present invention, the term "addition reactivity" means a property that allows an addition reaction with a hydrogen atom bonded to a silicon atom by a well-known hydrosilylation reaction.

(In the formula, R ¹ is an independently substituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or 1 to 6 carbon atoms, which does not contain an addition-reactive carbon-carbon double bond. an alkoxy group, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

（式中、Ｒ^１、Ｒ^２は上記の通りである。） <(A) component>
The component (a) is a Si—H group-containing compound represented by the following formula (1).

(In the formula, R ¹ and R ² are as described above.)

Specific examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n. Alkyl groups having 1 to 12 carbon atoms such as −hexyl, n-octyl, n-decyl, cyclopentyl and cyclohexyl groups; aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; tolyl, xsilyl, ethylphenyl, Alkylaryl groups having 7 to 12 carbon atoms such as propylphenyl, butylphenyl, pentylphenyl and hexylphenyl groups; and aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl groups can be mentioned.

Specific examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, and n-hexyloxy. , Cyclopentyloxy, cyclohexyloxy group and the like.

Among these, R ^1, preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group.

On the other hand, ^{specific examples of the divalent hydrocarbon group having 1 to 12 carbon atoms of R 2} include carbons such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and decamethylene groups. Linear, branched or cyclic alkylene group having 1 to 12 atoms; arylene group having 6 to 12 carbon atoms such as phenylene, biphenylene and naphthylene group, and phenylene methylene, methylene phenylene methylene group having 7 to 12 carbon atoms. Examples include an aralkylene group.

Among these, an arylene group having 6 to 12 carbon atoms is preferable, and a phenylene group is more preferable.

Specific examples of the component (a) include those represented by the following formulas, but are not limited thereto. Me represents a methyl group.

The compound represented by the formula (1) may be used alone or in combination of two or more.

<(B) component>
The component (b) is a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule.

Examples of the polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds of the component (b) in one molecule include (i) carbon atoms forming the skeleton of the polycyclic hydrocarbon. An addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and (ii) a hydrogen atom bonded to a carbon atom forming the backbone of a polycyclic hydrocarbon is an addition reaction. Addition-reactive carbon-carbon between two adjacent carbon atoms among the carbon atoms substituted by the sex carbon-carbon double bond-containing group and the carbon atoms forming the framework of (iii) polycyclic hydrocarbons. Those in which a double bond is formed and the hydrogen atom bonded to the carbon atom forming the backbone of the polycyclic hydrocarbon is replaced by an addition-reactive carbon-carbon double bond-containing group, etc. Can be used.

Specific examples of the polycyclic hydrocarbon are 5-vinylbicyclo [2.2.1] hept-2-ene represented by the following formula (3) and 6-vinylbicyclo represented by the formula (4). [2.2.1] Hept-2-ene and the like can be mentioned, and these can also be used as a mixture (hereinafter, when it is not necessary to distinguish between them, they may be collectively referred to as "vinyl norbornene").

The vinyl group substitution position of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type), and the difference in these arrangements may cause the reactivity of the compound to be particularly different. Since there is no difference, it may be a combination of isomers of both configurations.

Specific examples of the polycyclic hydrocarbon other than vinylnorbornene include dicyclopentadiene and its derivatives.

（式中、Ｒ^１は上記と同じ意味を表し、ｎ＝０〜１０である。） The addition reaction product of the component (a) and the component (b) is not particularly limited, but is preferably represented by the following formula (5), and in particular, the following in which R ¹ is a methyl group. The one represented by the formula (6) is more preferable.

(In the formula, R ¹ has the same meaning as above, and n = 0 to 10.)

（式中、Ｒ^１、ｎは上記と同じである。） The skeleton composed of the addition reaction product of the component (a) and the component (b) is composed of a divalent residue having a bond derived from the addition-reactive carbon-carbon double bond. For example, the skeleton composed of the addition reaction product represented by the above formula (5) is represented by the following formula.

^{(Wherein, R} 1, n are as defined above.)

Such a compound having an addition reaction product containing a polycyclic hydrocarbon and a phenylene group as a main skeleton can be particularly preferably used because it gives a cured product having excellent hardness, crack resistance, and heat resistance.

The addition reaction product of the component (a) and the component (b) can be synthesized, for example, by the method described in JP-A-2005-133073.

As an example, by adding reaction of the component (b) to 1 mol of the component (a) in an amount of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less in the presence of a hydrosilylation reaction catalyst. Can be prepared.

In this case, known hydrosilylation reaction catalysts can be used, and specific examples thereof include carbon powder carrying a platinum metal, platinum black, second platinum chloride, platinum chloride acid, and platinum chloride acid. Examples thereof include reaction products with monovalent alcohols, complexes of platinum chloride acid and olefins, platinum-based catalysts such as platinum bisacetoacetate; platinum-based metal catalysts such as palladium-based catalysts and rhodium-based catalysts. The addition reaction conditions, the use of the solvent, and the like are not particularly limited and may be as known.

In the above reaction, an excess molar amount of the polycyclic hydrocarbon (b) is reacted with the compound represented by the formula (a) (1), so that the addition reaction product of the component (A) is (b). ) It is possible to have two addition-reactive carbon-carbon double bonds derived from polycyclic hydrocarbons in one molecule.

（式中、Ｒ^１は、上記と同じ意味を表し、Ｒ^３は、水素原子またはメチル基のいずれかであり、Ｒ^４は、置換または非置換の炭素原子数１〜８の二価炭化水素基である。） <Ingredient (c)>
The component (A) is, for example, one of two addition-reactive carbon-carbon double bonds (at both ends) present in one molecule of the addition reaction product of the component (a) and the component (b). , Or both, and (c) the SiH group of the siloxane compound represented by the following formula (2) can be obtained by hydrosilylation reaction.

(In the formula, R ¹ has the same meaning as above, R ³ is either a hydrogen atom or a methyl group, and R ⁴ is a substituted or unsubstituted divalent hydrocarbon having 1 to 8 carbon atoms. It is a group.)

Further, as the component (A), first, a silicon-containing addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule was obtained by an addition reaction between the component (a) and the component (b). It can then be obtained by hydrosilylating both of the two addition-reactive carbon-carbon double bonds present at both ends of the molecule of the obtained product with the SiH group of the siloxane compound of component (c). ..
In this case, the component (A) is a silicon-containing addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, and (c) a siloxane compound represented by the above formula (2). An addition reaction product, which is a (meth) acrylic group-containing compound, wherein the silicon-containing addition reaction product is addition of (a) the Si—H group-containing compound and (b) the polycyclic hydrocarbon. It becomes a reaction product. As the component (A) of the present invention, a (meth) acrylic group-containing compound having such a (meth) acrylic group at both molecular ends is preferable.

（式中、Ｒ^３は水素原子またはメチル基のいずれかである。） Examples of the component (c) include a siloxane compound represented by the following formula (7).

(In the formula, R ³ is either a hydrogen atom or a methyl group.)

The hydrosilylation reaction conditions, the use of the solvent, and the like are not particularly limited and may be as known.

<Ingredient (d)>
In addition, the component (A) includes one or both of the addition-reactive carbon-carbon double bonds present at both ends of the addition reaction product of the component (a) and the component (b), and (d) the following formula. It can also be obtained by hydrosilylating the SiH group of the halogen-containing siloxane compound represented by (8) and then reacting it with a hydroxyl group acrylic acid ester compound.
R ⁵ _3-m X _m SiH (8)
(In the formula, R ⁵ independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms that does not contain an addition-reactive carbon-carbon double bond, X is a halogen atom, and m is 1 or 2. Is.)

Specific examples of the halogen atom of X include chlorine, bromine, iodine and the like, and chlorine is preferable.

Specific examples of a monovalent hydrocarbon group having 1 to 6 carbon atoms that does not contain an addition-reactive carbon-carbon double bond of R ^{5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec.} Alkyl groups such as −butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl group; phenyl group is mentioned, and methyl group and phenyl group are particularly preferable.

（式中、Ｐｈはフェニル基を表す。） Specific examples of the component (d) include those represented by the following formulas, but are not limited thereto.

(In the formula, Ph represents a phenyl group.)

Examples of the hydroxyl group type acrylic acid ester compound include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and the like, and 2-hydroxyalkyl acrylate is preferable. ..

（式中、ｎ＝０〜１０である。） Preferred specific examples of the component (A) include those represented by the following formulas, but are not limited thereto.

(In the formula, n = 0 to 10.)

（式中、Ｒ^３は、水素原子またはメチル基のいずれかであり、ｎ＝０〜１０である。） As the component (A), a compound represented by the following formula (3) is particularly preferable.

(In the formula, R ³ is either a hydrogen atom or a methyl group, and n = 0 to 10.)

The component (A) can be used alone or in combination of two or more.

[(B) component]
The component (B) is a polymerization initiator that polymerizes a polymerizable functional group such as a (meth) acrylic group of the component (A), and the component (B) is an organic peroxide that generates radicals by heat, ultraviolet rays, or the like. A photopolymerization initiator that generates radicals by the light of the above can be used.

(Organic peroxide)
As the organic peroxide, an organic peroxide having a 10-hour half-life temperature of 50 to 150 ° C. is preferable from the viewpoint of controlling the storage stability and curability of the composition and the heat-resistant temperature of the quantum dots. More preferably, it is an organic peroxide at 60 to 110 ° C.

Specific examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1,1 -Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-ditetrabutylperoxy-cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane , 2,5-Dimethyl-2,5-di (t-butylperoxy) hexin, 1,6-bis (p-toluyl peroxycarbonyloxy) hexane, di (4-methylbenzoylperoxy) hexamethylenebis Examples thereof include carbonate, 2,5-dimethoxy-2,5-di (2-ethylhexanoylperoxy) hexane, and 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane.

Organic peroxides are also commercially available, for example from NOF CORPORATION. Specifically, perbutyl NHP (50.6), perhexyl PV (53.2), perbutyl PV (54.6), perloyl 355 (59.4), perloyl L (61.6), perocta O (65. 3), Perloyl SA (65.9), Perhexa 25O (66.2), Perhexyl O (69.9), Niper-PMB (70.6), Perbutyl O (72.1), Niper BMT (73.1) ), Niper BW (73.6), Perhexa MC (83.2), Perhexa TMH (86.7), Perhexa HC (87.1), Perhexa C (90.7), Pertetra A (94.7), Perhexyl I (95.0), Perbutyl MA (96.1), Perbutyl355 (97.1), Perbutyl L (98.3), Perbutyl I (98.7), Perbutyl E (99.0), Perhexyl Z (99.4), Perhexa 25Z (99.7), Perbutyl A (101.9), Perhexa 22 (103.1), Perbutyl Z (104.3), Perhexa V (104.5), Perbutyl P (119). .2), Park Mill D (116.4), Perhexyl D (116.4), Perhexa 25B (117.9), Perbutyl C (119.5), Perbutyl D (123.7), Permenta H (128.0). ), Perhexin 25B (128.4), Park Mill P (145.1) and the like. The numbers in parentheses following the compound name are the respective 10-hour half-life temperatures (unit: ° C.).

Of the above organic peroxides, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane is preferable from the viewpoint of compatibility with the component (A) and a 10-hour half-life temperature. (Perhexa® 25O, manufactured by Nichiyu Co., Ltd., 10-hour half-life temperature 66.2 ° C.).

These organic peroxides can be used alone or in combination of two or more.

The amount of the organic peroxide added may be an effective amount, but is usually 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A).

(Photopolymerization initiator)
Specific examples of the photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2. -Methyl-1-phenyl-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1 -On, phenylglycylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-) Examples thereof include morpholinophenyl) -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like.

Of the above photopolymerization initiators, 2,2-diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenyl-propane-1-one (IGM Resins) are preferable from the viewpoint of compatibility with the component (A). B.V. Omnirad 1173), Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IGM Resins B.V. Omnirad 819), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) IGM Resins B.V. Omnirad TPO H).

These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of curability.

[Other ingredients]
The radical-curable composition of the present invention contains a known antioxidant such as 2,6-di-t-butyl-4-methylphenol in order to suppress the occurrence of coloring, cloudiness, oxidative deterioration, etc. of the cured product. It may be blended. Further, in order to impart resistance to photodegradation, a light stabilizer such as a hindered amine-based stabilizer may be added. Further, if necessary, an inorganic filler such as fumed silica may be blended in order to improve the strength, or a dye, a pigment, a flame retardant or the like may be blended. An adhesive aid (silane coupling agent, etc.) may be added to improve the adhesive strength.

Further, the radical curable composition of the present invention may contain a phosphor or quantum dots as a wavelength conversion material. Quantum dots are usually particles having an average particle size of 20 nm or less, and can absorb and convert light energy. The color of light can be adjusted by changing the particle size of quantum dots. Since the band gap is determined by the size of the particle size, it is possible to obtain light with high color purity by making the particle size uniform.

Quantum dots radiate in the visible light region, and examples thereof include CdSe-based particles having shells such as CdS, ZnSe, and ZnS. Cadmium-free quantum dots such as InP, CuInS ₂ , AgInS ₂ , Te, PbS, and InAs can also be used. Any conventional quantum dot can be used in the present invention.

As described above, quantum dots generally contain a catalytic poison of an addition reaction, and if an addition-curing composition is used as a binder material for the quantum dots, curing failure may occur. Further, since quantum dots have low heat resistance, it is difficult to withstand the curing conditions of an addition-curable material.
On the other hand, since the radical-curable silicone composition of the present invention can be cured at a low temperature by radical curing, the above-mentioned problems when the addition-curable composition is used can be avoided, and it is useful as a binder material for quantum dots. Is.

[Cured product]
The present invention also provides a cured product of the radical curable composition.
The radical-curable silicone composition of the present invention can be cured at a low temperature by radical curing, and the cured product obtained by curing the radical-curable composition of the present invention has excellent transparency and good hardness. Therefore, it is useful for applications such as a sealing material for LED elements and a wavelength conversion filter.
Further, when the radical curable silicone composition of the present invention having a polycyclic hydrocarbon skeleton is used as a sealing material for an optical element, the obtained sealing material (cured product) has a high gas barrier property, so that it can be obtained from the outside. It is possible to prevent the invasion of corrosive gas. It is also useful as a material for sealing quantum dots that are sensitive to moisture.

[Curing method and conditions]
Among the radical-curable compositions of the present invention, known methods and conditions can be adopted as the curing method and curing conditions of the thermal radical curing type containing an organic peroxide. As an example, it can be cured in a nitrogen atmosphere at 70 to 150 ° C. for 10 minutes to 5 hours. In particular, when the polymerization initiator is an organic peroxide having a 10-hour half-life temperature of 50 to 150 ° C., it is preferable because it can be cured at a lower temperature.

Further, a photocurable type radical curable composition containing a photopolymerization initiator can be cured by irradiating with light such as ultraviolet rays. Examples of the light source of ultraviolet rays include UV LED lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, xenon lamps and the like. The irradiation amount (integrated light amount) of ultraviolet rays is, for example, preferably 1 to 10,000 mJ / cm ² and more preferably 10 to 10 with respect to a sheet obtained by molding the composition of the present invention into a thickness of about 2.0 mm. It is 9,000 mJ / cm ² . That is, when ultraviolet rays having an illuminance of 100 mW / cm ² are used, they can be cured by irradiating the ultraviolet rays for about 0.01 to 100 seconds.

Hereinafter, the present invention will be specifically described with reference to Examples, but these Examples do not limit the present invention in any way. In the following, the reaction products FT-IR, NMR, and GPC were measured by a conventional method, and the viscosity at 25 ° C. was measured by a B-type rotary viscometer.

[Synthesis Example 1]
Vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo [2.2.1] Hept Add 1,785 g (14.88 mol) of an isomer mixture of -2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene in approximately equal molar amounts, and 455 g of toluene, and add an oil bath. Was heated to 85 ° C.
3.6 g of carbon powder carrying a 5% mass of platinum metal was added thereto, and 1,698 g (8.75 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes with stirring. After completion of the dropping, the mixture was stirred at 110 ° C. for 24 hours and then cooled to 25 ° C. Then, the platinum metal-supported carbon was filtered off, and toluene and excess vinyl norbornene were distilled off under reduced pressure to obtain a colorless and transparent oily reaction product (ab-1) (viscosity at 25 ° C.: 12,820 mPa. s) 3,362 g was obtained.
As a result of FT-IR, NMR, and GPC analysis of the reaction product, in the following formula (9), about 41 mol% of the compound with n = 0, about 32 mol% of the compound with n = 1, and the compound with n = 2. It was a mixture of about 27 mol%. The content of the addition-reactive carbon-carbon double bond in the mixture was 0.36 mol / 100 g.

[Synthesis Example 2]
200 g of (ab-1) obtained in Synthesis Example 1 was dissolved in 100 g of toluene and 0.2 g of dibutylhydroxytoluene was added to a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. Then, it was heated to 80 ° C. using an oil bath. To this, 0.15 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5% by mass in terms of platinum) was added, and while stirring, the organohydrogen represented by the following formula (10) was added. 189.6 g of disiloxane was added dropwise. After completion of the dropping, the mixture was stirred at 95 ° C. for 2 hours, and then toluene was distilled off under reduced pressure to obtain 376.7 g of a colorless and transparent oily reaction product (A-1) (viscosity at 25 ° C.: 870 mPa · s). rice field.

[Synthesis Example 3]
Vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo [2.2.1] Hept Add 270 g (2.25 mol) of a mixture of -2-ene and 6-vinylbicyclo [2.2.1] hepto-2-ene in approximately equal molar amounts of isomers, and 2.5 g of toluene, and add an oil bath. Was heated to 85 ° C.
To this, 0.19 g of carbon powder carrying a 5% mass of platinum metal was added, and 174.5 g (0.90 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise with stirring. After completion of the dropping, the mixture was stirred at 110 ° C. for 24 hours and then cooled to 25 ° C. Then, the platinum metal-supported carbon was filtered off, and toluene and excess vinyl norbornene were distilled off under reduced pressure to obtain a colorless and transparent oily reaction product (ab-2) (viscosity at 25 ° C.: 1,710 mPa. s) 311 g was obtained.
As a result of FT-IR, NMR, and GPC analysis of the reaction product, the compound of n = 0 was about 74 mol%, the compound of n = 1 was about 21 mol%, and the compound of n = 2 was found in the above formula (9). It was a mixture of about 5 mol%. The content of the addition-reactive carbon-carbon double bond in the mixture was 0.37 mol / 100 g.

[Synthesis Example 4]
In a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 50 g of the reaction product (ab-2) obtained in Synthesis Example 3 was dissolved in 25 g of toluene, and dibutylhydroxytoluene 0. 05 g was added and heated to 80 ° C. using an oil bath. To this, 0.025 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5% by mass in terms of platinum) was added, and the organohydrogenge represented by the above formula (10) was stirred with stirring. 48.7 g of siloxane was added dropwise. After completion of the dropping, the mixture was stirred at 95 ° C. for 2 hours, and then toluene was distilled off under reduced pressure to obtain 90 g of a colorless and transparent oily reaction product (A-2) (viscosity at 25 ° C.: 530 mPa · s).

[Examples 1 to 4 and Comparative Examples 1 and 2]
The components (ab-1), (A-1), and (A-2) obtained in the above synthesis example and the component (B) below are blended in the amounts shown in Table 1 (numerical values represent parts by mass). Each was mixed to prepare a radical curable composition (thermosetting type and ultraviolet curable type).

(B) Ingredient:
(Organic peroxide)
(B-1) Perhexa (registered trademark) 25O (manufactured by NOF CORPORATION, 10-hour half-life temperature 66.2 ° C)
(Photopolymerization initiator)
(B-2) Omnirad 1173 (manufactured by IGM Resins VV)

The compositions obtained in Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 2.

[Hardness]
-The hardness of the cured product having a thickness of 2 mm prepared by heating the thermosetting composition in a hot air circulation oven at 80 ° C. for 2 hours in a nitrogen atmosphere was measured for type A hardness at 23 ° C.

-The ultraviolet curable composition is irradiated with ultraviolet light having a wavelength of 365 nm at 25 ° C. in a nitrogen atmosphere using an eye UV electronic controller (model UBX0601-01) manufactured by Eye Graphics Co., Ltd. 8,000 mJ / The hardness of the cured product having a thickness of 2 mm, which was cured by irradiating ultraviolet rays so as to be cm ^{2, was measured for type A hardness at 23 ° C.}

[Light transmittance]
-For the light transmittance of a cured product having a thickness of 2 mm produced by heating a heat-curable composition in a hot air circulation oven at 80 ° C. in a nitrogen atmosphere for 2 hours, the light transmittance of straight light having a wavelength of 400 nm at 25 ° C. The rates were measured using a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science).

-The ultraviolet curable composition is irradiated with ultraviolet light having a wavelength of 365 nm at 25 ° C. in a nitrogen atmosphere using an eye UV electronic controller (model UBX0601-01) manufactured by Eye Graphics Co., Ltd. 8,000 mJ / For the hardness of a 2 mm thick cured product that was cured by irradiating it with ultraviolet rays so that it became cm ² , the light transmission rate of straight light with a wavelength of 400 nm at 25 ° C was measured with a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science). Each was measured using.

As shown in Table 2, Examples 1 to 4 using the radically curable composition of the present invention cure at a low temperature in a short time and have high transparency. On the other hand, in Comparative Examples 1 and 2 using the composition having no (meth) acrylic group, curing did not occur under the above curing conditions.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

Claims (7)

(A) (a) A Si—H group-containing compound represented by the following formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule. A (meth) acrylic group-containing compound having a skeleton consisting of an addition reaction product and having a (meth) acrylic group at one or both molecular ends, and

(In the formula, R ¹ is an independently substituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or 1 to 6 carbon atoms, which does not contain an addition-reactive carbon-carbon double bond. an alkoxy group, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(B) A radical curable composition containing a polymerization initiator. Addition reaction between a silicon-containing addition reaction product in which the component (A) has two addition-reactive carbon-carbon double bonds in one molecule and (c) a siloxane compound represented by the following formula (2). A (meth) acrylic group-containing compound that is a product.
The radical curing according to claim 1, wherein the silicon-containing addition reaction product is (a) an addition reaction product of the Si—H group-containing compound and (b) the polycyclic hydrocarbon. Mold composition.

(In the formula, R ¹ has the same meaning as above, R ³ is either a hydrogen atom or a methyl group, and R ⁴ is a substituted or unsubstituted divalent hydrocarbon having 1 to 8 carbon atoms. It is a group.) The polycyclic hydrocarbon is either 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene, or a combination thereof. The radical-curable composition according to claim 1 or 2, wherein the composition is characterized by the above. The radical-curable composition according to any one of claims 1 to 3, wherein the component (A) is a compound represented by the following formula (3).

(In the formula, R ³ is either a hydrogen atom or a methyl group, and n = 0 to 10.) The radical-curable composition according to any one of claims 1 to 4, wherein the polymerization initiator is an organic peroxide or a photopolymerization initiator. The radical curable composition according to claim 5, wherein the organic peroxide has a 10-hour half-life temperature of 50 to 150 ° C. A cured product according to any one of claims 1 to 6, which is a cured product of the radical curing type composition.