JP6694238B2 - Photocurable resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a photocurable resin composition and a method for producing the same.

  A photo-curing system using energy rays such as ultraviolet rays is useful for improving productivity and addressing recent environmental problems. For example, it is known that an epoxy resin composition using an anhydride-based curing agent forms a transparent cured product and is suitable as a sealing material for optical semiconductor elements such as light emitting diodes and photodiodes. Therefore, a photocationic curable material using an epoxy resin has been proposed.

  In recent years, the photocurable resin has been required to have higher performance as its applicable range is expanded. In particular, in the field of photosensitive coating agents, photocurable resins for nanoimprints, encapsulating materials for semiconductors such as organic EL or solar cells, the transparency, heat yellowing resistance, light resistance, and adhesion are excellent, and the surface after curing is excellent. A photocurable resin having no tackiness and high productivity has been demanded. Therefore, mainly bisphenol A type epoxy resins, bisphenol F type epoxy resins and epoxy resins having an organic resin skeleton such as (3 ′, 4′-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate, which have been conventionally used, are mainly used. With the composition as the component, sufficient properties have not been obtained.

  Up to now, many attempts have been made to increase the reactivity of an epoxy compound by using an alicyclic epoxy compound and a vinyl ether compound in combination with a cationic photocurable material (see, for example, Patent Documents 1 and 2). Attempts have also been made to use polyfunctional vinyl ether compounds (see, for example, Patent Documents 3 and 4). Further, it has been attempted to improve reactivity and control mechanical properties of a cured product by using a specific phenol resin in a material in which an epoxy compound and a vinyl ether compound are used in combination (see, for example, Patent Document 5).

  On the other hand, a composition for use in optical semiconductors, in which an epoxy compound is mixed with an inorganic filler, is disclosed (for example, see Patent Document 6). Further, a composition of an organopolysiloxane having an epoxy group for use as a photo semiconductor has been disclosed (see, for example, Patent Document 7). Furthermore, application of a methacryloxy group-containing silicone composition to optical semiconductor applications has been proposed (see, for example, Patent Document 8).

  In addition, a composition for use in optical semiconductors containing a specific other functional methacryloxy group-containing compound has been disclosed (see, for example, Patent Document 9).

  Furthermore, recently, in order to efficiently use the light generated from the optical semiconductor, it has been required to increase the refractive index of the resin.

JP-A-6-298911 JP, 9-328634, A Japanese Patent No. 2667934 JP, 4-120182, A Japanese Patent No. 4235698 JP, 2007-284475, A Japanese Patent No. 4322949 JP, 2008-131009, A JP, 2010-189471, A

  However, the above-mentioned conventionally proposed techniques have the following problems.

  Since the photocurable resin using the epoxy compound and the vinyl ether compound in combination disclosed in Patent Documents 1 to 5 uses the epoxy compound and the vinyl ether compound having low heat yellowing and light resistance, they have high heat yellowing and light resistance. It is difficult to adapt to the applications that require Also, since the refractive index is low, the light generated from the optical semiconductor cannot be efficiently used.

  Also in the composition in which the inorganic filler is mixed with the epoxy compound disclosed in Patent Document 6, since the epoxy compound and the vinyl ether compound having low heat yellowing resistance and light resistance are used, high heat yellowing resistance and light resistance are obtained. It is difficult to adapt to the applications that require Also, since the refractive index is low, the light generated from the optical semiconductor cannot be efficiently used.

  Although the composition disclosed in Patent Document 7 is relatively excellent in terms of mechanical properties such as adhesion, it does not necessarily reach a satisfactory level with respect to heat yellowing and light resistance. Also, since the refractive index is low, the light generated from the optical semiconductor cannot be efficiently used.

  When the composition disclosed in Patent Document 8 is used as a photocurable resin, heat yellowing and light resistance are excellent, but tack remains on the surface, making it difficult to apply to a coating agent or the like. Also, since the refractive index is low, the light generated from the optical semiconductor cannot be efficiently used.

  The composition disclosed in Patent Document 9 is difficult to be applied to applications requiring high heat yellowing and light resistance because an ether bond such as polybutylene glycol reduces heat yellowing and light resistance. Is. Also, since the refractive index is low, the light generated from the optical semiconductor cannot be efficiently used.

The present invention has been made in view of the above problems, thermal yellowing resistance, light resistance, transparency, high refractive index, and surface tackiness (stickiness) is sufficiently small cured product capable of forming a photocurable A resin composition and a method for producing the same are provided. Further, the present invention is a sealing material for an optical semiconductor using the photocurable resin composition, a die bonding material for an optical semiconductor, an adhesive, a coating agent, a photocurable resin composition for nanoimprint, an optical lens, an ink, An object is to provide an optical semiconductor package and an optical semiconductor device.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above objects can be achieved by a photocurable resin composition containing an organopolysiloxane having a specific structure, and to complete the present invention. I arrived.

That is, the present invention is as follows.
[1]
Organopolysiloxane (I) 100 having a structural unit F1 represented by the following general formula (1) and a structural unit M1 represented by the following general formula (2) as units forming a cyclic organopolysiloxane. Mass part,
10 to 200 parts by mass of inorganic particles,
Containing a photo radical generator 0.050 to 20 parts by mass,
The refractive index of the inorganic particles is 1.8 or more,
Photocurable resin composition.
(In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, R ² is 2 carbon atoms 10 represents an unsaturated chain-containing hydrocarbon group, a cyclohexenyl group, a norbornenyl group, an ether bond-containing unsaturated hydrocarbon group, or an unsaturated fatty acid ester group, which is an unsaturated bond-containing group, and X represents — (CH _{2 ) 2 -, - (CH 2} ) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH 2) 8 _{-, - (CH 2) 9} -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - shows a, a is an integer of 1 or more. )
(In the general formula (2), R ¹ and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, Y _{is, - (CH 2) 2 -} , - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 - _{, - (CH 2) 8 -} , - (CH 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - shows a, n is It represents an integer of 1 to 3, and b represents an integer of 1 or more.)
[2]
The photocurable resin composition according to [1], wherein the ratio (a / b) of the a to the b is 0.010 or more and 5.0 or less.
[3]
The photocurable resin composition according to [1] or [2], further including a structural unit M2 represented by the following general formula (3) as a unit constituting a cyclic organopolysiloxane.
(In the general formula (3), R ¹ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, Z _{is, - (CH 2) 2 -} , - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 - _{, - (CH 2) 8 -} , - (CH 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - indicates, c is, Indicates an integer of 1 or more.)
[4]
The photocurable resin composition according to [3], wherein the ratio (a / c) of the a to the c is 0.0010 or more and 3.0 or less.
[5]
The photocurable resin composition according to any one of [1] to [4], wherein the inorganic particles have an average particle diameter of 0.1 to 100 nm.
[6]
[1] to [5], wherein the inorganic particles contain at least one element selected from the group consisting of zirconium , titanium, zinc, iron, copper, chromium, cadmium, carbon, tungsten, antimony, nickel, and platinum. The photocurable resin composition according to any one of 1.
[7]
The photocurable resin composition according to any one of [1] to [4], wherein R ² is an acryloxy group or a methacryloxy group.
[8]
The photocurable resin composition according to any one of [1] to [7], further including a structural unit S represented by the following general formula (4) as a unit constituting a cyclic organopolysiloxane.
In (the general formula (4), R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, d is an integer of 1 or more Show.)
[9]
The photocurable resin composition according to [8], wherein the ratio (d / a) of the d to the a is 0.10 or less.
[10]
The organopolysiloxane (I) according to any one of [1] to [9], containing only the structural unit F1 represented by the general formula (1) as the structural unit containing R ² . Photocurable resin composition.
[11]
The photocurable resin composition according to any one of [1] to [10], wherein R ¹ is an alkyl group having 1 to 10 carbon atoms.
[12]
The photocurable resin composition according to any one of [1] to [11], wherein R ¹ is a methyl group.
[13]
The photocurable resin composition according to any one of [1] to [12], wherein the functional group equivalent of the unsaturated bond-containing group represented by R ² is 20 to 10,000 g / mol.
[14]
The weight average molecular weight of the organopolysiloxane (I) is 500 to 1,000,000,
The photocurable resin composition according to any one of [1] to [13], wherein the organopolysiloxane (I) has a viscosity at 25 ° C. of 1.0 to 1,000,000 mPa · s.
[15]
Organopolysiloxane (II) 0 having a structural unit F1 ′ represented by the following general formula (5) and a structural unit T ′ represented by the following general formula (6) as units constituting the cyclic organopolysiloxane 10 to 100 parts by mass,
The photocurable resin composition according to any one of [1] to [14].
(In the general formula (5), R ^{1 'is} an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, R ^2' has a carbon number 2 to 10 represents an unsaturated chain hydrocarbon group, a cyclohexenyl group, a norbornenyl group, an ether bond-containing unsaturated hydrocarbon group, or an unsaturated bond-containing group which is an unsaturated fatty acid ester group, and X ′ represents — _{(CH 2) 2 -, -} (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH _{2) 8 -, - (CH} 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - indicates, e is an integer greater than or equal to 1 Is shown.)
(In the general formula (6), R ^{1 'is} an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, f is an integer equal to or larger than 0 And the sum of e and f represents an integer of 3 to 20.)
[16]
The photocurable resin composition according to [15], wherein R ^{1 ′} is an alkyl group having 1 to 10 carbon atoms.
[17]
The photocurable resin composition according to [15] or [16], wherein R ^{1 ′} is a methyl group.
[18]
The photocurable resin composition according to any one of [15] to [17], wherein R ^{2 ′} is an acryloxy group or a methacryloxy group.
[19]
The photocurable resin composition according to any one of [15] to [18], wherein the total functional group equivalent of the unsaturated bond-containing groups represented by R ² and R ^{2 ′} is 20 to 10000 g / mol. object.
[20]
The weight average molecular weight of the organopolysiloxane (II) is 500 to 1,000,000,
The photocurable resin composition according to any one of [15] to [19], wherein the organopolysiloxane (II) has a viscosity at 25 ° C. of 1.0 to 1,000,000 mPa · s.
[21]
The content of the photoradical generator is 0.50 to 10 parts by mass based on 100 parts by mass of the total amount of the organopolysiloxane (I) and the organopolysiloxane (II), [1] to [20] ] The photocurable resin composition in any one of these.
[22]
Further containing a hydrosilylation reaction catalyst,
The content of the hydrosilylation reaction catalyst is 0.0010 parts by mass or less based on 100 parts by mass of the total amount of the organopolysiloxane (I) and the organopolysiloxane (II), [1] to [21]. The photocurable resin composition according to any one of 1.
[23]
A hydrogen polysiloxane (a) having a structural unit represented by the following general formula (7) as a unit constituting a cyclic organopolysiloxane,
In (the general formula (7), R ^{1 ''} is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, j is 1 or more Indicates an integer.)
An organosiloxane (b1) having one vinyl group directly bonded to a silicon atom and containing at least one hydrolyzable group directly bonded to a silicon atom ;
An organic compound (c) having two or more unsaturated bond-containing groups, which are unsaturated chain hydrocarbon groups, cyclohexenyl groups, norbornenyl groups, ether bond-containing unsaturated hydrocarbon groups, or unsaturated fatty acid ester groups; ,
An addition reaction step of obtaining an organopolysiloxane by an addition reaction in the presence of a hydrosilylation reaction catalyst (d),
A mixing step of mixing the organopolysiloxane, the inorganic particles (e) having a refractive index of 1.8 or more, and a photoradical generator,
A method for producing a photocurable resin composition.
[24]
The method for producing a photocurable resin composition according to [23], wherein the hydrogen polysiloxane (a) further has a structural unit represented by the following general formula (8).
(In the general formula (8), R ^{1 ''} are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, k Represents an integer of 0 or more, and j + k is an integer of 3 to 20.)
[25]
In the addition reaction step, the organosiloxane (b2) having one vinyl group directly bonded to a silicon atom and having no hydrolyzable group directly bonded to a silicon atom is further subjected to an addition reaction [23] or [ 24] The method for producing a photocurable resin composition according to item 24.
[26]
An encapsulant for optical semiconductors, comprising the photocurable resin composition according to any one of [1] to [22].
[27]
A die-bonding material for optical semiconductor, comprising the photocurable resin composition according to any one of [1] to [22].
[28]
An adhesive containing the photocurable resin composition according to any one of [1] to [22].
[29]
A coating material containing the photocurable resin composition according to any one of [1] to [22].
[30]
A curable resin composition for nanoimprint, comprising the photocurable resin composition according to any one of [1] to [22].
[31]
An optical lens comprising the photocurable resin composition according to any one of [1] to [22].
[32]
An ink containing the photocurable resin composition according to any one of [1] to [22] and a colorant.
[33]
An optical semiconductor package obtained by molding the encapsulating material for optical semiconductor according to [26].
[34]
An optical semiconductor device manufactured using the encapsulating material for an optical semiconductor according to [26].

According to the present invention, a photocurable resin composition capable of forming a cured product having heat yellowing resistance, light resistance, transparency, high refractive index, and sufficiently low surface tack (stickiness) and a method for producing the same. Can be provided. In addition, it has excellent heat yellowing and light resistance, has a high refractive index, and has a sufficiently low surface tack (stickiness) for optical semiconductors, die bonding materials for optical semiconductors, adhesives, coating agents, photocuring for nanoimprinting. A resin composition, an optical lens, an ink, an optical semiconductor package, and an optical semiconductor device can be provided.

It is sectional drawing which shows one Embodiment of OLED display element using the sealing material for semiconductors of this embodiment.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. It should be noted that the present invention is not limited to the following description, and various modifications can be carried out within the scope of the gist thereof.

[Photocurable resin composition]
The photocurable resin composition of the present embodiment comprises a cyclic organopolysiloxane composed of a structural unit F1 represented by the following general formula (1) and a structural unit M1 represented by the following general formula (2). Having 100 parts by mass of the organopolysiloxane (I), 10 to 200 parts by mass of the inorganic particles, and 0.050 to 20 parts by mass of the photoradical generator, and the refractive index of the inorganic particles is It is 1.8 or more.

[Organopolysiloxane (I)]
The organopolysiloxane (I) has a structural unit F1 represented by the following general formula (1) and a structural unit M1 represented by the following general formula (2) as units constituting the cyclic organopolysiloxane. ..
(In the general formula (1), R ¹ represents a substituted or unsubstituted C 1-10 alkyl group, a substituted or unsubstituted C 3-10 cycloalkyl group, a substituted or unsubstituted aryl group, Alternatively, it represents a substituted or unsubstituted aralkyl group, R ² represents an unsaturated bond-containing group having 2 to 10 carbon atoms, X represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and a is , Represents the content ratio of the structural unit F1, and represents an integer of 1 or more.)
(In the general formula (2), R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, A substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n represents an integer of 1 to 3, b Represents the content ratio of the structural unit M1 and represents an integer of 1 or more.)

[Structural unit F1]
The structural unit F1 represented by the general formula (1) is a unit that constitutes the cyclic organopolysiloxane.

In the general formula (1), R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, or A substituted or unsubstituted aralkyl group is shown. Such R ¹ is not particularly limited, but includes, for example, methyl group, ethyl group, propyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, And an alkyl group having 1 to 10 carbon atoms such as octyl group; a cycloalkyl group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecane group; phenyl group, tolyl group , An aryl group such as a xylyl group, a cumenyl group, and a mesityl group; an aralkyl group such as a benzyl group, a phenethyl group, and a phenylpropyl group; or part or all of hydrogen atoms bonded to carbon atoms of these groups. A group in which is substituted with a substituent is exemplified.

  The substituent is not particularly limited, and examples thereof include a hydroxy group, a cyano group, and a halogen atom. The substituted alkyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, and a 3,3,3-trifluoropyr group.

Among these, as R ¹ in the general formula (1), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

In the general formula (1), R ² represents an unsaturated bond-containing group having 2 to 10 carbon atoms. The unsaturated bond-containing group having 2 to 10 carbon atoms is not particularly limited, and examples thereof include vinyl group, allyl group, isopropenyl group, 3-butenyl group, 2-methylpropenyl group, 4-pentenyl group, 5-hexenyl. Group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group and other unsaturated chain hydrocarbon groups; cyclohexenyl group, norbornenyl group and other unsaturated cyclic hydrocarbon groups; vinyl ether group, allyl Examples thereof include ether bond-containing unsaturated hydrocarbon groups such as ether groups; cyclic unsaturated hydrocarbon groups such as cyclohexenyl groups; and unsaturated fatty acid ester groups such as acryloxy groups and methacryloxy groups.

Among these, as R ² , an acryloxy group represented by the following general formula (9) or a methacryloxy group represented by the following general formula (10) (hereinafter, collectively referred to as “(meth) acryloxy group”) Preferred). By using the (meth) acryloxy group, the reactivity of the photocurable resin composition, that is, the property of facilitating photocuring and rapidly proceeding the reaction tends to be further improved.

The organopolysiloxane (I) preferably contains only the structural unit F1 represented by the general formula (1) as a structural unit containing R ² . With such a structure, the refractive index tends to be further improved.

The functional group equivalent of the unsaturated bond-containing group represented by R ² is preferably 20 to 10,000 g / mol, more preferably 50 to 9000 g / mol, and further preferably 100 to 8,000 g / mol. When the functional group equivalent of the unsaturated bond-containing group represented by R ² is 20 g / mol or more, heat-resistant yellowing and light resistance of the cured product of the photocurable resin composition tend to be further improved. Further, when the functional group equivalent of the unsaturated bond-containing group represented by R ² is 10000 g / mol or less, the refractive index of the photocurable resin composition tends to be further improved. The functional group equivalent of the unsaturated bond-containing group represented by R ² can be measured by the method described in Examples below.

In the general formula (1), X represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Examples of the divalent hydrocarbon group having 2 to 10 carbon atoms is not particularly limited, for _{example, - (CH 2) 2 -} , - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2 _{) 5 -, - (CH 2} ) 6 -, - (CH 2) 7 -, - (CH 2) 8 -, - (CH 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH ₂ —, —C (CH ₃ ) ₂ — and the like. Among _{this, - (CH 2) 2 -} , - (CH 2) 3 -, and - (CH _{2) 4} - is the raw material of the easy availability and reactivity, i.e. photocuring easily quickly react It is preferable from the viewpoint of proceeding.

[Structural unit M1]
The constitutional unit M1 represented by the general formula (2) is a unit constituting a cyclic organopolysiloxane.

In formula (2), R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or It represents an unsubstituted aryl group or a substituted or unsubstituted aralkyl group. Specifically, as R ¹ and R ³ , the same groups as those exemplified in the above general formula (1) can be exemplified. Note that R ¹ in R ¹ and the general formula of the general formula (1) (2) may be the same or different.

Among these, as R ¹ and / or R ³ in the general formula (2), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

In the general formula (2), Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Although it does not specifically limit as a C2-C10 bivalent hydrocarbon group, For example, the group similar to the group illustrated by X in the said General formula (1) can be illustrated. Among _{this, - (CH 2) 3 -} , - (CH 2) 4 -, and - (CH _{2) 6} - is the raw material of the easy availability and reactivity, i.e. photocuring easily quickly react It is preferable from the viewpoint of proceeding. In addition, X in the general formula (1) and Y in the general formula (2) may be the same or different.

  In general formula (2), n is an integer of 1-3. From the viewpoint of improving the adhesiveness, it is preferably an integer of 2 to 3, and more preferably an integer of 3. From the viewpoint of storage stability, it is preferably an integer of 1.

  The ratio of a to b (a / b) is preferably 0.010 or more and 5.0 or less, more preferably 0.020 or more and 4.5 or less, still more preferably 0.050 or more and 4.0 or less. Is. When the ratio (a / b) is 0.010 or more, the ratio of the F1 unit becomes relatively large, and the refractive index of the photocurable resin composition of this embodiment tends to be further improved. Further, when the ratio (a / b) is 5.0 or less, the ratio of M1 units becomes relatively large, and the light resistance tends to be further improved.

[Structural unit M2]
The organopolysiloxane (I) may further have a structural unit M2 represented by the following general formula (3) as a unit that constitutes the cyclic organopolysiloxane.
(In the general formula (3), R ¹ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, A substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group is shown, Z is a divalent hydrocarbon group having 2 to 10 carbon atoms, and c is the content ratio of the structural unit M2. Indicates an integer of 1 or more.)

In formula (3), R ¹ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or It represents an unsubstituted aryl group or a substituted or unsubstituted aralkyl group. Specifically, as R ¹ and R ⁴ , the same groups as those exemplified in the general formula (1) can be exemplified. Note that R ¹ in R ¹ and the general formula of the general formula (1) in (3) in may be the same or different.

Among these, as R ¹ and / or R ⁴ in the general formula (3), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

In general formula (3), Z represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Although it does not specifically limit as a C2-C10 bivalent hydrocarbon group, For example, the group similar to the group illustrated by X in the said General formula (1) can be illustrated. Among _{this, - (CH 2) 3 -} , - (CH 2) 4 -, and - (CH _{2) 6} - is the raw material of the easy availability and reactivity, i.e. photocuring easily quickly react It is preferable from the viewpoint of proceeding. In addition, X in the general formula (1) and Z in the general formula (3) may be the same or different.

  The ratio of a to c (a / c) is preferably 0.0010 or more and 3.0 or less, more preferably 0.0020 or more and 2.8 or less, and further preferably 0.0050 or more and 2.5 or less. Is. When the ratio (a / c) is 0.0010 or more, the ratio of the F1 unit becomes relatively large, and the refractive index of the photocurable resin composition of this embodiment tends to be further improved. Further, when the ratio (a / c) is 3.0 or less, the ratio of the M2 unit becomes relatively large, and the storage stability tends to be further improved.

[Structural unit S]
The organopolysiloxane (I) may further have a structural unit S represented by the following general formula (4) as a unit that constitutes the cyclic organopolysiloxane.
(In the general formula (4), R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, Alternatively, it represents a substituted or unsubstituted aralkyl group, and d represents the content ratio of the structural unit S and represents an integer of 1 or more.)

In the general formula (4), R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, or A substituted or unsubstituted aralkyl group is shown. Specific examples of R ¹ include the same groups as those exemplified in the above general formula (1). The above general formula (1) R ¹ and the general formula in the (4) R ¹ in may be the same or different.

Among these, as R ¹ in the general formula (4), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

  The ratio of d to a (d / a) is preferably 0.10 or less, more preferably 0.0001 or more and 0.08 or less, and still more preferably 0.001 or more and 0.06 or less. When the ratio (d / a) is 0.0001 or more, heat yellowing tends to be further improved. In addition, when the ratio (d / a) is 0.10 or less, it is possible to prevent SiH from reacting with an unsaturated bond and gelling at the time of solvent evaporation or storage, and thus product stability and storage stability. Sex tends to improve.

The total functional group equivalent weight of the unsaturated bond-containing groups contained in the organopolysiloxane (I) is preferably 20 to 10000 g / mol, more preferably 50 to 9000 g / mol, and further preferably 100 to 8000 g. / Mol. When the total functional group equivalent weight of the unsaturated bond-containing group is 20 g / mol or more, the heat-resistant yellowing and the light resistance of the cured product of the photocurable resin composition tend to be further improved. Moreover, when the total functional group equivalent of the unsaturated bond-containing group is 10000 g / mol or less, the refractive index of the photocurable resin composition tends to be further improved. The functional group equivalent of the unsaturated bond-containing group represented by R ² can be measured by the method described in Examples below.

  The weight average molecular weight of the organopolysiloxane (I) is preferably 500 to 1,000,000, more preferably 700 to 800,000, and further preferably 1000 to 500,000. When the weight average molecular weight of the organopolysiloxane (I) is 500 or more, the dispersion stability of the inorganic particles tends to be further improved. Further, when the weight average molecular weight of the organopolysiloxane (I) is 1,000,000 or less, the refractive index of the photocurable resin composition tends to be further improved. The weight average molecular weight can be measured by the method described in Examples.

  The viscosity of the organopolysiloxane (I) at 25 ° C. is preferably 1.0 to 1,000,000 mPa · s, more preferably 5.0 to 500,000 mPa · s, and further preferably 10 to 100,000 mPa · s. When the viscosity of the organopolysiloxane (I) at 25 ° C. is 1.0 mPa · s or more, the dispersion stability of the inorganic particles tends to be further improved. Further, when the viscosity of the organopolysiloxane (I) at 25 ° C. is 1,000,000 mPa · s or less, the handleability tends to be further improved. The viscosity at 25 ° C can be measured by the method described in the examples.

[Inorganic particles]
In this embodiment, the inorganic particles are particles made of an inorganic substance or an inorganic compound. Specifically, it refers to a compound containing no hydrocarbon. The use of inorganic particles further improves the refractive index.

  Examples of the element forming the inorganic particles include elements of Groups 1 to 16 of the periodic table. This element is not particularly limited, but an element belonging to groups 2 to 14 of the periodic table is preferable. Specific examples thereof include Group 2 elements (Mg, Ca, Ba, etc.), Group 3 elements (La, Ce, Eu, Ac, Th, etc.), Group 4 elements (Ti, Zr, Hf, etc.), Group 5 elements ( V, Nb, Ta, etc.), Group 6 elements (Cr, Mo, W, etc.), Group 7 elements (Mn, Re, etc.), Group 8 elements (Fe, Ru, Os, etc.), Group 9 elements (Co, Rh, etc.). Ir, etc.), Group 10 elements (Ni, Pd, Pt, etc.), Group 11 elements (Cu, Ag, Au, etc.), Group 12 elements (Zn, Cd, etc.), Group 13 elements (Al, Ga, In, etc.), And Group 14 elements (Si, Ge, Sn, Pb, etc.).

  Examples of the inorganic compound containing these elements include oxides (including complex oxides), halides (fluorides, chlorides, bromides, iodides), oxo acid salts (nitrates, sulfates, phosphates, borates). Acid salts, perchlorates, carbonates, etc.), carbon monoxide, carbon dioxide, carbon disulfide, and other compounds formed from such elements, and hydrocyanic acid, hydrocyanates, cyanates, and thiocyanates. Salts such as acid salts and carbides may be mentioned.

  Among the carbon compounds, those that are exceptionally classified as inorganic compounds include, for example, diamond, lonsdaylite, graphite, graphene, fullerenes (buckminsterfullerene, carbon nanotube, carbon nanohorn, etc.), glassy carbon, and carbine. , Allotropes of carbon such as amorphous carbon and carbon nanofoam.

  One inorganic particle may include one or more of the above elements. The plural kinds of elements may be present uniformly or unevenly in the particles, and the surface of the particles of the compound of one element may be covered with the compound of another element. These inorganic particles may be used alone or in combination of two or more.

Among these, preferred inorganic particles are not particularly limited, for example, zirconium , titanium, zinc, iron, copper, chromium, cadmium, carbon, tungsten, antimony, nickel, and at least selected from the group consisting of platinum. Contains one element. More specifically, zirconium oxide, zirconium and other zirconium oxides and zirconium composite oxides; titanium oxide, barium titanate, strontium titanate and other titanium oxides and titanium composite oxides; zinc, zinc oxide, zinc sulfide, etc. , Zinc oxide and zinc composite oxide; iron, iron oxides such as iron, ferric oxide and diiron trioxide; copper, copper oxide such as cupric chloride, copper oxide and copper compounds Chromium oxides such as chromium oxide; cadmium oxides and cadmium compounds such as cadmium oxide and cadmium sulfide; carbon compounds such as diamond; tungsten compounds; antimony compounds; nickel compounds; platinum and the like. Among these, from the viewpoint of availability and stability, zirconium oxide, zirconium oxide such as zircon and zirconium composite oxide, titanium oxide, barium titanate, titanium oxide such as strontium titanate and titanium composite oxide. More preferable. The surface of these particles may be covered with SiO ₂ , Al ₂ O ₃ or the like. These may be used alone or in combination of two or more. By using such inorganic particles, the refractive index tends to be further improved.

  The average particle diameter (average value of the outer diameter of the particles) of the inorganic particles (particularly spherical particles) is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and further preferably 1 to 30 nm. is there. When the average particle size of the inorganic particles is 100 nm or less, problems such as light scattering tend to be less likely to occur when the curable resin composition is used as an optical material. Further, when the average particle diameter of the inorganic particles is 0.1 nm or more, it tends to be possible to suppress the change in the characteristic peculiar to the substance forming the inorganic particles. The average particle size of the inorganic particles can be measured with a transmission electron microscope.

  The refractive index of the inorganic particles is 1.8 or more from the viewpoint of increasing the refractive index. From the viewpoint of the balance between the refractive index design and the film forming property, the refractive index of the inorganic particles is preferably 1.8 to 4.5, more preferably 1.8 to 3.0, and further preferably 1. 8 to 2.5. The refractive index of the inorganic particles can be measured by the method described in Examples.

The density of the high refractive index inorganic particles is not particularly limited, but is preferably 2.5 to 8 g / cm ³ in order to facilitate obtaining a high refractive index in a molded product or the like. From the viewpoint of the balance between the refractive index design and the moldability, the density of the inorganic particles is more preferably 3.5 to 5.5 g / cm ³ .

  The shape and crystal form of the inorganic particles are not particularly limited, and may be various shapes such as spherical, crystalline, scale-like, columnar, tubular, fibrous, hollow, porous, and beaded shapes. You may.

  The content of the inorganic particles is 10 to 200 parts by mass, preferably 15 to 180 parts by mass, and more preferably 20 to 160 parts by mass with respect to 100 parts by mass of the organopolysiloxane (I). When the content of the inorganic particles is 10 parts by mass or more, a high refractive index can be obtained. Further, when the content of the inorganic particles is 200 parts by mass or less, a curable resin composition and a cured product having excellent transparency can be obtained.

[Organopolysiloxane (II)]
The photocurable resin composition of the present embodiment is represented by the structural unit F1 ′ represented by the following general formula (5) and the following general formula (6) with respect to 100 parts by mass of the organopolysiloxane (I). Further, 0.10 to 100 parts by mass of the organopolysiloxane (II) having the structural unit T ′ described above as a unit constituting the cyclic organopolysiloxane may be further contained. The inclusion of the organopolysiloxane (II) tends to increase the crosslink density of the cured product obtained from the curable resin composition and further improve the refractive index.
(In the general formula (5), R ^{1 ′} is a substituted or unsubstituted C 1-10 alkyl group, a substituted or unsubstituted C 3-10 cycloalkyl group, a substituted or unsubstituted aryl group. Or a substituted or unsubstituted aralkyl group, R ^{2 ′} represents an unsaturated bond-containing group having 2 to 10 carbon atoms, and X ′ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. , E represents the content ratio of the structural unit F1 ′, and represents an integer of 1 or more.)
(In the general formula (6), R ^{1 ′} is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. Or a substituted or unsubstituted aralkyl group, f represents the content ratio of the structural unit T ′, represents an integer of 0 or more, and the sum of e and f represents an integer of 3 to 20.)

[Structural unit F1 ']
The structural unit F1 ′ represented by the general formula (5) is a unit that constitutes the cyclic organopolysiloxane.

In formula (5), R ^{1 ′} represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, or Represents a substituted or unsubstituted aralkyl group. Specific examples of R ^{1 ′} include the same groups as those exemplified in the general formula (1). R ¹ in the general formula (1) and R ^{1 ′} in the general formula (5) may be the same or different.

Among these, as R ^{1 ′} in the general formula (5), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

In general formula (5), R2 ^' shows a C2-C10 unsaturated bond containing group. The unsaturated bond-containing group having 2 to 10 carbon atoms is not particularly limited, and examples thereof include the same groups as those exemplified for R ² in the above general formula (1). Among these, a (meth) acryloxy group is preferable. By using the (meth) acryloxy group, the reactivity of the photocurable resin composition, that is, the property of facilitating photocuring and rapidly proceeding the reaction tends to be further improved. R ² in the general formula (1) and R ^{2 ′} in the general formula (5) may be the same or different.

In formula (5), X ′ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Although it does not specifically limit as a C2-C10 bivalent hydrocarbon group, For example, the group similar to the group illustrated by X in the said General formula (1) can be illustrated. Among _{this, - (CH 2) 3 -} , - (CH 2) 4 -, and - (CH _{2) 6} - is the raw material of the easy availability and reactivity, i.e. photocuring easily quickly react It is preferable from the viewpoint of proceeding. In addition, X in the general formula (1) and X ′ in the general formula (5) may be the same or different.

[Structural unit T ']
The constitutional unit T ′ represented by the general formula (6) is a unit constituting a cyclic organopolysiloxane.
In the general formula (6), R ^{1 ′} represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, or Represents a substituted or unsubstituted aralkyl group. Specific examples of R ^{1 ′} include the same groups as those exemplified in the general formula (1). R ¹ in the general formula (1) and R ^{1 ′} in the general formula (6) may be the same or different.

Among these, as R ^{1 ′} in the general formula (6), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

  The content of the organopolysiloxane (II) is preferably 0.10 to 100 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 100 parts by mass of the organopolysiloxane (I). 5 to 80 parts by mass. When the content of the organopolysiloxane (II) is 0.10 parts by mass or more, the viscosity is lowered and the workability tends to be further improved. Moreover, when the content of the organopolysiloxane (II) is 100 parts by mass or less, the light resistance tends to be further improved.

The functional group equivalent of the unsaturated bond-containing group represented by R ^{2 ′} is preferably 20 to 10000 g / mol, more preferably 50 to 9000 g / mol, and further preferably 100 to 8000 g / mol. When the functional group equivalent of the unsaturated bond-containing group represented by R2 ^' is 20 g / mol or more, the light resistance of the cured product of the curable resin composition tends to be further improved. Further, by functional group equivalents of the unsaturated bond-containing group represented by R 2 ^'is not more than 10000 g / mol, there is a tendency that the refractive index of the curable resin composition is more improved. The functional group equivalent of the unsaturated bond-containing group represented by R ^{2 ′} can be measured by the method described in Examples below.

  The weight average molecular weight of the organopolysiloxane (II) is preferably 500 to 1,000,000, more preferably 700 to 800,000, and further preferably 1000 to 500,000. When the weight average molecular weight of the organopolysiloxane (II) is 500 or more, the dispersion stability of the inorganic particles tends to be further improved. Further, when the weight average molecular weight of the organopolysiloxane (II) is 1,000,000 or less, the refractive index of the curable resin composition tends to be further improved. The weight average molecular weight can be measured by the method described in Examples.

  The viscosity of the organopolysiloxane (II) at 25 ° C is preferably 1.0 to 1,000,000 mPa · s, more preferably 5.0 to 500,000 mPa · s, and further preferably 10 to 100,000 mPa · s. .. When the viscosity of the organopolysiloxane (II) at 25 ° C. is 1.0 mPa · s or more, the dispersion stability of the inorganic particles tends to be further improved. Moreover, when the viscosity of the organopolysiloxane (II) at 25 ° C. is 1,000,000 mPa · s or less, the handleability of the curable resin composition tends to be further improved. The viscosity at 25 ° C can be measured by the method described in Examples below.

[Organopolysiloxane (III)]
The curable resin composition of the present embodiment is a straight-chain organopolysiloxane (III) 0.10 having an unsaturated bond-containing group having 2 to 10 carbon atoms per 100 parts by mass of the organopolysiloxane (I). ˜100 parts by mass may be further contained. By containing the organopolysiloxane (III), the light resistance of the cured product obtained from the curable resin composition tends to be improved.

  The content of the organopolysiloxane (III) is preferably 0.10 to 100 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 100 parts by mass of the organopolysiloxane (I). 5 to 80 parts by mass.

In the photocurable resin composition, the total functional group equivalent of the unsaturated bond-containing groups represented by R ² and R ^{2 ′} is preferably 20 to 10000 g / mol, more preferably 50 to 9000 g / mol. , And more preferably 100 to 8000 g / mol. By total functional group equivalent of the unsaturated bond-containing group represented by R ² and R ^{2 'is} 20 g / mol or more, thermal yellowing resistance of the cured product of the photocurable resin composition, light resistance is further improved There is a tendency. Further, by total functional group equivalent of the unsaturated bond-containing group represented by R ² and R ^{2 'is} not more than 10000 g / mol, there is a tendency that the refractive index of the photocurable resin composition is further improved. The total functional group equivalent of the unsaturated bond-containing groups represented by R ² and R ^{2 ′} can be measured by the method described in Examples below.

  The weight average molecular weight of the combination of the organopolysiloxane (I) and the organopolysiloxane (II) is preferably 500 to 1,000,000, more preferably 700 to 800,000, and further preferably 1000 to 500,000. When the weight average molecular weight of the organopolysiloxane (I) and the organopolysiloxane (II) is 500 or more, the dispersion stability of the inorganic particles tends to be further improved. When the weight average molecular weight of the organopolysiloxane (I) and the organopolysiloxane (II) is 1,000,000 or less, the refractive index of the photocurable resin composition tends to be further improved. The weight average molecular weight can be measured by the method described in Examples.

  The viscosity at 25 ° C. of the organopolysiloxane (I) and the organopolysiloxane (II) is preferably 1.0 to 1,000,000 mPa · s, more preferably 5.0 to 500000 mPa · s, It is preferably 10 to 100,000 mPa · s. When the combined viscosity of the organopolysiloxane (I) and the organopolysiloxane (II) at 25 ° C. is 1.0 mPa · s or more, the dispersion stability of the inorganic particles tends to be further improved. Further, when the viscosity of the organopolysiloxane (I) and the organopolysiloxane (II) together at 25 ° C. is 1,000,000 mPa · s or less, the handleability of the photocurable resin composition tends to be further improved. The viscosity at 25 ° C can be measured by the method described in Examples below.

[Photo radical generator]
The photoradical generator is not particularly limited as long as it radically polymerizes the unsaturated bond-containing groups with each other by light. Triazine derivatives described in JP-A-60104 and the like; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684 and JP-B-44- 6413, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, etc., and diazonium compounds described in U.S. Pat. No. 3,567,453; U.S. Pat. No. 2,848,328. , U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,853, the organic azide compounds described in JP-B-36-22062. Ortho-quinone diazides described in JP-B-37-13109, JP-B-38-18015, and JP-B-45-9610; JP-B-55-39162 and JP-A-59-14023. And various other onium compounds described in "Macromolecules, Volume 10, page 1307 (1977)"; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patent 109,851, European Patent 126,712, and "Journal of Imaging Science (J.Imag.Sci.), Volume 30," Page 174 (1986) "and the like; metal allene complexes; JP-A-6-213861; (Oxo) sulfonium organic boron complex described in JP-A-6-255347; titanocenes described in JP-A-61-151197; "Coordination Chemistry Review, Vol. 84, No. 85. Page 277 (1988) "and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triaryl described in JP-A-3-209477. Imidazole dimer; carbon tetrabromide; organic halogen compounds described in JP-A-59-107344. The photo-radical generator may be used alone or in combination of two or more.

  The content of the photo radical generator is 0.050 to 20 parts by mass, preferably 0.10 to 15 parts by mass, relative to 100 parts by mass of the total amount of the organopolysiloxane (I) and the organopolysiloxane (II). Parts, and more preferably 1.0 to 10 parts by mass. When the content of the photo radical generator is 0.050 part by mass or more, the curability of the photocurable resin composition is further improved. Moreover, when the content of the photo radical generator is 20 parts by mass or less, a photocurable resin composition and a cured product having excellent light resistance can be obtained. When the curable resin composition does not contain the organopolysiloxane (II), the content of the heat radical generator is in the range based on 100 parts by mass of the organopolysiloxane (I).

[Hydrosilylation reaction catalyst]
The curable resin composition of the present embodiment may further contain a hydrosilylation reaction catalyst. Examples of the hydrosilylation reaction catalyst include those described below.

  The content of the hydrosilylation reaction catalyst is preferably 0.0010 parts by mass or less, more preferably 0 to 0. 0, based on 100 parts by mass of the total amount of the organopolysiloxane (I) and the organopolysiloxane (II). It is 0800 parts by mass, more preferably 0 to 0.00050 parts by mass. When the content of the hydrosilylation reaction catalyst is within the above range, the light resistance tends to be further improved. When the curable resin composition does not contain the organopolysiloxane (II), the content of the hydrosilylation reaction catalyst is in the range based on 100 parts by mass of the organopolysiloxane (I).

[Other ingredients]
In the photocurable resin composition of the present embodiment, (meth) acrylate monomers and oligomers, vinyl (meth) acrylate, and the like, if necessary, for the purpose of promoting curability with respect to light energy (improvement of sensitivity). You may add the radically polymerizable compound of these.

  In addition, addition of deterioration inhibitors, release agents, diluents, antioxidants, heat stabilizers, flame retardants, plasticizers, surfactants, etc. within a quantitative and qualitative range that does not depart from the scope of the present invention. Agents can be added.

[Method for producing curable resin composition]
The method for producing the curable resin composition of the present embodiment,
A hydrogen polysiloxane (a) having a structural unit represented by the following general formula (7) as a unit constituting a cyclic organopolysiloxane,
(In the general formula (7), R ^{1 ″} represents a substituted or unsubstituted C 1-10 alkyl group, a substituted or unsubstituted C 3-10 cycloalkyl group, a substituted or unsubstituted aryl. A group or a substituted or unsubstituted aralkyl group, and j represents the content ratio of the structural unit and represents an integer of 1 or more.)
An organosiloxane (b1) having one vinyl group directly bonded to a silicon atom and containing one or more hydrolyzable groups,
An organic compound (c) having two or more unsaturated bond-containing groups,
An addition reaction step of obtaining an organopolysiloxane by an addition reaction in the presence of a hydrosilylation reaction catalyst (d),
The method has a mixing step of mixing the organopolysiloxane, the inorganic particles (e) having a refractive index of 1.8 or more, and a photoradical generator.

[Addition reaction step]
[Hydrogen polysiloxane (a)]
The hydrogen polysiloxane (a) is a compound having the constitutional unit represented by the general formula (7) as a unit constituting the cyclic organopolysiloxane.

In general formula (7), R ^{1 ″} represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, Alternatively, it represents a substituted or unsubstituted aralkyl group. Specific examples of R ^{1 ″} include the same groups as those exemplified in the above general formula (1).

Among these, as R ^{1 ″} in the general formula (7), an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is more preferable. By using such a group, heat yellowing and light resistance tend to be further improved.

The hydrogen polysiloxane (a) preferably further has a structural unit represented by the following general formula (8). By further containing a structural unit represented by the following general formula (8), heat yellowing and light resistance tend to be further improved.
(In the general formula (8), R ^{1 ″} is each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted group. Or an unsubstituted aryl group or a substituted or unsubstituted aralkyl group, k represents the content ratio of the structural unit, represents an integer of 0 or more, and j + k is an integer of 3 to 20.)

The hydrogen polysiloxane (a) is not particularly limited, and examples thereof include compounds represented by the following general formulas (11) to (13). The hydrogen polysiloxane (a) may be used alone or in combination of two or more.

[Organosiloxane (b1)]
The organosiloxane (b1) is a compound having one vinyl group directly bonded to a silicon atom and one or more hydrolyzable groups. Such an organosiloxane (b1) is not particularly limited, but examples thereof include compounds represented by the following general formula (14). The organosiloxane (b1) may also include organopolysiloxane.
(In the general formula (14), R ^{3 ″} each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted group. Or an unsubstituted aryl group and any one selected from the group consisting of a substituted or unsubstituted aralkyl group, Y ″ represents a divalent hydrocarbon group having 0 to 8 carbon atoms, and n is 1 to 1 It is an integer of 3.)

  The hydrolyzable group is not particularly limited, but examples thereof include a methoxy group and an ethoxy group.

  The organosiloxane (b1) may be used alone or in combination of two or more.

[Organosiloxane (b2)]
In the addition reaction step, the organosiloxane (b2) having one vinyl group directly bonded to a silicon atom and having no hydrolyzable group may be further subjected to an addition reaction. The organosiloxane (b2) is not particularly limited, but examples thereof include compounds represented by the following general formula (15). The organosiloxane (b2) may also include organopolysiloxane.
(In the general formula (15), R ^{4 ″} is each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted group Or an unsubstituted aryl group and a substituted or unsubstituted aralkyl group, and Z ″ represents a divalent hydrocarbon group having 0 to 8 carbon atoms.

  The organosiloxane (b2) may be used alone or in combination of two or more.

[Organic compound (c)]
The organic compound (c) is a compound having two or more unsaturated bond-containing groups. The organic compound (c) is not particularly limited, but examples thereof include compounds represented by the following general formula (16).
(In the general formula (16), R ^{2 ″} represents an unsaturated bond-containing group having 2 to 10 carbon atoms, and X ″ represents a divalent hydrocarbon group having 0 to 8 carbon atoms.)

  Particularly, X ″ is preferably a divalent hydrocarbon group having 1 to 4 carbon atoms. As a result, the hydrosilylation reaction tends to proceed more efficiently. Further, since X ″ is a divalent hydrocarbon group having 1 to 4 carbon atoms, the boiling point of the organic compound (c) is lowered, and the surplus organic compound (c) is easily distilled off from the reaction solution. It tends to be possible.

  The organic compound (c) may be used alone or in combination of two or more.

  The amount (molar amount) of the organic compound (c) used in the addition reaction step is the molar amount of the SiH group of the hydrogen polysiloxane (a) and the organosiloxane ( It is preferable to add so as to be larger than the sum of the molar amounts of the vinyl groups of b1) and the organosiloxane (b2).

Specifically, the amount ratio of the organic compound (c) represented by the following formula is preferably 1.2 to 3.0, more preferably 1.3 to 2.5, and further preferably It is 1.4 to 2.0. When the amount of the organic compound (c) used is 1.2 or more, the reactivity tends to be further improved. Further, when the amount of the organic compound (c) used is 3.0 or less, the purification load tends to be reduced.
Use amount ratio of organic compound (c) = [molar amount of organic compound (c)] / [(molar amount of SiH group of hydrogen polysiloxane (a))-(molar amount of vinyl group of organosiloxane (b1)) + Molar amount of vinyl group of organosiloxane (b2)]

[Hydrosilylation reaction catalyst (d)]
The hydrosilylation reaction catalyst (d) is not particularly limited, and any conventionally known catalyst can be used. More specifically, platinum black, secondary platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetoacetate. A platinum group metal-based catalyst other than the platinum-based catalyst, such as a palladium-based catalyst or a rhodium-based catalyst. The hydrosilylation reaction catalyst (d) may be used alone or in combination of two or more.

  The amount of the hydrosilylation reaction catalyst (d) used is preferably 0.010 to 100 ppm, more preferably 0.020 to 50 ppm, and even more preferably 100 parts by mass of the product organopolysiloxane. It is 0.050 to 20 ppm. When the amount of the hydrosilylation reaction catalyst (d) used is 0.010 ppm or more, a sufficient catalytic effect tends to be obtained. Further, when the amount of the hydrosilylation reaction catalyst (d) used is 100 ppm or less, the cost tends to be further reduced.

The addition reaction temperature is preferably room temperature to 110 ° C, more preferably 40 ° C to 100 ° C, and further preferably 50 to 90 ° C. When R ² is a (meth) acryloxy group, the addition reaction temperature is preferably 40 ° C to 100 ° C. When the addition reaction temperature is within the above range, gelation due to the reaction of the unsaturated bond-containing group tends to be more suppressed.

〔solvent〕
The above addition reaction may be carried out in a solvent, if necessary. The solvent is not particularly limited, but examples thereof include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane and octane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and isobutyl acetate. Solvents; ether solvents such as diisopropyl ether, 1,4-dioxane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol monomethyl ether acetate; and alcohol solvents such as isopropanol; or mixtures thereof. Solvents may be mentioned.

The atmosphere of the addition reaction may be air or an inert gas. Among these, an inert gas such as nitrogen, argon, and helium is preferable because the obtained organopolysiloxane is less colored. Further, when R ² is a (meth) acryloxy group, a small amount of oxygen can be introduced for the purpose of preventing the polymerization reaction of the (meth) acryloxy group.

When R ² is a (meth) acryloxy group, a phenothiazine, a hindered phenol-based compound, an amine-based compound, a quinone-based compound or the like is added to the reaction system for the purpose of preventing the polymerization reaction of the (meth) acryloxy group. It is preferable to add a polymerization inhibitor. The type and amount of such a polymerization inhibitor is not particularly limited as long as it can prevent the polymerization reaction of the (meth) acryloxy group, that is, an acryloxy group or a methacryloxy group, without hindering the progress of the hydrosilylation reaction by adding them. Not done.

[Catalyst removal step]
The method for producing an organopolysiloxane may have a catalyst removal step of removing the hydrosilylation reaction catalyst (d) from the organopolysiloxane after the addition reaction. The catalyst removal is not particularly limited, and examples thereof include a method of washing with water and a method of removing with an adsorbent such as activated alumina or activated carbon.

  The residual amount (content) of the hydrosilylation reaction catalyst (d) is preferably 0 to 0.0010 parts by mass, more preferably 0 to 0.00080 parts by mass with respect to 100 parts by mass of the product organopolysiloxane. It is a mass part, More preferably, it is 0-0.00050 mass part. When the residual amount of the hydrosilylation reaction catalyst (d) is 0.0010 parts by mass or less, heat yellowing resistance and light resistance tend to be further improved. The residual amount of the hydrosilylation reaction catalyst (d) can be measured by analyzing the curable resin composition.

  In addition, the surplus organic compound (c) and a solvent that can be used if necessary may be distilled off under heating and / or reduced pressure.

  In the above production method, the organopolysiloxane (I) and the organopolysiloxane (I) are prepared by adjusting the amounts of the hydrogen polysiloxane (a), the organosiloxane (b1), the organosiloxane (b2), and the organic compound (c) used. The organopolysiloxane (II) can be produced simultaneously. In addition, a method of mixing the organopolysiloxane (I) produced by the above-mentioned organopolysiloxane production method and the separately produced organopolysiloxane (II) can also be mentioned.

[Mixing process]
The mixing step is a step of mixing the obtained organopolysiloxane, inorganic particles, and a photoradical generator. By this step, the inorganic particles and the photoradical generator are dispersed in the curable resin composition. The method of mixing and dispersing is not particularly limited, but a wet method of removing a solvent by mixing a solution containing an organopolysiloxane, a solution containing inorganic particles, and a solution containing a photoradical generator, and a bead mill dispersion method. , A jet mill dispersion method, a ball mill dispersion method, an ultrasonic homogenizer dispersion method, a paint shaker dispersion method and the like. Among these, the wet method, the bead mill dispersion method and the jet mill dispersion method are more preferable from the viewpoint of dispersibility and simplicity. In the wet method, a solution containing inorganic particles and a photoradical generator may be used.

[Use]
The photocurable resin composition of the present embodiment is liquid or solid before curing, and can be a cured product by performing a predetermined treatment. For example, by subjecting the photocurable resin composition to ultraviolet irradiation treatment, the unsaturated bond-containing group is polymerized starting from the photoradical generator to obtain a cured product. Hereinafter, each use of the photocurable resin composition of the present embodiment will be described, but the use of the photocurable resin composition of the present embodiment is not limited to the following.

[Optical semiconductor encapsulant]
The photocurable resin composition of this embodiment can be used as a sealing material for optical semiconductors. The encapsulant for optical semiconductors containing the photocurable resin composition of the present embodiment can be used as an encapsulant for OLED display elements, photovoltaic modules, and the like. An optical semiconductor package formed by molding the encapsulating material for an optical semiconductor of the present embodiment and an optical semiconductor device manufactured using the encapsulating material for an optical semiconductor of the present embodiment are also within the scope of the present invention.

  FIG. 1 is a sectional view showing an embodiment of an OLED display device using the semiconductor encapsulant of this embodiment. In the OLED display element 10, after the hole injecting electrode 2, the hole transporting layer 3, the light emitting layer 4 and the electron injecting electrode 5 are sequentially formed on the base material 1, they are sealed with the semiconductor encapsulating material 6 of the present embodiment. After that, the base material 7 can be formed by a method of pasting the base material 7 together. Such whole surface sealing with a solid film is a particularly effective method when flexible materials are used as the base materials 1 and 7.

  As a method for forming a multilayer structure in which the hole injection electrode 2, the hole transport layer 3, the light emitting layer 4, and the electron injection electrode 5 are sequentially laminated on the base material 1, there are known methods such as resistance heating vapor deposition and ionization. A beam sputtering method, an inkjet method that can be formed at normal pressure, a printing method, or the like can be used. Next, the method for applying the semiconductor encapsulant on the multilayer structure is not particularly limited as long as it is a method capable of uniformly applying the semiconductor encapsulant. For example, a printing method such as screen printing or flexo printing may be used. The thing and the method of applying using a dispenser are mentioned.

  After the base material 7 is bonded to the semiconductor encapsulating material 6, the semiconductor encapsulating material 6 can be cured by irradiating with energy rays from the base material 7 side or the base material 1 side. Any type of energy ray may be used as long as it can cure the semiconductor sealing material 6, and examples thereof include light such as ultraviolet rays and radiation. The light source that can be used here is not particularly limited as long as it cures the semiconductor encapsulating material 6 within a predetermined working time, and for example, a light source that can irradiate light having a wavelength of ultraviolet light or visible light is used. be able to. Specific examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, and an electrodeless discharge lamp. As described above, the semiconductor encapsulating material of the present embodiment can be used for encapsulating various semiconductor elements such as an OLED display element. In particular, since the semiconductor encapsulant of the present embodiment can be prepared as a cured product at room temperature when it is a cured product, it prevents thermal deterioration or deformation due to heat of the base material or element found in conventional photocurable resins. be able to. Further, since it has high adhesion to the base material and the element, it can be preferably used for sealing a semiconductor element of precision equipment such as FPD, and particularly preferably for sealing an OLED display element.

  The cured product formed by curing the photocurable resin composition is also suitably used as a sealing material for other optical semiconductor devices. The photocurable resin composition may be used as a die bonding paste, and the cured product may be formed as a die bond material. The cured product of the photocurable resin composition can be suitably used for optical semiconductor device applications such as a chip coating material for covering the periphery of a chip and a lens material. In this case, examples of the optical semiconductor include an LED lamp, a chip LED, a semiconductor laser, a photo coupler, and a photodiode.

  The optical semiconductor device has a housing material, a silicon chip provided in the housing, and a sealing material that is a cured product of the photocurable resin composition of the present embodiment and seals the silicon chip. The material of the housing material is not particularly limited, but examples thereof include aromatic polyamides such as polyphthalamide, engineering plastics such as 66 nylon, ceramics, etc. In the case of polyphthalamide, particularly high adhesion is exhibited.

  It is preferable that the housing material contains glass fiber because the adhesive strength is increased. The content of the glass fiber is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass, based on the mass of the housing material. When the content of the glass fiber is within these numerical ranges, the effect of the present invention is more remarkably exhibited.

〔Coating agent〕
The photocurable resin composition of this embodiment can also be used as a coating agent having photosensitivity. The coating material containing the photocurable resin composition of the present embodiment is capable of curing a thin film at high speed in air, and thus coating on a resin film, substrate or the like that is required to be cured at high speed without heating. It is also suitably used as a material. Specifically, a coating material for forming an antireflection film used for a flat panel display (FPD) or the like can be mentioned.

  A photosensitive coating agent containing a photocurable resin composition is applied on the surface of a transparent substrate (for example, a resin substrate of polymethylmethacrylate, polycarbonate, polystyrene, and triacetylcellulose, or an inorganic material such as glass). Then, by photocuring the coating film, a cured film having a thickness of 10 nm to 1 μm can be formed as an antireflection film, a scratch prevention film, or the like. Since it is necessary to form a relatively thin film with a high degree of precision when applying it on a substrate, the microgravure method, roll coating method, flow coating method, spin coating method, die coating method, cast transfer method, and spray coating method are used. The method is used.

  The photocurable resin composition of the present embodiment can be cured in a short time by applying it to a substrate or the like to form a thin film, and irradiating the thin film with energy rays such as ultraviolet rays and heating. Curing of the photocurable resin composition may be carried out by energy beam irradiation and heating in combination. The photocurable resin composition of the present embodiment can be sufficiently put into practical use without containing a solvent or the like, but it may be diluted with a solvent or the like for viscosity adjustment, or a sol containing porous fine particles or the like. It may be in the form of. When diluted with a solvent or the like, or when used in the form of a sol containing porous fine particles or the like, in order to volatilize the solvent component in advance, before irradiation with light, at a temperature of 50 to 150 ° C. for about several minutes May be heated. Further, the curing can be further promoted by heating similarly after the exposure.

〔adhesive〕
Since the photocurable resin composition of the present embodiment is cured by light irradiation, it can be suitably used as a photosensitive adhesive. The adhesive containing the photocurable resin composition of the present embodiment can be used in the form of liquid, solid, sol, etc. described above, and can exhibit excellent adhesiveness without being hindered by humidity.

[Curable resin composition for nanoimprint]
The photocurable resin composition of the present embodiment can also be suitably used as a photocurable resin for nanoimprint. By using the photocurable resin for nanoimprinting containing the photocurable resin composition of the present embodiment, it is possible to perform microfabrication by pressing the original plate onto the substrate coated with the photocurable resin without using a conventional exposure device. Can be realized.

〔ink〕
By adding a colorant to the photocurable resin composition of this embodiment, an ink having photosensitivity can be obtained. The ink containing the photocurable resin composition of the present embodiment and the colorant also has a feature that the viscosity can be relatively easily lowered, and combined with the colorant together with the excellent photocurability. Therefore, the ink can be suitably used as a photosensitive ink.

  The colorant used in the photosensitive ink is not particularly limited, but various organic pigments and inorganic pigments can be used. Specifically, white pigments such as titanium oxide, zinc white, lead white, lithobon, and antimony oxide; black pigments such as aniline black, iron black, and carbon black; yellow lead, yellow iron oxide, Hansa Yellow (100, 50 , 30 etc.), yellow pigments such as titanium yellow, benzine yellow, and permanent yellow; orange pigments such as chrome vermilion, permanent orange, balkan first orange, and indanthrene brilliant orange; iron oxide, permanent brown, and para. Brown pigments such as brown; red pigments such as red iron oxide, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolite face tread, and quinacridone red pigments; cobalt purple, mann Purple pigments such as purple, first violet, methyl violet lake, indanthrene brilliant violet, dioxazine violet; ultramarine blue, navy blue, cobalt blue, alkali blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue and Blue pigments such as indigo; green pigments such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine; other various fluorescent pigments, metal powder Examples thereof include pigments and extender pigments. The amount of these colorants is preferably 1 to 50% by mass, and more preferably 5 to 25% by mass, based on the total amount of the photocurable resin composition.

  A pigment dispersant may be optionally used together with the colorant. Examples of pigment dispersants include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylenes. Activators such as alkyl phenyl ether, glycerin ester, sorbitan ester, and polyoxyethylene fatty acid amide; styrene, styrene derivative, vinylnaphthalene derivative, acrylic acid, acrylic acid derivative, maleic acid, maleic acid derivative, itaconic acid, itaconic acid derivative , A fumaric acid, and a fumaric acid derivative, a block copolymer or a random copolymer composed of two or more kinds of monomers, and salts thereof.

  As a method for dispersing the colorant, there is a method using various dispersing machines such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker. A centrifuge or a filter may be used for the purpose of removing coarse particles of the pigment dispersion.

  The average particle size of the pigment particles in the pigment ink is selected in consideration of stability in the ink, image density, gloss feeling, light resistance, etc., but the particle size is appropriately selected from the viewpoint of improving gloss and texture. Preferably.

[Optical lens]
The cured product of the photocurable resin composition of the present embodiment can be suitably used as an optical lens by taking advantage of its heat-resistant yellowing property and high transparency. The optical lens including the photocurable resin composition of the present embodiment is, for example, a lens material such as a spectacle lens, an optical device lens, a CD or DVD pickup lens, an automobile headlamp lens, and a projector lens. It is also suitably used for various optical members such as optical fibers, optical waveguides, optical filters, optical adhesives, optical disk substrates and display substrates.

  Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples. In Examples and Comparative Examples, measurement and evaluation were performed by the following methods.

<Calculation of reaction rate of SiH>
0.05 g of a solution before the start of the reaction and 0.05 g of the sampled reaction solution (a solution after the lapse of 72 hours from the start of the reaction, which is a reaction solution in the organopolysiloxane synthesis in Examples and Comparative Examples described later) Each was dissolved in 1 g of a solvent to obtain a measurement sample. The ¹ H NMR measurement of this measurement sample was performed using α-400 (400 MHz) manufactured by JASCO Corporation at 100 times of integration, and the obtained results were analyzed.

The reaction rate of SiH was calculated according to the following formula by obtaining the area ratio of the peak of 0.2 ppm derived from Si—CH ₃ before the reaction and the peak of 4.6 ppm derived from SiH.
Reaction rate (%) of SiH = [((X1-Y1) / X1] × 100
X1: peak area ratio before reaction: (peak area of SiH before reaction) / (peak area of Si—CH ₃ before reaction)
Y1: peak area of SiH after the peak area ratio after the reaction :( reaction) / (peak area of Si-CH ₃ after the reaction)

<Identification of molecular structure>
20 mg of each sample of the organopolysiloxanes (A1) to (A2) and (B1) prepared in Examples and Comparative Examples described later were dissolved in 1 g of deuterated chloroform solvent to prepare a measurement sample. The ¹ H NMR measurement of this measurement sample was performed using α-400 (400 MHz) manufactured by JASCO Corporation at an integration number of 200 times, and the obtained results were analyzed.

A solution prepared by dissolving 0.3 g of each sample in 1 g of deuterated chloroform solvent was used as a measurement sample. The ¹³ C NMR measurement of this measurement sample was performed using α-400 (400 MHz) manufactured by JASCO Corporation at an integration count of 20,000, and the obtained results were analyzed.

Further, 0.15 g of each sample was dissolved in 1 g of deuterated chloroform solvent, and a solution containing 8% by mass of chromium (III) acetylacetonate (Cr (acac) ₃ ) added to the sample was used as a measurement sample. did. ²⁹ Si NMR measurement of this measurement sample was performed using α-400 (400 MHz) manufactured by JASCO Corporation at an integration number of 4000 times, and the obtained results were analyzed.

^The results obtained by ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR were analyzed to identify the molecular structures of organopolysiloxanes A1) to (A2) and (B1).

<Calculation of functional group equivalent of unsaturated bond-containing group>
30 mg of each sample of the organopolysiloxanes (A1) to (A2) and (B1) produced in the examples and comparative examples described later were dissolved in 1 g of deuterated chloroform solvent as a measurement sample. The ¹ H NMR measurement of this measurement sample was performed 200 times with α-400 (400 MHz) manufactured by JASCO Corporation, and the obtained results were analyzed to determine the average composition in one molecule of organopolysiloxane. I asked.

Further, 0.15 g of each sample was dissolved in 1 g of a deuterated chloroform solvent, and 8% by mass of Cr (acac) ₃ was added to the sample as a measurement sample. The ²⁹ Si NMR of this measurement sample was measured 4000 times by using α-400 (400 MHz) manufactured by JASCO Corporation, and the obtained results were analyzed to determine the average composition in one molecule of organopolysiloxane. I asked.

^The results obtained by ¹ H NMR and ²⁹ Si NMR were analyzed to calculate the functional group equivalent of the unsaturated bond-containing group ((meth) acryloxy group) (mass per 1 mol of the functional group).

<Calculation of weight average molecular weight>
100 mg of each sample of organopolysiloxanes (A1) to (A2) and (B1) produced in Examples and Comparative Examples described later were dissolved in 2 g of chloroform solvent and filtered through a 0.45 μm filter. The measurement sample solution was used.

The eluent (chloroform) was passed through a column having the following constitution at a column temperature of 40 ° C. under the condition of a flow rate of 1 mL / min.
(Column structure)
Guard column: TskguardcolumnH-H (registered trademark) manufactured by Tosoh Corporation
Separation column: Tskgel (registered trademark) G5000H manufactured by Tosoh Corp., Tskgel (registered trademark) G3000H manufactured by Tosoh Corp., and Tskkel (registered trademark) G1000H manufactured by Tosoh Corp. are each arranged in series.

  In addition, molecular weights manufactured by Polymer Laboratories of 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, 580 A calibration curve obtained from the elution time of the monodisperse polypolystyrene standard substance of known molecular weight and the styrene monomer (molecular weight 104) by RI detection was prepared in advance. From the elution time of the measurement sample solution and the detection intensity, the molecular weight was calculated using the above calibration curve.

<Refractive index of inorganic particles>
The refractive index of the inorganic particles was determined by the following method using a standard refraction liquid (manufactured by Cargill). However, when a standard refractive liquid having a desired refractive index was not available, a reagent having a known refractive index was used instead.
(1) The dispersion liquid of inorganic particles was taken in an evaporator to evaporate the dispersion medium.
(2) This was dried with a vacuum dryer at 120 ° C. to give a powder.
(3) A few drops of a standard refraction liquid having a known refractive index were dropped on a glass plate, and the above powder was mixed therein.
(4) The operation of (3) above was carried out with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid became transparent was taken as the refractive index of the inorganic particles.

<Viscosity measurement>
The viscosities of the organopolysiloxanes (A1) to (A2) and (B1) measurement samples prepared in Examples and Comparative Examples described later at 25 ° C. were measured using a TVE-22H manufactured by Toki Sangyo Co., Ltd.

<Heat resistant yellowing>
YI (yellowness) was measured by a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta Co., Ltd. using a cured product having a thickness of 3 mm produced in Examples and Comparative Examples described later as a measurement sample. Next, the cured product was wrapped in aluminum foil and heat-treated under air at 150 ° C. for 150 hours. After that, YI (yellowness) was measured again with a spectrophotometer CM-3600d (trade name) manufactured by Konica Minolta. The change in YI before and after this heat treatment was defined as ΔYI, and the heat-resistant yellowing was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: When ΔYI is less than 1.0 ◯: When ΔYI is 1.0 or more and less than 3.0 ×: When ΔYI is 3.0 or more

<Light resistance>
YI (yellowness) was measured by a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta Co., Ltd. using a cured product having a thickness of 3 mm produced in Examples and Comparative Examples described later as a measurement sample. Next, the cured product was set in a constant temperature dryer at a constant temperature of 50 ° C., and a UV irradiation device (manufactured by Ushio Inc., trade name: SP-7) equipped with a 365 nm bandpass filter was used to obtain a wavelength of 365 nm. Was irradiated for 100 hours at an illuminance of 4 W / cm ² . After that, YI (yellowness) was measured again with a spectrophotometer CM-3600d (trade name) manufactured by Konica Minolta. The change in YI before and after UV irradiation was defined as ΔYI, and the light resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: When ΔYI is less than 1.0 ◯: When ΔYI is 1.0 or more and less than 3.0 ×: When ΔYI is 3.0 or more

<Transparency>
Using a 1 mm thick cured product produced in Examples and Comparative Examples described later as a measurement sample and using a haze meter NDH 5000W (trade name) manufactured by Nippon Denshoku Industries Co., Ltd., "JIS K7105: Optical of Plastic" The total light transmittance was measured according to "Characteristic test method". Based on the obtained total light transmittance, the transparency was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: When the total light transmittance is 95% or more ◯: When the total light transmittance is 85% or more and less than 95% ×: When the total light transmittance is less than 85%

<Refractive index>
Using a cured product having a thickness of 1 mm produced in Examples and Comparative Examples described below as a measurement sample, using MODEL 2010 PRISM COUPLER (trade name) manufactured by Metricon, mode: single film mode, measurement wavelength: 633 nm, 25 The refractive index was measured at ° C.
(Evaluation criteria)
⊚: When the refractive index is 1.60 or more ◯: When the refractive index is 1.50 or more and less than 1.60 ×: When the refractive index is less than 1.50

<Surface tackiness>
Using a bar coater, the photocurable resin compositions of Examples and Comparative Examples were uniformly applied on a glass substrate so as to have a thickness of 12 μm. After that, the glass substrate was exposed to an integrated light amount of 2000 mJ / cm ² by using an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The cured film 30 seconds after the end of exposure was touched with a finger and surface tackiness was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: No stickiness and fingers do not stick.
X: Sticky and fingers stick.

[Example 1]
<Production of Organopolysiloxane (A1)>
The following components were added to a 0.5 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 80 ° C. with stirring under a nitrogen gas atmosphere.
Component (a): 1,3,5,7-tetramethylcyclotetrasiloxane 15 g (0.06 mol)
Component (b1): vinyl trimethoxysilane 3.7 g (0.03 mol)
Component (b2): dimethylphenylvinylsilane 28.34 (0.18 mol)
Component (c): 14 g (0.1 mol) of 3-butenyl methacrylate
Solvent: Toluene 216g
Polymerization inhibitor: Hydroquinone monomethyl ether 0.05g

  Then, an isopropanol solution of chloroplatinic acid was added in an amount such that platinum metal was 20 ppm with respect to the weight of the organopolysiloxane as the addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while maintaining the temperature at 55 to 65 ° C by heat retention, water cooling or air cooling. The "weight of the organopolysiloxane as the addition reaction product" means that the component (b1) and the component (b2) are all reacted with the component (a), and the component (c) is with respect to the remaining reaction points. The weight of the organopolysiloxane when reacted.

When the content of the flask was analyzed 72 hours after the start of the reaction, the reaction rate of SiH groups was 95%. Then, it was treated with activated carbon and the volatile components were distilled off to obtain 51 g of an organopolysiloxane (A1) represented by the following general formula (15). The functional group equivalent of the unsaturated bond-containing group of the obtained organopolysiloxane (A1) was 1083 g / mol, the weight average molecular weight calculated from GPC measurement was 800, and the viscosity at 25 ° C. was 37 mPa · s. ..
As a result of ²⁹ Si NMR measurement, the following peaks corresponding to the constituent units were observed.
F1: -19.9 ppm
M1: -41.5ppm
M2: -1.2 ppm
S: -34.6 ppm
The ratio (a / b) of the structural unit F1 to the structural unit M1 was 2.0.
The ratio (d / a) of the structural unit F1 and the structural unit S was 0.05.

<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 100 parts by mass of organopolysiloxane (A1) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refractive index: 2.2, 30% by mass solution) 100 parts by mass in terms of zirconium oxide was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Example 2]
<Production of cured product and evaluation of characteristics>
To 100 parts by mass of organopolysiloxane (A1), a dispersion of barium titanate (E2) in methyl cellosolve (manufactured by JGC Catalysts & Chemicals, average particle size: 10 nm, refractive index: 2.3, 10% by mass solution) was added to titanic acid. 100 parts by mass in terms of barium were mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Example 3]
<Production of Organopolysiloxane (A2) having unsaturated bond-containing group>
The following components were added to a 0.5 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 80 ° C. with stirring under a nitrogen gas atmosphere.
Component (a): 1,3,5,7-tetramethylcyclotetrasiloxane 20 g (0.08 mol)
Component (b1): Vinyltrimethoxysilane 4.9 g (0.03 mol)
Component (b2): 23.3 g (0.2 mol) of vinyltrimethylsilane
Component (c): 3-butenyl methacrylate 19 g (0.1 mol)
Solvent: Toluene 230g
Polymerization inhibitor: Hydroquinone monomethyl ether 0.05g

  Then, an isopropanol solution of chloroplatinic acid was added in an amount such that platinum metal was 20 ppm with respect to the weight of the organopolysiloxane as the addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while maintaining the temperature at 55 to 65 ° C by heat retention, water cooling or air cooling.

When the content of the flask was analyzed 72 hours after the start of the reaction, the reaction rate of SiH groups was 96%. Then, it was treated with activated carbon and the volatile components were distilled off to obtain 53 g of an organopolysiloxane (A2) represented by the following general formula (16). The functional group equivalent weight of the obtained organopolysiloxane (A2) was 867 g / mol, the weight average molecular weight calculated from GPC measurement was 700, and the viscosity at 25 ° C. was 29 mPa · s.
As a result of ²⁹ Si NMR measurement, the following peaks corresponding to the constituent units were observed.
F1: -20.0ppm
M1: -41.5ppm
M2: 3.1 ppm
S: -34.6 ppm
The ratio (a / b) of the structural unit F1 to the structural unit M1 was 2.0.
The ratio (d / a) of the structural unit F1 and the structural unit S was 0.04.

<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 100 parts by mass of organopolysiloxane (A2) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refractive index: 2.2, 30% by mass solution) 100 parts by mass in terms of zirconium oxide was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Example 4]
<Production of Organopolysiloxane (B1)>
The following components were added to a 0.5 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 80 ° C. with stirring under a nitrogen gas atmosphere.
Component (a): 15 g (0.06 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane
Component (c): 3-butenyl methacrylate 70 g (0.5 mol)
Solvent: Toluene 200g,
Polymerization inhibitor: Hydroquinone monomethyl ether 0.05g

  Then, an isopropanol solution of chloroplatinic acid was added in an amount such that platinum metal was 20 ppm with respect to the weight of the organopolysiloxane as the addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while maintaining the temperature at 55 to 65 ° C by heat retention, water cooling or air cooling.

When the content of the flask was analyzed 72 hours after the start of the reaction, the reaction rate of SiH groups was 99%. Then, it was treated with activated carbon and the volatile components were distilled off to obtain 44 g of an organopolysiloxane (B1) represented by the following general formula (17). The functional group equivalent of the obtained organopolysiloxane (B1) was 200 g / mol, the weight average molecular weight calculated from GPC measurement was 600, and the viscosity at 25 ° C. was 20 mPa · s.
As a result of ²⁹ Si NMR measurement, the following peaks corresponding to the constituent units were observed.
F1: -19.9 ppm

<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 50 parts by mass of organopolysiloxane (A1) and 50 parts by mass of organopolysiloxane (B1) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refraction) Ratio: 2.2, 30 mass% solution) was mixed in an amount of 100 parts by mass in terms of zirconium oxide, and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Example 5]
<Organopolysiloxane (B2)>
As the organopolysiloxane (B2), X-22-164B manufactured by Shin-Etsu Chemical Co., Ltd. represented by the following general formula (18) was used.

<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 50 parts by mass of organopolysiloxane (A1) and 50 parts by mass of organopolysiloxane (B2) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refraction) Ratio: 2.2, 30 mass% solution) was mixed in 100 parts by mass in terms of zirconium oxide, and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Example 6]
<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 100 parts by mass of organopolysiloxane (A1) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle diameter: 3 nm, refractive index: 2.2, 30% by mass solution) 10 parts by mass in terms of zirconium oxide was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Example 7]
<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 100 parts by mass of organopolysiloxane (A1) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refractive index: 2.2, 30% by mass solution) 200 parts by mass in terms of zirconium oxide was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Comparative Example 1]
<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 100 parts by mass of organopolysiloxane (B1) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refractive index: 2.2, 30% by mass solution) 100 parts by mass in terms of zirconium oxide was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Comparative example 2]
<Production of cured product and evaluation of characteristics>
Methanol dispersion of zirconium oxide (E1) in 100 parts by mass of organopolysiloxane (B2) (manufactured by Sakai Chemical Co., Ltd., trade name: SZR-M, average particle size: 3 nm, refractive index: 2.2, 30% by mass solution) 100 parts by mass in terms of zirconium oxide was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Comparative Example 3]
<Epoxy group-containing organopolysiloxane (C1)>
As the epoxy group-containing organopolysiloxane (C1), an epoxy group-containing organopolysiloxane manufactured by Shin-Etsu Chemical Co., which is represented by the following general formula (21), was used.

<Production and characterization of photocurable resin composition>
100 parts by mass of the epoxy group-containing organopolysiloxane (C1) is mixed with 3 parts by mass of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (manufactured by San-Apro, trade name: CPI-100P), and the whole becomes uniform. After stirring until degassing.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Comparative Example 4]
<Epoxy resin (C2)>
As the epoxy resin (C2), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical, Celoxide 2021P) was used.

<Production and characterization of photocurable resin composition>
3,4-Epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical, Celoxide 2021P) and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (trade name: CPI -100P) 3 parts by mass were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Comparative Example 5]
<Methacrylic resin (C3)>
As the methacrylic resin (C3), 30 parts by mass of isobornyl methacrylate and 70 parts by mass of polybutylene glycol dimethacrylate (Acryester PBOM manufactured by Mitsubishi Rayon) were used.

<Production and characterization of photocurable resin composition>
30 parts by mass of isobornyl methacrylate, 70 parts by mass of polybutylene glycol dimethacrylate (manufactured by Mitsubishi Rayon, Acryester PBOM) and 1 part by mass of bis (4-t-butylcyclohexyl) peroxydicarbonate (NOF, perloyl TCP). Partial mixing was performed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

[Comparative Example 6]
<Production of cured product and evaluation of characteristics>
Methyl ethyl ketone dispersion of colloidal silica (E3) in 100 parts by mass of organopolysiloxane (A1) (manufactured by Nissan Chemical Industries, trade name: MEK-ST, average particle size: 15 nm, refractive index: 1.4, 30% by mass solution) 100 parts by mass in terms of colloidal silica was mixed and stirred at 50 ° C. for 12 hours. Then, the volatile components were distilled off to obtain a photocurable resin composition.

  100 parts by mass of the obtained photocurable resin composition, 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184) as a photoradical generator, 2-methyl-1- [4 3 parts by mass of -methylthio-phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., trade name: IRGACURE907) were mixed, and the mixture was stirred until the whole became uniform and then defoamed.

A silicon spacer (length 50 mm x width 50 mm x height 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm) to form a mold, and the photocurable resin composition is poured into the spacer. Sandwiched between glass plates. Then, an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with a high pressure mercury lamp was used to perform exposure from the glass plate side so that the integrated light amount was 2000 mJ / cm ² . Then, the mold was removed to obtain a cured product. The curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH. The performance of the obtained cured product is shown in Table 1.

  An organopolysiloxane having one or more unsaturated bond-containing groups in one molecule and having constitutional units of a combination of the constitutional units F1 and M1 represented by the general formulas (1) and (2) was obtained. .. Inorganic particles could be uniformly dispersed by locally having a site forming a crosslinked structure composed of the structural unit F1 and a site composed of siloxane containing the structural unit M1 in the molecular structure.

  Further, according to Examples 1 to 7, in any of heat yellowing resistance, light resistance, transparency, high refractive index and surface tackiness (stickiness), the level required particularly in optical semiconductor applications is sufficiently satisfied. An organopolysiloxane capable of forming a transparent cured product and a curable resin composition using the same were obtained.

  Since Comparative Examples 1 to 6 do not have the configuration of the present embodiment described above, the predetermined characteristics of heat yellowing resistance, light resistance, transparency, high refractive index and surface tackiness (stickiness), and these From the viewpoint of the balance of characteristics, the practically sufficient characteristics could not be obtained.

  According to the photocurable resin composition of the present invention, it is possible to form a transparent cured film having excellent heat yellowing resistance, light resistance, and high refractive index, and the surface tack (stickiness) of the cured film surface is sufficient. An extremely small amount of the photocurable resin composition can be obtained. The present invention is also suitably used for an encapsulant for optical semiconductors, a photosensitive adhesive, a photosensitive coating agent, a photocurable resin for nanoimprint, an optical lens, a photosensitive ink using the photocurable resin composition. Can be done.

  1, 7 ... Base material, 2 ... Hole injection electrode, 3 ... Hole transport layer, 4 ... Light emitting layer, 5 ... Electron injection electrode, 6 ... Encapsulating material for semiconductor, 10 ... OLED display element.

Claims (34)

Organopolysiloxane (I) 100 having a structural unit F1 represented by the following general formula (1) and a structural unit M1 represented by the following general formula (2) as units forming a cyclic organopolysiloxane. Mass part,
10 to 200 parts by mass of inorganic particles,
Containing a photo radical generator 0.050 to 20 parts by mass,
The refractive index of the inorganic particles is 1.8 or more,
Photocurable resin composition.
(In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, R ² is 2 carbon atoms 10 represents an unsaturated chain-containing hydrocarbon group, a cyclohexenyl group, a norbornenyl group, an ether bond-containing unsaturated hydrocarbon group, or an unsaturated fatty acid ester group, which is an unsaturated bond-containing group, and X represents — (CH _{2 ) 2 -, - (CH 2} ) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH 2) 8 _{-, - (CH 2) 9} -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - shows a, a is an integer of 1 or more. )
(In the general formula (2), R ¹ and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, Y _{is, - (CH 2) 2 -} , - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 - _{, - (CH 2) 8 -} , - (CH 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - shows a, n is It represents an integer of 1 to 3, and b represents an integer of 1 or more.)   The photocurable resin composition according to claim 1, wherein the ratio (a / b) of the a to the b is 0.010 or more and 5.0 or less. The photocurable resin composition according to claim 1 or 2, further comprising a structural unit M2 represented by the following general formula (3) as a unit constituting a cyclic organopolysiloxane.
(In the general formula (3), R ¹ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, Z _{is, - (CH 2) 2 -} , - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 - _{, - (CH 2) 8 -} , - (CH 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - indicates, c is, Indicates an integer of 1 or more.)   The photocurable resin composition according to claim 3, wherein a ratio (a / c) of the a to the c is 0.0010 or more and 3.0 or less.   The photocurable resin composition according to claim 1, wherein the inorganic particles have an average particle diameter of 0.1 to 100 nm. Any of claims 1 to 5, wherein the inorganic particles contain at least one element selected from the group consisting of zirconium , titanium, zinc, iron, copper, chromium, cadmium, carbon, tungsten, antimony, nickel, and platinum. The photocurable resin composition according to claim 2. The photocurable resin composition according to claim 1, wherein R ² is an acryloxy group or a methacryloxy group. The photocurable resin composition according to claim 1, further comprising a structural unit S represented by the following general formula (4) as a unit constituting a cyclic organopolysiloxane.
In (the general formula (4), R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, d is an integer of 1 or more Show.)   The photocurable resin composition according to claim 8, wherein a ratio (d / a) of the d to the a is 0.10 or less. The photocuring according to any one of claims 1 to 9, wherein the organopolysiloxane (I) contains only the structural unit F1 represented by the general formula (1) as the structural unit containing R ^2. Resin composition. The photocurable resin composition according to claim 1, wherein R ¹ is an alkyl group having 1 to 10 carbon atoms. The photocurable resin composition according to claim 1, wherein R ¹ is a methyl group. The photocurable resin composition according to claim 1, wherein the functional group equivalent of the unsaturated bond-containing group represented by R ² is 20 to 10000 g / mol. The weight average molecular weight of the organopolysiloxane (I) is 500 to 1,000,000,
The photocurable resin composition according to claim 1, wherein the organopolysiloxane (I) has a viscosity at 25 ° C. of 1.0 to 1,000,000 mPa · s. Organopolysiloxane (II) 0 having a structural unit F1 ′ represented by the following general formula (5) and a structural unit T ′ represented by the following general formula (6) as units constituting the cyclic organopolysiloxane 10 to 100 parts by mass,
The photocurable resin composition according to claim 1.
(In the general formula (5), R ^{1 'is} an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, R ^2' has a carbon number 2 to 10 represents an unsaturated chain hydrocarbon group, a cyclohexenyl group, a norbornenyl group, an ether bond-containing unsaturated hydrocarbon group, or an unsaturated bond-containing group which is an unsaturated fatty acid ester group, and X ′ represents — _{(CH 2) 2 -, -} (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH _{2) 8 -, - (CH} 2) 9 -, - (CH 2) 10 -, - CH (CH 3) CH 2 -, or -C (CH _{3) 2} - indicates, e is an integer greater than or equal to 1 Is shown.)
(In the general formula (6), R ^{1 'is} an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, f is an integer equal to or larger than 0 And the sum of e and f represents an integer of 3 to 20.) The photocurable resin composition according to claim 15, wherein R ^{1 ′} is an alkyl group having 1 to 10 carbon atoms. The photocurable resin composition according to claim 15 or 16, wherein R ^{1 ′} is a methyl group. The photocurable resin composition according to claim 15, wherein R ^{2 ′} is an acryloxy group or a methacryloxy group. The photocurable resin composition according to claim 15, wherein a total functional group equivalent of the unsaturated bond-containing groups represented by R ² and R ^{2 ′} is 20 to 10000 g / mol. The weight average molecular weight of the organopolysiloxane (II) is 500 to 1,000,000,
The photocurable resin composition according to claim 15, wherein the organopolysiloxane (II) has a viscosity at 25 ° C. of 1.0 to 1,000,000 mPa · s.   21. The content of the photoradical generator is 0.50 to 10 parts by mass based on 100 parts by mass of the total amount of the organopolysiloxane (I) and the organopolysiloxane (II). The photocurable resin composition according to any one of claims. Further containing a hydrosilylation reaction catalyst,
The content of the hydrosilylation reaction catalyst is 0.0010 parts by mass or less based on 100 parts by mass of the total amount of the organopolysiloxane (I) and the organopolysiloxane (II). The photocurable resin composition according to claim 1. A hydrogen polysiloxane (a) having a structural unit represented by the following general formula (7) as a unit constituting a cyclic organopolysiloxane,
In (the general formula (7), R ^{1 ''} is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, j is 1 or more Indicates an integer.)
An organosiloxane (b1) having one vinyl group directly bonded to a silicon atom and containing at least one hydrolyzable group directly bonded to a silicon atom ;
An organic compound (c) having two or more unsaturated bond-containing groups, which are unsaturated chain hydrocarbon groups, cyclohexenyl groups, norbornenyl groups, ether bond-containing unsaturated hydrocarbon groups, or unsaturated fatty acid ester groups; ,
An addition reaction step of obtaining an organopolysiloxane by an addition reaction in the presence of a hydrosilylation reaction catalyst (d),
A mixing step of mixing the organopolysiloxane, the inorganic particles (e) having a refractive index of 1.8 or more, and a photoradical generator,
A method for producing a photocurable resin composition. The method for producing a photocurable resin composition according to claim 23, wherein the hydrogen polysiloxane (a) further has a structural unit represented by the following general formula (8).
(In the general formula (8), R ^{1 ''} are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, k Represents an integer of 0 or more, and j + k is an integer of 3 to 20.) The organosiloxane (b2) having one vinyl group directly bonded to a silicon atom and having no hydrolyzable group directly bonded to a silicon atom is further subjected to an addition reaction in the addition reaction step. A method for producing the photocurable resin composition according to item 4.   An encapsulant material for optical semiconductors, comprising the photocurable resin composition according to claim 1.   A die bond material for optical semiconductors, comprising the photocurable resin composition according to claim 1.   An adhesive containing the photocurable resin composition according to claim 1.   A coating material comprising the photocurable resin composition according to claim 1.   A curable resin composition for nanoimprinting, comprising the photocurable resin composition according to claim 1.   An optical lens comprising the photocurable resin composition according to claim 1.   An ink comprising the photocurable resin composition according to any one of claims 1 to 22 and a colorant.   An optical semiconductor package obtained by molding the encapsulant for optical semiconductors according to claim 26.   An optical semiconductor device manufactured using the encapsulating material for optical semiconductors according to claim 26.