JP6437776B2 - Photocurable resin composition and use thereof - Google Patents

Description

  The present invention relates to a photocurable resin composition, an optical semiconductor encapsulant, an adhesive, a coating agent, a nanoimprint photocurable resin composition, an optical lens, ink, an optical semiconductor package, and an optical semiconductor device.

  A photocuring system using energy rays such as ultraviolet rays is useful for improving productivity and responding to environmental problems in recent years. 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. Thus, a photocationic curable material using an epoxy resin has been proposed.

  In recent years, higher performance has been required for photo-curable resins as their application range is expanded. In particular, in the field of semiconductor encapsulants such as photosensitive coating agents, nano-imprinting photo-curable resins, organic EL or solar cells, the surface after curing is excellent in transparency, heat yellowing, light resistance and adhesion There has been a demand for a photocurable resin having no tackiness and high productivity. For this reason, bisphenol A type epoxy resins, bisphenol F type epoxy resins and (3 ′, 4′-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate epoxy resins, which have been used conventionally, are mainly used. In the composition as a component, sufficient characteristics cannot be obtained.

  To date, 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 photocationic curable 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). Furthermore, in a material using an epoxy compound and a vinyl ether compound in combination, an attempt has been made to improve reactivity and control mechanical properties of a cured product by using a specific phenol resin (see, for example, Patent Document 5).

  On the other hand, a composition for use in an optical semiconductor in which an inorganic filler is blended with an epoxy compound is disclosed (for example, see Patent Document 6). Moreover, the composition for the optical semiconductor of the organopolysiloxane which has an epoxy group is disclosed (for example, refer 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).

  Moreover, the composition for optical semiconductor use containing a specific other functional methacryloxy group containing compound is disclosed (for example, refer patent document 9).

JP-A-6-298911 JP-A-9-328634 Japanese Patent No. 2667934 Japanese Patent Laid-Open No. 4-120182 Japanese Patent No. 4235698 JP 2007-284475 A Japanese Patent No. 4322949 JP 2008-131209 A JP 2010-189471 A

  The photo-curable resin used in combination with the epoxy compound and the vinyl ether compound disclosed in Patent Documents 1 to 5 uses an epoxy compound and a vinyl ether compound that have low heat resistance and low light resistance, and therefore has high heat resistance and light resistance. Therefore, it is difficult to adapt to applications that require the

  Similarly, in a composition in which an inorganic filler is blended with an epoxy compound disclosed in Patent Document 6, since an epoxy compound and a vinyl ether compound having low heat resistance and light resistance are used, high heat resistance and light resistance are high. Therefore, it is difficult to adapt to applications that require the

  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 resistance and light resistance.

  When the composition disclosed in Patent Document 8 is used for a photocurable resin, although heat-resistant yellowing and light resistance are excellent, tack remains on the surface, so that it is difficult to adapt to a coating agent or the like.

  The composition disclosed in Patent Document 9 is difficult to adapt to applications where high heat yellowing and light resistance are required because ether bonds such as polybutylene glycol reduce heat yellowing and light resistance. It is.

  The present invention has been made in view of the above problems, and is a photocurable resin that is excellent in heat yellowing resistance, light resistance, and adhesion, and can form a cured product with sufficiently small surface tack (stickiness). An object is to provide a composition. The present invention also provides an optical semiconductor encapsulant, an adhesive, a coating agent, a nanoimprint photocurable resin composition, an optical lens, an ink, an optical semiconductor package, and an optical semiconductor using the photocurable resin composition. An object is to provide a semiconductor device.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a photocurable resin composition containing an organopolysiloxane having a specific structure. It came to be completed.

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 constituting the cyclic organopolysiloxane. Part by mass;
Containing 0.05 to 20 parts by mass of a photo radical generator,
Photocurable resin composition.
(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, 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 represents 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, and b Represents the content ratio of the structural unit M1 and represents an integer of 1 or more.)
[2]
The photocurable resin composition according to [1], wherein the ratio of a to b (a / b) is 0.010 or more and 5.0 or less.
[3]
The photocuring property according to [1] or [2], wherein the organopolysiloxane (I) further includes a structural unit M2 represented by the following general formula (3) as a unit constituting the cyclic organopolysiloxane. Resin composition.
(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; Z represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and c represents a content ratio of the structural unit M2. 1 represents an integer of 1 or more.)
[4]
The photocurable resin composition according to [3], wherein the ratio of a to c (a / 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 R ² is an acryloxy group or a methacryloxy group.
[6]
The said organopolysiloxane (I) has further the structural unit S represented by following General formula (4) as a unit which comprises cyclic organopolysiloxane in any one of the preceding clauses [1]-[5]. The photocurable resin composition as described.
(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, d represents the content rate of the said structural unit S, and shows an integer greater than or equal to 1.)
[7]
The photocurable resin composition according to [6], wherein the ratio of d to a (d / a) is 0.10 or less.
[8]
Any one of the preceding items [1] to [7], wherein the organopolysiloxane (I) contains only the structural unit F1 represented by the general formula (1) as the structural unit containing the R ^2. The photocurable resin composition described in 1.
[9]
The photocurable resin composition according to any one of [1] to [8], wherein R ¹ is an alkyl group having 1 to 10 carbon atoms.
[10]
The photocurable resin composition according to any one of [1] to [9], wherein R ¹ is a methyl group.
[11]
The functional group equivalent of the unsaturated bond-containing group represented by R ² of the organopolysiloxane (I) is 20 to 10000 g / mol, according to any one of [1] to [10] above. Photocurable resin composition.
[12]
The organopolysiloxane (I) has a weight average molecular weight of 500 to 1,000,000,
The photocurable resin composition according to any one of [1] to [11], wherein the viscosity of the organopolysiloxane (I) at 25 ° C is 1.0 to 1,000,000 mPa · s.
[13]
For 100 parts by mass of the organopolysiloxane (I),
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. Further containing 10 to 100 parts by mass,
The photocurable resin composition according to any one of [1] to [12] above.
(In the general formula (5), 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, or 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, or a substituted or unsubstituted aryl group. Alternatively, it represents a substituted or unsubstituted aralkyl group, f represents the content 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.)
[14]
The photocurable resin composition according to [13], wherein R ^{1 ′} is an alkyl group having 1 to 10 carbon atoms.
[15]
The photocurable resin composition according to [13] or [14], wherein R ^{1 ′} is a methyl group.
[16]
The photocurable resin composition according to any one of [13] to [15], wherein R ^{2 ′} is an acryloxy group or a methacryloxy group.
[17]
The total functional group equivalent of the unsaturated bond-containing group represented by R ^{2 'of} the R ² and the organopolysiloxane (II) of the organopolysiloxane (I) is a 20~10000g / mol, items [ [13] The photocurable resin composition according to any one of [16].
[18]
The organopolysiloxane (I) and the organopolysiloxane (II) have a weight average molecular weight of 500 to 1,000,000,
The photocuring according to any one of [13] to [17], wherein the viscosity of the organopolysiloxane (I) and the organopolysiloxane (II) at 25 ° C. is 1.0 to 1,000,000 mPa · s. Resin composition.
[19]
For 100 parts by mass of the organopolysiloxane (I),
The photocurable resin composition according to any one of [1] to [18], further including 0 to 0.001 part by mass of a hydrosilylation reaction catalyst.
[20]
The sealing material for optical semiconductors containing the photocurable resin composition as described in any one of said item [1]-[19].
[21]
An adhesive comprising the photocurable resin composition according to any one of [1] to [19].
[22]
A coating material comprising the photocurable resin composition according to any one of [1] to [19].
[23]
A curable resin composition for nanoimprint, comprising the photocurable resin composition according to any one of [1] to [19].
[24]
An optical lens comprising the photocurable resin composition according to any one of [1] to [19].
[25]
An ink comprising the photocurable resin composition according to any one of [1] to [19] above and a colorant.
[26]
The optical semiconductor package which shape | molded the sealing material for optical semiconductors of previous clause [20].
[27]
The optical semiconductor device manufactured using the sealing material for optical semiconductors of the preceding clause [20].

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition which is excellent in heat-resistant yellowing, light resistance, and adhesiveness, and can form hardened | cured material with sufficiently few surface tacks (stickiness) can be provided. In addition, it is excellent in heat yellowing, light resistance and adhesion, and has a sufficiently small surface tack (stickiness), sealing material for optical semiconductor, adhesive, coating agent, photocurable resin composition for nanoimprint, optical lens, ink An optical semiconductor package and an optical semiconductor device can be provided.

It is sectional drawing which shows one Embodiment of the 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. In addition, this invention is not limited to the following description, It can implement by changing variously within the range of the summary.

[Photocurable resin composition]
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 constituting the cyclic organopolysiloxane. Part by mass;
And 0.05 to 20 parts by mass of a photo radical generator.
(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, 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 represents 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, and b Represents the content ratio of the structural unit M1 and represents an integer of 1 or more.)

[Organopolysiloxane (I)]
The organopolysiloxane (I) has the structural unit F1 represented by the general formula (1) and the structural unit M1 represented by the general formula (2) as units constituting the cyclic organopolysiloxane. .

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

In 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, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, And an alkyl group having 1 to 10 carbon atoms such as an octyl group; a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclodecane group; a phenyl group and a tolyl group Aryl groups such as xylyl group, cumenyl group and mesityl group; aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group; or part or all of hydrogen atoms bonded to carbon atoms of these groups And a group substituted with a substituent.

  Although it does not specifically limit as a substituent, For example, a hydroxyl group, a cyano group, a halogen atom, etc. are mentioned. 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, R ¹ in the general formula (1) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group. By using such a group, heat yellowing resistance and light resistance tend to be further improved.

In general formula (1), R ² represents an unsaturated bond-containing group having 2 to 10 carbon atoms. Although it does not specifically limit as a C2-C10 unsaturated bond containing group, For example, a vinyl group, an allyl group, an 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 group Examples include ether bond-containing unsaturated hydrocarbon groups such as ether groups; cyclic unsaturated hydrocarbon groups such as cyclohexenyl groups; unsaturated fatty acid ester groups such as acryloxy groups and methacryloxy groups.

Among these, as R ² , acryloxy group represented by the following general formula (9) or methacryloxy group represented by the following general formula (10) (hereinafter, these are collectively referred to as “(meth) acryloxy group”). Is preferred). By using the (meth) acryloxy group, the reactivity of the photocurable resin composition, that is, the property of being easily photocured and promptly reacting 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 . By adopting such a configuration, the hardness tends to be further improved.

The functional group equivalent of the unsaturated bond-containing group represented by R ² of the organopolysiloxane (I) is preferably 20 to 10,000 g / mol, more preferably 50 to 9000 g / mol, and still more preferably 100 to 8000 g / mol. When the functional group equivalent of the unsaturated bond-containing group represented by R ² is 20 g / mol or more, the heat-resistant yellowing and light resistance of the cured product of the photocurable resin composition tend 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 hardness of the cured product of the photocurable resin composition is 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 described later.

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 can be mentioned. Among these, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, and — (CH ₂ ) ₄ — are readily available and reactive, that is, are easy to photocur and react quickly. It is preferable from the viewpoint of progress.

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

In 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 group. An unsubstituted aryl group, or a substituted or unsubstituted aralkyl group is shown. Specifically, as R ¹ and R ³ , 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) (2) may be the same or different.

Among these, as R < ¹ > and / or R < ³ > in General formula (2), a C1-C10 alkyl group is preferable and a methyl group is more preferable. By using such a group, heat yellowing resistance and light resistance tend to be further improved.

In 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 these, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, and — (CH ₂ ) ₆ — are readily available and reactive, that is, are easy to photocur and react quickly. It is preferable from the viewpoint of progress. 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 adhesion, it is preferably an integer of 2 to 3, 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, and further preferably 0.050 or more and 4.0 or less. It is. When the ratio (a / b) is 0.010 or more, the ratio of F1 units is relatively increased, and the hardness of the cured product of the photocurable resin composition tends to be further improved. Further, when the ratio (a / b) is 5.0 or less, the ratio of M1 units is relatively increased, and the adhesion to the substrate 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 constituting 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; Z represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and c represents a content ratio of the structural unit M2. 1 represents an integer of 1 or more.)

In general formula (3), R ¹ and R ⁴ each independently represent 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 group, An unsubstituted aryl group, or a substituted or unsubstituted aralkyl group is shown. 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, in General Formula (3), as R < ¹ > and / or R < ⁴ >, a C1-C10 alkyl group is preferable and a methyl group is more preferable. By using such a group, heat yellowing resistance and light resistance tend to be further improved.

In the 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 these, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, and — (CH ₂ ) ₆ — are readily available and reactive, that is, are easy to photocur and react quickly. It is preferable from the viewpoint of progress. 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. It is. When the ratio (a / c) is 0.0010 or more, the ratio of F1 units is relatively increased, and the hardness of the cured product of the photocurable resin composition tends to be further improved. Further, when the ratio (a / c) is 3.0 or less, the ratio of M2 units is relatively increased, 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 constituting 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, Or a substituted or unsubstituted aralkyl group is shown, d represents the content rate of the said structural unit S, and shows an integer greater than or equal to 1.)

In 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. Specifically, examples of R ¹ include the same groups as those exemplified in the 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, in the general formula (4), the R ^1, preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group. By using such a group, heat yellowing resistance and light resistance tend to be further improved.

  The ratio of d to a (d / a) is preferably 0.10 or less, more preferably 0.00010 or more and 0.080 or less, and further preferably 0.0010 or more and 0.060 or less. When the ratio (d / a) is 0.00010 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 suppress SiH from reacting with an unsaturated bond and gelling at the time of distilling off the solvent or at the time of storage. However, it tends to be improved.

The total functional group equivalent of the unsaturated bond-containing group contained in the organopolysiloxane (I) is preferably 20 to 10000 g / mol, more preferably 50 to 9000 g / mol, and still more preferably 100 to 8000 g. / Mol. When the total functional group equivalent of the unsaturated bond-containing group is 20 g / mol or more, the heat-resistant yellowing and light resistance of the cured product of the photocurable resin composition tend to be further improved. Moreover, it exists in the tendency which the hardness of the hardened | cured material of a photocurable resin composition improves more because the total functional group equivalent of an unsaturated bond containing group is 10000 g / mol or less. The functional group equivalent of the unsaturated bond-containing group represented by R ² can be measured by the method described in Examples described later.

  The weight average molecular weight of the organopolysiloxane (I) is preferably 500 to 1,000,000, more preferably 700 to 800,000, and still more preferably 1,000 to 500,000. When the weight average molecular weight of the organopolysiloxane (I) is 500 or more, the dispersion stability of the phosphor and the colorant of the photocurable resin composition tends to be further improved. Moreover, when the weight average molecular weight of organopolysiloxane (I) is 1,000,000 or less, the hardness of the photocurable resin composition tends to be further improved. In addition, a weight average molecular weight can be measured by the method as described in an Example.

  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 at 25 ° C. of the organopolysiloxane (I) is 1.0 mPa · s or more, the dispersion stability of the phosphor and the colorant of the photocurable resin composition tends to be further improved. Further, when the viscosity of the organopolysiloxane (I) at 25 ° C. is 1000000 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.

[Organopolysiloxane (II)]
The photocurable resin composition of this 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). It may further contain 0.10 to 100 parts by mass of organopolysiloxane (II) having the structural unit T ′ as a unit constituting the cyclic organopolysiloxane. By containing organopolysiloxane (II), the crosslinking density of the cured product obtained from the photocurable resin composition increases, and the hardness and gas barrier properties tend to be improved.
(In the general formula (5), 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, or 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, or a substituted or unsubstituted aryl group. Alternatively, it represents a substituted or unsubstituted aralkyl group, f represents the content 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 constituting the cyclic organopolysiloxane.

In General 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. Specifically, as R ^{1 ′} , the same groups as those exemplified in the general formula (1) can be exemplified. In addition, R < ¹ > in the said General formula (1) and R < ^{1 '} > in General formula (5) may be same or different.

Among these, as R < ^{1 '} > in General formula (5), a C1-C10 alkyl group is preferable and a methyl group is more preferable. By using such a group, heat yellowing resistance and light resistance tend to be further improved.

In General Formula (5), R ^{2 ′} represents an unsaturated bond-containing group having 2 to 10 carbon atoms. Examples of the unsaturated bond-containing group having 2 to 10 carbon atoms is not particularly limited, for example, can be exemplified the same groups as exemplified for R ² in 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 being easily photocured and promptly reacting tends to be further improved. In addition, R ² in the general formula (1) and R ^{2 ′} in the general formula (5) may be the same or different.

In the general 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 these, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, and — (CH ₂ ) ₆ — are readily available and reactive, that is, are easy to photocur and react quickly. It is preferable from the viewpoint of progress. X in the general formula (1) and X ′ in the general formula (5) may be the same or different.

[Structural unit T ']
The structural unit T ′ represented by the general formula (6) is a unit constituting the cyclic organopolysiloxane.

In 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. Specifically, as R ^{1 ′} , the same groups as those exemplified in the general formula (1) can be exemplified. In addition, R < ¹ > in the said General formula (1) and R < ^{1 '} > in General formula (6) may be same or different.

Among these, as R < ^{1 '} > in General formula (6), a C1-C10 alkyl group is preferable and a methyl group is more preferable. By using such a group, heat yellowing resistance 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, further 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, workability tends to be further improved because the viscosity is lowered. Moreover, it exists in the tendency for adhesiveness to improve more because content of organopolysiloxane (II) is 100 mass parts or less.

Photocurable resin composition, the total functional group equivalent of the unsaturated bond-containing group represented by R ^{2 'R 2} and organopolysiloxane organopolysiloxane (I) (II) is preferably 20～10000G / It is mol, More preferably, it is 50-9000 g / mol, More preferably, it is 100-8000 g / mol. When the total functional group equivalent of the unsaturated bond-containing group represented by R ² and R ^{2 ′} is 20 g / mol or more, the heat-resistant yellowing and light resistance of the cured product of the photocurable resin composition are 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 hardness of the cured product of the photocurable resin composition is more improved . In addition, the total functional group equivalent of the unsaturated bond-containing group represented by R ² and R ^{2 ′} can be measured by the method described in Examples described later.

  The weight average molecular weight of the organopolysiloxane (I) and the organopolysiloxane (II) is preferably 500 to 1,000,000, more preferably 700 to 800,000, and still more preferably 1,000 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 phosphor and the colorant of the photocurable resin composition tends to be further improved. Moreover, when the weight average molecular weight of organopolysiloxane (I) and organopolysiloxane (II) is 1,000,000 or less, the hardness of the photocurable resin composition tends to be further improved. In addition, a weight average molecular weight can be measured by the method as described in an Example.

  The viscosity of the organopolysiloxane (I) and the organopolysiloxane (II) at 25 ° C. is preferably 1.0 to 1000000 mPa · s, more preferably 5.0 to 500000 mPa · s, and still more preferably. 10 to 100,000 mPa · s. When the viscosity of the organopolysiloxane (I) and the organopolysiloxane (II) at 25 ° C. is 1.0 mPa · s or more, the dispersion stability of the phosphor and the colorant of the photocurable resin composition is further improved. There is a tendency. Moreover, when the viscosity of the organopolysiloxane (I) and the organopolysiloxane (II) at 25 ° C. is 1000000 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 described later.

[Method for producing organopolysiloxanes (I) and (II)]
The production method of organopolysiloxane (I) and / or (II) is:
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 alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted aryl group. A group or a substituted or unsubstituted aralkyl group, and j represents the content 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 addition reaction in the presence of the hydrosilylation reaction catalyst (d);

  By adjusting the amount of hydrogenpolysiloxane (a), organosiloxane (b1), and organic compound (c), only organopolysiloxane (I) can be produced, or organopolysiloxane (I) and organopolysiloxane Siloxane (II) can be produced.

  In the addition reaction step, an 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.

[Hydrogen polysiloxane (a)]
The hydrogen polysiloxane (a) is a compound having the structural 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, Or a substituted or unsubstituted aralkyl group is shown. Specifically, as R ^{1 ″,} the same groups as those exemplified in the general formula (1) can be exemplified.

Among these, as R < ^{1 ''} in General formula (7), a C1-C10 alkyl group is preferable and a methyl group is more preferable. By using such a group, heat yellowing resistance 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 having a structural unit represented by the following general formula (8), heat-resistant yellowing and light resistance tend to be further improved.
(In the general formula (8), each R ^{1 ″} is 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, and a substituted group. Or an unsubstituted aryl group or a substituted or unsubstituted aralkyl group, k represents the content of the structural unit, represents an integer of 0 or more, and j + k is an integer of 3 to 20.)

In addition, the hydrogen polysiloxane (a) is not particularly limited, and examples thereof include compounds represented by the following general formulas (11) to (13). Hydrogen polysiloxane (a) may be used individually by 1 type, or may use 2 or more types together.

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

  In addition, although it does not specifically limit as a hydrolysable group, For example, a methoxy group and an ethoxy group are mentioned.

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

[Organosiloxane (b2)]
The organosiloxane (b2) is a compound having one vinyl group directly bonded to a silicon atom and having no hydrolyzable group. Although it does not specifically limit as organosiloxane (b2), For example, the compound represented by following General formula (15) is mentioned. The organosiloxane (b2) can also include an organopolysiloxane.
(In the general formula (15), each R ^{4 ″} is 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 any one selected from the group consisting of an unsubstituted aryl group and a substituted or unsubstituted aralkyl group, and Z ″ represents a divalent hydrocarbon group having 0 to 8 carbon atoms.)

  Organosiloxane (b2) may be used individually by 1 type, or may use 2 or more types together.

[Organic compound (c)]
The organic compound (c) is a compound having two or more unsaturated bond-containing groups. Although it does not specifically limit as an organic compound (c), For example, the compound represented by following General formula (16) is mentioned.
(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.)

  In particular, X ″ is preferably a divalent hydrocarbon group having 1 to 4 carbon atoms. As a result, the hydrosilylation reaction tends to proceed more efficiently. In addition, when X ″ is a divalent hydrocarbon group having 1 to 4 carbon atoms, the boiling point of the organic compound (c) decreases, and the excess organic compound (c) is more easily distilled off from the reaction solution. It tends to be possible.

  An organic compound (c) may be used individually by 1 type, or may use 2 or more types together.

  In the addition reaction step, the amount of use (molar amount) of the organic compound (c) is determined from the viewpoint of reacting to the end without leaving any SiH groups, and the amount of SiH groups in the hydrogen polysiloxane (a), as well as organosiloxane ( It is preferable to add so that it may become larger than the sum of the molar amount of the vinyl group of b1) and organosiloxane (b2).

Specifically, the usage-amount ratio of the organic compound (c) represented by a following formula becomes like this. Preferably it is 1.2-3.0, More preferably, it is 1.3-2.5, More preferably 1.4-2.0. When the amount of the organic compound (c) used is 1.2 or more, the reactivity tends to be further improved. Moreover, it exists in the tendency which can reduce the load of refinement | purification because the usage-amount ratio of an organic compound (c) is 3.0 or less.
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)) + Mole 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-based catalysts such as platinum black, secondary platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. A platinum group metal catalyst other than the platinum catalyst, such as a palladium catalyst and a rhodium 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 still more preferably based on 100 parts by mass of the product organopolysiloxane. 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. Moreover, it exists in the tendency for cost to fall more because the usage-amount of a hydrosilylation reaction catalyst (d) is 100 ppm or less.

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 derived from the reaction of the unsaturated bond-containing group tends to be further suppressed.

  You may perform the said addition reaction in a solvent as needed. The solvent is not particularly limited. For example, 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 a mixture thereof A solvent is mentioned.

The atmosphere for the addition reaction may be either air or inert gas. Among these, in an inert gas such as nitrogen, argon, and helium is preferable in that the resulting 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.

Further, when R ² is a (meth) acryloxy group, for the purpose of preventing the polymerization reaction of the (meth) acryloxy group, the reaction system includes phenothiazine, a hindered phenol compound, an amine compound, and a quinone compound. It is preferable to add a polymerization inhibitor. The type and amount of such a polymerization inhibitor are particularly limited as long as the addition of them can prevent the polymerization reaction of (meth) acryloxy groups, that is, acryloxy groups or methacryloxy groups, without hindering the progress of the hydrosilylation reaction. Not.

[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. Although it does not specifically limit as catalyst removal, For example, the method of removing with adsorption materials, such as washing with water and activated alumina, activated carbon, is mentioned.

  The surplus organic compound (c) and the solvent that can be used as necessary may be distilled off under heating and / or reduced pressure.

  As described above, the organopolysiloxanes (I) and (II) can be obtained.

[Photoradical generator]
The photoradical generator is not particularly limited as long as it can radically polymerize unsaturated bond-containing groups with light. For example, JP-B-59-1281, JP-B-61-9621, and JP-A-60 Triazine derivatives described in JP-60104; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-B-44- Diazonium compounds described in Japanese Patent No. 6413, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and US Pat. No. 3,567,453; US Pat. No. 2,848,328 , Organic azide compounds described in U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,853; Ortho-quinonediazides described in Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, Japanese Patent Publication No. 45-9610, Japanese Patent Publication No. 55-39162, and Japanese Patent Publication No. 59-14023. And various onium compounds described in “Macromolecules, Vol. 10, page 1307 (1977)”; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patent No. 109,851, European Patent No. 126,712, and “Journal of Imaging Science (J. Imag. Sci.), Vol. 30, 174 (1986) ", etc .; JP-A-6-213861, and (Oxo) sulfonium organoboron complexes described in JP-A-6-255347; titanocenes described in JP-A-61-151197; “Coordination Chemistry Review”, Vols. 84, 85 277 (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 Examples include imidazole dimer; carbon tetrabromide; and organic halogen compounds described in JP-A-59-107344. A photoradical generator may be used individually by 1 type, or may use 2 or more types together.

  The content of the photo radical generator is 0.050 to 20 parts by mass with respect to 100 parts by mass of organopolysiloxane (I) or 100 parts by mass of organopolysiloxane (I) and organopolysiloxane (II). Preferably, it is 0.10-15 mass parts, More preferably, it is 1.0-10 mass parts. When the content of the photoradical generator is 0.050 part by mass or more, the curability of the photocurable resin composition is further improved. Moreover, the photocurable resin composition and cured | curing material which are excellent in light resistance are obtained because content of a photoradical generator is 20 mass parts or less.

[Hydrosilylation catalyst]
The photocurable resin composition may contain the hydrosilylation reaction catalyst used in the above production method. The residual amount (content) of the hydrosilylation reaction catalyst is preferably 0 with respect to 100 parts by mass of the organopolysiloxane (I) or 100 parts by mass of the organopolysiloxane (I) and the organopolysiloxane (II). It is -0.0010 mass part, More preferably, it is 0-0.00080 mass part, More preferably, it is 0-0.00050 mass part. When the content 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 photocurable resin composition.

[Other ingredients]
The curable resin composition of the present embodiment includes (meth) acrylate monomers and oligomers and vinyl (meth) acrylate for the purpose of accelerating curability with respect to energy such as ultraviolet rays (improvement of sensitivity) as necessary. A radical polymerizable compound such as may be added.

  In addition, addition of deterioration inhibitors, mold release agents, diluents, antioxidants, thermal stabilizers, flame retardants, plasticizers, surfactants, and the like within the quantitative and qualitative range not departing from the scope of the present invention An agent can be blended.

[Method for producing photocurable resin composition]
Although it does not specifically limit as a manufacturing method of a photocurable resin composition, For example, the method of mixing organopolysiloxane (I) and a photoradical generator is mentioned. Moreover, in the said manufacturing method of organopolysiloxane, by adjusting the usage-amount of hydrogen polysiloxane (a), organosiloxane (b1), organosiloxane (b2), and organic compound (c), organopolysiloxane ( I) and organopolysiloxane (II) can be produced simultaneously. Furthermore, you may mix organopolysiloxane (I) manufactured with the manufacturing method of the said organopolysiloxane, and organopolysiloxane (II) manufactured separately.

[Use]
The photocurable resin composition of the present embodiment is liquid or solid before curing, and can be cured by applying 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, and a cured product is obtained. Hereinafter, although each use of the photocurable resin composition of this embodiment is demonstrated, the use of the photocurable resin composition of this embodiment is not restricted to the following.

[Encapsulant for optical semiconductors]
The photocurable resin composition of this embodiment can be used as a sealing material for optical semiconductors. The sealing material for optical semiconductors containing the photocurable resin composition of this embodiment can be used as sealing materials, such as an OLED display element and a photovoltaic power generation module. An optical semiconductor package formed by molding the optical semiconductor sealing material of the present embodiment and an optical semiconductor device manufactured using the optical semiconductor sealing material of the present embodiment are also within the scope of the present invention.

  FIG. 1 is a cross-sectional view showing an embodiment of an OLED display element using the semiconductor sealing material of this embodiment. The OLED display element 10 is formed by sequentially forming the hole injection electrode 2, the hole transport layer 3, the light emitting layer 4, and the electron injection electrode 5 on the substrate 1, and then sealing with the semiconductor sealing material 6 of this embodiment. Then, the substrate 7 can be formed by a method of pasting together. Such full sealing with a solid film is a particularly effective method when a flexible material is used as the base materials 1 and 7.

  As a method of forming a multilayer structure in which a hole injection electrode 2, a hole transport layer 3, a light emitting layer 4, and an electron injection electrode 5 are sequentially laminated on the base material 1, a resistance heating vapor deposition method, A beam sputtering method, an ink jet 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, but for example, by a printing method such as screen printing or flexographic printing. And a method of applying using a dispenser.

  After the base material 7 is bonded to the semiconductor sealing material 6, the semiconductor sealing material 6 can be cured by irradiating energy rays from the base material 7 side or the base material 1 side. Any energy ray may be used as long as it cures 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 can cure the semiconductor sealing material 6 within a predetermined working time. 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 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. Thus, the semiconductor sealing material of this embodiment can be used for sealing various semiconductor elements including OLED display elements. In particular, the semiconductor encapsulant of this embodiment can produce a cured product at room temperature when used as a cured product, thereby preventing thermal degradation and thermal deformation of the substrate and elements found in conventional thermosetting resins. be able to. Further, since it has high adhesion to a substrate or an element, it can be preferably used for sealing a semiconductor element of a precision instrument such as an FPD, and particularly preferably used 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 coat material and a lens material that coat the periphery of the chip. In this case, examples of the optical semiconductor include an LED lamp, a chip LED, a semiconductor laser, a photocoupler, and a photodiode.

  The optical semiconductor device includes 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, and examples thereof include aromatic polyamides such as polyphthalamide, engineering plastics such as 66 nylon, and ceramics. In the case of polyphthalamide, particularly high adhesion is exhibited.

  It is preferable that glass fiber is contained in the housing material because the adhesive strength increases. The glass fiber content 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. Since the coating material containing the photocurable resin composition of the present embodiment can cure a thin film at high speed in the air, coating on a resin film, a substrate, etc. that are 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 used. In order to form a cured film having a refractive index of 1.4 or less as a coating material for forming an antireflection film, the photocurable resin composition preferably contains porous fine particles in which voids are formed.

  Examples of the porous fine particles include silica particles having an average particle diameter of 5 nm to 1 μm, and silica particles having an average particle diameter of 5 to 100 nm are preferable from the viewpoint of transparency of the cured film. Specific examples of commercially available products include “Aerosil” (trade name, manufactured by Nippon Aerosil Co., Ltd.), a fumed silica having a hydrophilic property or a hydrophobic treatment on the surface, and a pearl necklace-shaped silica sol in which silica particles are linearly connected. There is a certain “Snowtex PS” (trade name, manufactured by Nissan Chemical Co., Ltd.). These porous fine particles are preferably used by adding the total amount of the porous fine particles in the range of 10 to 70 parts by mass with respect to 100 parts by mass of the photocurable resin composition, and using a homogenizer or the like, the photocurable resin is used. It is preferable to disperse uniformly in the composition.

  A photosensitive coating agent containing a photocurable resin composition is applied on the surface of a transparent substrate (for example, a resin substrate of polymethyl methacrylate, polycarbonate, polystyrene, and triacetyl cellulose, or an inorganic material such as glass). Then, by curing the coating film, a cured film having a thickness of 10 nm to 1 μm can be formed as an antireflection film or a scratch prevention film. Since it is necessary to form a relatively thin film with high precision when applying on a substrate, the microgravure method, roll coating method, flow coating method, spin coating method, die coating method, cast transfer method, and spray coating are used. Laws are 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 or heating. The photocurable resin composition may be cured by using both energy beam irradiation and heating. The photocurable resin composition of the present embodiment can be sufficiently put into practice without containing a solvent or the like, but may be diluted with a solvent or the like for viscosity adjustment, or a sol containing porous fine particles or the like. It is good also as a form. When diluted with a solvent, etc., and when used in the form of a sol containing porous fine particles, etc., in order to volatilize the solvent component in advance, before light irradiation, it is about several minutes at 50 to 150 ° C. Heating may be performed. Moreover, hardening can also be further accelerated | stimulated by heating similarly after 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 above-described liquid, solid, sol form, etc., and can exhibit excellent adhesiveness without being inhibited by humidity.

[Curable resin composition for nanoimprint]
The photocurable resin composition of this embodiment can also be suitably used as a photocurable resin for nanoimprint. By using the photo-curable resin for nanoimprinting containing the photo-curable resin composition of the present embodiment, fine processing can be performed by pressing the original plate against the substrate coated with the photo-curable resin without using a conventional exposure apparatus. Can be realized.

〔ink〕
By adding a colorant to the photocurable resin composition of the present embodiment, a photosensitive ink can be obtained. The ink containing the photocurable resin composition of the present embodiment and the colorant also has a feature that it is relatively easy to lower the viscosity, and is mixed with the colorant in combination with excellent photocurability. Therefore, it can be suitably used as a photosensitive ink.

  The colorant used in the photosensitive ink is not particularly limited. For example, various organic pigments and inorganic pigments can be used. Specifically, white pigments such as titanium oxide, zinc white, lead white, litbon, 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 vermilon, permanent orange, balkan first orange, and indanthrene brilliant orange; iron oxide, permanent brown, and para Brown pigments such as brown; Red pigments such as Bengala, Cadmium Red, Antimony Zhu, Permanent Red, Rhodamine Lake, Alizarin Lake, Thioindigo Red, PV Carmine, Monolite Face Tread, and Quinacridone Red Pigment; Cobalt Purple, Man Purple, first bilet, methyl violet lake, indanthrene brilliant violet, dioxazine violet, etc .; ultramarine, bitumen, cobalt blue, alkali blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue and Blue pigments such as indigo; green pigments such as chromium green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine; other fluorescent pigments, metal powder Examples thereof include pigments and extender pigments. The amount of these colorants is preferably 1 to 50% by mass, more preferably 5 to 25% by mass, based on the total amount of the photocurable resin composition.

  A pigment dispersant may be used together with the colorant as necessary. 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 ethers, glycerin esters, sorbitan esters, and polyoxyethylene fatty acid amides; styrene, styrene derivatives, vinyl naphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives , Fumaric acid, and block copolymers or random copolymers composed of two or more monomers selected from fumaric acid derivatives, and salts thereof.

  Examples of the method for dispersing the colorant include 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. For the purpose of removing coarse particles of the pigment dispersion, a centrifuge or a filter may be used.

  The average particle size of the pigment particles in the pigment ink is selected in consideration of the stability in the ink, image density, glossiness, light resistance, etc., but the particle size is also selected appropriately from the viewpoint of improving gloss and improving texture. It is preferable to do.

[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 and high transparency. Optical lenses containing the photocurable resin composition of the present embodiment include, for example, lens materials such as spectacle lenses, optical equipment lenses, CD and DVD pickup lenses, automobile headlamp lenses, and projector lenses. 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>
Deuterated chloroform was added to 0.05 g of the solution before the start of the reaction and the sampled reaction solution (the reaction solution in the synthesis of organopolysiloxane in the examples and comparative examples described later and 72 hours after the start of the reaction). Each sample was dissolved in 1 g of a solvent to prepare a measurement sample. ¹ H NMR measurement of this measurement sample was performed using 400 MHz (manufactured by JASCO Corporation α-400) at a total number of 100 times, and the obtained results were analyzed.

The reaction rate of SiH was calculated according to the following formula by calculating the area ratio between the 0.2 ppm peak derived from Si—CH ₃ before and after the reaction and the 4.6 ppm peak derived from SiH. Evaluation was made according to the criteria.
SiH reaction rate (%) = [((X1-Y1) / X1] × 100
X1: Ratio of peak area before reaction: (peak area of SiH before reaction) / (peak area of Si—CH ₃ before reaction)
Y1: Peak area ratio after reaction: (SiH peak area after reaction) / (peak area of Si—CH ₃ after reaction)
(Evaluation criteria)
◎: When the reaction rate of SiH is 98% or more ○: When the reaction rate of SiH is 90% or more and less than 98% ×: When the reaction rate of SiH is less than 90%

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

Further, a solution obtained by dissolving 0.3 g of each sample in 1 g of deuterated chloroform solvent was used as a measurement sample. The measurement of ¹³ C NMR of this measurement sample was performed using α-400 manufactured by JASCO Corporation at an integration count of 20000, 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 in which 8 mass% of chromium (III) acetylacetonate (Cr (acac) ₃ ) was added to the sample was used as a measurement sample. did. The measurement of ²⁹ Si NMR of this measurement sample was performed using α-400 manufactured by JASCO Corporation at a total 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 (A) and (B1) to (B2).

<Calculation of functional group equivalent of unsaturated bond-containing group>
A solution obtained by dissolving 30 mg of each of the organopolysiloxanes (A1) to (A2) and (B1) prepared in Examples and Comparative Examples described later in 1 g of deuterated chloroform solvent was used as a measurement sample. ¹ H NMR measurement of this measurement sample was performed using α-400 manufactured by JASCO Corporation at an integration count of 200 times, and the obtained results were analyzed to determine the average composition in one molecule of organopolysiloxane.

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

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

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

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

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

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

<Heat resistant yellowing>
Each cured product having a thickness of 3 mm produced in Examples and Comparative Examples described later was used as a measurement sample, and YI (yellowness) was measured with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta.

  Next, each cured product was wrapped in aluminum foil and heat-treated at 150 ° C. for 150 hours under air. Thereafter, YI (yellowness) was measured again with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta.

The change in YI before and after the heat treatment was ΔYI, and heat 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>
Each cured product having a thickness of 3 mm produced in Examples and Comparative Examples described later was used as a measurement sample, and YI (yellowness) was measured with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta.

Next, each cured product was set in a constant temperature dryer kept constant at 50 ° C., and an illuminance at 365 nm using a UV irradiation device (trade name: SP-7, manufactured by USHIO INC.) Equipped with a 365 nm bandpass filter. Irradiated with 4 W / cm ² of light for 100 hours. Thereafter, YI (yellowness) was again measured with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta.

The change in YI before and after UV irradiation was ΔYI, and heat 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

<Surface tackiness>
Using a bar coater, each of the photocurable resin compositions of Examples and Comparative Examples was uniformly applied to a thickness of 12 μm on a glass substrate. Then, the said glass substrate was exposed so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation device (made by Sen Engineering Co., Ltd.) provided with the 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 completion of exposure was touched with a finger, and surface tackiness was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: There is no stickiness and fingers do not stick.
X: There is stickiness and fingers stick.

<Adhesion>
A curable resin composition produced in Examples and Comparative Examples in a mold of polyphthalamide resin (Amodel 4122 manufactured by Solvay) in which a depression of 10 mmφ and 1 mm depth is formed in the center of a 20 mm × 20 mm × 2 mm flat plate Articles were cast and heated to obtain each test piece.

The number of times until peeling occurred was visually observed for the obtained test piece with a small thermal shock apparatus TSE-11 manufactured by Espec Corp. at room temperature to −40 ° C. (15 minutes) to 120 ° C. (15 minutes) to room temperature. Observed. Based on the obtained number of times, the adhesion was evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎: When peeling did not occur after 500 cycles ○: When peeling occurred between 200 cycles and less than 500 cycles ×: When peeling occurred in less than 200 cycles

[Example 1]
<Production of organopolysiloxane (A1) having an unsaturated bond-containing group>
To a 0.5 L three-necked flask equipped with a stirrer, thermometer and reflux condenser,
(A) 1,3,5,7-tetramethylcyclotetrasiloxane 20 g (0.08 mol) as a component,
As the component (b1), 4.9 g (0.03 mol) of vinyltrimethoxysilane,
(B2) 23.3 g (0.2 mol) of vinyltrimethylsilane as component
(C) 19 g (0.1 mol) of 3-butenyl methacrylate as a component,
230 g of toluene,
Then, 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) was added, and the mixture was heated to 80 ° C. with stirring in a nitrogen gas atmosphere.

  Thereafter, an isopropanol solution of chloroplatinic acid was added in an amount such that the platinum metal was 20 ppm based on the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 55 to 65 ° C. by heat insulation, water cooling or air cooling. The “weight of the organopolysiloxane that is an addition reaction product” means that the component (b1) and the component (b2) all react with the component (a) and the component (c) with respect to the remaining reaction point. The weight of organopolysiloxane when reacted.

  When the contents of the flask were analyzed after 72 hours from the start of the reaction, the reaction rate of SiH groups was 96%. Thereafter, the obtained reaction solution was treated with activated carbon, and volatile components were distilled off to obtain 53 g of an organopolysiloxane (A1) represented by the following general formula (17).

The functional group equivalent of the unsaturated bond-containing group of the obtained organopolysiloxane (A1) 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 structural units were observed.
F1: -20.0 ppm
M1: -41.5ppm
M2: 3.1 ppm
S: -34.6 ppm
The ratio (a / b) between the structural unit F1 and the structural unit M1 was 2.0.
The ratio (d / a) between the structural unit F1 and the structural unit S was 0.04.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of organopolysiloxane (A1), 3 parts by mass of 1-hydroxy-cyclohexyl-phenylketone (manufactured by BASF Japan, trade name: IRGACURE184), 2-methyl-1- [4-methylthio-phenyl] -2- 3 parts by mass of morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF Japan Ltd.) was mixed, stirred until the whole became uniform, and then defoamed to obtain a photocurable resin composition.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Moreover, about surface tack property and adhesiveness evaluation, the hardened | cured material was obtained by the said method. Table 1 shows the performance of the obtained cured product.

[Example 2]
<Production of organopolysiloxane (A2)>
To a 0.5 L three-necked flask equipped with a stirrer, thermometer and reflux condenser,
(A) 1,3,5,7-tetramethylcyclotetrasiloxane 15 g (0.06 mol) as component,
As the component (b1), 3.7 g (0.03 mol) of vinyltrimethoxysilane,
(B2) Dimethylphenylvinylsilane 28.34 (0.18 mol) as component
(C) 14 g (0.1 mol) of 3-butenyl methacrylate as a component,
216 g of toluene,
Then, 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) was added, and the mixture was heated to 80 ° C. with stirring in a nitrogen gas atmosphere.

  Thereafter, an isopropanol solution of chloroplatinic acid was added in an amount such that the platinum metal was 20 ppm based on the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 55 to 65 ° C. by heat insulation, water cooling or air cooling.

  When the contents of the flask after 72 hours from the start of the reaction were analyzed, the reaction rate of SiH groups was 95%. Thereafter, the obtained reaction solution was treated with activated carbon, and volatile components were distilled off to obtain 51 g of an organopolysiloxane (A2) represented by the following general formula (18).

The functional group equivalent of the unsaturated bond-containing group of the obtained organopolysiloxane (A2) 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 structural units were observed.
F1: -19.9 ppm
M1: -41.5ppm
M2: -1.2 ppm
S: -34.6 ppm
The ratio (a / b) between the structural unit F1 and the structural unit M1 was 2.0.
The ratio (d / a) between the structural unit F1 and the structural unit S was 0.05.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of organopolysiloxane (A2), 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184), 2-methyl-1- [4-methylthio-phenyl] -2- 3 parts by mass of morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF Japan Ltd.) was mixed, stirred until the whole became uniform, and then defoamed to obtain a photocurable resin composition.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

Example 3
<Production of organopolysiloxane (B1)>
To a 0.5 L three-necked flask equipped with a stirrer, thermometer and reflux condenser,
(A) 1,3,5,7-tetramethylcyclotetrasiloxane 15 g (0.06 mol) as component,
(C) 70 g (0.5 mol) of 3-butenyl methacrylate as a component,
200 g of toluene,
Then, 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) was added, and the mixture was heated to 80 ° C. with stirring in a nitrogen gas atmosphere.

  Thereafter, an isopropanol solution of chloroplatinic acid was added in an amount such that the platinum metal was 20 ppm based on the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 55 to 65 ° C. by heat insulation, water cooling or air cooling.

  When the contents of the flask after 72 hours from the start of the reaction were analyzed, the reaction rate of SiH groups was 99%. Thereafter, the obtained reaction solution was treated with activated carbon, and volatile components were distilled off to obtain 44 g of an organopolysiloxane (B1) represented by the following general formula (19).

The functional group equivalent of the unsaturated bond-containing group 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 structural units were observed.
F1: -19.9 ppm

<Manufacture and characteristic evaluation of cured product>
50 parts by mass of organopolysiloxane (A1), 50 parts by mass of organopolysiloxane (B1), 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184), 2-methyl-1- [4-Methylthio-phenyl] -2-morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF Japan Ltd.) is mixed with 3 parts by mass, stirred until the whole becomes uniform, defoamed and photocured. A functional resin composition was obtained.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

Example 4
<Organopolysiloxane (B2)>
As the organopolysiloxane (B2), X-22-164B manufactured by Shin-Etsu Chemical Co., shown by the following general formula (20) was used.

<Manufacture and characteristic evaluation of cured product>
50 parts by mass of organopolysiloxane (A1), 50 parts by mass of organopolysiloxane (B2), 3 parts by mass of 1-hydroxy-cyclohexyl-phenylketone (manufactured by BASF Japan, trade name: IRGACURE184), 2-methyl-1- [4-Methylthio-phenyl] -2-morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF Japan Ltd.) is mixed with 3 parts by mass, stirred until the whole becomes uniform, defoamed and photocured. A functional resin composition was obtained.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

[Comparative Example 1]
<Manufacture and characteristic evaluation of cured product>
100 parts by mass of organopolysiloxane (B1), 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan, trade name: IRGACURE184), 2-methyl-1- [4-methylthio-phenyl] -2- 3 parts by mass of morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF Japan Ltd.) was mixed, stirred until the whole became uniform, and then defoamed to obtain a photocurable resin composition. A cured product was obtained using the mold or film of the photocurable resin composition by the above method. Table 1 shows the performance of the obtained cured product.

[Comparative Example 2]
<Manufacture and characteristic evaluation of cured product>
100 parts by mass of organopolysiloxane (B2), 3 parts by mass of 1-hydroxy-cyclohexyl-phenylketone (manufactured by BASF Japan, trade name: IRGACURE184), 2-methyl-1- [4-methylthio-phenyl] -2- 3 parts by mass of morpholinopropan-1-one (trade name: IRGACURE907, manufactured by BASF Japan Ltd.) was mixed, stirred until the whole became uniform, and then defoamed to obtain a photocurable resin composition.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

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

<Production and characteristic evaluation of photocurable resin composition>
Mixing 100 parts by mass of the epoxy group-containing organopolysiloxane (C1) with 3 parts by mass of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (manufactured by San Apro, trade name: CPI-100P) makes the whole uniform. The mixture was stirred until defoaming to obtain a photocurable resin composition.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

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

<Production and characteristic evaluation of photocurable resin composition>
3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical Industries, Celoxide 2021P) and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (manufactured by San Apro, trade name: CPI) −100P) 3 parts by mass were mixed, stirred until the whole became uniform, and then defoamed to obtain a photocurable resin composition.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

[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 (manufactured by Mitsubishi Rayon, Acryester PBOM) were used.

<Production and characteristic evaluation of photocurable resin composition>
30 parts by mass of isobornyl methacrylate, 70 parts by mass of polybutylene glycol dimethacrylate (manufactured by Mitsubishi Rayon, acrylate ester PBOM) and 1 mass of bis (4-tert-butylcyclohexyl) peroxydicarbonate (manufactured by NOF Corporation, Parroyl TCP) The mixture was mixed and stirred until the whole became uniform, and then defoamed to obtain a photocurable resin composition.

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, it exposed from the said glass plate side so that it might become the integrated light quantity 2000mJ / cm < ² > using the ultraviolet irradiation apparatus (made by Sen Engineering) provided with the high pressure mercury lamp. Thereafter, the mold was removed to obtain a cured product. Curing was performed in an environment of temperature: 23 ° C. and humidity: 60% RH.

  Further, the surface tackiness and adhesion evaluation were obtained by the above methods. Table 1 shows the performance of the obtained cured product.

  According to Examples 1 to 4, the sealing material for optical semiconductors, the photosensitive adhesive, the photosensitive coating agent, and the light for nanoimprinting are particularly good in any points of heat yellowing, light resistance, surface tackiness, and adhesion. An organopolysiloxane capable of forming a transparent cured product sufficiently satisfying the level required for a curable resin, an optical lens, and a photosensitive ink, and a curable resin composition using the same were obtained.

  Since Comparative Examples 1 to 5 do not have the configuration of the present embodiment described above, from the viewpoint of predetermined characteristics among heat yellowing resistance, light resistance, surface tackiness, and adhesion, and a balance of these characteristics In practice, sufficient characteristics were not obtained.

  According to the photocurable resin composition of the present invention, it is possible to form a transparent cured film excellent in heat yellowing resistance, light resistance and adhesion, and the surface tack (stickiness) on the surface of the cured film is sufficient. A small amount of the photocurable resin composition can be obtained. The present invention is also suitably used for an optical semiconductor encapsulant, a photosensitive adhesive, a photosensitive coating agent, a nanoimprinting photocurable resin, an optical lens, and a photosensitive ink using the photocurable resin composition. Can be.

  DESCRIPTION OF SYMBOLS 1,7 ... Base material, 2 ... Hole injection electrode, 3 ... Hole transport layer, 4 ... Light emitting layer, 5 ... Electron injection electrode, 6 ... Semiconductor sealing material, 10 ... OLED display element.

Claims (20)

The structural unit F1 represented by the following general formula (1), the structural unit M1 represented by the following general formula (2), the structural unit M2 represented by the following general formula (3), and the following general formula (4 a structural unit S, represented by), and shall be the units constituting the cyclic organopolysiloxanes, organopolysiloxane (I) 100 parts by weight,
Containing 0.050 to 20 parts by mass of a photo radical generator ,
In the following general formulas (1) to (4),
The ratio of a to b (a / b) is 0.010 or more and 5.0 or less,
The ratio of a to c (a / c) is 0.0010 or more and 3.0 or less,
the ratio of d to a (d / a) is 0.10 or less,
The organopolysiloxane (I) contains only the structural unit F1 represented by the following general formula (1) as the structural unit containing R ² ,
The organo functional group equivalent of the unsaturated bond-containing group represented by R ² in the polysiloxane (I) is 100~8000g / mol, a photocurable resin composition.
(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, Alternatively, it represents a substituted or unsubstituted aralkyl group, and R ² represents a vinyl group, an allyl group, an isopropenyl group, a 3-butenyl group, a 2-methylpropenyl group, a 4-pentenyl group, a 5-hexenyl group, or a 6-heptenyl group. Group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, cyclohexenyl group, norbornenyl group, vinyl ether group, allyl ether group, cyclohexenyl group, acryloxy group, or methacryloxy group, and X is carbon number 2 10 represents a divalent hydrocarbon group of 10 to 10, and a represents the content 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, and b Represents the content ratio of the structural unit M1 and represents an integer of 1 or more.)
(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; Z represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and c represents a content ratio of the structural unit M2. 1 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, Alternatively, it represents a substituted or unsubstituted aralkyl group, d represents the content of the structural unit S, represents an integer of 1 or more, and the sum of a, b, c and d represents an integer of 20 or less. ) The photocurable resin composition according to claim 1, wherein R ² is an acryloxy group or a methacryloxy group. Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, the photocurable resin composition according to claim 1 or 2. The photocurable resin composition according to any one of claims 1 to 3 , wherein R ¹ is a methyl group. The organopolysiloxane (I) has a weight average molecular weight of 500 to 1,000,000,
The organo viscosity at 25 ° C. polysiloxane (I) is 1.0~1000000mPa · s, the photocurable resin composition according to any one of claims 1-4. For 100 parts by mass of the organopolysiloxane (I),
Organopolysiloxane (II) 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 ( (However, it does not include the structural unit M1 represented by the general formula (2)) and further contains 0.10 to 100 parts by mass.
The photocurable resin composition as described in any one of Claims 1-5 .
(In the general formula (5), 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, or a substituted or unsubstituted aryl group. Or a substituted or unsubstituted aralkyl group, wherein R ^{2 ′} is a vinyl group, an allyl group, an isopropenyl group, a 3-butenyl group, a 2-methylpropenyl group, a 4-pentenyl group, a 5-hexenyl group, 6 -Heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, cyclohexenyl group, norbornenyl group, vinyl ether group, allyl ether group, cyclohexenyl group, acryloxy group, or methacryloxy group, and X ′ represents A divalent hydrocarbon group having 2 to 10 carbon atoms, and e represents the content 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, or a substituted or unsubstituted aryl group. Alternatively, it represents a substituted or unsubstituted aralkyl group, f represents the content 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.) The photocurable resin composition according to claim 6 , wherein R ^{1 ′} is an alkyl group having 1 to 10 carbon atoms. The photocurable resin composition according to claim 6 or 7 , wherein R ^{1 '} is a methyl group. The photocurable resin composition according to any one of claims 6 to 8 , wherein R ^{2 '} is an acryloxy group or a methacryloxy group. The total functional group equivalent of the unsaturated bond-containing group represented by R ^{2 'of} the R ² and the organopolysiloxane (II) of the organopolysiloxane (I) is a 20~10000g / mol, claim the photocurable resin composition according to any one of 6-9. The organopolysiloxane (I) and the organopolysiloxane (II) have a weight average molecular weight of 500 to 1,000,000,
The viscosity at 25 ° C. of the organopolysiloxane (I) and the organopolysiloxane (II) is a 1.0~1000000mPa · s, the photocurable resin composition according to any one of claims 6-10 object. For 100 parts by mass of the organopolysiloxane (I),
The photocurable resin composition according to any one of claims 1 to 11 , further comprising 0 to 0.0010 parts by mass of a hydrosilylation reaction catalyst. Comprising a photocurable resin composition according to any one of claims 1 to 12 for an optical semiconductor sealing material. , The adhesive comprising a photocurable resin composition according to any one of claims 1 to 12. In any one of claims 1 to 12 comprising a photo-curable resin composition according coating material. Claim 1 contains a photocurable resin composition according to any one of 12, nanoimprint curable resin composition. Claim 1 contains a photocurable resin composition according to any one of 12, optical lenses. An ink comprising the photocurable resin composition according to any one of claims 1 to 12 and a colorant. An optical semiconductor package formed by molding the optical semiconductor sealing material according to claim 13 . An optical semiconductor device manufactured using the optical semiconductor sealing material according to claim 13 .