TW202146489A - Radically curable composition and cured product - Google Patents

Abstract

The invention provides a radically curable composition curable at a low temperature, characterized by comprising (A) a skeleton comprising an addition reaction product of (a) an Si-H group containing compound represented by formula (1) and (b) a polycyclic hydrocarbon having one molecules of an addition reactive carbon-carbon double bond in two molecules, a (meth) acrylic group-containing compound having a (meth) acrylic group at one or both molecular terminals; and (B) a polymerization initiator, wherein each of R1 independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which does not contain an addition reactive carbon-carbon double bond, or an alkoxy group having 1 to 6 carbon atoms, and R2 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.

Description

Radical hardening composition and hardened product

The present invention relates to a radical-curable composition and a cured product.

Light-emitting diodes (LEDs) are not only useful for backlights of liquid crystal displays (LCDs) and automotive headlights, which are characterized by low power consumption, long life, and design, with the background of dramatically improving their luminous efficiency. In the field, the market for general lighting has also expanded rapidly. These LED lamps are constituted by sealing LED elements mounted on a substrate with a sealing material made of a transparent resin. As a sealing material for sealing this LED, an addition hardening type silicon oxide composition has been widely used from the viewpoint of having excellent heat resistance (Patent Document 1). However, since the sealing material made of a silicon oxide composition has low gas barrier properties, 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 optical elements using an organically modified addition-curable silicone composition having a polycyclic hydrocarbon skeleton has been proposed. Since the sealing material obtained from these compositions has high bulk barrier properties, it can prevent the intrusion of corrosive gas from the outside, and can suppress the discoloration of the silver electrode (Patent Documents 2 and 3).

In recent years, quantum dots with excellent wavelength conversion efficiency have been attracting attention as wavelength conversion materials. Quantum dots must be sealed with materials with high gas barrier properties due to their weak resistance to moisture. On the other hand, most of the quantum dots contain the catalyst poison of the addition reaction. If the addition-hardening type composition is used as the adhesive material of the quantum dots, the curing failure may occur. Furthermore, since quantum dots have low heat resistance, it is difficult to withstand the hardening conditions of an addition hardening type material. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-292714 [Patent Document 2] Japanese Patent Laid-Open No. 2008-069210 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-046604

[The problem to be solved by the invention]

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a radical-curable polysiloxane composition which can be cured at a low temperature. [means to solve the problem]

(式中，R¹ 分別獨立為不含加成反應性碳-碳雙鍵、取代或非取代之碳原子數1~12之1價烴基或碳原子數1~6之烷氧基，R² 表示取代或非取代之碳原子數1~12之2價烴基)， (B)聚合起始劑。In order to solve the above-mentioned problems, the present invention provides a radically curable composition characterized by containing: (A) a (meth)acryloyl group-containing compound having a compound represented by (a) represented by the following formula (1). The skeleton formed by the addition reaction product of the Si-H group compound and the polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in (b) 1 molecule, and at the single-molecule end or the two-molecule end has a (meth)acryloyl group, and

(in the formula, R ^{1 is} independently an addition-reactive carbon-carbon double bond, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms, R ² Represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms), (B) a polymerization initiator.

According to the radical hardening type composition of the present invention, it can be hardened at low temperature.

(式中，R¹ 表示與上述相同意義，R³ 為氫原子或甲基之任一者，R⁴ 為取代或非取代之碳原子數1~8之二價烴基)。In the radical-hardening composition of the present invention, it is preferable that the aforementioned (A) component is a silicon-containing addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, and (c) is represented by the following formula (2) The (meth)acryloyl group-containing compound represented by the addition reaction product of the siloxane compound, the above-mentioned silicon-containing addition reaction product is (a) the above-mentioned Si-H group-containing compound and (b) the above-mentioned many Addition reaction products of cyclic hydrocarbons.

(In the formula, R ¹ represents 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 group having 1 to 8 carbon atoms).

According to the radical-curable composition of the present invention, the curability is further excellent.

The radical hardening composition of the present invention is more preferably any of the aforementioned polycyclic hydrocarbon-based 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene one or a combination of these.

According to the radical-curable composition of the present invention, a cured product excellent in hardness, crack resistance, heat resistance, and gas barrier properties can be obtained.

(式中，R³ 為氫原子或甲基之任一者，n=0~10)。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, n=0-10).

According to the radical-curable composition of the present invention, a cured product having more excellent hardness, crack resistance, heat resistance, and gas barrier properties can be obtained.

In the radical hardening composition of the present invention, preferably, the aforementioned polymerization initiator is an organic peroxide or a photopolymerization initiator.

These polymerization initiators can more effectively harden the composition of the present invention.

In this case, the above-mentioned organic peroxide is a 10-hour half-life temperature of 50 to 150°C.

According to these organic peroxides, the storage stability and curability of the composition are excellent in controllability.

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

Since the cured product of the present invention has excellent transparency and good hardness, it is useful for applications such as sealing materials for optical elements and filters. [Inventive effect]

The free radical hardening type silicone composition of the present invention can be hardened at low temperature by free radical hardening, so it can be used as a binder material for quantum dots, and the cured product obtained by curing the free radical hardening type composition of the present invention is due to It has excellent transparency and good hardness, so it is useful for applications such as sealing materials for LED elements and wavelength conversion filters.

The inventors of the present invention, as a result of earnestly examining in order to achieve the above-mentioned object, found that the above-mentioned problems can be solved by a radical-curable composition containing the components (A) and (B) described later, and thus completed the present invention.

(式中，R¹ 分別獨立為不含加成反應性碳-碳雙鍵、取代或非取代之碳原子數1~12之1價烴基或碳原子數1~6之烷氧基，R² 表示取代或非取代之碳原子數1~12之2價烴基)， (B)聚合起始劑。That is, the present invention is a radical hardening type composition characterized by containing: (A) a (meth)acryloyl group-containing compound having a Si-H-containing compound represented by (a) the following formula (1) The skeleton formed by the addition reaction product of the compound of the base and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in the molecule, and having (methyl) group) acrylyl group, and

(in the formula, R ^{1 is} independently an addition-reactive carbon-carbon double bond, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms, R ² Represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms), (B) a polymerization initiator.

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

[Radical hardening type composition] The radical-curable composition of the present invention contains components (A) and (B) described later as essential components. In addition to the above-mentioned essential components, the composition may further contain optional components as necessary.

Each component is explained in detail below.

(式中，R¹ 分別獨立為不含加成反應性碳-碳雙鍵、取代或非取代之碳原子數1~12之1價烴基或碳原子數1~6之烷氧基，R² 表示取代或非取代之碳原子數1~12之2價烴基)。[Component (A)] Component (A) is a (meth)acryloyl group-containing compound having (a) a Si-H group-containing compound represented by the following formula (1) and (b) in 1 molecule A molecular chain formed by an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds, and having a (meth)acryloyl group at one or both ends of the molecule. These (meth)acryloyl group-containing compounds have skeletons formed by addition reaction products of (a) the aforementioned Si-H group-containing compounds and (b) the aforementioned polycyclic hydrocarbons, and are located at the monomolecular terminals. Or it has a (meth)acryloyl group at both molecular ends. In addition, in the present invention, the term "addition reactivity" means the property that an addition reaction can be performed with a hydrogen atom bonded to a silicon atom by a conventional hydrosilylation reaction.

(in the formula, R ^{1 is} independently an addition-reactive carbon-carbon double bond, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms, R ² Represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms).

(式中，R¹ 、R² 如上述)。<(a) component> (a) component is a Si-H group containing compound represented by following formula (1).

(wherein, R ¹ and R ^{2 are} as described above).

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms for R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-butyl Amyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl and other alkyl groups with 1 to 12 carbon atoms; phenyl, naphthyl and other aryl groups with 6 to 12 carbon atoms; toluene Alkyl aryl groups with 7 to 12 carbon atoms, such as base, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, etc.; benzyl, phenethyl, etc. Aralkyl groups with 7 to 12 carbon atoms, etc.

In addition, specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a second butoxy group, and a third butyl group. oxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy and the like.

Among these, as R ¹ , an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group is more preferable.

On the other hand, specific examples of the divalent hydrocarbon group having 1 to 12 carbon atoms in ^{R 2 include methylene, ethylidene, propylidene, trimethylene, pentamethylene, hexamethylene, heptapethylene} Linear, branched or cyclic alkylene with 1 to 12 carbon atoms, such as methylene, octamethylene, nonamethylene, decamethylene, etc.; phenylene, biphenylene, naphthylene Aryl group with 6 to 12 carbon atoms such as phenylmethylene; aralkyl group with 7 to 12 carbon atoms such as phenylmethylene, methylene phenylene methylene, etc.

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

Although the specific example of (a) component is shown by the following formula, it is not limited to these. In addition, Me represents a methyl group.

Moreover, the compound represented by Formula (1) may be used individually by 1 type, and may be used in combination of 2 or more types.

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

As the polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule of the component (b), two adjacent carbon atoms among the carbon atoms forming the skeleton of the polycyclic hydrocarbon (i) can be used which forms an addition-reactive carbon-carbon double bond, (ii) hydrogen atoms bonded to carbon atoms forming the skeleton of a polycyclic hydrocarbon are substituted by a group containing an addition-reactive carbon-carbon double bond, (iii) ) An addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms in the carbon atoms forming the skeleton of the polycyclic hydrocarbon, and the hydrogen atoms bound to the carbon atoms forming the skeleton of the polycyclic hydrocarbon are added Substitutes of reactive carbon-carbon double bonds, etc.

Specific examples of the above-mentioned polycyclic hydrocarbons include 5-vinylbicyclo[2.2.1]hept-2-ene represented by the following formula (3), and 6-vinylbicyclo[2.2.2. 1] Hept-2-ene, etc., these can also be used as a mixture (Hereinafter, when it is unnecessary to distinguish these, it may be collectively referred to as "vinyl norbornene").

In addition, the substitution position of the vinyl group of the above vinyl norbornene may be either cis (exo type) or trans position (endo type), and the reactivity of the compound is not affected by the difference in these configurations. There are special differences, so the isomers of the two configurations can also be combined.

Moreover, as a specific example of the said polycyclic hydrocarbon other than vinyl norbornene, dicyclopentadiene and its derivative(s) are illustrated.

(式中，R¹ 表示與上述相同意義，n=0~10)。The addition reaction product of the component (a) and the component (b) is not particularly limited, but it is preferably represented by the following formula (5), and particularly preferably represented by the following formula (6) in which ^{R 1 is a methyl group} expressor.

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

(式中，R¹ 表示與上述相同意義)。The skeleton formed by the addition reaction product of the component (a) and the component (b) consists of a divalent residue having a bond derived from the addition-reactive carbon-carbon double bond. For example, the skeleton formed by the addition reaction product represented by the above formula (5) is represented by the following formula.

(In the formula, R ¹ has the same meaning as described above).

The compound having the main skeleton of the addition reaction product of such a polycyclic hydrocarbon and a phenylene group can be used as a hardened product excellent in 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 No. 2005-133073.

As an example, the amount of the component (b) is more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less with respect to 1 mol of the component (a), in the hydrosilylation reaction. It is prepared by an addition reaction in the presence of a medium.

In this case, a conventional one can be used as the hydrosilylation catalyst, and specific examples thereof include platinum metal-supported carbon powder, platinum black, platinum chloride, chloroplatinic acid, chloroplatinic acid and a monohydric alcohol. Reaction products, complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetylacetate, platinum-based catalysts such as palladium-based catalysts, rhodium-based catalysts, etc. In addition, the conditions for the addition reaction, the use of the solvent, and the like are not particularly limited as long as they are conventionally known.

Since the above-mentioned reaction is performed with an excess molar amount of the (b) polycyclic hydrocarbon with respect to the compound represented by the formula (1) in (a), the addition reaction product of the component (A) may have 2 in 1 molecule. Addition-reactive carbon-carbon double bonds derived from (b) polycyclic hydrocarbons.

(式中，R¹ 表示與上述相同意義，R³ 為氫原子或甲基之任一者，R⁴ 為取代或非取代之碳原子數1~8之二價烴基)。<(c) Component> (A) Component can be obtained by adding two (at both ends) addition-reactive carbon-carbon dipoles in one molecule of the addition reaction product of (a) and (b) components. One or both of the bonds are obtained by subjecting (c) the SiH group of the siloxane compound represented by the following formula (2) to a hydrosilylation reaction.

(In the formula, R ¹ represents 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 group having 1 to 8 carbon atoms).

And (A) component is obtained by first adding (a) component and (b) component to obtain a silicon-containing addition reaction product having two addition-reactive carbon-carbon double bonds in 1 molecule, and secondly The obtained product is obtained by subjecting both of the two addition-reactive carbon-carbon double bonds existing at both ends of the molecule to a hydrosilylation reaction with the SiH group of the siloxane compound of the component (c). In this case, the component (A) is preferably a combination of 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). The (meth)acryloyl group-containing compound of the addition reaction product, the above-mentioned silicon-containing addition reaction product is the addition reaction of (a) the above-mentioned Si-H group-containing compound and (b) the above-mentioned polycyclic hydrocarbon product. As the component (A) of the present invention, a (meth)acryloyl group-containing compound having these (meth)acryloyl groups at the molecular terminals of both ends is preferable.

(式中，R³ 為氫原子或甲基之任一者)。As the component (c), for example, a siloxane compound represented by the following formula (7) is exemplified.

(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 as long as they are conventionally known.

(式中，R⁵ 分別獨立為不含加成反應性碳-碳雙鍵之碳原子數1~6之1價烴基，X為鹵素原子，m為1或2)。<Component (d)> In addition, the component (A) can be obtained by causing one or both of the addition-reactive carbon-carbon double bonds to exist at both ends of the addition reaction product of the component (a) and the component (b). It is obtained by performing a hydrosilylation reaction with the SiH group of the halogen-containing siloxane compound (d) represented by the following formula (8), and then reacting a hydroxyl type acrylate compound.

(in the formula, R ^{5 is} each independently a monovalent hydrocarbon group with 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).

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

Specific examples of the monovalent hydrocarbon group with 1 to 6 carbon atoms that do not contain an addition-reactive carbon-carbon double bond for R ^{5 include methyl, ethyl, n-propyl, isopropyl, n-butyl,} Alkyl groups such as isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and cyclohexyl; phenyl, etc., particularly preferred are methyl and phenyl.

(式中，Ph表示苯基)。As a specific example of (d) component, what is represented by the following formula is illustrated, but it is not limited to these.

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

Examples of the hydroxyl-type acrylate compound include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and the like, preferably It is 2-hydroxyalkyl acrylate.

(式中，n=0~10)。Although a preferable specific example of (A) component is illustrated by the following formula, etc., it is not limited to these.

(in the formula, n=0~10).

(式中，R³ 為氫原子或甲基之任一者，n=0~10)。The component (A) is particularly preferably a compound represented by the following formula (3).

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

(A) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

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

(organic peroxide) The organic peroxide is preferably an organic peroxide having a half-life temperature of 50 to 150°C for 10 hours, more preferably from the viewpoints of the storage stability and curability of the composition, and the heat resistance temperature of the quantum dots. 60~110℃ organic peroxide.

Specific examples of organic peroxides include benzyl peroxide, tert-butyl peroxybenzoate, o-methylbenzyl peroxide, p-methylbenzyl peroxide Peroxide, di-tert-butyl peroxide, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane , 1,1-di-tetrabutylperoxy-cyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl -2,5-bis(tert-butylperoxy)hexyne, 1,6-bis(p-tolylperoxycarbonyloxy)hexane, bis(4-methylbenzylperoxy) base) hexamethylene biscarbonate, 2,5-dimethoxy-2,5-bis(2-ethylhexylperoxy)hexane, 2,5-dimethyl-2,5 -Di(2-ethylhexylperoxy)hexane, etc.

In addition, organic peroxides can also be obtained commercially, for example, from NOF Corporation. Specific examples are PERBUTYL NHP (50.6), PERHEXYL PV (53.2), PERBUTYL PV (54.6), PEROYL 355 (59.4), PEROYL L (61.6), PEROCTA O (65.3), PEROYL SA (65.9), PERHEXA 25O (66.2) , PERHEXYL O (69.9), NYPER PBM (70.6), PERBUTYL O (72.1), NYPER BMT (73.1), NYPER 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), PERBUTYL 355(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), PERCUMYL D (116.4), PERHEXYL D (116.4) , PERHEXA 25B (117.9), PERBUTYL C (119.5), PERBUTYL D (123.7), PERMENTA H (128.0), PERHEXYL 25B (128.4), PERCUMYL P (145.1), etc. The numbers in parentheses following the above-mentioned compound names are respectively the 10-hour half-life temperature (unit: °C).

Among the above-mentioned organic peroxides, 2,5-dimethoxy-2,5-bis(2-ethylhexyl peroxide) is preferred from the viewpoint of compatibility with the component (A) and a half-life temperature of 10 hours. oxy) hexane (manufactured by NOF Corporation, PERHEXA (registered trademark) 25O, 10-hour half-life temperature 66.2°C).

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

The addition amount of the organic peroxide 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 (A) component.

(photopolymerization initiator) Specific examples of the photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy- Cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl )benzyl]phenyl}-2-methylpropan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, bis(2,4,6-trimethylbenzyl) )-phenylphosphine oxide, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, etc.

Among the above-mentioned photopolymerization initiators, 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-keto (Omnirad 1173 manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (Omnirad 819 manufactured by IGM Resins BV), 2,4,6-trimethyl Benzyl-diphenylphosphine oxide (Omnirad TPO H from IGM Resins BV).

These photopolymerization initiators may 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 relative to 100 parts by mass of the component (A) from the viewpoint of curability

[other ingredients] In the radical-curable composition of the present invention, conventional antioxidants such as 2,6-di-tert-butyl-4-methylphenol can also be blended in order to suppress the occurrence of coloration, cloudiness, and oxidative deterioration of the cured product. In addition, in order to impart resistance to light deterioration, a light stabilizer such as a hindered amine-based stabilizer may be formulated. Furthermore, if necessary, inorganic fillers such as fumed silica, dyes, pigments, flame retardants, etc. may also be prepared in order to increase the strength. Adhesion aids (silane coupling agents, etc.) may also be prepared in order to improve the adhesive force.

The radical hardening composition of the present invention can also be formulated with phosphors or quantum dots as wavelength conversion materials. Quantum dots are usually particles with an average particle size of 20 nm or less, which can absorb and convert light energy. Quantum dots can adjust the color of light by changing their particle size. Since the band gap is determined by the size of the particle size, light with high color purity can be obtained by making the particle size uniform.

As quantum dots that emit light in the visible light region, for example, CdSe-based particles having a shell such as CdS, ZnSe, or ZnS are used. In addition, cadmium-free quantum dots such as _{InP, CuInS 2} , AgInS ₂ , Te, PbS, and InAs can also be used. The present invention can also use any kind of quantum dots from the past.

As mentioned above, most of the quantum dots contain catalyst poisoning of additional reactions. If an addition-hardening composition is used as the adhesive material of quantum dots, poor hardening may occur. Furthermore, since quantum dots have low heat resistance, it is difficult to withstand the hardening conditions of an addition hardening type material. On the other hand, the radical hardening composition of the present invention can be hardened at low temperature by radical hardening, so it can avoid the above-mentioned problems in the case of using an addition hardening composition, and can be used as a binder material for quantum dots. it works.

[hardened product] The present invention also provides a cured product of the above-mentioned radical-curable composition. The radical curing composition of the present invention can be cured at low temperature by radical curing. The cured product obtained by curing the radical curing composition of the present invention has excellent transparency and good hardness, so it is suitable for use in LED devices. Useful for applications such as sealing materials and wavelength conversion filters. In addition, if the radical-curable composition of the present invention having a polycyclic hydrocarbon skeleton is used as a sealing material for optical elements, the obtained sealing material (hardened product) can prevent corrosion from the outside due to its high gas barrier properties. Gas intrusion. Therefore, it is also useful as a material for sealing quantum dots that are not resistant to water.

[Hardening method and hardening conditions] In the radical-curable composition of the present invention, conventional methods and conditions can be adopted as the curing method and curing conditions of the thermal radical-curing type containing organic peroxide. As an example, it can be hardened under the conditions of 10 minutes to 5 hours at 70 to 150° C. in a nitrogen atmosphere. In particular, when the polymerization initiator is an organic peroxide with a half-life temperature of 50 to 150° C. for 10 hours, it is preferable that it can be cured at a lower temperature.

Moreover, the radical hardening type composition of the photohardening type containing a photopolymerization initiator can be hardened by irradiating light, such as an ultraviolet-ray. As a light source of ultraviolet rays, for example, UV LED lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps are exemplified. The irradiation dose (cumulative light dose) of ultraviolet rays is, for example, when the composition of the present invention is formed into a sheet having a thickness of about 2.0 mm, preferably 1 to 10,000 mJ/cm ² , more preferably 10 to 9,000 mJ/cm ² . That is, in the case of using ^{ultraviolet rays with an illuminance of 100 mW/cm 2} , it can be cured by irradiating ultraviolet rays for about 0.01 to 100 seconds. [Example]

The following examples are used to specifically illustrate the present invention, but these examples do not limit the present invention in any way. In addition, in the following, the FT-IR, NMR and GPC of the reaction product were measured by the usual method, and the viscosity at 25 degreeC was measured by the B-type rotational viscometer.

[Synthesis Example 1] In a 5L 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; 5-vinylbicyclo) was added [2.2.1] Hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene (about equimolar isomer mixture) 1,785g (14.88mol) and toluene 455g, used The oil bath was heated to 85°C. 3.6 g of carbon powder supporting 5% by mass of platinum metal was added thereto, and 1,698 g (8.75 moles) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 180 minutes while stirring. After completion of the dropwise addition, the mixture was stirred at 110°C for 24 hours, and then cooled to 25°C. Then, the carbon carrying platinum metal was removed by filtration, and toluene and excess vinyl norbornene were distilled off under reduced pressure to obtain 3,362 g of a colorless and transparent oily reaction product (ab-1) (viscosity at 25°C: 12,820 mPa·s). The results of FT-IR, NMR and GPC analysis of the reaction product show that in the following formula (9), the compound with n=0 is about 41 mol%, the compound with n=1 is about 32 mol%, and the compound with n=2 is about 32 mol%. Compounds are approximately 27 mol% mixture. And the content of addition-reactive carbon-carbon double bonds 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 in a 1 L 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, and 0.2 g of dibutylhydroxytoluene was added. , heated to 80°C using an oil bath. To this was added 0.15 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5 mass % in terms of platinum), and the following formula (10) was added dropwise while stirring. Organohydrogendisiloxane 189.6g. After the dropwise addition, 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).

[Synthesis Example 3] In a 5L 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, add vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; 5-vinylbicyclo[2.2.1] Hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene (about equimolar isomer mixture) 270g (2.25mol) and toluene 2.5g, heated to 85g using an oil bath °C. 0.19 g of carbon powder supporting 5% by mass of platinum metal was added thereto, and 174.5 g (0.90 mol) of 1,4-bis(dimethylsilyl)benzene was added dropwise with stirring. After completion of the dropwise addition, the mixture was stirred at 110°C for 24 hours, and then cooled to 25°C. Subsequently, the carbon carrying platinum metal was removed by filtration, and toluene and excess vinyl norbornene were removed by vacuum distillation to obtain 311 g of a colorless and transparent oily reaction product (ab-2) (viscosity at 25°C: 1,710 mPa)・s). The results of FT-IR, NMR and GPC analysis of the reaction product show that the compound with n=0 in the aforementioned formula (9) is about 74 mol%, the compound with n=1 is about 21 mol%, and the compound with n=2 About 5 mol% of the mixture. And the content of addition-reactive carbon-carbon double bonds in the mixture was 0.37 mol/100 g.

[Synthesis Example 4] In a 500 mL 4-neck flask equipped with a stirring device, a cooling tube, 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, 0.05 g of dibutylhydroxytoluene was added, and the mixture was used. The oil bath was heated to 80°C. To this was added 0.025 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5 mass % in terms of platinum), and the organic compound represented by the formula (10) was added dropwise with stirring. Hydrodisiloxane 48.7g. After the dropwise addition, 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-mentioned synthesis examples and the following (B) components were respectively mixed in the preparation amounts shown in Table 1 (numerical values indicate parts by mass) to prepare radicals. Curable composition (thermo-curable and UV-curable).

(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 B.V.)

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

[hardness] ・Thermosetting type With respect to the hardness of a hardened product having a thickness of 2 mm produced by heating the composition in a hot air circulating oven at 80° C. for 2 hours under a nitrogen atmosphere, the measurement of type A hardness at 23° C. was performed.

・Ultraviolet curing type is for the use of EYE GRAPHYTICS Co., Ltd. EYE UV electronic control device (model UBX0601-01) to expose the composition to 8,000mJ/cm ² of ultraviolet light with a wavelength of 365 nm in a nitrogen atmosphere at 25°C. The hardness of a 2mm thick cured product was irradiated with ultraviolet rays in a manner to measure the A-type hardness at 23°C.

[Light transmittance] ・Thermosetting type The light transmittance of a cured product with a thickness of 2 mm produced by heating the composition in a hot air circulating oven at 80° C. for 2 hours in a nitrogen atmosphere was measured using a spectrophotometer U-3900 (manufactured by Hitachi High-Technologies). Light transmittance of straight light with a wavelength of 400nm at 25°C.

・Ultraviolet curing type is for the use of EYE GRAPHYTICS Co., Ltd. EYE UV electronic control device (model UBX0601-01) to expose the composition to 8,000mJ/cm ² of ultraviolet light with a wavelength of 365 nm in a nitrogen atmosphere at 25°C. A 2 mm thick cured product was irradiated with ultraviolet rays to be cured, and the light transmittance of the straight incoming light with a wavelength of 400 nm at 25° C. was measured using a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Co., Ltd.).

As shown in Table 2, Examples 1 to 4 using the radical-curable composition of the present invention were cured at low temperature and in a short time, and had high transparency. On the other hand, in the comparative examples 1-2 which used the composition which does not have a (meth)acryloyl group, hardening did not generate|occur|produce in the said hardening conditions.

In addition, this invention is not limited to the said embodiment. The above-mentioned embodiments are examples, and all those having substantially the same structure as the technical idea described in the scope of the patent application of the present invention and exhibiting the same functions and effects are included in the technical scope of the present invention.

Claims (7)

A radical hardening type composition characterized by containing: (A) a (meth)acryloyl group-containing compound having (a) a Si-H group-containing compound represented by the following formula (1) and ( b) A skeleton formed by an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having a (meth)acryloyl group at one or both ends of the molecule ,and

(in the formula, R ^{1 is} independently an addition-reactive carbon-carbon double bond, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms, R ² Represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms), (B) a polymerization initiator. The radical-hardening composition according to claim 1, wherein the component (A) is a silicon-containing addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, and (c) is represented by the following formula ( 2) The (meth)acryloyl group-containing compound of the addition reaction product of the siloxane compound represented, the above-mentioned silicon-containing addition reaction product is (a) the above-mentioned Si-H group-containing compound and (b) The addition reaction product of the aforementioned polycyclic hydrocarbon,

(In the formula, R ¹ represents 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 group having 1 to 8 carbon atoms). The radical hardening type composition according to claim 1 or 2, wherein the polycyclic hydrocarbons are 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2 - any one of the alkenes or a combination of these. The radical hardening composition according to claim 1 or 2, 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, n=0-10). The radical hardening type composition according to claim 1 or 2, wherein the aforementioned polymerization initiator is an organic peroxide or a photopolymerization initiator. The radical hardening type composition according to claim 5, wherein the organic peroxide has a 10-hour half-life temperature of 50 to 150°C. A hardened product characterized by being the hardened product of the radical hardening composition according to any one of claims 1 to 6.