Curable organopolysiloxane compositions and use thereof

Abstract

Provided is a novel curable organopolysiloxane composition and the like that can be used in the production of semiconductor components and the like. A curable organopolysiloxane composition comprising: (A1) an organopolysiloxane having no curable functional group having an aliphatic unsaturated bond within the molecule, and containing at least 20 mol% or more of siloxane units represented by SiO 4 / 2 (A1-1) in the total siloxane units; (A2) an organopolysiloxane having at least one monovalent hydrocarbon group having an aliphatic unsaturated bond in one molecule; (B) an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule; (C) a first hydrosilylation catalyst that exhibits activity by irradiation of high-energy rays; and (D) a second hydrosilylation catalyst microencapsulated by a thermoplastic resin having a softening point in the temperature range of 50 to 200°C.

Description

Technical Field

[0001] This invention relates to a curable organopolysiloxane composition comprising two different types of hydrosilanization reaction catalysts, a method for manufacturing a cured organopolysiloxane product cured by hydrosilanization reaction, and a method for manufacturing semiconductor components or display devices. Background Technology

[0002] In the manufacture of semiconductor components and the like, organopolysiloxane compositions having a curing mechanism by irradiation or heating with high-energy rays such as UV are known (for example, Patent Documents 1-4).

[0003] Furthermore, dual-curing organopolysiloxane compositions with two curing mechanisms—high-energy irradiation and heating—are known (e.g., Patent Document 5). Dual-curing organopolysiloxane compositions typically become a gel-like semi-cured material upon irradiation with high-energy rays and are temporarily fixed onto a substrate. The final cured material is then obtained by heating the semi-cured material.

[0004] Because of this two-stage process, the dual-cured organopolysiloxane composition has the advantage of being easy to assemble after being temporarily fixed to the substrate and before heating. However, it has been confirmed that the technology in Patent Document 5 has room for improvement in terms of the temporary fixing force to the substrate.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2019 / 208756

[0008] Patent Document 2: Japanese Patent Application Publication No. 2006-177989

[0009] Patent Document 3: Japanese Patent Application Publication No. 2017-110137

[0010] Patent Document 4: Japanese Patent Application Publication No. 9-67440

[0011] Patent Document 5: International Publication No. 2022 / 004463 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] The present invention provides a novel curable organopolysiloxane composition, etc., which can be used in the manufacture of semiconductor components, etc.

[0014] Solution for solving the problem

[0015] Based on the results of research on a novel concept that improves manufacturing efficiency by adjusting the adhesive properties of the semi-cured product of a dual-curing organopolysiloxane composition in the manufacture of semiconductor components, the inventors have completed an invention with the following configuration.

[0016] That is, the present invention provides curable organopolysiloxane compositions, etc., as shown below.

[0017] [1] A curable organopolysiloxane composition comprising:

[0018] (A1) The molecule does not contain any curing reactive functional groups with aliphatic unsaturated bonds, and contains at least 20 mol% of SiO2 as a component of all siloxane units. 4 / 2 The organopolysiloxane represented by the siloxane unit;

[0019] (A2) An organopolysiloxane having at least one monovalent hydrocarbon group containing an aliphatic unsaturated bond in one molecule;

[0020] (B) An organohydrogen polysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0021] (C) A first hydrosilylation catalyst exhibiting activity upon irradiation with high-energy rays; and

[0022] (D) A second hydrosilanization catalyst microencapsulated from a thermoplastic resin with a softening point in the temperature range of 50 to 200 °C.

[0023] [2] The curable organopolysiloxane composition according to [1], wherein

[0024] Component (A1) is composed of the following average unit formula (1).

[0025] (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e (1)

[0026] (In the formula, each R) 1 Independently, it is a monovalent hydrocarbon group with 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond; R 2It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d, and e are numbers that satisfy the following conditions: 0.35≤a≤0.70, 0≤b≤0.20, 0≤c≤0.20, 0.30≤d≤0.65, 0≤e≤0.05, and a+b+c+d=1).

[0027] The term refers to organopolysiloxanes.

[0028] [3]

[0029] According to the curable organopolysiloxane composition of [1] or [2], wherein component (A1) is contained in an amount ranging from 20% to 70% by mass relative to the total amount of component (A1), component (A2) and component (B).

[0030] [4]

[0031] The curable organopolysiloxane composition according to any one of [1] to [3], wherein both component (C) and component (D) contain platinum group metals, and the molar ratio of the platinum group metals in the two components ((C) / (D)) is in the range of 0.01 to 200.

[0032] [5]

[0033] The curable organopolysiloxane composition according to any one of [1] to [3], wherein component (A2) comprises at least a branched organopolysiloxane.

[0034] [6]

[0035] According to the curable organopolysiloxane composition of [5], the above-mentioned branched organopolysiloxane is contained in an amount ranging from 1 to 20% by mass relative to the total amount of components (A1), (A2) and (B).

[0036] [7]

[0037] The curable organopolysiloxane composition according to any one of [1] to [6], wherein the content of the hydrosilylation reaction inhibitor is less than 0.1% by mass relative to the curable organopolysiloxane composition described above.

[0038] [8]

[0039] The curable organopolysiloxane composition according to any one of [1] to [7] is a single-component composition.

[0040] [9]

[0041] The curable organopolysiloxane composition according to any one of [1] to [8], wherein the semi-cured product obtained by irradiating the curable organopolysiloxane composition according to any one of [1] to [8] with high-energy rays to carry out the first hydrosilanization reaction has an adhesion strength of 0.1 MPa or more to the substrate.

[0042]

[10]

[0043] A cured product of a curable organopolysiloxane composition according to any one of [1] to [9].

[0044]

[11]

[0045] A semiconductor device or display device comprising a solidified material according to

[10] .

[0046]

[12] A method for manufacturing an organopolysiloxane cured product, the method comprising:

[0047] (i) Irradiating the curable organopolysiloxane composition according to any one of [1] to [9] with high-energy rays to carry out a first hydrosilylation reaction to obtain a semi-cured product; and

[0048] (ii) The semi-cured material is heated at a temperature at which the (D) component exhibits activity to carry out the second hydrosilanization reaction, thereby obtaining the cured material.

[0049]

[13]

[0050] According to the manufacturing method described in

[12] , the above-mentioned semi-cured material is obtained in the presence of a shield or structure that partially obstructs the irradiation of high-energy rays.

[0051]

[14]

[0052] According to the manufacturing method described in

[12] or

[13] , (i) and (ii) are performed simultaneously or separately.

[0053]

[15]

[0054] A method for manufacturing a semiconductor device or display device, the method comprising the method according to any one of

[12] to

[14] .

[0055] The effects of the invention

[0056] According to one aspect of the present invention, a curable organopolysiloxane composition is provided that can provide a semi-cured product exhibiting adhesion to a substrate after high-energy radiation irradiation. Furthermore, according to one aspect of the present invention, a curable organopolysiloxane composition with excellent rapid curing properties and curing properties in the light-shielding portion is provided. Furthermore, according to one aspect of the present invention, a curable organopolysiloxane composition in which the adhesion of the final cured product itself can be improved is provided.

[0057] According to the present invention, which has this effect, the bonding stability of semi-cured materials during temporary fixation in the manufacture of semiconductor devices and the like is improved, as well as the bonding stability of the final cured material, resulting in an improvement in overall manufacturing efficiency. Detailed Implementation

[0058] Regarding the numerical ranges described in this specification, the upper and lower limits can be arbitrarily combined. For example, if the numerical range is described as "preferably 30 to 100, more preferably 40 to 80", then the ranges of "30 to 80" and "40 to 100" are also included in the numerical ranges described in this specification. Furthermore, for example, if the numerical range is described as "preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less", then the ranges of "30 to 80" and "40 to 100" are also included in the numerical ranges described in this specification.

[0059] In addition, the numerical ranges described in this specification, such as "60 to 100", refer to the range of "60 or more and 100 or less".

[0060] 1. Curable organopolysiloxane composition

[0061] As one aspect, this invention provides a curable organopolysiloxane composition (hereinafter also referred to as "the composition of this invention"). The composition of this invention comprises: (A1) a molecule lacking curable reactive functional groups containing aliphatic unsaturated bonds, and containing at least 20 mol% of SiO₂ as a percentage of all siloxane units. 4 / 2 (A2) An organopolysiloxane containing a siloxane unit; (B) An organopolysiloxane having at least one monovalent hydrocarbon group containing an aliphatic unsaturated bond in one molecule; (C) An organohydrogen polysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule; (D) A first hydrosilylation catalyst that exhibits activity upon irradiation with high-energy rays; and (E) A second hydrosilylation catalyst microencapsulated from a thermoplastic resin with a softening point in the temperature range of 50 to 200 °C.

[0062] The components constituting the composition of the present invention will be described in detail below.

[0063] 1.1 Component (A): Organopolysiloxane

[0064] Component (A) is an organopolysiloxane, which forms the basis of this invention. The composition of this invention, as component (A), comprises: (A1) a molecule lacking curing reactive functional groups containing aliphatic unsaturated bonds, and containing at least 20 mol% of SiO2 as a percentage of all siloxane units. 4 / 2 The organopolysiloxane represented by the siloxane unit; and (A2) an organopolysiloxane having at least one monovalent hydrocarbon group containing an aliphatic unsaturated bond in a molecule.

[0065] Previous dual-curing type curable organopolysiloxane compositions, after being semi-cured by high-energy radiation, could be temporarily fixed to the substrate itself, but the semi-cured products cured under high-energy radiation environment (e.g., room temperature of 15-30°C) did not show adhesion to the substrate.

[0066] In contrast, the composition of the present invention, by containing component (A1), exhibits adhesion to the substrate during the semi-cured stage after curing by high-energy radiation. Therefore, in the manufacture of semiconductor devices, for example, this prevents the temporarily fixed semi-cured material from peeling off from the substrate. Furthermore, since the composition of the present invention exhibits adhesion to the substrate during the semi-cured stage, heating is unnecessary to achieve this adhesion. Therefore, the composition according to the present invention can improve the manufacturing efficiency of semiconductor devices and the like.

[0067] Furthermore, the composition of the present invention can also improve the adhesion of the final cured product obtained from the semi-cured product.

[0068] The following provides further details about ingredients (A1) and (A2).

[0069] 1. 1. 1 Ingredients (A1)

[0070] Component (A1) is a molecule that does not contain any curing reactive functional groups with aliphatic unsaturated bonds, and contains at least 20 mol% of SiO2 as a component of all siloxane units. 4 / 2 The organopolysiloxane represents the siloxane unit.

[0071] In one embodiment of the invention, based on all siloxane units (100 mol%), the branched siloxane units are composed of SiO₂. 4 / 2 The proportion of the indicated siloxane units is at least 40 mol%, preferably 50 mol%, and more preferably in the range of 50 to 65 mol%.

[0072] In one aspect of the invention, component (A1) is an organopolysiloxane having the following average compositional formula (1).

[0073] (R1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e (1)

[0074] In the above average composition formula (1), each R 1 Independently, it is a monovalent hydrocarbon group with 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond; R 2 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers that satisfy the following conditions: 0.35≤a≤0.70, 0≤b≤0.20, 0≤c≤0.20, 0.30≤d≤0.65, 0≤e≤0.05, and a+b+c+d=1.

[0075] As R 1 The optional monovalent hydrocarbon group with 1 to 10 carbon atoms that does not have aliphatic unsaturated bonds may include, for example, alkyl and aryl groups.

[0076] Specifically, the aforementioned alkyl groups include, for example, propyl groups such as methyl, ethyl, n-propyl, and isopropyl; butyl groups such as n-butyl, isobutyl, sec-butyl, and tert-butyl; and pentyl, hexyl, heptyl, octyl, nonyl, and decyl. It should be noted that these groups also include structural isomers.

[0077] Specifically, the aforementioned aryl groups include, for example, phenyl, tolyl, xylyl, and naphthyl.

[0078] In one embodiment of the present invention, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

[0079] In one embodiment of the invention, 70 to 100 mol% of the organic groups bonded to silicon atoms in component (A1) is preferably methyl, 80 to 100 mol% is more preferably methyl, and 88 to 100 mol% is even more preferably methyl.

[0080] By keeping the methyl content in component (A1) within this range, it is possible to increase the content of components composed of SiO2. 4 / 2 The reinforcement effect and adhesion of the cured product of the siloxane unit are shown.

[0081] Furthermore, in one aspect of the present invention, the proportion of the above-mentioned aryl group in the component (A1) to all silicon-bonded organic groups is preferably in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and even more preferably completely free of aryl group (i.e., 0 mol%).

[0082] By keeping the aryl content in component (A1) within the aforementioned range, it is possible to prevent component (A1) from becoming hot-meltable, thus facilitating the preparation of the target liquid composition. Furthermore, it can enhance the effect of SiO₂ content derived from the molecule. 4 / 2 The effects of the cured siloxane unit on reinforcement, improved adhesion, and improved colorfastness at high temperatures are described.

[0083] As R 2 The alkyl group having 1 to 10 carbon atoms can be the same as described above. In one embodiment of the invention, R 2 Preferably, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

[0084] In the above average composition formula (1), a represents the general formula R. 1 3SiO 1 / 2 The proportion of siloxane units. Preferably, a satisfies 0.35≤a≤0.70, more preferably 0.35≤a≤0.55, and even more preferably 0.40≤a≤0.50.

[0085] If a is within the above range, the cured product containing the composition of the present invention can be endowed with excellent adhesive properties and mechanical strength.

[0086] In the above average composition formula (1), b represents the general formula R. 1 2SiO 2 / 2 The proportion of siloxane units. b preferably satisfies 0 ≤ b ≤ 0.20, more preferably satisfies 0 ≤ b ≤ 0.10.

[0087] If b is within the above range, the viscosity of the composition of the present invention can be prevented from becoming too high. In one embodiment of the present invention, b can be 0, preferably 0.

[0088] In the above average composition formula (1), c represents the general formula R. 1 SiO 3 / 2 The proportion of siloxane units. c preferably satisfies 0 ≤ c ≤ 0.20, more preferably satisfies 0 ≤ c ≤ 0.10.

[0089] If c is within the above range, the viscosity of the composition of the present invention can be prevented from becoming too high, and the resulting cured product can be endowed with excellent mechanical strength. In one embodiment of the present invention, c can be 0, preferably 0.

[0090] In the above average composition formula (1), d represents SiO 4 / 2 The proportion of siloxane units. d preferably satisfies 0.30≤d≤0.65, more preferably 0.50≤d≤0.65.

[0091] If d is within the above range, the cured product containing the composition of the present invention can be endowed with excellent adhesive properties and mechanical strength.

[0092] In the above average composition formula (1), e represents the general formula R. 2 O 1 / 2 The number of units proportional to the above. Furthermore, the above units are based on R. 2 The difference can be a hydroxyl or alkoxy group bonded to a silicon atom that may be contained in the organopolysiloxane. That is, component (A1) may contain a small amount of hydroxyl or alkoxy groups. Examples of alkoxy groups include, for instance, methoxy and ethoxy groups.

[0093] e preferably satisfies 0≤e≤0.05, and more preferably satisfies 0≤e≤0.03.

[0094] In one embodiment of the invention, component (A1) is an organopolysiloxane having the following average compositional formula (1-1).

[0095] (Me3SiO 1 / 2 ) a (Me2SiO 2 / 2 ) b (MeSiO 3 / 2 ) c (SiO 4 / 2 ) d (HO 1 / 2 ) e (1-1)

[0096] In the above average composition formula (1-1), Me is a methyl group; a, b, c, d and e are numbers that satisfy the following conditions: 0.40≤a≤0.50, 0≤b≤0.10, 0≤c≤0.10, 0.50≤d≤0.65, 0≤e≤0.03, and a+b+c+d=1.

[0097] Component (A1) can be either liquid or solid at room temperature.

[0098] In one aspect of the present invention, from the viewpoint of being able to impart superior adhesive properties and mechanical strength to the cured product containing the composition of the present invention, the weight-average molecular weight (Mw) of the organopolysiloxane of component (A1), as determined by gel permeation chromatography (GPC) using toluene as solvent, is preferably 15,000 or more, more preferably in the range of 15,000 to 100,000.

[0099] In one aspect of the invention, from the viewpoint of enabling rapid semi-curing and improving the adhesion of the semi-cured material, component (A1) is preferably contained in an amount ranging from 20% to 70% by mass, more preferably from 25% to 60% by mass, and even more preferably from 30% to 50% by mass, relative to the total amount (100% by mass) of components (A1), (A2), and (B).

[0100] In one aspect of the invention, the content ratio of component (A1) to component (A2) [component (A1) / component (A2)] by mass can be 0.10 or more, 0.30 or more, 0.50 or more, or 0.60 or more.

[0101] In addition, the content ratio can be below 10.0, below 7.00, below 5.00, below 3.00, below 2.00, below 1.00, or below 0.80.

[0102] 1.1.2 Ingredients (A2)

[0103] Component (A2) is an organopolysiloxane having at least one monovalent hydrocarbon group containing an aliphatic unsaturated bond in one molecule, which contains an aliphatic unsaturated hydrocarbon group that is added to a silane group (-SiH) during hydrosilylation.

[0104] In one embodiment of the invention, component (A2) is an organopolysiloxane having the following average compositional formula (2).

[0105] R 3 f R 4 g SiO (4-f-g) / 2 (2)

[0106] In the above average composition formula (2), R 3 It is an alkenyl group with 2 to 12 carbon atoms; R 4 It is a group selected from the group consisting of monovalent hydrocarbon groups, hydroxyl groups and alkoxy groups with 1 to 12 carbon atoms that do not have aliphatic unsaturated bonds; f and g are numbers that satisfy 1≤f+g≤3 and 0.001≤f / (f+g)≤0.33.

[0107] R 3 The alkenyl groups having 2 to 12 carbon atoms specifically include, for example, vinyl, propenyl (including allyl), butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl. It should be noted that these groups also include structural isomers.

[0108] In one embodiment of the present invention, the alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, and even more preferably a group selected from the group consisting of vinyl, allyl and hexenyl.

[0109] As R 4 The optional monovalent hydrocarbon group having 1 to 12 carbon atoms without aliphatic unsaturated bonds may include, for example, alkyl and aryl groups.

[0110] Specifically, the aforementioned alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, etc.; butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.; pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. It should be noted that these groups also include structural isomers.

[0111] Specifically, the aforementioned aryl groups include, for example, phenyl, tolyl, xylyl, and naphthyl.

[0112] In one embodiment of the present invention, the monovalent hydrocarbon group is preferably an alkyl or aryl group having 1 to 10 carbon atoms, more preferably an alkyl or aryl group having 1 to 8 carbon atoms, and even more preferably methyl or phenyl.

[0113] As R 4 Optional alkoxy groups specifically include, for example, methoxy, ethoxy, etc.

[0114] As described above, in the above average composition formula (2), f and g are numbers that satisfy 1≤f+g≤3 and 0.001≤f / (f+g)≤0.33. If f+g is 1 or more, the flexibility of the cured material can be improved; if f+g is 3 or less, the mechanical strength of the cured material can be improved.

[0115] Furthermore, if f / (f+g) is 0.001 or higher, the mechanical strength of the cured material can be improved; if f / (f+g) is 0.33 or lower, the flexibility of the cured material can be improved.

[0116] The molecular structure of the organopolysiloxane as component (A2) can be linear, branched, or cyclic. Furthermore, the organopolysiloxane as component (A2) can be a mixture of one or more compounds having such a molecular structure.

[0117] In one embodiment of the invention, component (A2) comprises at least a branched organopolysiloxane. Furthermore, in another embodiment of the invention, component (A2) comprises both linear and branched organopolysiloxanes.

[0118] By including branched organopolysiloxane as component (A2), a semi-cured product of the composition of the present invention can be obtained more rapidly. Furthermore, the adhesive strength of the semi-cured product can also be improved.

[0119] The linear organopolysiloxanes that may be included as component (A2) can be compounds represented by the following general formula (3).

[0120] R 5 3SiO(R 5 2SiO) m1 SiR 5 3(3)

[0121] In the above general formula (3), each R 5 Independently, it is a monovalent hydrocarbon group that is either unsubstituted or halogenated, and has at least two R groups per molecule. 5 It is a monovalent hydrocarbon group containing an aliphatic unsaturated bond, and the rest are R 5 It can be methyl or phenyl. As a monovalent hydrocarbon group containing an aliphatic unsaturated bond, alkenyl groups with 2 to 12 carbon atoms can be listed above, and specific examples and preferred groups are as described above.

[0122] Furthermore, in the above general formula (3), from the viewpoint of improving flowability and precise filling, m1 can be an integer in the range of 5 to 1000. In addition, m1 can also be an integer greater than 1000. When m1 is an integer greater than 1000, the organopolysiloxane is in a raw gel state at room temperature.

[0123] In one embodiment of the invention, component (A2) comprises an organopolysiloxane having two monovalent hydrocarbon groups containing aliphatic unsaturated bonds in one molecule. In another embodiment of the invention, component (A2) comprises a linear organopolysiloxane having monovalent hydrocarbon groups containing aliphatic unsaturated bonds only at both ends of the molecular chain.

[0124] The branched organopolysiloxanes that may be included as component (A2) can be compounds represented by the following general formula (4).

[0125] (R 6 3SiO 1 / 2 ) a1 (R 6 2SiO 2 / 2 ) b1 (R 6 SiO 3 / 2 ) c1 (SiO 4 / 2 ) d1 (R 7 O 1 / 2)e1 (4)

[0126] In the above general formula (4), each R 6 Independently, it is a monovalent hydrocarbon group having 1 to 10 carbon atoms (however, all R in a molecule) 6 (1-50 mol% of which are alkenyl); R 7It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a1, b1, c1, d1 and e1 are numbers that satisfy the following conditions: 0.10≤a1≤0.90, 0≤b1≤0.70, 0≤c1≤0.80, 0≤d1≤0.65, 0≤e1≤0.05, where c1+d1>0.20 and a1+b1+c1+d1=1.

[0127] Furthermore, in the above general formula (4), as R 6 The optional monovalent hydrocarbon groups having 1 to 10 carbon atoms specifically include, for example, alkyl, alkenyl, and aryl groups, as described above for specific examples and preferred groups. Furthermore, R 6 It can also be an aryl group such as benzyl. Furthermore, it is preferred that all R groups in one molecule are present. 6 2-45 mol% of which are alkenyl groups, more preferably all R in one molecule 6 The content of alkenyl groups is 2 to 35 mol%. By keeping the content of alkenyl groups within the above range, the mechanical strength (hardness, etc.) of the resulting cured product can be good.

[0128] In the above general formula (4), as R 7 Specific examples and preferred groups of alkyl groups having 1 to 10 carbon atoms are as described above. Furthermore, a1 is preferably a number satisfying 0.15 ≤ a1 ≤ 0.85; b1 is preferably a number satisfying 0 ≤ b1 ≤ 0.60; c1 is preferably a number satisfying 0 ≤ c1 ≤ 0.75, more preferably 0. Furthermore, d1 is preferably a number satisfying 0.15 ≤ d1 ≤ 0.65, more preferably a number satisfying 0.20 ≤ d1 ≤ 0.65. Here, c1 or d1 can be 0, but as described above, c1 + d1 > 0.20. Furthermore, e1 is preferably a number satisfying 0 ≤ e1 ≤ 0.03.

[0129] In one embodiment of the invention, the branched organopolysiloxane is preferably included in an amount ranging from 1 to 20% by mass, more preferably from 2 to 15% by mass, and even more preferably from 3 to 10% by mass, relative to the total amount (100% by mass) of components (A1), (A2), and (B). This allows for a more rapid preparation of the semi-cured product of the composition of the invention. Furthermore, the adhesive strength of the semi-cured product can also be improved.

[0130] In one aspect of the invention, the content ratio of linear organopolysiloxane to branched organopolysiloxane [linear organopolysiloxane / branched organopolysiloxane] in component (A2) may be 20.0 or less, 18.0 or less, 16.0 or less, 14.0 or less, 12.0 or less, or 10.0 or less by mass.

[0131] In addition, the content ratio can be 0.10 or higher, 0.50 or higher, 1.00 or higher, 3.00 or higher, 5.00 or higher, or 6.00 or higher.

[0132] Component (A2) can be either liquid or solid at room temperature. Furthermore, the weight-average molecular weight (Mw) of component (A2), as determined by gel permeation chromatography (GPC) using toluene as a solvent, is preferably 20,000 or less, more preferably 15,000 or less, and particularly preferably in the range of 100 to 15,000. By using a relatively low molecular weight component (A2), the overall viscosity of the composition can be reduced.

[0133] The amount of component (A2) added relative to the total amount (100% by mass) of components (A1) and (A2) is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, and even more preferably 1 to 40% by mass. By keeping the amount of component (A2) added within this range, a balance can be achieved in the adhesive properties, mechanical strength, and hardness of the cured product obtained from the composition of one aspect of the present invention. In particular, when the molecular weight and alkenyl content of component (A2) are within the above-mentioned preferred range, the overall viscosity of the composition and the amount of component (A2) added can be suppressed, while the amount of component (A1) added can be relatively increased, thereby further improving the adhesive properties and mechanical strength such as hardness of the cured product.

[0134] 1.2 Component (B): Organohydrogen polysiloxane

[0135] Component (B) is an organohydrogen polysiloxane that acts as a crosslinking agent. The composition of the present invention comprises an organohydrogen polysiloxane containing at least two hydrogen atoms bonded to silicon atoms as component (B).

[0136] Component (B) is a compound containing a silane group (-SiH) added to a monovalent hydrocarbon group containing an aliphatic unsaturated bond in component (A2) during the hydrosilylation reaction.

[0137] In one embodiment of the invention, component (B) is an organohydrogen polysiloxane having the following average compositional formula (5).

[0138] H x R 8 y SiO (4-x-y) / 2 (5)

[0139] In the above average composition formula (5), R 8 It is a group selected from the group consisting of monovalent hydrocarbon groups, hydroxyl groups and alkoxy groups with 1 to 12 carbon atoms that do not have aliphatic unsaturated bonds; x and y are numbers that satisfy 1≤x+y≤3 and 0.01≤x / (x+y)≤0.33.

[0140] As R 8 The optional monovalent hydrocarbon group with 1 to 12 carbon atoms that does not have aliphatic unsaturated bonds may include, for example, alkyl and aryl groups.

[0141] Specifically, the aforementioned alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, etc.; butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.; pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. It should be noted that these groups also include structural isomers.

[0142] Specifically, the aforementioned aryl groups include, for example, phenyl, tolyl, xylyl, and naphthyl.

[0143] In one embodiment of the present invention, the monovalent hydrocarbon group is preferably an alkyl or aryl group having 1 to 10 carbon atoms, more preferably an alkyl or aryl group having 1 to 8 carbon atoms, and even more preferably methyl or phenyl.

[0144] As R 8 Optional alkoxy groups specifically include, for example, methoxy, ethoxy, etc.

[0145] As described above, in the above average composition formula (5), x and y are numbers that satisfy 1≤x+y≤3 and 0.01≤x / (x+y)≤0.33, and preferably numbers that satisfy 1.5≤x+y≤2.5 and 0.05≤x / (x+y)≤0.2.

[0146] If x+y is 1 or more, the softness of the cured product containing the composition of the present invention can be improved. Furthermore, if x+y is 3 or less, the mechanical strength of the cured product containing the composition of the present invention can be improved.

[0147] Furthermore, if x / (x+y) is 0.01 or higher, the mechanical strength of the cured product containing the composition of the present invention can be improved. Furthermore, if x / (x+y) is 0.33 or lower, the flexibility of the cured product containing the composition of the present invention can be improved.

[0148] Specifically, the organohydropolysiloxane of component (B) may include, for example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrosiloxy)methylsilane, tris(dimethylhydrosiloxy)phenylsilane, 1-(3-epoxypropoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-di(3-epoxypropoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1-(3-epoxypropoxypropyl)-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, molecular chain Two-terminated trimethylsiloxy-terminated methylhydrosiloxane, two-terminated trimethylsiloxy-terminated dimethylsiloxane / methylhydrosiloxane copolymer, two-terminated dimethylhydrosiloxy-terminated dimethylpolysiloxane, two-terminated dimethylhydrosiloxy-terminated dimethylsiloxane / methylhydrosiloxane copolymer, two-terminated trimethylsiloxy-terminated methylhydrosiloxane / diphenylsiloxane copolymer, two-terminated trimethylsiloxy-terminated methylhydrosiloxane / diphenylsiloxane / dimethylsiloxane copolymer, hydrolysis condensate of trimethoxysilane, and (CH3)2HSiO 1 / 2 Unit and SiO 4 / 2 A copolymer composed of units, consisting of (CH3)2HSiO 1 / 2 Unit, SiO 4 / 2 Unit and (C6H5)SiO 3 / 2 Copolymers composed of units and mixtures of two or more of them, etc.

[0149] In one embodiment of the present invention, the viscosity of the organohydrogen polysiloxane of component (B) at 25°C is preferably 1 to 10,000 mPa·s, more preferably 1 to 5,000 mPa·s, and even more preferably 1 to 1,000 mPa·s. It should be noted that, in this specification, viscosity (mPa·s) refers to the value measured using a type B viscometer at 25°C.

[0150] The content of component (B) can be relative to the amount of monovalent hydrocarbon groups containing aliphatic unsaturated bonds in 1 mole of component (A2), and the amount of silicon atoms bonded to hydrogen atoms in component (B) is 0.1 to 5.0 moles, preferably in the range of 0.5 to 3.0 moles.

[0151] If the content of component (B) is above the lower limit of the above range, the mechanical strength of the cured article containing the composition of the present invention can be improved. Furthermore, if it is below the upper limit of the above range, the softness of the cured article containing the composition of the present invention can be improved.

[0152] 1.3 Component (C): First hydrosilylation catalyst

[0153] Component (C) is a first hydrosilylation catalyst that exhibits activity upon irradiation with high-energy rays; it is a catalyst known as a high-energy ray-activated catalyst or a photoactivated catalyst. Unlike component (D) described later, component (C) is a catalyst that has not been microencapsulated, but it will not be activated unless irradiated with high-energy rays, and the curing reaction will not occur, thus maintaining the pot life of the composition of the present invention.

[0154] In addition, component (C) is rapidly cured by high-energy radiation. It can achieve rapid curing for parts that have been irradiated with high-energy radiation, but for light-shielded parts that cannot be fully irradiated by high-energy radiation due to the structure of the object (such as the internal structure of semiconductor components or the enclosed parts of display devices), it has the characteristic of gradually curing at room temperature.

[0155] The compositions of the present invention are prepared by using the component (C) having this characteristic in conjunction with the component (D) described later, in order to more reliably allow the curing reaction to occur throughout the entire composition.

[0156] Furthermore, by containing the aforementioned component (A1), the composition of the present invention can bond the semi-cured product obtained after high-energy ray irradiation even when the curing reaction caused by component (C) is incomplete. Therefore, it can improve the stability of temporary fixation in the manufacture of semiconductor devices, etc., and thus improve manufacturing efficiency.

[0157] Examples of high-energy rays include ultraviolet rays, X-rays, and electron beams. From the viewpoint of catalyst activation efficiency, ultraviolet rays are preferred. Furthermore, the irradiation dose of high-energy rays varies depending on the type of catalyst; for example, if ultraviolet rays are used, the cumulative irradiation dose at a wavelength of 365 nm is preferably 100 mJ / cm². 2 ~10J / cm 2 Within the range.

[0158] Specifically, component (C) includes, for example, (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), and (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum. (IV), Trimethyl(acetylacetone)platinum (IV), Trimethyl(3,5-heptanedione)platinum (IV), Trimethyl(methyl acetoacetate)platinum (IV), Bis(2,4-pentanedione)platinum (II), Bis(2,4-hexanedione)platinum (II), Bis(2,4-heptanedione)platinum (II), Bis(3,5-heptanedione)platinum (II), Bis(1-phenyl-1,3-butanedione)platinum (II), Bis(1,3-diphenyl-1,3-propanedione)platinum (II) and Bis(hexafluoroacetylacetone)platinum (II), etc.

[0159] From the perspective of versatility and ease of acquisition, (methylcyclopentadienyl)trimethylplatinum (IV) and bis(2,4-pentanedione)platinum (II) are preferred.

[0160] The content of component (C) is preferably 1 to 50 ppm by mass, more preferably 5 to 30 ppm by mass, relative to the total amount of metal atoms in the catalyst and the total amount of the composition.

[0161] 1.4 Component (D): Second hydrosilylation catalyst

[0162] Component (D) is a second hydrosilanization catalyst microencapsulated from a thermoplastic resin with a softening point in the temperature range of 50 to 200°C. When used in conjunction with component (C), component (D), as described above, enables rapid and complete curing of light-shielding portions that cannot be adequately irradiated by high-energy rays, by heating above the aforementioned softening point temperature to induce a catalyst response.

[0163] Furthermore, component (D) does not act as a catalyst below the softening point of the thermoplastic resin, so even if irradiated with high-energy rays, the curing reaction originating from component (D) will not proceed.

[0164] Thus, the composition of the present invention combines the different curing properties derived from two hydrosilaneization catalysts, but in the absence of their respective triggers (i.e., irradiation by high-energy rays or heating above the softening point), the catalyst is in an inactive state, so the curing reaction does not occur, and a good pot life can be maintained.

[0165] The second hydrogen silanization catalyst used in component (D) specifically includes, for example, platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts. Among these, platinum-based catalysts are preferred.

[0166] Furthermore, this platinum-based catalyst comprises platinum group compounds such as platinum micropowder, platinum black, platinum-supported silica micropowder, platinum-supported activated carbon, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, platinum olefin complexes, and platinum alkenylsiloxane complexes. Among these, platinum alkenylsiloxane complexes are preferred. In particular, due to their good stability, platinum-alkenylsiloxane complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are preferred.

[0167] In one embodiment of the present invention, the thermoplastic resin used for the microcapsules constituting component (D) preferably has a softening point of 80°C or higher and 160°C or lower. The thermoplastic resin includes, for example, polyolefin resins, polystyrene resins, acrylic resins, cellulose resins, thermoplastic silicone resins, polycarbonate resins, etc.

[0168] It should be noted that microencapsulated hydrosilylation catalysts are described in Japanese Patent Application Publication Nos. 2-9448 and 2-14244, and can be prepared using the methods described in these documents.

[0169] Furthermore, component (D) releases or diffuses the catalyst at a temperature above the softening point of the thermoplastic resin used for microencapsulation, exhibiting catalytic activity. Therefore, the temperature at which catalytic activity is exhibited varies depending on the type of thermoplastic resin, and is typically 80°C or higher, preferably 100°C, and more preferably 120°C or higher.

[0170] The content of component (D) is in the range of 0.1 to 50 ppm by mass, preferably 0.5 to 30 ppm by mass, and more preferably 1 to 10 ppm by mass relative to the total amount of metal atoms in the catalyst in the composition.

[0171] In one embodiment of the present invention, both component (C) and component (D) comprise platinum group metals. In this embodiment, the molar ratio ((C) / (D)) of the amount of platinum group metal in component (C) and component (D) is typically in the range of 0.01 to 200, preferably in the range of 0.1 to 100.

[0172] If the molar ratio is below the upper limit mentioned above, the curing reaction at high temperature can be accelerated. Furthermore, if the molar ratio is above the lower limit mentioned above, a curing reaction at low temperature can be carried out in a short time.

[0173] It should be noted that, among components (C) and (D), when rapid curing caused by high-energy ray irradiation is emphasized, the content of component (C) is preferably greater than that of component (D).

[0174] 1.5 Optional Ingredients

[0175] In addition to components (A), (B), (C), and (D) of components (A1) and (A2), the composition of one embodiment of the present invention may, as needed, contain other organopolysiloxanes; adhesive agents; inorganic fillers such as silica, glass, alumina, and zinc oxide; organic resin micropowders such as polymethyl methacrylate; phosphors; heat resistant agents; dyes; pigments; flame retardant agents; solvents, etc.

[0176] In one aspect of the invention, the adhesive agent may be a substance represented, for example, by the following structural formula (where Me is methyl).

[0177] [Chemical Formula 1]

[0178]

[0179] Furthermore, in one aspect of the invention, the content of the adhesive agent may be 0.01 to 5.0% by mass, 0.1 to 2.5% by mass, 0.4 to 1.5% by mass, or 0.5 to 1.0% by mass, based on the total amount of the composition (100% by mass).

[0180] Furthermore, the composition of one embodiment of the present invention preferably contains substantially no hydrosilanization reaction inhibitor. Typically, hydrosilanization reaction inhibitors are added to curable compositions cured by hydrosilanization to improve pot life and obtain a stable composition; however, these inhibitors also inhibit the curing reaction of the composition.

[0181] However, in the compositions of the present invention, components (C) and (D) are inactive as catalysts before being given their respective triggers. Furthermore, in one embodiment of the composition of the present invention, the amount of curing reactive functional groups in component (A) is also suppressed.

[0182] Therefore, the composition of one aspect of the present invention has a practically sufficient service life even without the use of a hydrosilanization reaction inhibitor. In the composition of one aspect of the present invention, the content of the hydrosilanization reaction inhibitor is specifically less than 0.1% by mass, more preferably less than 0.01% by mass, or preferably below the detection limit, relative to the total amount of the composition (100% by mass).

[0183] Specifically, inhibitors of hydrosilylation reactions include, for example, acetylene compounds such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3-ol, and 1-ethynyl-1-cyclohexanol; enynyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; cycloalkenylsiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; oligomers of methylvinylsiloxanes with two terminal hydroxyl groups or modified oligomers; and triazole compounds such as benzotriazole.

[0184] 1.6 Method for manufacturing the composition of the present invention and its form

[0185] One aspect of the composition of the present invention can be manufactured by uniformly mixing components (A), (B), (C), and (D), which contain components (A1) and (A2), as well as optional components to be used as needed, at room temperature using mechanical force such as a mixer.

[0186] Furthermore, the composition of one aspect of the present invention can be a single-component (single-liquid) composition having at least hydrosilanization reaction curing properties, or a multi-component composition having two or more components (two-liquid). Even if the composition of one aspect of the present invention is a single-liquid composition, it can be stored for a long time at room temperature in a sealed container without the use of hydrosilanization reaction inhibitors, thus having a practically sufficient shelf life.

[0187] 1.7 Properties of semi-cured products comprising the compositions of the present invention

[0188] A semi-cured product obtained by irradiating a composition of one aspect of the present invention with high-energy rays to induce a first hydrosilylation reaction preferably has an adhesive strength of 0.1 MPa or more, more preferably 0.5 MPa or more, and even more preferably 1.0 MPa or more against a substrate (e.g., glass, aluminum plate, etc.). The method for measuring this adhesive strength is described in the examples described later.

[0189] By having adhesive strength within the aforementioned range, the semi-cured material can, for example, improve the stability of temporary fixation during the manufacture of semiconductor devices, thereby improving manufacturing efficiency.

[0190] 1.8 Methods of using the compositions of the present invention

[0191] The compositions of the present invention can be applied to an object using known coating or injection methods and cured by the curing methods described later.

[0192] The compositions of the present invention are applicable, for example, to bonding between components, as well as to components and the interior of components, including light-shielding portions, such as the interior of components, fine irregularities, or narrow gap structures. Therefore, the compositions of the present invention are preferably applied or injected into the object using a dispensing machine. This allows for precise, fine, and / or small-volume application or injection. The dispensing machine can be a pneumatic, valve, screw, volumetric, or jet dispensing machine.

[0193] Furthermore, as described above, the catalyst in the composition of the present invention will not be activated at temperatures below the softening point or glass transition point of the wall material, i.e., the thermoplastic resin, of component (D). Therefore, in order to ensure the flowability of the composition, it can be applied to the object after heating within the temperature range where component (D) is not activated. This improves the flowability, compact filling properties, and / or coatability of the composition of the present invention.

[0194] 2. Method for manufacturing organopolysiloxane cured products

[0195] As one aspect, the present invention provides a method for manufacturing a cured organopolysiloxane product obtained by curing the cured organopolysiloxane composition described in "1. Curable Organopolysiloxane Composition" above (hereinafter also referred to as "the manufacturing method of the present invention"). The manufacturing method of the present invention includes at least the following (i) and (ii).

[0196] (i) Irradiating the curable organopolysiloxane composition described in "1. Curable Organopolysiloxane Composition" with high-energy rays to induce a first hydrosilylation reaction, thereby obtaining a semi-cured product; and

[0197] (ii) The semi-cured material is heated at a temperature at which component (D) exhibits activity to carry out a second hydrosilanization reaction, thereby obtaining a cured material.

[0198] The above (i) and (ii) can be performed simultaneously or separately.

[0199] Performing (i) and (ii) "simultaneously" does not mean that the high-energy irradiation and the heating must begin simultaneously. That is, the heating in (ii) can begin midway through the high-energy irradiation in (i). Alternatively, the high-energy irradiation in (i) can begin midway through the heating in (ii).

[0200] "Perform" the above (i) and (ii) separately means that after either the high-energy ray irradiation in (i) or the heating in (ii) is completed, the other treatment begins.

[0201] When performing (i) and (ii) above respectively, (i) can be performed first or (ii) can be performed first, but from the viewpoint of obtaining the effect of temporary fixation stability brought about by the adhesion of the substrate by the semi-cured material, which is a feature of the present invention, it is preferable to perform (i) first.

[0202] 2.1 Regarding the above (i)

[0203] In (i) above, the composition of the present invention activates only component (C) by irradiation with high-energy rays, and rapidly becomes a semi-cured product through a first hydrosilanization reaction.

[0204] In (i) above, the timing of irradiation with high-energy rays is arbitrary; it can be done just before application to the object. Furthermore, additional irradiation with high-energy rays may be performed thereafter. The amount of high-energy irradiation is as described in “1. Curable Organopolysiloxane Composition” above, but is not limited to that amount; any amount sufficient to obtain a semi-cured product of the composition of the present invention is acceptable.

[0205] In one aspect of the invention, (i) can be performed in the presence of a shield or structure that partially obstructs the irradiation of high-energy rays. Even under such conditions, the curing reaction of the shielded portion can proceed via (ii) described above.

[0206] Furthermore, (i) above can be irradiated with high-energy rays using a light source that is difficult to produce a light-blocking part, just like a point UV light source, so that the first hydrogen silanization reaction in (i) can proceed rapidly.

[0207] 2.2 Regarding the above (ii)

[0208] In (ii) above, the composition of the present invention is heated at a temperature at which component (D) exhibits activity while component (C) is activated, and becomes the final cured product through a second hydrosilanization reaction.

[0209] The heating temperature in (ii) needs to be higher than the softening point or glass transition point of the wall material of the microcapsule containing the catalyst of component (D), i.e., the thermoplastic resin. Specifically, although it varies depending on the thermoplastic resin, it can be, for example, above 80°C, above 100°C, or above 120°C, and can be below 200°C, below 180°C, or below 160°C.

[0210] In addition, the heating time also depends on the type and amount of each component in the composition of the present invention and the heating temperature, but it is usually 1 minute to 10 hours, preferably 3 minutes to 5 hours, and more preferably 5 minutes to 2 hours.

[0211] 3. Semiconductor devices, display devices

[0212] As one aspect, the present invention provides a semiconductor device or display device (hereinafter also referred to as "the semiconductor device or display device of the present invention"). The semiconductor device or display device of the present invention is formed by comprising a cured product of the curable organopolysiloxane composition described in "1. Curable organopolysiloxane composition" above.

[0213] Specifically, the aforementioned semiconductor devices include, for example, any semiconductor device such as optical semiconductors, light-emitting semiconductors, power semiconductors, light-reflecting materials, semiconductor elements, IC chips, etc.

[0214] The aforementioned display device includes any display, etc.

[0215] 4. Manufacturing methods for semiconductor devices and display devices

[0216] As one aspect, the present invention provides a method for manufacturing a semiconductor device or display device (hereinafter also referred to as "the method for manufacturing a semiconductor device or display device of the present invention"). The method for manufacturing a semiconductor device or display device of the present invention comprises (i) and (ii) of the manufacturing method of the present invention described in "2. Method for manufacturing organopolysiloxane cured products" above.

[0217] Furthermore, in one embodiment of the method for manufacturing the semiconductor device or display device of the present invention, as described in “1.8 Method for Applying the Composition of the Present Invention” above, the composition of the present invention is applied to the object, and then (i) and (ii) of the manufacturing method of the present invention described in “2. Method for Manufacturing Organopolysiloxane Cured Products” above are performed.

[0218] The method for manufacturing a semiconductor device or display device according to the present invention contains component (A1), and even if the curing reaction caused by component (C) is incomplete, the semi-cured product obtained after high-energy ray irradiation can still adhere to the substrate. Therefore, the stability of temporary fixing used for component alignment can be improved, resulting in improved manufacturing efficiency.

[0219] Example

[0220] The present invention will be further described below based on embodiments, but the present invention is not limited to the following embodiments.

[0221] A curable organopolysiloxane composition containing the following components as formulated in Table 1 was obtained. Subsequently, a curing reaction was carried out under the following conditions, and the UV-based rapid curing property and the curing property of the light-shielding portion of the composition were evaluated. Furthermore, the adhesion to substrates was evaluated by performing adhesion tests on the semi-cured product obtained through UV-based rapid curing using the following methods. These evaluation results are shown in Table 1. It should be noted that in each average compositional formula, Me, Vi, and Ph represent methyl, vinyl, and phenyl, respectively.

[0222] <Ingredients (A)>

[0223] • Composition (A1): Based on the average unit formula: (Me3SiO) 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0224] The indicated organopolysiloxane (vinyl content = 0 mol%) has a weight-average molecular weight (Mw) of 18,500 as determined by GPC using toluene as solvent.

[0225] • Composition (A2-1): Based on the average unit formula:

[0226] ViMe2SiO(Me2SiO) 300 SiViMe2

[0227] The term refers to a linear polydimethylsiloxane with dimethyl vinyl-terminated ends (vinyl content = 0.23% by mass).

[0228] • Composition (A2-2): Based on the average unit formula:

[0229] ViMe2SiO(Me2SiO) 140 SiViMe2

[0230] The term refers to a linear polydimethylsiloxane with dimethyl vinyl-terminated ends (vinyl content = 0.44% by mass).

[0231] • Composition (A2-3): 80% by mass of the above-mentioned component (A2-1) and 20% by mass of silazane-treated fumed silica (average primary particle size determined by laser diffraction scattering: 0.1-0.2 μm) as masterbatch.

[0232] • Composition (A2-4): Based on average unit formula:

[0233] Si(OSiMe2Vi)4

[0234] The indicated branched polydimethylsiloxane (vinyl content = 27% by mass)

[0235] • Composition (A2-5): Based on average unit formula:

[0236] PhSi(OSiMe2Vi)3

[0237] The indicated branched polydimethylsiloxane (vinyl content = 21% by mass)

[0238] It should be noted that the above-mentioned component (A1) does not contain any curing reactive functional groups with aliphatic unsaturated bonds within its molecule, and contains at least 20 mol% of SiO2 as a component of all siloxane units. 4 / 2 The siloxane unit is represented as an organopolysiloxane. Furthermore, the components (A2-1) to (A2-5) are all organopolysiloxanes having at least one monovalent hydrocarbon group containing an aliphatic unsaturated bond in one molecule.

[0239] <Ingredient (B)>

[0240] • Composition (B1): Methylhydrosiloxane-dimethylsiloxane copolymer with trimethylsiloxy groups at both ends of the molecular chain (silicon atom bonded hydrogen atom content = 0.7% by mass)

[0241] • Composition (B2): Dimethylsiloxane with dimethylhydrosiloxy groups at both ends of the molecular chain (silicon atom bonded to hydrogen atom content = 0.13% by mass)

[0242] • Component (B3): Composed of average unit formula:

[0243] (PhSiO 3 / 2 ) 0.4 (HMe2SiO 1 / 2 ) 0.6

[0244] The indicated branched organohydrogen polysiloxane (SiH group content = 0.62% by mass)

[0245] • Component (B4): Composed of average unit formula:

[0246] (HMe2SiO 1 / 2 ) 0.52 (Me2SiO 2 / 2 ) 0.15 (SiO 4 / 2 ) 0.33 The indicated branched organohydrogen polysiloxane (SiH group content = 0.79% by mass)

[0247] In addition, the above components (B1) to (B4) are organohydrogen polysiloxanes containing at least two hydrogen atoms bonded to silicon atoms in one molecule.

[0248] <Ingredient (C)>

[0249] • Composition (C1): (Methylcyclopentadienyl)trimethylplatinum(IV) complex (a catalyst for the curing reaction via hydrosilylation under ultraviolet (UV) irradiation)

[0250] <Ingredient (D)>

[0251] • Composition (D1): Platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum atom content = 4000 ppm by mass) dispersed in polycarbonate microcapsules (softening point = 150°C) with an average particle size of 2 μm.

[0252] • Composition (D2): Platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum atom content = 4000 ppm by mass) dispersed in acrylic resin microcapsules (softening point = 100°C) with an average particle size of 2 μm.

[0253] <Other Ingredients>

[0254] • Adhesion initiator: An adhesion initiator represented by the following structural formula (where Me is a methyl group).

[0255] [Chemical Formula 2]

[0256]

[0257] [UV fast curing]

[0258] 0.1 mL of the prepared liquid composition of each sample was dropped onto an aluminum plate and emitted from an ultraviolet (UV) light source at a speed of 4 J / cm². 2 The amount of UV light irradiated.

[0259] Light source: UV LED point light source: ULEDN-101 (NS-Lighting Co., Ltd.)

[0260] Wavelength: 365nm

[0261] Irradiation dose: UV energy: maximum 4000mW / cm 2

[0262] Ten minutes after the UV light irradiation begins, touch the surface of the UV-irradiated composition (semi-cured product) with your hand. If it is sticky, it is considered cured; if it is not sticky, it is considered uncured.

[0263] [Curing properties of the light-shielding portion]

[0264] The prepared liquid compositions of each sample were coated onto an aluminum plate in a width of 25 mm, a length of 75 mm, and a thickness of 1.0 mm. Under light-shielding conditions with an aluminum plate covering the coated plate, the mixture was subjected to a light-absorbing process at 4 J / cm². 2The same UV light intensity as described above was applied. Afterward, heat curing was performed in a circulating oven (150°C, 1 hour). Regarding the curing of the light-shielded portion, the cover of the aluminum plate was removed. If the composition (cured product) adhered tightly to the coated aluminum plate, it was considered cured. Conversely, if the composition (cured product) was sticky and could be peeled off the coated aluminum plate, it was considered uncured.

[0265] [Curing properties of the light-shielding portion]

[0266] 0.1 mL of the prepared liquid composition of each sample was dropped onto an aluminum plate at a concentration of 4 J / cm². 2 The aluminum plate was irradiated with the same amount of UV light as described above. It was then placed on a glass substrate and aged at room temperature for 30 minutes. The adhesive strength of the composition (semi-cured product) was evaluated using a die shear test based on JISK 6854-2.

[0267]

[0268] As shown in Table 1, the compositions of Examples 1 and 2, which contain both component (C) and component (D), exhibit good UV-curing properties and good curing properties in the light-shielding portion. Furthermore, the compositions of Examples 1 and 2, which contain component (A1), show high adhesion to glass substrates after UV curing.

[0269] On the other hand, the composition of Comparative Example 2, which does not contain component (D), exhibits poor curability of the light-shielding portion. Furthermore, the compositions of Comparative Examples 1 and 2, which do not contain component (A1), do not show adhesion to the glass substrate after UV curing.

[0270] As can be seen from the above, the composition of the present invention containing components (A1), (A2), (B), (C), and (D) exhibits good rapid curing properties upon irradiation by high-energy rays and good curing properties of the light-shielding portion after thermal curing. Furthermore, it has excellent adhesion to the substrate after UV curing, thereby improving the stability of temporary fixation in the manufacturing of semiconductor devices and the like.

Claims

1. A curable organopolysiloxane composition, said curable organopolysiloxane composition comprising: (A1) a molecule lacking curable reactive functional groups containing aliphatic unsaturated bonds, and containing at least 20 mol% of SiO2 as a percentage of all siloxane units. 4 / 2 The organopolysiloxane represented by the siloxane unit; (A2) An organopolysiloxane having at least one monovalent hydrocarbon group containing an aliphatic unsaturated bond in one molecule; (B) An organohydrogen polysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule; (C) A first hydrosilylation catalyst exhibiting activity upon irradiation with high-energy rays; and (D) A second hydrosilanization catalyst microencapsulated from a thermoplastic resin with a softening point in the temperature range of 50 to 200 °C.

2. The curable organopolysiloxane composition according to claim 1, wherein component (A1) is composed of the following average unit formula (1). (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e (1) (In the formula, each R) 1 Independently, it is a monovalent hydrocarbon group with 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond; R 2 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d, and e are numbers that satisfy the following conditions: 0.35≤a≤0.70, 0≤b≤0.20, 0≤c≤0.20, 0.30≤d≤0.65, 0≤e≤0.05, and a+b+c+d=1). The term refers to organopolysiloxanes.

3. The curable organopolysiloxane composition according to claim 1, wherein component (A1) is contained in an amount ranging from 20% to 70% by mass relative to the total amount of components (A1), (A2), and (B).

4. The curable organopolysiloxane composition according to claim 1, wherein both component (C) and component (D) contain platinum group metals, and the molar ratio of the platinum group metals in the two components ((C) / (D)) is in the range of 0.01 to 200.

5. The curable organopolysiloxane composition according to claim 1, wherein component (A2) comprises at least a branched organopolysiloxane.

6. The curable organopolysiloxane composition according to claim 5, wherein the branched organopolysiloxane is contained in an amount ranging from 1 to 20% by mass relative to the total amount of components (A1), (A2), and (B).

7. The curable organopolysiloxane composition according to claim 1, wherein the content of the hydrosilylation reaction inhibitor is less than 0.1% by mass relative to the curable organopolysiloxane composition.

8. The curable organopolysiloxane composition according to claim 1, wherein the curable organopolysiloxane composition is a single-component composition.

9. The curable organopolysiloxane composition according to claim 1, wherein, The semi-cured product obtained by irradiating the curable organopolysiloxane composition of claim 1 with high-energy rays to carry out the first hydrosilanization reaction has an adhesion strength of 0.1 MPa or more to the substrate.

10. A cured product, said cured product being a cured product of a curable organopolysiloxane composition according to any one of claims 1 to 9.

11. A semiconductor device or display device, said semiconductor device or display device being formed comprising the cured material according to claim 10.

12. A method for manufacturing a cured organopolysiloxane, the method comprising: (i) irradiating a curable organopolysiloxane composition according to any one of claims 1 to 9 with high-energy radiation to induce a first hydrosilylation reaction thereby obtaining a semi-cured product; and (ii) The semi-cured material is heated at a temperature at which the (D) component exhibits activity to allow a second hydrosilanization reaction to proceed, thereby obtaining a cured material.

13. The manufacturing method according to claim 12, wherein the semi-cured material is obtained in the presence of a shield or structure that partially obstructs the irradiation of high-energy rays.

14. The manufacturing method according to claim 12, wherein (i) and (ii) are performed simultaneously or separately.

15. A method of manufacturing a semiconductor device or display device, the method of manufacturing the semiconductor device or display device comprising the method according to claim 12.

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