CURABLE ORGANOPOLYSILOXANE COMPOSITION AND OPTICAL MEMBER MADE OF THE CURED PRODUCT

Abstract

[Problem] To provide a new light diffusing material that exhibits superior light transmittance, light diffusion, and mechanical properties. [Solution] A material according to the present invention is formed from a curable organopolysiloxane composition and a cured product obtained therefrom, the composition containing the following components A-C: A) an organopolysiloxane that has, in a molecule thereof, at least two radical reactive groups and / or reactive groups that can be cross-linked by means of a hydrosilylation reaction, and in which aryl groups account for less than 0-10 mol% of all the organic groups bonded to silicon atoms in the molecule; B) one or more types of inorganic fillers; and C) one or more types of organic silicon compounds that are different from the component A and that are selected from the group consisting of C1 and C2, wherein C1 is an organic silicon compound that is different from the component A and that has, in a molecule thereof, a reactive functional group that can bond with the reactive groups in the component A, a hydrolyzable silyl group and / or a silicon-atom-bonding hydroxyl group, and two or more silicon atoms, and C2 is an organic silicon compound that is different from the component A and that has, in a molecule thereof, a reactive functional group that can bond with the reactive groups in the component A and that has three or more carbon atoms, a hydrolyzable silyl group and / or a silicon-atom-bonding hydroxyl group, and one or more silicon atoms. In the composition, the mass of the component B is 30-95% with respect to the total mass of the composition. The material exhibits superior properties in terms of light transmittance, light diffusion, and so forth.

Description

[Technical field]

[0001] The present invention relates to a curable organopolysiloxane composition comprising an organopolysiloxane having a reactive group and in which the proportion of aryl groups in all organic groups bonded to silicon atoms in the molecule is 0 mol % or more and less than 10 mol %; one or more inorganic fillers; and one or more compounds selected from the group consisting of organosilicon compounds having a functional group capable of reacting with the reactive group possessed by the organopolysiloxane, a hydrolyzable silyl group and / or a SiOH group, and having two or more silicon atoms per molecule, and organosilicon compounds having a reactive functional group having 3 or more carbon atoms capable of bonding to the reactive group possessed by the organopolysiloxane, a hydrolyzable silyl group and / or a silicon-bonded hydroxyl group, and having one or more silicon atoms in the molecule, the composition containing 30 to 95 mass % of the inorganic filler in the entire composition; and a material obtained by curing the curable organopolysiloxane composition, in particular a material exhibiting light diffusibility, and an optical member made of the material. [Background technology]

[0002] It is known that a light-diffusing resin composition is used in lighting, LCD backlights, etc., to make the light from the light source uniform and eliminate unevenness in the light, or to increase the diffuse reflectance of light and improve the illuminance. It is known to use a composition using silicone as a matrix component as a light-diffusing resin composition. It is known to use a silicone resin composition in an optical member, including such a light-diffusing resin composition. For example, JP-A-2010-18662 describes the use of a silicone resin composition containing silica and curable by a hydrosilylation reaction in an optical waveguide plate. JP-A-2011-184625 describes a light-diffusing dimethyl silicone rubber composition containing dimethylpolysiloxane, inorganic filler such as fine powder silica, and silicone elastomer particles containing phenyl group-containing siloxane units, as a light-diffusing resin composition. In addition, JP-A-2012-167253 describes a light-diffusing dimethyl silicone rubber composition containing a crosslinkable dimethyl silicone rubber, an inorganic filler, and optionally a dispersant (wetter). Furthermore, JP 2015-129213 A describes an addition-curing silicone rubber composition containing an alkenyl-containing linear polyorganosiloxane, an alkenyl-containing MT or MQ or MTQ resin, a polyorganohydrogensiloxane, and a hydrosilylation catalyst, and containing 0.1 to 10 parts by mass of spherical silica having an average particle size of 0.2 to 10 μm per 100 parts by mass of the composition, and a light-diffusing silicone rubber obtained from the composition. JP 2016-49764 A describes an optical semiconductor element encapsulation composition containing a hydrosilylation-curing silicone composition having a phenyl group, a phosphor, and light-diffusing organic particles selected from crosslinked polymethyl methacrylate particles and crosslinked polystyrene particles. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2010-18662 A [Patent Document 2] JP 2011-184625 A [Patent Document 3] JP 2012-167253 A [Patent Document 4] JP 2015-129213 A [Patent Document 5] JP 2016-49764 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, there is still a demand for new light diffusing materials with excellent light transmittance, light diffusibility, and mechanical properties. In addition to these properties, there is also a demand for light diffusing materials with high durability in reflow soldering processes. The present invention aims to provide a curable organopolysiloxane composition that can give a cured product that can be used as a light diffusing material with a good balance of these properties. In addition, the present invention aims to provide a curable organopolysiloxane composition that can be widely used for optical members, including materials for use as sealants for increasing the light extraction efficiency from light emitting devices such as light emitting diodes (LEDs). [Means for solving the problem]

[0005] The curable organopolysiloxane composition of the present invention comprises the following Components A to C: A) an organopolysiloxane having at least two radical reactive groups and / or reactive groups crosslinkable by a hydrosilylation reaction in the molecule, and in which 0 to less than 10 mol % of the organic groups bonded to silicon atoms in the molecule (silicon-bonded organic groups) are aryl groups; B) one or more inorganic fillers; and C) organosilicon compounds different from component A, which are C1 and C2: C1) an organosilicon compound different from component A, which has in its molecule a reactive functional group capable of bonding with a reactive group in component A, and a hydrolyzable silyl group and / or a silicon-bonded hydroxyl group, and which has two or more silicon atoms in its molecule; C2) an organosilicon compound different from component A, which has in its molecule a reactive functional group having 3 or more carbon atoms capable of bonding to a reactive group in component A, and a hydrolyzable silyl group and / or a silicon atom-bonded hydroxyl group, and which has in its molecule one or more silicon atoms; one or more compounds selected from the group consisting of and the mass of component B is 30 to 95% relative to the mass of the entire composition. The term "0 to less than 10 mol %" regarding the amount of aryl groups means that the amount of aryl groups is 0 mol %, i.e., that no aryl groups are present, or that aryl groups are present but in an amount of less than 10 mol %. Here, the organic group bonded to a silicon atom (silicon-bonded organic group) refers to an organic group such as a radical reactive group, a hydrosilylation reactive group, other monovalent hydrocarbon groups, and an alkoxy group bonded to a silicon atom constituting a polyorganosiloxane. Note that, although component A) may contain a very small amount of hydroxyl groups bonded to a silicon atom or hydrogen atoms bonded to a silicon atom, the effect is minor, so the content of aryl groups required to realize the technical effect of the present invention can be determined by considering only the proportion (content) of aryl groups in the organic groups bonded to silicon in component A).

[0006] In the above composition, Component A is preferably one or more organopolysiloxanes selected from the group consisting of components A1 and A2 below. A1) a linear or branched organopolysiloxane having in the molecule at least two radical reactive groups and / or reactive groups crosslinkable by a hydrosilylation reaction, and in which at least 0 mol % and less than 10 mol % of the silicon-bonded organic groups in the molecule are aryl groups; A2)i)R 1 SiO 3 / 2 Units (wherein R 1 represents a group selected from the group consisting of a monovalent organic group, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms), and optionally further comprises SiO 4 / 2 A resin building block which may have units; and ii) (R 2 2SiO 2 / 2 ) n (In the formula, R 2 each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and n represents a number in the range of 3 to 1000. R 1 and R 2 At least a portion of R is a reactive group capable of crosslinking by a radical reaction and / or a hydrosilylation reaction, and R 1 and R 2 An organopolysiloxane in which the proportion of aryl groups having 6 to 14 carbon atoms in the total number of moles of groups (excluding hydroxyl groups) is from 0 to less than 10 mol %, preferably from 0 to 5 mol %.

[0007] In the above composition, the inorganic filler B is preferably at least one type selected from the group consisting of spherical silica particles, spherical alumina particles, and fluorescent fillers.

[0008] More preferably, the spherical silica particles are spherical fused silica particles, and the spherical alumina particles are spherical fused alumina particles.

[0009] In a preferred embodiment of the above composition, component C has the following general formula: (R a R b 2SiO) p -K-(SiR b 2-Y-Si(R b ) q (OR c ) 3-q ) r (In the formula, R a represents a reactive group capable of bonding with the reactive group of component A; R b R independently represents a group selected from the group consisting of monovalent hydrocarbon groups, halogenated hydrocarbon groups, and cyanoalkyl groups; cindependently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxyalkyl group having a total of 2 to 10 carbon atoms; K represents a group represented by the average composition formula (R b 3SiO 1 / 2 ) s (R b 2SiO 2 / 2 ) t (R b SiO 3 / 2 ) u (SiO 4 / 2 ) v (OR c ) w (In the formula, R b and R c is as defined above, s, t, u, v, and w each represent the number of each unit, and each represents a number from 0 to 500, provided that all of t, u, and v are not 0, and the value of s+w is u+2v or less; Y represents an oxygen atom, a divalent hydrocarbon group, or a linear or branched organopolysiloxane chain or a silicone resin structural block represented by the general formula: [ka] (In the formula, R b is as defined above, Z is a divalent hydrocarbon group; within the range possible depending on the structure of K, p is a number from 1 to 10, r is a number from 1 to 10, and q is a number from 0 to 2. It is an organosilicon compound represented by the formula:

[0010] More preferably, component C has the following structural formula: [ka] {where, R a represents a reactive group capable of bonding with the reactive group of component A; R b represents a group selected from the group consisting of monovalent hydrocarbon groups, halogenated hydrocarbon groups, and cyanoalkyl groups; R crepresents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxyalkyl group having a total of 2 to 10 carbon atoms; m is a number in the range of 0 to 500, a is 0, 1, or 2, and Y is an oxygen atom, a divalent hydrocarbon group, or a group represented by the general formula: [ka] (In the formula, R b is as defined above, and Z is a divalent hydrocarbon group. It is an organosilicon compound represented by the formula:

[0011] The present invention further provides a cured product obtained from any of the above curable organopolysiloxane compositions.

[0012] The cured product of the present invention preferably has a light transmittance of 40% or more.

[0013] The cured product of the present invention preferably has a light diffusibility such that, when the straight-transmitted light intensity is set to 1 in a bidirectional transmittance distribution function measured using a white light source (a white LED formed by combining a blue LED and a yellow phosphor), the transmitted light intensity at a light receiving position inclined at 45 degrees to the axis of the straight-transmitted light with the measurement sample as the center is 0.65 or more.

[0014] The cured product of the present invention preferably has an elongation at break in the range of 30% or more.

[0015] The present invention also provides an optical component comprising a cured product of the above-mentioned curable organopolysiloxane composition.

[0016] The optical member of the present invention is preferably a light-diffusing coating film material for a light-receiving sensor having a thickness of 500 μm or less.

[0017] The optical member is preferably a sealant for a light-emitting diode or an organic electroluminescent device.

[0018] The present invention also provides an optical device including the optical member described above.

[0019] The present invention further provides a coating agent comprising the above-mentioned curable organopolysiloxane composition and an organic solvent, which can be used to form a light diffusing layer on a substrate. Effect of the Invention

[0020] The curable organopolysiloxane composition of the present invention has an excellent balance of light transmittance, light diffusion properties, and mechanical properties, and can exhibit good elongation at break in terms of mechanical properties. In addition, the cured product obtained from the curable organopolysiloxane composition of the present invention has a molecular design with a low content of aryl groups bonded to silicon atoms, and is characterized by having higher flexibility and greater elongation at break than organopolysiloxane compositions with a large number of aryl groups, and is excellent in conformity to deformation of the substrate. A substrate provided with a coating layer made of the cured product has the advantage of being less prone to warping and deformation. The cured product obtained from the curable composition of the present invention is suitable as a material used as an optical member, particularly an optical member for an optical device, and is suitable for use, for example, as a sealant for light-emitting diodes and organic electroluminescent elements, or as a light diffusion material, for example, a light diffusion film or light diffusion coating agent for a light-receiving sensor. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 is an SEM photograph showing a fracture surface of the sample of Example 5. [Diagram 2] FIG. 2 is a SEM photograph showing a fracture surface of the sample of Comparative Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The present invention will now be described in more detail.

[0023] The curable organopolysiloxane composition of the present invention contains, as essential components, the above-mentioned components A, B, and C. Components A, B, and C are each described below. Note that, unless otherwise specified, when referring to the number of groups per molecule in this specification, it refers to the average number per molecule.

[0024] <Component A> Component A may be one organopolysiloxane having at least two radical reactive groups and / or hydrosilylation reactive groups in the molecule, and in which 0 to less than 10 mol %, particularly preferably 0 to 5 mol %, of the organic groups bonded to silicon atoms in the molecule (silicon atom-bonded organic groups) are aryl groups, particularly preferably phenyl groups, or a combination of two or more organopolysiloxanes. Examples of organopolysiloxanes that can be used as component A include the following. (Aa) an organopolysiloxane having two or more types of radical reactive groups in the molecule; (Ab) an organopolysiloxane having one or more types of groups having two or more hydrosilylation reactive carbon-carbon double bonds in the molecule; and (Ac) An organopolysiloxane having two or more hydrosilylation reactive silicon-bonded hydrogen atoms (SiH) in the molecule. In addition to the reactive groups described above, Aa to Ac may optionally further contain a condensation reactive group. Here, the condensation reactive group refers to a group capable of forming a Si-O-Si bond by a condensation reaction, optionally by hydrolysis and condensation reaction.

[0025] These Aa to Ac can be used alone or in combination of two or more kinds so that organopolysiloxanes are crosslinked with each other by a radical reaction to produce a cured product, organopolysiloxanes are crosslinked with each other by a hydrosilylation reaction to produce a cured product, or organopolysiloxanes are crosslinked with each other by a combination of a radical reaction and a hydrosilylation reaction to produce a cured product.

[0026] For example, to obtain a composition that cures by a radical reaction, it is preferable to use one or more of Aa as component A. Also, to obtain a composition that cures by a hydrosilylation reaction, it is preferable to use a combination of Ab and Ac as component A. To obtain a composition that cures by a combination of a radical reaction and a hydrosilylation reaction, it is preferable to use a combination containing one or more of each of Aa, Ab, and Ac as component A, or a combination of one or more of each of Ab and Ac when the carbon-carbon double bond of component Ab is also radical reactive.

[0027] Examples of organopolysiloxanes that are different from one another among the above components Aa to Ac include organopolysiloxanes that are the same in that they have the same reactive groups, but have different bonding positions of the reactive groups relative to the organopolysiloxane skeleton and / or different reactive group contents, or organopolysiloxane skeletons themselves that are different from one another.

[0028] [Component Aa] Component Aa is an organopolysiloxane having two or more radical reactive groups of one or more types in the molecule. The radical reactive groups of component Aa are functional groups that can crosslink with each other by a free radical mechanism in the presence of a heat or photoradical initiator and / or under irradiation with high energy rays, such as ultraviolet rays or electron beams, and optionally in the presence of a crosslinking agent. Examples of the radical reactive groups include groups containing a secondary carbon-carbon bond, and more specifically, unsaturated carboxylate groups such as alkenyl groups, acrylates and methacrylates. The radical reactive groups of component Aa may be one type or two or more types in combination. When two or more types of radical reactive groups are used in combination, even if one molecule has two or more types of radical reactive groups, two or more different organopolysiloxanes each having different radical reactive groups can be used in combination. Component Aa may optionally have a condensation reactive group in addition to the radical reactive group. The condensation reactive group is not particularly limited as long as it is a group that can form a Si-O-Si bond by a condensation reaction, and examples of the condensation reactive group include condensation reactive groups selected from a hydroxyl group and an alkoxy group.

[0029] Preferably, component Aa has the average formula: R 11 a1 R 12 b1 SiO (4-a1―b1) / 2 (1) or a mixture of two or more thereof. In the formula, R 11 is a radically reactive group, preferably a radically reactive group that contains a carbon-carbon double bond. R 12 is a group selected from substituted or unsubstituted monovalent hydrocarbon groups having no radically reactive carbon-carbon double bonds, hydroxyl groups, and alkoxy groups, where R 12 At least a portion of R may be a substituted or unsubstituted aryl group, and the proportion of the aryl group is 11 and R 12 The condition is that the total number of moles (excluding hydroxyl groups) of the aryl groups is 0 to less than 10 mol %, preferably 0 to 5 mol %. In particular, the smaller the amount of aryl groups, the more advantageous it is that the turbidity of the cured product can be suppressed within the range. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. a1 and b1 are numbers that satisfy the following conditions: 1≦a1+b1≦3 and 0.001≦a1 / (a1+b1)≦0.33. Furthermore, it is preferable that a1 and b1 are numbers that satisfy the following conditions: 1.5≦a1+b1≦2.5 and 0.005≦a1 / (a1+b1)≦0.2. This is because by making a1+b1 equal to or greater than the lower limit of the above range, the flexibility of the resulting cured product can be increased, while by making a1+b1 equal to or less than the upper limit of the above range, the mechanical strength of the resulting cured product can be increased. In addition, by making a1 / (a1+b1) equal to or greater than the lower limit of the above range, the mechanical strength of the cured product can be increased, while by making a1 / (a1+b1) equal to or less than the upper limit of the above range, the flexibility of the resulting cured product can be increased.

[0030] In the above average composition formula (1), R 11 The radical reactive group represented by can be selected from alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, and dodecenyl groups; acrylic-containing groups, such as 3-acryloxypropyl groups and 4-acryloxybutyl groups; and methacrylic-containing groups, such as 3-methacryloxypropyl groups and 4-methacryloxybutyl groups. In the above average composition formula, R 12Examples of the monovalent hydrocarbon group having no radical reactive carbon-carbon double bond represented by include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, and pyrenyl; and aralkyl groups such as benzyl, phenethyl, naphthylethyl, naphthylpropyl, anthracenylethyl, phenanthrylethyl, and pyrenylethyl. These alkyl groups may have some of their hydrogen atoms substituted with halogen atoms or hydroxyl groups. These aryl and aralkyl groups may have one or more hydrogen atoms substituted with alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; and / or halogen atoms such as chlorine and bromine. The radical reactive group R of component Aa 11 is preferably a group selected from a vinyl group, an allyl group, a hexenyl group, an acryl-containing group, and a methacryl-containing group.The monovalent hydrocarbon group contained in component Aa is particularly preferably a group selected from a methyl group and a phenyl group which is an aryl group.

[0031] The above component Aa can be an organopolysiloxane having a cyclic molecular structure consisting of D units only, or a linear molecular structure consisting of D units only or D units and M units. Alternatively, component Aa may be an organopolysiloxane having a branched molecular structure or a resinous (network) molecular structure, and examples of branched or resinous organopolysiloxanes include, but are not limited to, MQ, MT, MQT, QT, MDQ, MDT, and MDQT type organopolysiloxanes. Here, M is represented by the general formula RSiO 1 / 2 where D is the general formula RSiO 2 / 2 where T is the general formula RSiO 3 / 2 and Q is SiO 4 / 2where R is generally an organic group, and the terms M, D, T, and Q units are well known in the silicone art.

[0032] The organopolysiloxane represented by the above average composition formula is a radical-reactive organopolysiloxane having a radical-reactive group. 12 When the alkyl group has a hydroxyl group and / or an alkoxy group as a radical, it can be condensation reactive in addition to radical reactive.

[0033] In one particularly preferred embodiment, component Aa is (Aa-1) A linear or branched organopolysiloxane having radical reactive groups only at the molecular chain terminals, and optionally (Aa-2) A radical-reactive group-containing organopolysiloxane resin having at least one branched siloxane unit in the molecule and having a radical-reactive group content in the range of 0.01 to 7.00 mass %. It includes.

[0034] Component (Aa-1) has a molecular chain end (Rad)R 21 2SiO 1 / 2 (wherein Rad represents a radical reactive group, and R 11 Corresponding to R 21 is R in the above average composition formula (1). 12 (corresponding to R 22 2SiO 2 / 2 R is a linear organopolysiloxane consisting of only siloxane units represented by the formula (1) or a branched organopolysiloxane further containing one or more T units and / or Q units. 22 is the R of the average composition formula (1) above. 12 The degree of siloxane polymerization of component (Aa-1), including the terminal siloxane units, is in the range of 7 to 1002. It is particularly preferable that such component (Aa-1) has a molecular chain having both ends thereof represented by (Rad)R 21 2SiO 1 / 2It is a linear organopolysiloxane terminated with a siloxane unit represented by the following formula:

[0035] Component (Aa-2) is a radical reactive group-containing organopolysiloxane resin, for example, represented by the average unit formula: (R 31 SiO 3 / 2 ) o1 (R 31 2SiO 2 / 2 ) p1 (R 31 3SiO 1 / 2 ) q1 (SiO 4 / 2 ) r1 (XO 1 / 2 ) s1 (2) Examples of the organopolysiloxane resin include those having a radical reactive group represented by the following formula: In the average unit formula (2) above, R 31 R in the average composition formula (1) of the component Aa 11 and R 12 X represents a group selected from a substituted or unsubstituted monovalent hydrocarbon group having no radical reactive carbon-carbon double bond, a hydroxyl group, and an alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. However, all of the R 31 Among these, at least the content of radical reactive groups in the organopolysiloxane resin satisfies the range of 0.01 to 7.00 mass%, preferably 0.05 to 6.00 mass%, R 31 is a radical reactive group, in particular R 31 3SiO 1 / 2 R on the siloxane unit represented by 31 At least a portion of the groups is preferably a radical reactive group.

[0036] Furthermore, in the above formula (2), (o1+r1) is a positive number, p1 is 0 or a positive number, q1 is 0 or a positive number, s1 is 0 or a positive number, and p1 / (o1+r1) is a number in the range of 0 to 10, q1 / (o1+r1) is a number in the range of 0 to 5, (o1+r1) / (o1+p1+q1+r1) is a number in the range of 0.3 to 0.9, and s1 / (o1+p1+q1+r1) is a number in the range of 0 to 0.4.

[0037] Particularly preferred as component (Aa-2) are compounds having the average unit formula: (Rad)R 31 2SiO 1 / 2 ) q11 (R 31 3SiO 1 / 2 ) q21 (SiO 4 / 2 ) r11 (3) (wherein Rad represents a radical reactive group, and R 11 has the same meaning as R 31 is R in the above average composition formula (1). 12 where q11+q21+r1 is a number in the range of 50 to 500, (q11+q21) / r11 is a number in the range of 0.1 to 2.0, and q11 is a number in the range in which the content of radical reactive groups in the organopolysiloxane resin is 0.01 to 7.00 mass%, preferably 0.05 to 6.00 mass%. Examples include radical reactive group-containing MQ organopolysiloxane resins represented by the following formula:

[0038] By using in combination component (Aa-1), which has radical reactive groups only at the molecular chain terminals, and component (Aa-2), which is an organopolysiloxane resin and has a certain amount of radical reactive groups, it is possible to obtain a cured product that has excellent fast-curing / fast-drying properties as a whole, as well as excellent mechanical strength and flexibility.

[0039] [Component Ab] Component Ab is an organopolysiloxane having two or more groups with one or more types of hydrosilylation reactive carbon-carbon double bonds in the molecule, and 0 mol% or more and less than 10 mol% of the silicon-bonded organic groups in the molecule are aryl groups, preferably phenyl groups. The hydrosilylation reactive groups in component Ab are not limited to specific ones as long as they can react with SiH groups to form C-Si bonds, but as described below, for example, monovalent hydrocarbon groups containing carbon-carbon double bonds can be mentioned, and more specifically, alkenyl groups, particularly alkenyl groups having carbon-carbon double bonds at the terminals can be mentioned. The hydrosilylation reactive groups in component Ab can be one type or two or more types in combination. When two or more types of hydrosilylation reactive groups are used in combination, even if one molecule has two or more types of hydrosilylation reactive groups, two or more different organopolysiloxanes each having different hydrosilylation reactive groups can be used in combination. Component Ab may optionally have a condensation reactive group in addition to the hydrosilylation reactive group. The condensation reactive group is not particularly limited as long as it is a group that can form a Si-O-Si bond by condensation reaction, and examples thereof include condensation reactive groups selected from a hydroxyl group and an alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms.

[0040] Preferably, component Ab has the average formula: R 41 a4 R 42 b4 SiO (4-a4―b4) / 2 (4) or a mixture of two or more thereof. In the formula, R 41 is a hydrosilylation reactive group, preferably a monovalent hydrocarbon group having a carbon-carbon double bond, preferably an alkenyl group. R 42 is a group selected from substituted or unsubstituted monovalent hydrocarbon groups other than hydrosilylation reactive groups, hydroxyl groups, and alkoxy groups, provided that R 42At least a portion of R may be a substituted or unsubstituted aryl group, and the proportion of the aryl group is 41 and R 42 The condition is that the total mole number of the above (excluding hydroxyl groups) is from 0 to less than 10 mol %, preferably from 0 to 5 mol %. a4 and b4 are numbers that satisfy the following conditions: 1≦a4+b4≦3 and 0.001≦a4 / (a4+b4)≦0.33. Furthermore, it is preferable that a4 and b4 are numbers that satisfy the following conditions: 1.5≦a4+b4≦2.5 and 0.005≦a4 / (a4+b4)≦0.2. This is because by making a4+b4 equal to or greater than the lower limit of the above range, the flexibility of the resulting cured product can be increased, while by making a4+b4 equal to or less than the upper limit of the above range, the mechanical strength of the resulting cured product can be increased. In addition, by making a4 / (a4+b4) equal to or greater than the lower limit of the above range, the mechanical strength of the cured product can be increased, while by making a4 / (a4+b4) equal to or less than the upper limit of the above range, the flexibility of the resulting cured product can be increased.

[0041] In the above average composition formula (4), R 41 Examples of the hydrosilylation reactive group represented by R include alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups. 41 In particular, R is preferably independently selected from a vinyl group, an allyl group, and a hexenyl group, and is particularly preferably a vinyl group. 42Examples of the monovalent hydrocarbon group other than the hydrosilylation reactive group represented by include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, and pyrenyl; and aralkyl groups such as benzyl, phenethyl, naphthylethyl, naphthylpropyl, anthracenylethyl, phenanthrylethyl, and pyrenylethyl. These alkyl groups may have a part of their hydrogen atoms substituted with halogen atoms or hydroxyl groups. These aryl and aralkyl groups may have one or more hydrogen atoms substituted with alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; and / or halogen atoms such as chlorine and bromine. The hydrosilylation reactive group R of component Ab 41 is preferably a group selected from a vinyl group, an allyl group, and a hexenyl group, and particularly preferably a vinyl group.The monovalent hydrocarbon group other than the hydrosilylation reactive group contained in component Ab is particularly preferably a group selected from a methyl group and a phenyl group as an aryl group.

[0042] The above component Ab can be an organopolysiloxane having a cyclic molecular structure consisting of D units, or a linear molecular structure consisting of D units or D units and M units. Alternatively, component Ab may be an organopolysiloxane having a branched molecular structure or a resinous (network) molecular structure, and examples of branched or resinous organopolysiloxanes include, but are not limited to, MQ, MT, MQT, QT, MDQ, MDT, and MDQT type organopolysiloxanes.

[0043] The organopolysiloxane represented by the above average composition formula (4) is a hydrosilylation-reactive organopolysiloxane having a hydrosilylation-reactive group. 42When the alkyl group has a hydroxyl group and / or an alkoxy group, it can be condensation reactive in addition to hydrosilylation reactive. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms.

[0044] In one particularly preferred embodiment, the component Ab is (Ab-1) a linear or branched organopolysiloxane having alkenyl groups only at the molecular chain terminals, and optionally (Ab-2) An alkenyl group-containing organopolysiloxane resin having at least one branched siloxane unit in the molecule and having a vinyl (CH2=CH-) group content in the range of 0.01 to 7.00 mass%. It includes.

[0045] Component (Ab-1) has a molecular chain end (Alk)R 42 2SiO 1 / 2 (Wherein, Alk is an alkenyl group having 2 or more carbon atoms and R 41 Corresponding to R 42 is R in the above average composition formula (4). 42 (corresponding to R 42 2SiO 2 / 2 The component (Ab-1) is a linear organopolysiloxane consisting of only siloxane units represented by the formula: or a branched organopolysiloxane further containing one or more T and / or Q units. The degree of siloxane polymerization of the component (Ab-1) is in the range of 7 to 1002, including the terminal siloxane units. It is particularly preferable that both ends of the molecular chain of the component (Ab-1) are (Alk)R 42 2SiO 1 / 2 It is a linear organopolysiloxane terminated with a siloxane unit represented by the following formula:

[0046] Component (Ab-2) is an alkenyl group-containing organopolysiloxane resin, for example, represented by the average unit formula: (R 51 SiO 3 / 2 ) o2 (R 512SiO 2 / 2 ) p2 (R 51 3SiO 1 / 2 ) q2 (SiO 4 / 2 ) r2 (XO 1 / 2 ) s2 (5) Examples of the alkenyl-containing organopolysiloxane resin include those represented by the following formula: In the average unit formula (5) above, R 51 R in the average composition formula (4) of the component Ab 41 and R 42 and X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. However, all of the R 51 Among these, at least the content of vinyl (CH2=CH-) groups in the organopolysiloxane resin satisfies the range of 0.01 to 7.00 mass%, preferably 0.05 to 6.00 mass%, so that R 51 is an alkenyl group, in particular R 51 3SiO 1 / 2 R on the siloxane unit represented by 51 At least a portion of these is preferably an alkenyl group.

[0047] In formula (5), (o2+r2) is a positive number, p2 is 0 or a positive number, q2 is 0 or a positive number, s2 is 0 or a positive number, and p2 / (o2+r2) is a number in the range of 0 to 10, q2 / (o2+r2) is a number in the range of 0 to 5, (o2+r2) / (o2+p2+q2+r2) is a number in the range of 0.3 to 0.9, and s2 / (o2+p2+q2+r2) is a number in the range of 0 to 0.4.

[0048] Particularly preferred as component (Ab-2) are ((Alk)R 51 2SiO 1 / 2 ) q21 (R 51 3SiO1 / 2 ) q22 (SiO 4 / 2 ) r2 (6) (In the formula, Alk is an alkenyl group having 2 or more carbon atoms, and R 51 is a group other than the hydrosilylation reactive group defined by the above average formula (5), q21+q22+r2 is a number in the range of 50 to 500, (q21+q22) / r2 is a number in the range of 0.1 to 2.0, and q21 is a number in the range such that the content of vinyl (CH2=CH-) groups in the organopolysiloxane resin is in the range of 0.01 to 7.00 mass%, preferably 0.05 to 6.00 mass%. Examples of the alkenyl-containing MQ organopolysiloxane resins include those represented by the following formula:

[0049] By using in combination component (Ab-1), which has alkenyl groups only at the molecular chain terminals, and component (Ab-2), which is an organopolysiloxane resin and has a certain amount of alkenyl groups, it is possible to obtain a cured reaction product that has excellent fast-curing / fast-drying properties as a whole composition, as well as excellent mechanical strength and flexibility.

[0050] [Preferred forms of components Aa and / or Ab] In this case, the components Aa and / or Ab are i)R 61 SiO 3 / 2 Units (wherein R 61 independently represent a group selected from the group consisting of a radical reactive group, a hydrosilylation reactive group, a monovalent organic group other than a radical reactive group and a hydrosilylation reactive group, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms), and optionally further comprises SiO 4 / 2 A resin building block which may have units; and ii) (R 62 2SiO 2 / 2 ) n (In the formula, R 62each independently represents a group selected from a radical reactive group, a hydrosilylation reactive group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and n represents a number in the range of 3 to 1000, preferably 20 to 300), 61 and R 62 at least a portion of R is a radical reactive group and / or a hydrosilylation reactive group, and R 61 and R 62 The ratio of aryl groups having 6 to 14 carbon atoms to the total number of moles of groups (excluding hydroxyl groups and hydrogen atoms) is 0 to less than 10 mol%, preferably 0 to 5.0 mol%. In this specification, a structure having such a resin structure block and a linear or branched block containing a linear structure portion (linear structure block) is referred to as a resin linear structure.

[0051] R 61 and R 62 The radical reactive group that can be represented by is R 11 R is a radical reactive group independently selected from those described above as radical reactive groups that R can represent. 61 and R 62 The radical reactive group represented by is preferably a group selected from a vinyl group, an allyl group, a hexenyl group, an acryl-containing group, and a methacryl-containing group, and is particularly preferably a vinyl group, an allyl group, or a hexenyl group. R 61 and R 62 The hydrosilylation reactive group that can be represented by is R 41 Examples of the hydrosilylation reactive group represented by R include groups independently selected from those described above. 61 and R 62 The hydrosilylation reactive group represented by is preferably a group selected from a vinyl group, an allyl group, and a hexenyl group, and particularly preferably a vinyl group.

[0052] R61 The monovalent organic group other than the radical reactive group and the hydrosilylation reactive group that may be represented by may be a substituted or unsubstituted monovalent hydrocarbon group that has poor radical reaction and hydrosilylation reactivity and does not have a carbon-carbon double bond. Examples of the substituted or unsubstituted monovalent hydrocarbon group include the following: alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, and pyrenyl group; and aralkyl groups such as benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group, phenanthrylethyl group, and pyrenylethyl group. These alkyl groups may have some of their hydrogen atoms substituted with halogen atoms or hydroxyl groups. Furthermore, these aryl and aralkyl groups may have one or more hydrogen atoms substituted with an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and / or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

[0053] R 61 Examples of the alkoxy group having 1 to 6 carbon atoms that can be represented include linear, branched, and cyclic alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, cyclohexyloxy, etc. As the alkoxy group, a methoxy group is particularly preferred.

[0054] R 62 Examples of the alkyl group having 1 to 20 carbon atoms and optionally substituted with a halogen atom that may be represented by include unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, and alkyl groups in which one or more hydrogen atoms of these alkyl groups have been substituted with a halogen atom, for example, a fluorine, chlorine, or bromine atom. As the alkyl group, a methyl group is particularly preferred. R62 Examples of the group selected from substituted or unsubstituted aryl groups having 6 to 14 carbon atoms that can be represented include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a pyrenyl group, as well as groups in which some or all of the hydrogen atoms bonded to these groups have been substituted with halogen atoms such as fluorine atoms, chlorine atoms, or bromine atoms. As the aryl group, a phenyl group is particularly preferred.

[0055] The linear or branched organopolysiloxane structural block containing the linear diorganopolysiloxane structural portion of ii) above is represented by the formula (R 62 2SiO 2 / 2 ) n or the linear diorganopolysiloxane is composed solely of a T unit (R 62 SiO 3 / 2 ) and / or a branched organopolysiloxane structure formed by bonding to Q units, preferably T units.

[0056] This component can have a structure formed by bonding the organopolysiloxane resin structural block of i) and the linear or branched organopolysiloxane block of ii), but the connecting portion between the resin structural block and the linear or branched organopolysiloxane structural block is preferably a -Si-O-Si- bond, -Si-R A -Si-(wherein, R Arepresents a linear or branched alkylene group having 2 to 14 carbon atoms, preferably 2 to 10), and combinations thereof. The method of forming the -Si-O-Si- bond between the structural block i) and the structural block ii) is not particularly limited, but for example, it can be formed by crosslinking the respective Si-OH and / or Si-OR groups (OR is a hydrolyzable group such as alkoxy having 1 to 6 carbon atoms) between the resin structural block i) and the linear or branched block ii) by a condensation reaction. Therefore, in this case, for example, a method of synthesizing the resin linear structure includes a method of forming the resin structural block i) first, and synthesizing a linear or branched diorganopolysiloxane block under conditions in which the linear or branched organopolysiloxane block is linked to the SiOH and / or SiOR group of the resin structural block. For example, a product having a desired structure can be obtained by ring-opening polymerization of a cyclic organopolysiloxane in the presence of a resin building block having SiOH and / or SiOR groups, optionally in the presence of an additional crosslinking agent. Such a synthesis reaction of organopolysiloxane itself can be carried out using a well-known method.

[0057] The connecting portion between the resin building block and the linear or branched organopolysiloxane building block containing a linear portion is -Si-R A -Si- group (wherein R A represents a linear or branched alkylene group having 2 to 14, preferably 2 to 10, carbon atoms), for example, a resin structural block having a hydrosilylation-reactive alkenyl group can be reacted with a linear or branched diorganopolysiloxane block having a silicon-bonded hydrogen atom (SiH group) to carry out a hydrosilylation reaction, whereby the alkenyl group possessed by the resin structural block can be converted to R A The organopolysiloxane having a resin-linear structure is obtained. The synthesis of the organopolysiloxane having a resin-linear structure can be carried out in accordance with the method described in JP-A-2010-1336, for example.

[0058] However, the method for synthesizing organopolysiloxanes having a resin linear structure including the above structures i) and ii) is not limited to the above-mentioned examples.

[0059] In the present invention, an organopolysiloxane having a resin linear structure may be used, but it is preferable to use a linear or branched organopolysiloxane.

[0060] In component A, the proportion of aryl groups in the groups bonded to the Si atoms of the siloxane units in the linear or branched organopolysiloxane is 0 to less than 10 mol%, preferably 0 to 5 mol%, so that the cured product obtained from the curable organopolysiloxane composition of the present invention has high flexibility and excellent elongation at break. Moreover, when component A is combined with components B and C, a cured product with excellent light diffusion properties and mechanical properties in balance can be obtained. In addition, the low content of aryl groups has the advantage of suppressing turbidity of the cured product.

[0061] [Component Ac] Component Ac is an organohydrogenpolysiloxane having, on average, two or more hydrosilylation-reactive silicon-bonded hydrogen atoms (SiH) in the molecule. Component Ac is used in combination with an organopolysiloxane (component Ab) having, on average, two or more groups per molecule capable of undergoing hydrosilylation reaction with SiH groups to obtain a hydrosilylation-curable composition. Component Ac functions as a crosslinking agent for component Ab.

[0062] Specific examples of such component Ac include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, methylhydrogenpolysiloxane terminated at both molecular chain ends with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer terminated at both molecular chain ends with trimethylsiloxy groups, and dimethylsiloxane-methylhydrogensiloxane copolymer terminated at both molecular chain ends with dimethylsiloxy groups. Hydrogensiloxy-blocked dimethylpolysiloxane, dimethylsiloxane-methylhydrogensiloxane copolymers blocked at both ends with dimethylhydrogensiloxy groups, methylhydrogensiloxane-diphenylsiloxane copolymers blocked at both ends with trimethylsiloxy groups, methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymers blocked at both ends with trimethylsiloxy groups, hydrolysis condensation products of trimethoxysilane, (CH3)2HSiO 1 / 2 Units and SiO 4 / 2 A copolymer consisting of (CH3)2HSiO units. 1 / 2 Units and SiO 4 / 2 Units and (C6H5)SiO 3 / 2 units, and mixtures of two or more of these.

[0063] In the curable composition of the present invention, component Ac is particularly preferably (Ac-1) a linear or branched organohydrogenpolysiloxane having silicon-bonded hydrogen atoms only at the molecular chain terminals, and optionally (Ac-2) Linear or resinous organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule It includes.

[0064] Component (Ac-1) is an organohydrogenpolysiloxane having silicon-bonded hydrogen atoms only at the molecular chain terminals, and functions as a chain extender in the hydrosilylation reaction with component (Ab) to improve the flexibility of the cured reaction product. Component (Ac-1) is preferably a linear organohydrogenpolysiloxane, and for example, one represented by the following structural formula can be preferably used. HMe2SiO(Ph2SiO) m1 SiMe2H HMe2SiO(Me2SiO) m1 SiMe2H HMePhSiO(PhSiO) m1 SiMePhH HMePhSiO(Me2SiO) m1 SiMePhH HMePhSiO(PhSiO) m1 (MePhSiO) n1 SiMePhH HMePhSiO(PhSiO) m1 (Me2SiO) n1 SiMePhH In the above formula, Me and Ph represent a methyl group and a phenyl group, respectively; m1 is a number from 1 to 100; and n1 is a number from 1 to 50.

[0065] Component (Ac-2) is a linear or resinous organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule, and is a component that can impart rapid curing properties to the composition when used in combination with component (Ac-1) above.

[0066] Examples of linear organohydrogenpolysiloxanes include methylhydrogenpolysiloxanes capped at both molecular chain terminals with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular chain terminals with dimethylhydrogensiloxane groups, methylhydrogensiloxane-diphenylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, and methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups.

[0067] On the other hand, the resinous organohydrogenpolysiloxane contains at least SiO 4 / 2 Units (Q units) and R 3 SiO 3 / 2 units (T units), R 3 3SiO 1 / 2 Unit (M unit), R 3 2HSiO 1 / 2 Unit (M H units), and optionally R 3 2SiO 1 / 2 Unit (D unit), R 3 HSiO 1 / 2 Units (D H units), more specifically, M H MQ type, M H Q type, M H MT type, M H T type, M H MQT type, M H QT type, M H MDQ type, M H MDD H Q type, M H DQ type, M H DD H Q type, M H MDT type, M H MDD H T type, M H DT type, M H DD H T type, MH MDQT type, M H MDD H QT type, M H DQT type, M H DD H Examples of the organohydrogenpolysiloxane resin include one or more organohydrogenpolysiloxane resins selected from the QT type. In the above formula, R 3 is a methyl group or a phenyl group.

[0068] <Component B> Component B is an inorganic filler that imparts optical functions such as light diffusion properties or wavelength conversion to the cured product obtained from the curable composition of the present invention. The inorganic filler may be any inorganic filler that can provide the desired optical functions such as light diffusion effects or wavelength conversion when combined with the organopolysiloxane of the present invention, and is not limited to a specific inorganic filler as long as such effects can be obtained. As the filler used in the curable composition of the present invention, it is preferable to use one or a combination of two or more selected from the group consisting of spherical silica particles, spherical alumina particles, and fluorescent fillers. By using the inorganic filler in an amount of 30 to 95% by mass based on the total mass of the curable organopolysiloxane composition of the present invention, a cured product having excellent optical effects and well-balanced mechanical properties can be obtained. The amount of the inorganic filler is preferably 40 to 95% by mass, particularly preferably 50 to 92.5% by mass, based on the total mass of the composition.

[0069] [Spherical silica particles] As silica particles, those having an irregular shape and those having a spherical shape are known. Particles of any shape may be used as long as they can improve the light diffusion properties of the cured product obtained from the curable organopolysiloxane composition of the present invention, but it is preferable to use spherical silica particles in the curable composition of the present invention. Particularly preferred as spherical silica particles are spherical fused silica particles spheroidized by a fusion method, for example, spherical fused silica particles obtained by melting crushed fine powdered silica in a flame and spheroidizing it, and commercially available ones can be used. When used in the present invention, the average particle size is 1 to 10 μm, particularly 2 to 5 μm (d 50 It is preferable to use spherical silica particles, particularly spherical fused silica particles, which are

[0070] [Spherical alumina particles] Particles of any shape may be used as long as they can improve the light diffusion properties of the cured product obtained from the curable organopolysiloxane composition of the present invention, but the alumina particles used in the present invention are preferably spherical. Particularly preferred spherical alumina particles are, for example, spherical fused alumina particles spheroidized by a melting method in which pulverized fine powdered alumina particles are melted in a flame to spheroidize them, and commercially available particles can be used. When used in the present invention, the average particle size is 1 to 10 μm, particularly 2 to 5 μm (d), as measured, for example, by the Coulter method or the laser diffraction scattering method. 50 It is preferable to use spherical alumina particles, particularly spherical fused alumina particles, which are fused spherical alumina particles.

[0071] [Fluorescent filler] It is also preferable to use a fluorescent filler (phosphor) as the inorganic filler used as component B of the present invention. The film, sheet, or coating layer containing the fluorescent filler obtained from the curable composition of the present invention also functions as a wavelength conversion material, and when placed on a light source, it can convert the wavelength of light from the light source. In addition, light diffusion properties can be imparted by using a fluorescent filler. The phosphor is not particularly limited, and examples thereof include yellow, red, green, and blue emitting phosphors made of oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, etc., which are widely used in light emitting diodes (LEDs) or organic electroluminescent devices (OLEDs). Examples of oxide phosphors include yttrium, aluminum, and garnet-based YAG-based green to yellow emitting phosphors containing cerium ions; terbium, aluminum, and garnet-based TAG-based yellow emitting phosphors containing cerium ions; and silicate-based green to yellow emitting phosphors containing cerium or europium ions. In addition, examples of oxynitride phosphors include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions. Examples of nitride phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based CaSn-based red light-emitting phosphors containing europium ions. Examples of sulfide phosphors include ZnS-based green color-emitting phosphors containing copper ions and aluminum ions. Examples of oxysulfide phosphors include Y2O2S-based red light-emitting phosphors containing europium ions. The curable organopolysiloxane composition of the present invention can use one of these phosphors or a combination of two or more of them. As for the phosphor, commercially available ones can be used.

[0072] <Component C> Component C is an organosilicon compound different from component A, and is represented by the following C1 and C2: C1) an organosilicon compound different from component A, which has in its molecule a reactive functional group capable of bonding with a reactive group in component A, and a hydrolyzable silyl group and / or a silicon-bonded hydroxyl group, and which has two or more silicon atoms in its molecule; C2) an organosilicon compound different from component A, which has in its molecule a reactive functional group having 3 or more carbon atoms capable of bonding to a reactive group in component A, and a hydrolyzable silyl group and / or a silicon atom-bonded hydroxyl group, and which has in its molecule one or more silicon atoms; The compound is one or more compounds selected from the group consisting of: By combining Component C with Component A and Component B, it is possible to significantly improve the breaking elongation without decreasing the breaking strength of the cured product obtained from the curable composition of the present invention. Furthermore, as a result of the improvement in breaking elongation, the high temperature durability, particularly the thermal shock resistance, of the cured product is improved, and there is an advantage in that deformation, cracking, peeling from members, etc. of the cured product due to a sudden temperature change (heat shock) can be prevented.

[0073] Component C is represented by the following general formula (7): (R a R b 2SiO) p -K-(SiR b 2-Y-Si(R b ) q (OR c ) 3-q ) r (7) This compound is an example of the above-mentioned C1 compound, and is preferably an organosilicon compound represented by R a is a radical reactive group or a hydrosilylation reactive group containing 3 or more carbon atoms, they are also examples of compounds of C2 described above.

[0074] In formula (7), R a represents a reactive group capable of bonding with the radical reactive group and / or hydrosilylation reactive group possessed by component A. When component A has a radical reactive group, R a It is preferable that R is also a radical reactive group capable of reacting with the radical reactive group. For example, amay be a group selected from alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, and dodecenyl groups; acrylic-containing groups, such as 3-acryloxypropyl groups and 4-acryloxybutyl groups; and methacrylic-containing groups, such as 3-methacryloxypropyl groups and 4-methacryloxybutyl groups. In addition, when the radical reactive group possessed by component A is an alkenyl group, an acrylic-containing group, or a methacrylic-containing group, an example of the reactive group possessed by component C can be a mercapto group. When component A has a hydrosilylation reactive group, R a may also be a group capable of forming a bond with the hydrosilylation reactive group possessed by Component A, and may be, for example, a group selected from alkenyl groups having 2 to 20 carbon atoms, such as a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, and dodecenyl group, and preferably a vinyl group, or may be a silicon-bonded hydrogen atom. R b R independently represents a group selected from the group consisting of monovalent hydrocarbon groups, halogenated hydrocarbon groups, and cyanoalkyl groups. b Examples of R include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and octyl groups; cycloalkyl groups, such as cyclopentyl and cyclohexyl groups; substituted or unsubstituted aryl groups, such as phenyl, tolyl, and naphthyl groups; aralkyl groups, such as benzyl, phenylethyl, and phenylpropyl groups; halogenated hydrocarbon groups, such as trifluoropropyl and chloropropyl groups; and cyanoalkyl groups, such as β-cyanoethyl and γ-cyanopropyl groups. b is preferably independently a methyl group or a phenyl group, and particularly preferably a methyl group. R care independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxyalkyl group having a total of 2 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Examples of the alkoxyalkyl group include a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group. R c are preferably independently a hydrogen atom, a methyl group, or an ethyl group.

[0075] In formula (7), K is the average composition formula (R b 3SiO 1 / 2 ) s (R b 2SiO 2 / 2 ) t (R b SiO 3 / 2 ) u (SiO 4 / 2 ) v (OR c ) w It represents an organosilane block or a linear or branched organopolysiloxane block represented by the following formula: In the formula, R b and R c is as defined for equation (7). Each of s, t, u, v, and w represents the number of each unit, and each represents a number from 0 to 500, provided that all of t, u, and v are not 0, and the value of s+w is equal to or less than u+2v), which represents a linear or branched organopolysiloxane chain or a silicone resin structural block.

[0076] In formula (7), Y is an oxygen atom, a divalent hydrocarbon group, or a group represented by the general formula: [ka] (8) (In the formula, R b is as defined above, and Z is a divalent hydrocarbon group. The divalent hydrocarbon groups represented by Z are preferably independently alkylene groups having 1 to 10 carbon atoms, and are particularly preferably selected from a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0077] In formula (7), p represents a number from 1 to 10, r represents a number from 1 to 10, and q represents a number from 0 to 2 within a possible range depending on the structure of K.

[0078] In one embodiment, K in formula (7) is absent, i.e., K represents a single bond, and p and r may be 1. In this case, the compound of formula (7) has the following formula: R a R b 2SiO-SiR b 2-Y-Si(R b ) q (OR c ) 3-q (9) It is expressed as: In formula (9), R a , R b , R c , Y, and q are as defined for equation (7).

[0079] The compound of formula (7) above is particularly represented by the following structural formula: [ka] (10) It is preferable that the organosilicon compound is represented by the following formula: In formula (10), R a , R b , R c , and Y are as defined in formula (7). a R is particularly preferably a vinyl group or a hydrogen atom. b is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or an octyl group, and is particularly preferably a methyl group. In formula (10), m is a number in the range of 0 to 500, and it is particularly preferable that m is a number that gives the compound a viscosity of 20 to 1,000,000 mPa s at 25° C. When the compound of formula (10) is a mixture of compounds having different molecular structures, for example, two or more compounds having different average values ​​of m, it is preferable that the value of m is such that the viscosity of the mixture is as described above. In formula (10), Y is as defined for formula (7). a is 0, 1 or 2, preferably 0 or 1, and particularly preferably 0.

[0080] Particularly preferred compounds of formula (10) are those represented by the following chemical formula: Vi(CH3)2Si-(OSi(CH3)2) n -OSi(OCH3)3 In the formula, Vi represents a vinyl group, and n is 1 to 50, preferably 2 to 30, and more preferably 3 to 25.

[0081] The organosilicon compounds represented by formula (7) or (10) can be produced according to known methods, for example, those described in JP-A-4-13767 and JP-A-63-270762. It is preferable that this organosilicon compound has a low content of low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5)) or is substantially free of these.

[0082] Particularly preferred examples of the compounds represented by formula (7) or (10) are organosilicon compounds represented by the following formula: R a (Me)2Si-(OSiMe2) n -Si(OMe)3(11) In formula (11), R a is a radical-reactive or hydrosilylation-reactive functional group, Me is a methyl group, and n is a number from 1 to 100, preferably from 2 to 50, and particularly preferably from 3 to 30. When the compound of formula (11) is a mixture of compounds with different n, n represents an average value. In addition, in formula (11), R a is particularly preferably a vinyl group or a hydrogen atom, where the vinyl group is a radical-reactive and / or hydrosilylation-reactive group and the hydrogen atom is a hydrosilylation-reactive group.

[0083] The above-mentioned examples of the C2 compound include R having radical reactivity and / or hydrosilylation reactivity in each of the above-mentioned organosilicon compounds. a A compound having 3 or more carbon atoms in the group and the following general formula: R a (R b ) q Si(OR c ) 3-q (7') Examples of the compound include compounds represented by the following formula: In formula (7'), R a represents a reactive functional group having 3 or more carbon atoms that can bond with the reactive group of component A, R b , R c , and q have the meanings defined for formula (7). In formula (7'), R a R is preferably a terminally unsaturated alkenyl group having 3 or more carbon atoms, and examples thereof include allyl and hexenyl. b R is preferably a group selected from methyl and phenyl groups, and particularly preferably a methyl group. c is preferably a group selected from methyl and ethyl groups, and particularly preferably a methyl group. It is particularly preferred that q is 0. Specific compounds represented by formula (7') include, but are not limited to, allyltrimethoxysilane, allyltriethoxylane, hexenyltrimethoxysilane, hexenyltriethoxysilane, methacrylpropyltrimethoxysilane, methacrylpropyltriethoxylane, acrylpropyltrimethoxysilane, and acrylpropyltriethoxylane.

[0084] The above-mentioned components C1 and C2 can both be used as component C of the present invention, but component C1 in particular is usually a non-volatile component, and therefore can perform stable surface treatment on component B, and has the advantage that the technical effects of the present invention can be stably achieved with a small amount of use compared to the case where volatile component C is used. Note that components C1 and C2 preferably have boiling points of 200°C or higher at 25°C and 1 atmospheric pressure, and are substantially non-volatile components.

[0085] [Cure accelerator] As described above, the curable organopolysiloxane composition of the present invention contains components A, B, and C as essential components, but the composition may also contain a curing accelerator or a curing catalyst for accelerating the curing reaction involving components A and C. Furthermore, the curable composition of the present invention may be cured by heat, including at room temperature, by using high-energy rays such as ultraviolet rays, or by a combination of these.

[0086] <Radical polymerization initiator> When component A has a radical reactive functional group, a radical polymerization initiator may be added to the composition as a radical reaction initiator to promote the curing of the curable composition. As the radical polymerization initiator, a known thermal radical polymerization initiator such as an azo compound or an organic peroxide can be used. As the organic peroxide, an alkyl peroxide and / or an acyl peroxide can be mentioned, for example, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, etc., but are not limited thereto. As the azo compound, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4-azobis-4-cyanovaleric acid, etc., can be mentioned, but are not limited thereto. The thermal radical polymerization initiator is preferably used in an amount equal to or greater than the number of moles of the radical reactive groups in component A in the curable organopolysiloxane composition of the present invention, and preferably equal to or greater than two times the number of moles. When a thermal radical polymerization initiator is used, the curable composition may be heated in order to cure the composition.

[0087] A photoradical polymerization initiator may be used together with or instead of the thermal radical polymerization initiator. A known initiator may be used as the photoradical polymerization initiator, and is not particularly limited. Specific examples of the photoradical polymerization initiator include, but are not limited to, acetophenone, benzophenone, o-benzoylbenzoic acid, p-benzoylbenzoic acid, 2,2-diethoxyacetophenone, 2,4-diethyl-9H-thioxanthen-9-one, 4,4'-dimethoxybenzyl, 2,2-dimethoxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-ethylanthraquinone, 1-hydroxycyclohexylphenylketone, 2-(hydroxyimino)propiophenone, 2-hydroxy-2-methylpropiophenone, 2-isopropoxy-2-phenylacetophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, and p,p'-tetramethyldiaminobenzophenone. In addition, initiators such as Omnirad 651, 184, 1173, 2959, 127, 907, 369, 369E, and 379EG (alkylphenone-based photopolymerization initiator, IGM Resins BV), Omnirad TPO H, TPO-L, and 819 (acylphosphine oxide-based photopolymerization initiator, IGM Resins BV), Omnirad MBF and 754 (intramolecular hydrogen abstraction type photopolymerization initiator, IGM Resins BV), and Irgacure OXE01 and OXE02 (oxime ester-based photopolymerization initiator, BASF) may be used. When a photoradical polymerization initiator is used, the curable composition may be irradiated with high-energy rays, such as ultraviolet rays, X-rays, or electron beams. In addition, when the radical reactive group of component A sufficiently undergoes a crosslinking reaction by irradiation with high energy rays alone, the curable composition of the present invention may be cured by irradiation with high energy rays alone without using a photoradical polymerization initiator. When a photoradical polymerization initiator is used, a photosensitizer may be used in addition to the photoradical polymerization initiator.It is known that the use of a sensitizer can increase the photon efficiency of the polymerization reaction, and allows light of a longer wavelength to be used for the polymerization reaction compared to the case where only a photoinitiator is used, and is therefore particularly effective when the coating thickness of the composition is relatively thick or when an LED light source with a relatively long wavelength is used for light irradiation. As sensitizers, anthracene-based compounds, phenothiazine-based compounds, perylene-based compounds, cyanine-based compounds, merocyanine-based compounds, coumarin-based compounds, benzylidene ketone-based compounds, (thio)xanthene or (thio)xanthone-based compounds, such as isopropylthioxanthone, 2,4-diethylthioxanthone, squalium-based compounds, (thia)pyrylium-based compounds, and porphyrin-based compounds, are known, and any photosensitizer can be used in the curable composition of the present invention, including but not limited to these.

[0088] The amount of the photoradical polymerization initiator added to the composition of the present invention is not particularly limited as long as the desired photoradical polymerization reaction occurs, but it is generally used in an amount of 0.01 to 5 mass %, preferably 0.05 to 1 mass %, relative to the total mass of the curable composition of the present invention.

[0089] A photosensitizer may be used in combination with the above-mentioned photocationic polymerization initiator or photoradical polymerization initiator. Examples of the photosensitizer include anthracene compounds, phenothiazine compounds, perylene compounds, cyanine compounds, merocyanine compounds, coumarin compounds, benzylidene ketone compounds, (thio)xanthene or (thio)xanthone compounds, such as isopropylthioxanthone, 2,4-diethylthioxanthone, squalium compounds, (thia)pyrylium compounds, and porphyrin compounds.

[0090] When component A has a radical reactive group, component C has a group reactive with the radical reactive group. The reactive group of component C preferably reacts with the radical reactive group of component A under conditions in which component A undergoes a radical polymerization reaction.

[0091] <Hydrosilylation reaction catalyst> When Component A or Components A and C have a hydrosilylation reactive functional group, a hydrosilylation reaction catalyst may be added to the composition of the present invention to accelerate the curing of the composition. (i) a hydrosilylation reaction catalyst that exhibits activity in a composition without exposure to high-energy radiation; (ii) a hydrosilylation reaction catalyst that is inactive in the absence of high-energy radiation but is active in a composition upon exposure to high-energy radiation; or (iii) a combination of (i) and (ii); can be used. When the curable composition of the present invention is cured at room temperature or by heating, catalyst (i) is used, and when the curing of the curable composition is accelerated by irradiation with high energy rays, catalyst (ii) is preferably used in addition to catalyst (i). When the curable composition of the present invention is cured by irradiation with high energy rays, catalyst (ii) can be used. When catalysts (i) and (ii) are used in combination, the amounts of catalyst (i) and catalyst (ii) added to the curable composition are preferably in the range of 100 / 0 to 5 / 95 (catalyst (i) / catalyst (ii)) in mass ratio.

[0092] Examples of high-energy rays include ultraviolet rays, X-rays, and electron beams, and among these, ultraviolet rays are preferred because they are highly efficient at activating the catalyst. When irradiating with high-energy rays, the amount of irradiation varies depending on the type of high-energy ray-activated hydrosilylation reaction catalyst, but in the case of ultraviolet rays, the cumulative amount of irradiation at a wavelength of 365 nm is 100 mJ / cm. 2 ~10J / cm 2 It is preferable that the range is within the range of 100 μm.

[0093] The catalyst (i) is a hydrosilylation catalyst that can activate the hydrosilylation reaction without irradiation with high energy rays. By using the catalyst (i), when the hydrosilylation reaction inhibitor is not contained or the amount of the inhibitor used is small, the curable composition of the present invention can be given a fast-curing / fast-drying curing profile. Examples of the hydrosilylation reaction catalyst of the catalyst (i) include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, and preferably platinum-based catalysts. Examples of the platinum-based catalyst include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, and other platinum compounds, and particularly preferred are platinum alkenylsiloxane complexes. Examples of this alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a portion of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the stability of this platinum-alkenylsiloxane complex is good. Furthermore, it is preferable to add an alkenylsiloxane such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, or 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, or an organosiloxane oligomer such as a dimethylsiloxane oligomer to the platinum-alkenylsiloxane complex, because this can improve the stability of the complex. It is particularly preferable to add an alkenylsiloxane.

[0094] The catalyst (i) is a catalyst that shows activity without irradiation with high energy rays, and among them, those that show activity even at relatively low temperatures are preferred. Specifically, the catalyst shows activity in the curable composition of the present invention in the temperature range of 0 to 200°C, and promotes the hydrosilylation reaction. The content of the catalyst (i) varies depending on the type of catalyst and the type of composition, but is usually an amount in which the metal atom in the catalyst is within the range of 0.01 to 50 ppm by mass relative to the curable composition. In particular, by using an alkenylsiloxane complex of platinum, the platinum content is preferably within the range of 1.5 to 30 ppm, and thus the curable composition of the present invention can be given fast curing / fast drying properties. If the amount of catalyst (i) added is too small, the curing time of the curable composition becomes long, and if the amount added is too large, the pot life may be too short, which may cause practical inconvenience, and the cost will increase, which is not preferable.

[0095] Catalyst (ii) is a hydrosilylation catalyst that is inactive in the absence of high-energy radiation but becomes active in the present composition upon exposure to high-energy radiation, and is known as a high-energy radiation-activated catalyst or a photoactivated catalyst.

[0096] Specific examples of catalyst (ii) include (methylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)trimethylplatinum(IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)dimethylethylplatinum(IV), (cyclopentadienyl)dimethylacetylplatinum(IV), (trimethylsilylcyclopentadienyl)trimethylplatinum(IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum(IV), (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum(IV), trimethyl(acetylacetonato)platinum(IV), trimethyl(3,5-phenylphenylsil ... Examples of suitable platinum complexes include platinum(II), platinum(IV), platinum(IV), bis(2,4-pentanedionato), platinum(II), bis(2,4-hexanedionato), platinum(II), bis(3,5-heptanedionato), platinum(II), bis(1-phenyl-1,3-butanedionato), platinum(II), bis(1,3-diphenyl-1,3-propanedionato), and bis(hexafluoroacetylacetonato). Of these, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedionato)platinum(II) are preferred in terms of versatility and ease of availability.

[0097] As a catalyst for curing the curable composition of the present invention, a combination of catalyst (i) and catalyst (ii) can be used. For example, the hydrosilylation reaction product obtained by the above catalyst (i) can be given secondary curing properties (hereinafter, sometimes referred to as "photocuring properties") by irradiation with high energy rays. In addition, by irradiating high energy rays in the presence of catalysts (i) and (ii), the curing reaction is promoted by catalyst (i) even in areas where sufficient light irradiation cannot be performed, and further curing reaction can be promoted for the reaction product that has been cured to the point of becoming non-fluid. In addition, compared to the case where only catalyst (i) is used, further rapid curing / rapid drying properties can be achieved by using catalyst (ii) in combination. The amount of catalyst (ii) added is an amount necessary to further cure the composition in the reaction product obtained by the above component (i) or an amount sufficient to improve rapid curing / rapid drying properties, preferably an amount in which the metal atoms in this catalyst are within the range of 1 to 50 ppm by mass, preferably 5 to 30 ppm by mass, relative to the present composition.

[0098] In the composition design of such a curable composition having high energy ray curability, for example photocurability, in addition to room temperature curability, the mass ratio of catalyst (i) to catalyst (ii) is preferably in the range of 90 / 10 to 5 / 95, more preferably in the range of 85 / 15 to 10 / 90. If the mass ratio is equal to or less than the upper limit, the effect of increasing the curing reaction rate by high energy ray irradiation can be obtained, and if the mass ratio is less than the lower limit, the curing reaction does not proceed sufficiently in a short time at a relatively low temperature such as room temperature, that is, a curing profile of fast curing / fast drying cannot be realized. In addition, after applying the curable composition of the present invention to a substrate or the like, the curable composition can be irradiated with ultraviolet light using a spot UV light source to prevent the composition from flowing.

[0099] When the curable composition of the present invention is a composition that cures by a hydrosilylation reaction, a hydrosilylation reaction inhibitor may be used as necessary. The hydrosilylation reaction inhibitor is usually used to improve the pot life of the curable composition. Examples of compounds that can be used as a hydrosilylation reaction inhibitor in the curable composition of the present invention include alkyne alcohols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and benzotriazole. The amount of the reaction inhibitor used is not limited, but is preferably within the range of 0.0001 to 5 parts by mass relative to the total of 100 parts by mass of the curable composition of the present invention.

[0100] When component A or components A and C constituting the curable composition of the present invention have a hydrosilylation reactive group, the amount of each component is preferably in the range of 0.1 to 10 moles, preferably in the range of 0.2 to 5.0 moles, and particularly preferably in the range of 0.5 to 2.0 moles, of silicon-bonded hydrogen atoms per mole of the hydrosilylation reactive carbon-carbon double bond. When the amount of silicon-bonded hydrogen atoms per mole of the hydrosilylation reactive carbon-carbon double bond is 0.1 moles or less, the curable composition may not be cured sufficiently. In addition, when the amount of silicon-bonded hydrogen atoms per mole of the hydrosilylation reactive carbon-carbon double bond exceeds 10 moles, the obtained cured product may become too hard or the breaking elongation of the cured product may decrease.

[0101] <Condensation reaction catalyst> A condensation reaction catalyst for promoting the reaction between the hydrolyzable silicon groups and / or silicon-bonded hydroxyl groups in Component C and the inorganic filler in Component B may be added to the curable composition of the present invention. The type of condensation reaction catalyst to be used in the present invention is not particularly limited, and examples thereof include organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, tin octenate, dibutyltin dioctate, and tin laurate; organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and dibutoxybis(ethylacetoacetate)titanium; acidic compounds such as hydrochloric acid, sulfuric acid, and dodecylbenzenesulfonic acid; alkaline compounds such as ammonia and sodium hydroxide; amine compounds such as 1,8-diazabicyclo[5.4.0]undecene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO); organic zirconium esters such as zirconium tetrapropylate and zirconium tetrabutylate; zirconium tributoxyacetylacetonate and zirconium butoxyacetylacetonate bisethylacetonate; Examples of the aluminum-based condensation promoter include organic zirconium chelates such as acetate and zirconium tetraacetylacetonate; oxozirconium compounds such as zirconium bis(2-ethylhexanoate)oxide and zirconium acetylacetonate(2-ethylhexanoate)oxide; aluminum alcoholates such as aluminum triethylate, aluminum triisopropylate, and aluminum tri(sec-butylate); aluminum chelate compounds such as diisopropoxyaluminum(ethylacetoacetate), aluminum tris(ethylacetoacetate), and aluminum tris(acetylacetonate); and aluminum acyloxy compounds such as hydroxyaluminum bis(2-ethylhexanoate). The amount of the condensation reaction catalyst used is not particularly limited, and can be any amount within the range in which the purpose of condensation reaction promotion is achieved. The use of the condensation reaction catalyst is optional, and it is not necessary to use it in the present composition.

[0102] [Other additives] If necessary, the curable organopolysiloxane composition of the present invention may contain added organopolysiloxanes other than the above-mentioned component A, inorganic fillers other than the above-mentioned component B, organic resin fine powders such as polymethacrylate resins, adhesion promoters, heat resistance agents, dyes, pigments, flame retardant agents, solvents, etc. These additives are known to those skilled in the art, and any amount and method for adding them may be used as long as the object of the present invention is not impaired.

[0103] In addition to the spherical silica particles (particularly preferably spherical fused silica particles), spherical alumina particles, particularly preferably spherical fused alumina particles, and particles selected from the group consisting of fluorescent fillers described above as component B, further inorganic fillers such as titanium oxide particles having an average particle size of 0.1 to 10.0 μm can be used. Such additional inorganic fillers may be blended in the curable composition for the purpose of further improving the reflection / scattering effect of the cured product obtained by curing the curable composition of the present invention.

[0104] [Characteristics of the cured product obtained from the curable composition of the present invention] The cured product obtained by curing the curable organopolysiloxane composition of the present invention preferably has a light transmittance of 40% or more. The light transmittance is a value measured in the visible light wavelength region (all range) using an ultraviolet-visible-near infrared spectrophotometer equipped with an integral class unit having a diameter of 150 mm. Furthermore, the cured product preferably has a light diffusibility in which the transmitted light intensity at a light receiving position inclined at 45 degrees from the measured sample to the straight transmitted light is 0.65 or more when the light scattering characteristics are measured using a Scattering Profiler for measuring a bidirectional transmittance distribution function equipped with a white light source (particularly, a white LED made by combining a blue LED and a yellow phosphor) and the straight transmitted light intensity is set to 1 in the bidirectional transmittance distribution function. The bidirectional transmittance distribution function (BTDF) is a function specific to a transmission position that indicates how much light component is transmitted and travels in each direction when light is incident from a certain direction at a certain position.

[0105] Furthermore, the cured product obtained from the curable organopolysiloxane composition of the present invention preferably has an elongation at break in the range of 30% or more. The cured product of the present invention is characterized in that the combination of components A and C significantly improves the elongation at break without significantly changing the breaking strength, as compared to a curable composition that contains component A but does not use component C. In addition, the hardness of the cured product according to the present invention is preferably in the range of Shore A hardness 30 to Shore D hardness 50. The hardness of the cured product generally increases as the amount of radical reactive groups or hydrosilylation reactive groups contained per unit volume or unit mass of the curable composition of the present invention increases, and therefore, the hardness of the cured product can be adjusted by adjusting the amount of reactive groups contained in the curable composition. In addition, the Shore A or Shore D hardness of the cured product can be adjusted by the proportion of the inorganic filler of component B contained in the curable composition. The cured product obtained from the curable organopolysiloxane composition of the present invention has high flexibility and excellent elongation at break, and is therefore preferable as a material used as a coating agent having light diffusion properties.

[0106] [Uses of the cured product of the present invention] The use of the curable organopolysiloxane composition of the present invention is not particularly limited. The use of the composition of the present invention can be an adhesive, a sealant, a protective agent, a coating agent, an underfill agent, etc. for electrical and electronic devices, and can be used as a member that requires light diffusion. Particularly preferred uses of the curable composition of the present invention include optical members, particularly optical members that require light diffusion. Further specific uses include light diffusion films or coating agents for light-receiving sensors, particularly light diffusion films and light diffusion coating agents for light-receiving sensors. Another specific use suitable for the curable composition of the present invention is a sealant for light-emitting diodes. The present invention also provides an optical device including an optical member formed using the curable composition of the present invention, such as a light-receiving sensor and a light-emitting diode. Light-emitting diodes include both inorganic light-emitting diodes (LEDs) and organic light-emitting diodes (OLEDs).

[0107] When the curable composition of the present invention is used as an optical component of a light-emitting diode, particularly as a sealant, the inorganic filler of component B is particularly preferably a fluorescent filler (phosphor).

[0108] The cured product obtained from the curable organopolysiloxane composition of the present invention is characterized by high flexibility and large elongation at break, since the amount of aryl groups, particularly preferably phenyl groups, in the total organic groups bonded to silicon atoms of the organopolysiloxane is less than 0 to 10 mol % (including 0 mol %), preferably 0 to 5 mol %. Therefore, it is suitable for use as a coating agent, particularly as a coating agent for optical members. When the curable composition of the present invention is used as an optical member such as a light diffusion coating, it is generally particularly preferred to use the composition so that the thickness of the cured product obtained from the curable composition is 10 to 500 μm. When the viscosity of the curable organopolysiloxane composition of the present invention is suitable for coating on a substrate, for example, a release substrate, it can be used as it is without diluting with a solvent. In addition, the composition of the present invention can be diluted with a solvent to make the viscosity of the composition suitable for coating on a release substrate. Therefore, the present invention provides a coating agent containing the above-mentioned curable organopolysiloxane composition and a solvent, particularly an organic solvent. This coating agent can be used to form a coating layer made of a cured product of the curable composition of the present invention on a substrate. This coating layer is not particularly limited, and can be, for example, a light diffusion layer for an optical component.

[0109] The cured product obtained from the curable organopolysiloxane composition of the present invention can be used as a member of a desired form, but when used as an optical member, it is preferably in the form of a film or sheet or thin film, particularly a thin coating film.For example, the curable composition of the present invention can be used to provide a solid silicone material in the form of a film or sheet (including thin films) having a thickness of 10 to 500 μm, preferably 20 to 300 μm, or a coating film.

[0110] Furthermore, when the curable organopolysiloxane composition of the present invention is used as a light diffusing material, when an inorganic filler of Component B, particularly spherical silica particles, particularly spherical fused silica particles, and / or particularly spherical alumina particles, particularly spherical fused alumina particles, is used, it is preferable that the thickness of the film, sheet or coating layer made of the cured product of the present invention is in the range of 3L to 200L (μm) relative to the particle size L (μm) of the filler.

[0111] The hardness of the solid silicone material that forms the film or sheet-like material, or the coating layer, depends on the substrate and is not particularly limited; however, from a practical standpoint, it is preferable that the hardness of the cured product obtained from the curable composition of the present invention is in the range of Shore A hardness of 30 to Shore D hardness of 50.

[0112] <Coating agent> The curable organopolysiloxane composition of the present invention can be used as a coating liquid by dissolving and suspending it in an organic solvent in order to form a film or sheet-like cured product or to form a coating film on a substrate. The organic solvent used to prepare the coating liquid is not particularly limited as long as it is a compound capable of dissolving all or a part of the components A and C in the composition, and is preferably one having a boiling point of 80°C or higher and lower than 200°C under 1 atmosphere (0.1013 MPa). Examples of solvents that can be used include i-propyl alcohol, t-butyl alcohol, cyclohexanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, mesitylene, 1,4-dioxane, dibutyl ether, anisole, 4-methylanisole, ethylbenzene, ethoxybenzene, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 2-methoxyethanol (ethylene glycol monomethyl ether), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ... Examples of the organic solvent include non-halogenated solvents such as ethyl acetate, butyl acetate, propyl propionate (also called "propyl propionate"), 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, octamethylcyclotetrasiloxane, and hexamethyldisiloxane, and halogenated solvents such as trifluoromethylbenzene, 1,2-bis(trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, trifluoromethylchlorobenzene, trifluoromethylfluorobenzene, and hydrofluoroether. These organic solvents may be used alone or in combination of two or more. In particular, i-propyl alcohol, methyl isobutyl ketone, and the like are preferably used.

[0113] <Method for forming the curable organopolysiloxane composition into a film, sheet, or thin film> There are no particular limitations on the method for forming the solid silicone material, which is the cured product obtained by curing the curable organopolysiloxane composition of the present invention, into a film, sheet, or thin film. For example, it can be performed by the following method.

[0114] (i) Film formation by molding When the solid silicone material obtained by curing the curable organopolysiloxane composition of the present invention has hot melt properties, it can be formed into a film on a desired substrate by a known molding method such as integral molding. Common molding methods include transfer molding, injection molding, and compression molding. For example, in transfer molding, the solid silicone material according to the present invention is filled into the plunger of a molding machine and automatically molded to obtain a film-like or thin film-like member as a molded product. As the molding machine, any of auxiliary ram type molding machines, slide type molding machines, double ram type molding machines, and low pressure encapsulation molding machines can be used. By using a release-type substrate as the substrate, it is possible to form a film or sheet-like cured product made of the solid silicone material of the present invention on the substrate and then transfer it onto another substrate for use.

[0115] (ii) Formation of a film by applying a film or sheet or thin film using a solvent, removing the solvent, and curing the film. Since the curable organopolysiloxane composition of the present invention can be uniformly dispersed in an organic solvent such as i-propyl alcohol or methyl isobutyl ketone, a film or sheet-like material can be obtained by applying a dispersion containing the curable organopolysiloxane composition to a desired substrate in the form of a film or sheet, removing the organic solvent by drying or other means, and curing the curable composition. When applying the dispersion to a film or sheet, it is preferable to adjust the viscosity of the dispersion using a solvent so that the viscosity of the entire dispersion is in the range of 100 to 10,000 mPa·s. When diluting with a solvent, it is preferable to use a solvent in the range of 2000 parts by mass or less relative to the total amount (100 parts by mass) of solids contained in the dispersion. As the coating method, gravure coating, offset coating, offset gravure, roll coating using an offset transfer roll coater or the like, reverse roll coating, air knife coating, curtain coating using a curtain flow coater or the like, comma coating, Mayer bar, spin coating, and other known methods used for the purpose of forming a cured layer can be used without limitation. In addition, the amount of the curable composition applied to the substrate is arbitrary, but it can be applied so that the film or sheet-like material formed after the organic solvent is removed and the curable composition is cured has a desired film thickness. As described below, by using a release substrate as the substrate to which the dispersion is applied, a film or sheet made of the solid silicone material of the present invention is formed on the release substrate, and then it can be separated from the substrate to obtain a film or sheet-like bulk material, and the film or sheet-like material can also be transferred from the substrate to another substrate. In addition, the curable organopolysiloxane composition of the present invention dissolved and dispersed in an organic solvent can be directly coated on a member of an optical device, and the solvent can be removed and then cured to form a coating film.

[0116] <Laminate> The solid silicone material obtained by curing the curable organopolysiloxane composition of the present invention can be used as an optical component, particularly in optical devices, such as light-emitting diodes (LEDs), organic electroluminescent devices (OLEDs), and light-receiving sensors. In this case, it is particularly preferred that the solid silicone material obtained from the curable composition of the present invention is disposed at the interface with air as a solid layer constituting the laminate portion in the optical device. In this case, if the laminate is a light-emitting device, such as a light-emitting diode or an organic electroluminescent device, it may have at least one layer containing a fluorescent filler (hereinafter also referred to as a "phosphor layer") between the light source and the solid silicone material of the present invention. In addition, when the solid silicone material according to the present invention is used as a light-diffusing material for diffusing light incident on a light-receiving sensor, particularly as a light-diffusing coating layer, light-diffusing film or sheet, it is particularly preferred to use spherical fused silica particles and / or spherical fused alumina particles as component B.

[0117] <Laminate having a film or sheet-like coating layer made of the solid silicone material of the present invention formed on a release substrate> A peelable substrate generally consists of a substrate and a release layer formed thereon, and a film- or sheet-like material formed on the release layer, generally by a coating method, is made in such a way that it can be easily peeled off from the substrate. First, a laminate in which a film-like or sheet-like material of a solid silicone material made of a cured product obtained from the curable composition of the present invention is arranged on a release layer will be described. The film or sheet-like material made of the solid silicone material of the present invention, and the laminate material containing it, may be required to be handled in a single form separated from the substrate, if desired. When a solid layer made of the solid silicone material of the present invention is arranged on the release layer, the film or sheet-like material made of the solid silicone material of the present invention, or the laminate material containing it, can be easily separated and handled from the release layer that constitutes the release substrate together with the substrate. Such a release substrate has a release layer facing the solid layer such as a film-like layer made of the solid silicone material of the present invention, and may further have another release layer as an option. The following configurations can be exemplified as the configuration of a laminate containing a release substrate and a solid layer made of the solid silicone material of the present invention. In the following examples, " / " means that each layer faces each other in the lamination direction of the laminate (generally the thickness direction perpendicular to the substrate). In addition, the substrate and the release layer may be integral or the same layer (a substrate having releasability by providing a material or physical unevenness). Example 1: Substrate / Release layer / Solid layer made of the solid silicone material of the present invention / Other optional layers (may be one layer or two or more layers) Example 2: Substrate / release layer / solid layer made of the solid silicone material of the present invention / any other layer (may be one layer or two or more layers) / release layer / substrate The term "other optional layers" as used herein refers to layers that may be used as desired, but are not required to be used. Examples of other optional layers include, but are not limited to, a pressure-sensitive adhesive layer.

[0118] In particular, as in Example 2 above, when a film- or sheet-like material made of the solid silicone material of the present invention, or a laminate material containing the same, is sandwiched between two release layers, the material with a solid layer made of the solid silicone material of the present invention can be transported (including exported overseas) while protected by a substrate, and at a desired time and place, the release substrates with release layers can be separated from both sides of the laminate, and only the film- or sheet-like material made of the solid silicone material of the present invention, or the laminate material containing the same, can be placed or laminated on a desired structure, for example, on the light source of a light-emitting device, or on the light incident surface side of a light-receiving sensor, etc. In particular, when the laminate material of the portion excluding the release substrate is a laminate sheet or the like having a solid layer made of the solid silicone material of the present invention and a phosphor layer, the handling and workability can be improved, which is useful.

[0119] The type of the above substrate is not particularly limited, but examples thereof include paperboard, cardboard paper, clay-coated paper, polyolefin-laminated paper, particularly polyethylene-laminated paper, synthetic resin film / sheet, natural fiber cloth, synthetic fiber cloth, artificial leather cloth, and metal foil. In particular, synthetic resin film / sheet is preferred as the substrate, and examples of synthetic resin include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon. The substrate is preferably in the form of a film or sheet. The thickness of the substrate is not particularly limited, and a substrate of a desired thickness can be used depending on the application. The above substrate itself may be made of a material that functions as a release layer, and / or may have a structure that has a release property by forming fine physical irregularities on the substrate surface.

[0120] The release layer may also be called a release liner, a release layer, or a release coating layer, and may preferably be a release layer having release coating ability such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent. Alternatively, the substrate surface may be physically formed with fine irregularities, or the substrate may be formed from a material that is difficult to adhere to the solid silicone material of the present invention. In these cases, a release layer made of a material different from the substrate may be further formed on the substrate, but no further release layer is necessary, and in this case, the release layer refers to the part of the substrate surface that exhibits release properties.

[0121] The solid layer made of the solid silicone material of the present invention can be formed by forming a film on the release layer of the above-mentioned release substrate using the same method as described above in <Method of forming a curable organopolysiloxane composition into a film, sheet, or thin film>. In particular, according to the above-mentioned method, it is preferable to apply a liquid in which the curable organopolysiloxane composition of the present invention is uniformly dispersed in an organic solvent such as i-propyl alcohol or methyl isobutyl ketone onto the release layer of a film-like substrate or a sheet-like substrate, and then remove the organic solvent by drying or other means, and cure the curable composition to form a solid layer made of a film-like or sheet-like solid silicone material on the release layer of the substrate. The film thickness of the film-like or sheet-like solid silicone material can be adjusted to a thickness suitable for the intended use, but when used as a light diffusing material, it is generally preferable that it is in the range of 10 to 500 μm as described above. In addition, when the composition of the present invention is used as an encapsulant for a light-emitting diode or an organic electroluminescent device, the thickness is preferably in the range of 10 to 500 μm.

[0122] The solid layer made of the solid silicone material of the present invention may be used alone, but it is more preferable that the solid layer is a laminated member in which the same or different layers are laminated on the solid layer. In particular, the other layers in the laminated member are preferably a cured layer or a solid organopolysiloxane layer (silicone layer) formed by curing an organopolysiloxane having a curing reactive functional group, and preferably a silicone cured layer formed by curing an organopolysiloxane having a hydrosilylation reactive group and / or a radical reactive group, a condensation or dealcoholization reactive group in the presence of a catalyst. Here, the organopolysiloxane having a curing reactive group may be linear, branched, cyclic, or resinous, and two or more types of curing reactions may be used in combination.

[0123] Particularly preferably, the other silicone layer disposed on the solid layer made of the solid silicone material obtained from the curable composition of the present invention is a polymeric solid organopolysiloxane, and is preferably a silicone layer made of the solid organopolysiloxane in which a phosphor described below is dispersed.

[0124] The layer other than the layer made of the solid silicone material formed from the curable organopolysiloxane composition of the present invention in the above laminated member may be one or more layers, or may be two or more layers having different functions. In addition, the thickness of the entire laminated member laminated on the solid layer made of the solid silicone material of the present invention is not particularly limited, but is preferably 5 μm or more, and from the viewpoint of handling and workability, may be 50 to 10,000 μm, and is particularly preferably in the range of 100 to 1,000 μm.

[0125] One or more layers laminated on the solid layer made of the solid silicone material of the present invention, particularly a silicone layer different from the solid layer, are preferably phosphor layers containing at least one type of phosphor. Such phosphor layers function in particular as wavelength conversion materials, and when placed on a light source, can convert the emission wavelength. The phosphors are not particularly limited, and examples thereof include yellow, red, green, and blue light-emitting phosphors made of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, oxysulfide-based phosphors, etc., which are widely used in light-emitting diodes (LEDs) or organic electroluminescent devices (OLEDs). Examples of oxide-based phosphors include yttrium, aluminum, and garnet-based YAG-based green to yellow light-emitting phosphors containing cerium ions; terbium, aluminum, and garnet-based TAG-based yellow light-emitting phosphors containing cerium ions; and silicate-based green to yellow light-emitting phosphors containing cerium or europium ions. In addition, examples of oxynitride phosphors include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions. Examples of nitride phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based CaSn-based red light-emitting phosphors containing europium ions. Examples of sulfide phosphors include ZnS-based green color-emitting phosphors containing copper ions or aluminum ions. Examples of oxysulfide phosphors include Y2O2S-based red light-emitting phosphors containing europium ions. In the laminate according to the present invention, two or more of these phosphors may be used in combination.

[0126] In the above laminate, solidThe silicone layer different from the main silicone material layer may be a silicone layer containing a reinforcing filler, which increases the mechanical strength of the silicone layer and improves the protective property or adhesion to the adjacent layer. The silicone layer may also be a silicone layer containing a thermally conductive filler or a conductive filler, which imparts thermal conductivity or electrical conductivity to the cured product. The phosphors and these fillers may be used in combination, and the surface of the particulate components of these phosphors may be surface-treated with a compound selected from alkoxysilanes, organohalosilanes, organosilazanes, and siloxane oligomers to improve dispersibility in the silicone layer.

[0127] The laminate has a structure in which a solid layer made of a solid silicone material formed from the curable composition of the present invention is disposed on a release layer, and more preferably further comprises a phosphor layer which is a silicone layer different from the solid layer and contains a phosphor, etc. When a solid layer made of a solid silicone material according to the present invention is disposed on a release layer, the solid layer made of the solid silicone material of the present invention or a laminate member containing the solid layer can be easily separated from the release layer constituting the laminate, and the separated laminate member can be used as it is in the manufacture of other structures as an optical member, etc.

[0128] <Laminate having a light source and a phosphor, light-emitting device> The solid layer made of the solid silicone material obtained from the curable composition of the present invention can be disposed at the interface with air. When disposed on a light source of a light emitting diode (LED) or an organic electroluminescent device (OLED), the solid layer made of the solid silicone material of the present invention can be disposed at the interface with air to improve the light extraction efficiency of the entire laminate including the light source. It is particularly preferable that such a laminate has a phosphor layer containing the same phosphor as described above as a wavelength conversion material of the light source, in particular, a silicone layer containing a phosphor. Here, it is preferable that the light emitted from the light source is wavelength converted by the phosphor layer and reaches the solid layer made of the solid silicone material of the present invention disposed at the interface with air, and the solid layer made of the solid silicone material of the present invention may be formed so as to cover a part or the whole of the phosphor layer, or may be disposed outside the phosphor layer via a functional layer of another laminate. The thickness of the entire laminate is not particularly limited, but is preferably 1 μm or more. In the case of a light emitting device, etc., it may be 50 to 10,000 μm excluding the thickness of the light source part, and is particularly preferably in the range of 100 to 1,000 μm.

[0129] <Improved light extraction efficiency and heat resistance> The laminate including the light source and the phosphor layer is a light-emitting device such as a light-emitting diode (LED) or an organic electroluminescent device (OLED), and the light extraction efficiency of the light-emitting device can be improved by adopting the above-mentioned arrangement of the light source, the phosphor layer, and the solid layer made of the solid silicone material of the present invention. Furthermore, by using the solid layer made of the solid silicone material of the present invention, coloring and the like caused by heat generation of the light-emitting device can be prevented in some cases compared to the case where a different material is used, and therefore, in particular, the heat resistance of the light-emitting device can be improved in some cases.

[0130] <Method of manufacturing laminate> The method for producing a laminate containing a cured product obtained from the curable organopolysiloxane composition of the present invention is not particularly limited, but is preferably a method including any one of the following steps (i) to (iii). The coating method and the like for this step are also not particularly limited, but examples thereof include the methods described above in the method for producing a film or sheet-like material formed from a cured product obtained from the curable composition of the present invention. (i) when the solid silicone material obtained by curing the curable organopolysiloxane composition of the present invention has hot melt properties, a step of molding the solid silicone material into a film, sheet or thin film on another structure; (ii) a step of dispersing the curable organopolysiloxane composition of the present invention in an organic solvent, applying the composition in the form of a film or thin film onto another structure, removing the organic solvent, and curing the composition; (iii) A step of laminating another structure on a film or sheet-like material made of a solid silicone material obtained by curing the curable organopolysiloxane composition of the present invention. When the film-like material is thin, it can be called a thin film material.

[0131] In particular, the solid silicone material obtained by curing the curable composition of the present invention can be handled in the form of a laminate that can be peeled off from the substrate, and the solid layer made of the solid silicone material of the present invention or the laminate member containing it can be easily separated from the release layer of the substrate and used. The solid layer made of the solid silicone material of the present invention or the laminate member containing it peeled off from the release layer is preferably used as an optical member or the like to manufacture other structures, such as optical devices or their members. Therefore, as a method for manufacturing a laminate containing the solid silicone material of the present invention, a manufacturing method comprising the following steps is particularly preferred. In particular, the other structure is preferably a precursor of a light-receiving sensor or a light-emitting device equipped with a light source or the like, and the manufacturing method is particularly preferably a method for manufacturing a light-emitting device or a light-receiving sensor equipped with a solid layer made of the solid silicone material of the present invention arranged at the interface with air. (A): a step of applying a liquid obtained by dispersing the curable organopolysiloxane composition of the present invention in an organic solvent onto a release layer of a release substrate in the form of a film or thin film, removing the organic solvent, and curing the composition to form a solid silicone material; (ii) a step of laminating the same or a different silicone layer on the film-like or thin-film-like solid silicone material obtained in the step (i); (c): A step of obtaining a laminate by peeling the film-like or thin-film-like solid silicone material obtained in the step (b) and the silicone layer laminated thereon as a single unit from the release layer; and (iv) A step of laminating the laminate obtained in the step (iii) on another structure.

[0132] <Characteristics and Preferred Applications of the Solid Silicone Material Obtained by Curing the Curable Organopolysiloxane Composition of the Present Invention> The curable composition of the present invention includes components A, B, and C, and by setting the ratio of aryl groups in the groups bonded to silicon atoms in component A to less than 0 to 10 mol%, preferably 0 to 5 mol%, the solid silicone material obtained by curing the curable composition has the characteristics of being highly flexible and having a large elongation at break. The curable organopolysiloxane composition of the present invention is suitable for use as a coating agent, in which the curable organopolysiloxane composition of the present invention is dissolved and dispersed in a solvent as desired. Furthermore, by combining component B with components A and C, the curable composition of the present invention can obtain a highly flexible solid silicone material, and the adhesiveness between the inorganic filler of component B and the matrix material composed of components A and C in the obtained solid silicone material is improved, and the elongation at break of the solid silicone material is significantly improved compared to when component C is not used. In addition, the solid silicone material obtained from the curable composition of the present invention has high flexibility and improved elongation at break, which increases the ability of the material itself to follow thermal deformation, thereby improving heat resistance.

[0133] The curable composition of the present invention is suitable for use as a coating agent for forming a coating layer on a substrate by applying the liquid obtained by dissolving at least a part of the components in the solvent as it is or diluting with a solvent and dispersing an inorganic filler in the solvent, and removing the solvent when a solvent is used, and curing the applied curable composition. When the cured product obtained from the curable composition of the present invention is used as a coating material, the thickness of the coating layer made of the solid silicone material after curing is preferably 10 to 500 μm, but is not limited to these thicknesses.

[0134] The curable composition of the present invention is suitable as a material used as an optical member for an optical device. In particular, the curable composition of the present invention is suitable for use as a light diffusing material for a light receiving sensor, particularly as a material for a light diffusing film or light diffusing layer arranged in front of the light receiving part of the sensor. In this case, component B is preferably spherical fused silica particles, spherical fused alumina particles, or a combination thereof. In addition, the curable composition of the present invention is preferable as a material for use as an optical member for a light emitting diode (LED) or an organic electroluminescent device (OLED), for example, as an encapsulant. For this use, the above-mentioned spherical fused silica particles, spherical fused alumina particles, or a combination thereof may be used as component B, and further, when a wavelength conversion function is to be imparted, it is preferable to use a fluorescent filler. However, the applications of the curable composition of the present invention are not limited to the above applications, and the composition can be used in any applications.

[0135] Furthermore, the solid silicone material obtained by curing the curable organopolysiloxane composition of the present invention has the advantage that it is highly durable in a reflow soldering process and is less discolored during the same process. EXAMPLES

[0136] Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following description of the examples and the compositional formulas or structural formulas shown in the tables, Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group, respectively. In addition, in this specification, the ratio (mol%) of the aryl group in the organic group bonded to the silicon atom of the organopolysiloxane is 13 C-, 29 a value determined by Si-NMR. However, when a compound having an aryl group is not used as a raw material for producing the organopolysiloxane, the ratio of the aryl group in the organic group is 0 mol% without measurement.

[0137] <Preparation of Solution A> Compositional formula: (Me3SiO 1 / 2 ) 0.415 (Me2ViSiO 1 / 2 ) 0.085 (SiO2) 0.50 Vinyl group-containing organopolysiloxane (41.7 g) represented by, average structural formula: (Me2ViSiO 1 / 2 )2(Me2SiO) 770 Vinyl group-containing organopolysiloxane (49.4 g) represented by, and compositional formula: (Me2HSiO 1 / 2 ) 0.645 (SiO2) 0.355 To a mixture of terminal SiH organohydrogenpolysiloxane (8.8 g) represented by, a platinum divinyldisiloxane complex was added in an amount such that the platinum content was 2.5 ppm, and the mixture was uniformly stirred using mechanical force to obtain Solution A. The amount of the aryl group in the group bonded to the silicon atom of the organopolysiloxane contained in Solution A is 0 mol%.

[0138] <Preparation of Solution B> Compositional formula: (Me3SiO 1 / 2 ) 0.34 (Me2ViSiO 1 / 2 ) 0.11 (SiO2) 0.55 Vinyl group-containing organopolysiloxane (30 g) represented by, average structural formula: (Me2ViSiO 1 / 2 )2(Me2SiO)530 and a vinyl group-containing organopolysiloxane (45 g) represented by the average structural formula: (Me2ViSiO 1 / 2 )2(Me2SiO) 150 Vinyl-containing organopolysiloxane (20 g) represented by the average structural formula: (MeSiO 1 / 2 )2(MeHSiO) 50 Organohydrogenpolysiloxane (4 g) containing terminal SiH groups represented by the formula: (MeViSiO) 22.5 (EpSiO 3 / 2 ) 31.1 (Me2SiO) 46.4 (OR) n (wherein Ep represents a gamma glycidoxypropyl group, and R represents Me or H), a platinum divinyldisiloxane complex was added in an amount to give a platinum content of 2.5 ppm, and further, the following additive 1, which is a compound represented by the structural formula: (MeViSiO 1 / 2 )(Me2SiO)3((MeO)3SiO 1 / 2 ) was added, and the mixture was stirred uniformly using mechanical force to obtain solution B. The amount of aryl groups in the groups bonded to silicon atoms of the organopolysiloxane contained in solution B was 0 mol %.

[0139] The average thickness of the sheet-like cured product in the following Examples and Comparative Examples was measured using a thickness meter (Nikon Corporation, DIGIMICRO MFC-101A).

[0140] The additives used in the following Reference Examples, Examples and Comparative Examples are as follows. Additive 1 Structural formula (Me2ViSiO 1 / 2 )(Me2SiO)3((MeO)3SiO 1 / 2 ) Additive 2 Average structural formula (Me2ViSiO 1 / 2 )(Me2SiO) 25 ((MeO)SiO 1 / 2 ) Additive 3 Allyltrimethoxysilane Additive 4 Composition formula (MeViSiO) 22.5 (EpSiO 3 / 2 ) 31.1 (Me2SiO) 46.4 (OR) n (Ep represents a gamma-glycidoxypropyl group, and R represents Me or H) Additive 5 Dodecyltrimethoxysilane Additive 6 Average structural formula (Me2ViSiO 1 / 2 )2(Me2SiO) 290 A polysiloxane having a vinyl end group represented by the formula: Additive 7 Average structural formula (Me3SiO 1 / 2 )(Me2SiO) 30 ((MeO)SiO 1 / 2 ) Additive 8 Vinyltrimethoxysilane

[0141] The fillers used in the following Reference Examples, Examples, and Comparative Examples are as follows. 50 ) is a value measured by the Coulter method or the laser diffraction scattering method. Filler I: Showa Denko Co., Ltd. Alumina beads with an average particle size of 5 μm Spherical alumina particles CB-P05 Filler II: Denka Co., Ltd. FB-3SDC, spherical fused silica particles with an average particle size of 3 μm Filler III Intematix YAG type yellow phosphor with average particle size of 8 μm NYAG4454-S

[0142] [How to prepare the cured product] The additives and fillers were added to the above solution A in the amounts shown in the table below, and the mixture was uniformly stirred mechanically while being degassed under reduced pressure to obtain each preparation solution. The resulting preparation liquid was pressed in a 1 mm thick mold at 125° C. for 15 minutes and then heated in an oven at 150° C. for 1 hour to produce a 1 mm thick sheet made of a cured product.

[0143] The tensile strength and elongation properties of the cured sheet were measured by cutting a 1 mm thick sample from the cured sheet using a Dumbbell Super Dumbbell Cutter SDK-300-D conforming to JIS K-6251-3. The breaking strength and elongation at break of this sample were measured at a tensile speed of 15 mm / min using a Shimadzu Autograph AGS-X equipped with a 1 kN load cell.

[0144] Furthermore, the fracture surfaces of the samples for which the above-mentioned fracture strength was measured were observed by SEM. The fracture surfaces were observed by SEM using a Hitachi SEM TM4000PLUS Microscope at a magnification of 8000 times. Interfacial peeling was defined as material peeling and breaking from the filler particle surface and / or near the filler particle surface, and cohesive failure was defined as material peeling and breaking away from the filler particle surface or its immediate vicinity.

[0145] The results obtained are shown in Tables 1 and 2 below.

[0146] [Table 1]

[0147] [Table 2]

[0148] 1 and 2 show SEM photographs of the fracture surfaces of the test samples of Example 5 and Comparative Example 3 after measuring the breaking strength. Figure 1: SEM image of the fracture surface of the sample of Example 5 Figure 2: SEM image of the fracture surface of the sample of Comparative Example 3 In the test sample of Example 5 shown in FIG. 1, the surfaces of the filler particles seen on the fracture surface were irregular and not smooth, and it was observed that the surfaces of the filler particles were covered with cured organopolysiloxane polymer. On the other hand, in the test sample of Comparative Example 3 shown in FIG. 2, the surfaces of the filler particles seen on the fracture surface are smooth and not covered with cured organopolysiloxane polymer, and peeling is found to have occurred at the interface between the filler particles and the organopolysiloxane polymer.

[0149] <Summary of Reference Example 1, Examples 1 to 7, and Comparative Examples 1 to 4> In comparison with the composition containing a filler without the additive of Reference Example 1, the curable compositions of Examples 1 to 7 contain additives 1 to 3 corresponding to component (C) of the present invention, which integrate the filler and the cured organopolysiloxane matrix, and prevent the matrix polymer from peeling off from the filler interface and breaking the material, and improve the breaking elongation property of the material from 43.7% to 50.0 to 61.9% without changing the breaking strength significantly (about 8 to 9 MPa). In addition, when a compound having a chemical structure different from component (C) of the present invention is used as an additive, it is presumed that a sufficiently strong bond cannot be formed between the filler surface and the organopolysiloxane matrix, but the breaking strength and breaking elongation are reduced, and the toughness is inferior to that of the cured product of the present invention. In addition, in Comparative Example 4, vinyltrimethoxysilane with a structure different from that of component (C) of the additive used was used. However, since the carbon chain of the reactive group bonded to the silicon atom of the vinyl group, which is the reactive group of vinyltrimethoxysilane, is short, the filler surface and the organopolysiloxane matrix cannot form a sufficient bond. As a result, the terminal functional groups of the organopolysiloxane matrix are blocked with vinyltrimethoxysilane, and the crosslinking between the polymers and the bonding between the filler and the matrix are insufficient, the breaking strength of the cured material is reduced, and the material itself becomes soft, causing the elongation at break to increase, and the originally intended hardness of the material cannot be maintained.

[0150] <Summary of Reference Examples 2 and 3, Examples 8 and 9> In comparison with the compositions not containing additives in Reference Examples 2 and 3, in Examples 8 and 9 using additives, the inclusion of Additive 1 of Component (C) of the present invention results in a bond being formed between the filler and the organopolysiloxane matrix via the additive, integrating the filler and the matrix, and preventing the organopolysiloxane from peeling off from the filler interface and breaking the material. As a result, the cured products of Examples 8 and 9 were able to improve the elongation at break of the material from 32.4% to 37.4% and from 55.7% to 73.6%, respectively, while maintaining almost the same breaking strength (about 6 to 8 MPa), compared with the case where Additive 1 was not used.

[0151] [Examples 10 to 14] <Preparation of film samples with a thickness of less than 100 μm> Filler I was added to the above-mentioned Solution A or Solution B (Solution B contained Additive 1) in an amount shown in Table 3 below, and an appropriate amount of propyl propionate solvent was added to appropriately adjust the viscosity of the composition. The mixture was then uniformly stirred using mechanical force while being degassed under reduced pressure to obtain each preparation solution. The resulting preparation liquid was applied onto a Matsunami Glass cover glass (24×60×0.13-0.17 mm) using a spin coater, and then heated in an oven at 150° C. for 1 hour to produce a cured product.

[0152] <Preparation of film samples with a thickness of 100 μm or more> Additive 1 and Filler I in the amounts shown in Table 3 below were added to the above-mentioned Solution A, and the mixture was uniformly stirred using mechanical force while being degassed under reduced pressure to obtain each preparation solution. The resulting preparation liquid was pressed at 125° C. for 15 minutes using a mold having the thickness shown in Table 3, and then heated in an oven at 150° C. for 1 hour to produce a cured product.

[0153] <Measurement of light diffusion properties and transmittance of film samples> The light transmission and scattering of the film samples prepared using the method described above was measured using a Genesia Gonio / Far Field Profiler. Using a bidirectional transmittance distribution function of 45 degrees, the transmitted light intensity of light incident perpendicularly to the surface of the measured sample, i.e., the linear transmitted light intensity, was set to 1. When the received light intensity at a position where the light receiving unit was tilted 45 degrees from the incident light axis centered on the measured sample was 0.65 or more, the film was determined to be a good light diffusing material (results shown with a circle in Table 3).

[0154] The visible and ultraviolet spectral characteristics, i.e., light transmittance, of the film samples were measured using a JASCO V770 ultraviolet, visible, and near infrared spectrophotometer equipped with a 150 mmφ integrating sphere unit.

[0155] The heat resistance of the above-mentioned film samples was also evaluated using a Malcom reflow machine RDT-250C by heating the samples between 160 and 200°C for 3 minutes, then rapidly heating them to 260°C or higher and holding them for 10 seconds, and then air-cooling them to 150°C. After repeating this operation three times, samples with a decrease in transmittance of less than 2% in the visible light range (380-740 nm) were deemed to have good heat resistance (the results are indicated by ◯ in Table 3).

[0156] [Table 3]

[0157] <Summary of Examples 10 to 14> The results of Examples 10 to 14 show that the curable organopolysiloxane composition of the present invention exhibits good light diffusivity and transmittance, and also has good heat resistance, whether the film is less than 100 μm thick or 500 μm thick.

Claims

1. Components A to C below: A) an organopolysiloxane having at least two radical reactive groups and / or reactive groups crosslinkable by a hydrosilylation reaction in the molecule, and in which 0 to less than 10 mol % of all organic groups bonded to silicon atoms in the molecule are aryl groups; B) One or more inorganic fillers selected from the group consisting of spherical silica particles, spherical alumina particles, and fluorescent fillers. ;and C) an organosilicon compound different from component A, The following C1 and C2: C1) A compound of the following general formula: (R ａ R ｂ ２ SiO) ｐ -K-(SiR ｂ ２ -Y-Si(R ｂ ) ｑ (OR ｃ ) ３－ｑ ) ｒ (In the formula, R ａ independently represents a reactive group capable of bonding with a reactive group of component A; R ｂ independently represents a group selected from the group consisting of monovalent hydrocarbon groups, halogenated hydrocarbon groups, and cyanoalkyl groups; R ｃ each independently represents an alkyl group having 1 to 10 carbon atoms; K represents an average composition formula (R ｂ ３ SiO １／２ ) ｓ (R ｂ ２ SiO ２／２ ) ｔ (R ｂ SiO ３／２ ) ｕ (SiO ４／２ ) ｖ (OR ｃ ) ｗ (In the formula, R ｂ and R ｃ are as defined above, s, t, u, v, and w each represent the number of each unit, and each represents a number from 0 to 500, provided that all of t, u, and v are not 0, and the value of s+w is u+2v or less; Y represents an oxygen atom, a divalent hydrocarbon group, or a linear or branched organopolysiloxane chain or a silicone resin structural block represented by the general formula: 【Chemistry 1】 (In the formula, R ｂ is as defined above, and Z is a divalent hydrocarbon group; and within the range possible depending on the structure of K, p is a number from 1 to 10, r is a number from 1 to 10, and q is a number of 0. An organosilicon compound represented by the formula: C2) A compound having the following structural formula: 【Chemistry 2】 {In the formula, R ａ represents a reactive group capable of bonding with the reactive group of component A; R ｂ represents a group selected from the group consisting of an alkyl group, a halogenated hydrocarbon group, and a cyanoalkyl group; R ｃ represents an alkyl group having 1 to 10 carbon atoms; m is a number ranging from 0 to 500, a is 0, and Y is an oxygen atom, a divalent hydrocarbon group, or a group represented by the general formula: 【Chemistry 3】 (In the formula, R ｂ is as defined above, and Z is a divalent hydrocarbon group. An organosilicon compound represented by the formula: One or more compounds selected from the group consisting of wherein the mass of component B is 30 to 95% based on the mass of the entire composition.

2. 2. The curable organopolysiloxane composition according to claim 1, wherein Component A is one or more organopolysiloxanes selected from the group consisting of Components A1 and A2 below. A1) linear or branched organopolysiloxane; A2) i) R １ SiO ３／２ Units (wherein R １ represents a group selected from the group consisting of a monovalent organic group, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms), and optionally further comprises SiO ４／２ A resin building block which may have units; and ii) (R ２ ２ SiO ２／２ ) ｎ (In the formula, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and n represents a number in the range of 3 to 1,000. R １ and R ２ At least a portion of R is a reactive group capable of crosslinking by a radical reaction and / or a hydrosilylation reaction, and R １ and R ２ An organopolysiloxane in which the proportion of aryl groups having 6 to 14 carbon atoms in the total number of moles of groups (excluding hydroxyl groups) is 0 to less than 10 mole %.

3. 2. The curable organopolysiloxane composition according to claim 1, wherein the spherical silica particles are spherical fused silica particles and the spherical alumina particles are spherical fused alumina particles.

4. A cured product obtained from the curable organopolysiloxane composition according to any one of claims 1 to 3.

5. The cured product according to claim 4, having a light transmittance of 40% or more.

6. 6. The cured product according to claim 4 or 5, wherein in a bidirectional transmittance distribution function using a white light source, when the straight transmitted light intensity is taken as 1, the transmitted light intensity at a light receiving position inclined at 45 degrees to the straight transmitted light centered on the measurement sample is 0.65 or more.

7. The cured product according to any one of claims 4 to 6, having a breaking elongation of 30% or more.

8. An optical member comprising the cured product according to any one of claims 4 to 7.

9. 9. The optical member according to claim 8, which is a light-diffusing coating film material for a light-receiving sensor having a thickness of 500 μm or less.

10. The optical member according to claim 8, which is a sealant for a light-emitting diode or an organic electroluminescent device.

11. An optical device comprising the optical member according to any one of claims 8 to 10.

12. A coating agent comprising the curable organopolysiloxane composition according to any one of claims 1 to 3 and an organic solvent.

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