Hot-melt-type curable organopolysiloxane composition

Abstract

A novel hot-melt-type curable organopolysiloxane composition and the like are required. This hot-melt-type curable organopolysiloxane composition comprises: (A) a chain organopolysiloxane having at least two alkenyl groups in a molecule; (B) organopolysiloxane components which do not contain an aliphatic unsaturated bond and are at least two selected from among the following components (B1)-(B3), where (B1) is an organopolysiloxane resin which contains, in a molecule, a siloxane unit (M unit) represented by R1 3SiO1 / 2 (in the formula, R1s each represent a monovalent organic group) and a siloxane unit (Q unit) represented by SiO4 / 2, and in which the ratio of the substance amount of the M unit to 1 mol of the Q unit is within the range of 0.50-2.00, (B2) is a linear or branched diorganopolysiloxane, and (B3) is an organopolysiloxane resin in which the component (B1) and the component (B2) are linked through a chemical bond; (C) a monofunctional or polyfunctional vinyl monomer; and (D) a radical polymerization initiator, wherein the ratio (R / P ratio) of the total mass R of the component (B1) and the component (B1) constituting the component (B3) to the total mass P of the component (A), the component (B2), and the component (B2) constituting the component (B3) exceeds 1.80.

Description

Hot-melt curable organopolysiloxane composition

[0001] The present invention relates to a hot-melt curable organopolysiloxane composition, a cured product of the composition, and a laminate containing the composition. The present invention also relates to a method for producing the cured product, a semiconductor device containing the cured product, and a method for producing a semiconductor device.

[0002] Curable organopolysiloxane compositions are used in a wide range of industrial fields because they cure to form cured products that have excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. Cured products of these curable organopolysiloxane compositions are less susceptible to discoloration than other organic materials and experience only small deterioration in physical properties, making them suitable for use as optical materials and sealants for semiconductor devices. Examples of hot-melt curable organopolysiloxane compositions include those described in Patent Documents 1 to 4.

[0003] International Publication No. 2023 / 042743 Pamphlet International Publication No. 2023 / 017746 Pamphlet International Publication No. 2015 / 194158 Pamphlet International Publication No. 2017 / 068762 Pamphlet

[0004] Under these circumstances, there has been a demand for new hot-melt curable organopolysiloxane compositions.

[0005] The present invention provides the following hot-melt curable organopolysiloxane composition, etc. [1] (A) a linear organopolysiloxane having two or more alkenyl groups in the molecule, (B) two or more types of organopolysiloxane components containing no aliphatic unsaturated bonds selected from the following components (B1) to (B3): (B1) an organopolysiloxane component having R １ ３ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and a siloxane unit (M unit) represented by SiO ４／２wherein the ratio of the amount of substance of M units to 1 mole of Q units is in the range of 0.50 to 2.00, (B2) a linear or branched diorganopolysiloxane, and (B3) an organopolysiloxane resin in which components (B1) and (B2) are linked by a chemical bond, (C) a monofunctional or polyfunctional vinyl monomer, and (D) a radical polymerization initiator, wherein the ratio (R / P ratio) of the total mass R of component (B1) and component (B3) constituting component (B3) to the total mass P of component (B2) constituting component (A), component (B2), and component (B3) is greater than 1.80. [2] The composition according to [1], which contains component (B3). [3] The component (B3) is the following: (b3-1)R １ ３ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and a siloxane unit (M unit) represented by SiO ４／２ (b3-2) a resinous organosiloxane block containing a siloxane unit (Q unit) represented by the formula: {R ２ ２ SiO ２／２} ｍ (In the formula, R ２the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), wherein the content ratio of component (b3-1) to component (b3-2) [component (b3-1):component (b3-2)] is 99:1 to 1:99 by mass; the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), wherein the content ratio of component (b3-1) to component (b3-2) [component (b3-1):component (b3-2)] is 99:1 to 1:99 by mass; the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), wherein the content ratio of component (b3-1):component (b3-2)] is 99:1 to 1:99 by mass; the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), wherein the content ratio of component (b3-1):component (b3-2) is 99:1 to 1:99 by mass; the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), wherein the content ratio of component (b3-1):component (b3-2) is 1.0 to 30.0 parts by mass relative to the total amount (100 parts by mass) of components (A) and (B1) is 1.0 to 30.0 parts ... [6] The composition according to any one of [1] to [5], wherein component (C) comprises a monofunctional or polyfunctional vinyl monomer having 8 to 30 carbon atoms. [7] The composition according to any one of [1] to [6], wherein component (D) comprises a photoradical polymerization initiator. [8] A method for producing a sheet or film of a hot-melt curable organopolysiloxane composition, comprising: (i) applying the composition according to any one of [1] to [7] to a substrate, and (ii) drying the applied composition by heating. [9] A laminate comprising the hot-melt curable organopolysiloxane composition according to any one of [1] to [7], and a substrate having a release surface and attached to one or both sides of the sheet- or film-like composition.

[10] The laminate according to [9], wherein the composition or a cured product of the composition is releasable from the substrate.

[11] A cured product of the hot-melt curable organopolysiloxane composition according to any one of [1] to [7].

[12] The cured product according to

[11] , which is in the form of a sheet or film.

[13] A semiconductor device comprising the cured product according to

[11] or

[12] .

[14] A method for producing a semiconductor device, comprising the method according to [8].

[0006] According to one aspect of the present invention, there is provided a hot-melt curable organopolysiloxane composition that is easy to handle. According to one aspect of the present invention, there is provided a hot-melt curable organopolysiloxane composition that can provide a cured product that has high adhesion to substrates. According to one aspect of the present invention, there is provided a hot-melt curable organopolysiloxane composition that can provide a cured product that has good adhesion to substrates. According to a preferred aspect of the present invention, there is provided a hot-melt curable organopolysiloxane composition that can be cured at room temperature and has high adhesion to substrates and can provide a cured product that has good adhesion to substrates.

[0007] The upper and lower limit values ​​of the numerical ranges described herein can be arbitrarily combined. For example, when a numerical range is described as "preferably 30 to 100, more preferably 40 to 80," the ranges "30 to 80" and "40 to 100" are also included in the numerical ranges described herein. Furthermore, when a numerical range is described as "preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less," the ranges "30 to 80" and "40 to 100" are also included in the numerical ranges described herein. In addition, when a numerical range described herein as "60 to 100," for example, means a range of "60 or more and 100 or less."

[0008] 1. Hot-melt curable organopolysiloxane composition One aspect of the present invention provides a hot-melt curable organopolysiloxane composition (hereinafter also referred to as "the composition of the present invention"). The composition of the present invention comprises (A) a linear organopolysiloxane having two or more alkenyl groups in the molecule, (B) two or more organopolysiloxane components containing no carbon-carbon multiple bonds selected from the following components (B1) to (B3): (B1) an organopolysiloxane component having R １ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and a siloxane unit (M unit) represented by SiO ４／２wherein the ratio of the amount of substance of M units to 1 mole of Q units is in the range of 0.50 to 2.00, (B2) a linear or branched diorganopolysiloxane, and (B3) an organopolysiloxane resin in which components (B1) and (B2) are chemically linked, (C) a monofunctional or polyfunctional vinyl monomer, and (D) a radical polymerization initiator. Furthermore, in the composition of the present invention, the ratio (R / P ratio) of the total mass R of component (B1) and component (B3) constituting component (B3) to the total mass P of component (B2) constituting components (A), (B2), and (B3) is greater than 1.80. The R / P ratio is an index relating to the hot-melt properties of the composition of the present invention. In the present invention, if the R / P ratio is 1.80 or less, the surface of the composition will have high tack at room temperature (e.g., 15 to 30°C, preferably 20 to 25°C; hereinafter, the same applies unless a specific temperature is specified), resulting in reduced workability. Furthermore, if the R / P ratio is too low, a hot-melt composition having flowability at room temperature will not be obtained. The lower limit of the R / P ratio is also preferably 1.85 or more, 1.90 or more, 1.95 or more, 2.00 or more, 2.10 or more, or 2.20 or more. The upper limit of the R / P ratio is not particularly limited, but may be, for example, 4.00 or less, 3.50 or less, 3.00 or less, 2.90 or less, 2.80 or less, or 2.70 or less. As used herein, the terms "hot melt type" or "having hot melt properties" refer to a property in which the softening point of a composition is between 50 and 200°C, the composition is solid at room temperature and does not have fluidity, but becomes fluid when heated to a high temperature (e.g., above 50°C). As used herein, "non-fluidity" means that the composition does not deform and / or flow in the absence of an external force. Non-fluidity can be evaluated, for example, by placing a molded composition of one embodiment of the present invention on a hot plate at 25°C and visually observing whether the composition does not substantially deform and / or flow in the absence of an external force or when a certain load is applied to the composition. As used herein, "adhesion" encompasses mechanical adhesion, chemical adhesion, and physical adhesion, regardless of the mechanism.Mechanical adhesion includes adhesion utilizing the so-called anchor effect, in which the composition penetrates into the irregularities of the adherend and hardens to fix the interface. Chemical adhesion includes adhesion called primary bonding, in which the composition and adherend are bonded by chemical interaction (e.g., covalent bond). Physical adhesion includes adhesion called secondary bonding, in which the composition spreads on the surface of the adherend and adheres by physical interaction (e.g., van der Waals force). Each component constituting the composition of the present invention will be described in detail below.

[0009] 1.1 Component (A): Linear Organopolysiloxane Component (A) is a linear organopolysiloxane that serves as a base polymer. The composition of the present invention contains, as component (A), a linear organopolysiloxane having two or more alkenyl groups in the molecule. In one embodiment of the present invention, the alkenyl group may be an alkenyl group having 2 to 12 carbon atoms. Specific examples of alkenyl groups having 2 to 12 carbon atoms include vinyl, propenyl (including allyl), butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups. These groups also include structural isomers. 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, still more preferably a group selected from the group consisting of vinyl, allyl, and hexenyl, with vinyl or hexenyl being particularly preferred. Furthermore, the bonding position of the alkenyl group in component (A) may be, for example, at the molecular chain terminal and / or at a molecular chain side chain, but component (A) preferably has an alkenyl group bonded to a silicon atom at a site other than the molecular chain terminal, and more preferably has an alkenyl group at a molecular chain side chain.

[0010] In component (A), the silicon-bonded group other than an alkenyl group may be a monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds. Specific examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds include alkyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups. Specific examples of the alkyl groups include methyl groups, ethyl groups, propyl groups such as n-propyl and isopropyl groups, butyl groups such as n-butyl, isobutyl, s-butyl, and t-butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, and dodecyl groups. These groups also include structural isomers. Specific examples of the aryl groups include phenyl groups, tolyl groups, xylyl groups, and naphthyl groups. Specific examples of the aralkyl groups include benzyl groups, phenethyl groups, 3-phenylpropyl groups, and 4-phenylbutyl groups. The halogenated alkyl group may be a group in which some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group have been substituted with halogen atoms such as chlorine atoms or bromine atoms, and specific examples include a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, etc. Among these, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, and even more preferably a methyl group or a phenyl group.

[0011] The molecular structure of component (A) may be linear, partially branched linear, branched, cyclic, network, dendritic, or the like. In one embodiment of the present invention, component (A) may be a mixture of two or more of these molecular structures. In another embodiment of the present invention, component (A) may be one or more selected from the group consisting of linear organopolysiloxanes, branched organopolysiloxanes, and mixtures thereof. In another embodiment of the present invention, component (A) may be a linear organopolysiloxane.

[0012] Specific examples of linear organopolysiloxanes include dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, dimethylpolysiloxanes capped at both molecular chain terminals with dimethylvinylsiloxy groups, methylphenylpolysiloxanes capped at both molecular chain terminals with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular chain terminals with dimethylvinylsiloxy groups, and dimethylpolysiloxane-methylvinylsiloxane copolymers capped at both molecular chain terminals with dimethylvinylsiloxy groups. trimethylphenylpolysiloxane copolymer, dimethylsiloxane-methylvinylsiloxane copolymer with both molecular chain terminals blocked by dimethylphenylsiloxy groups, dimethylpolysiloxane with both molecular chain terminals blocked by methylvinylphenylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer with both molecular chain terminals blocked by trimethylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer with both molecular chain terminals blocked by dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer with both molecular chain terminals blocked by dimethylphenylsiloxy groups, and the like.

[0013] Branched organopolysiloxanes include, for example, MDT resins, MQ resins, MDQ resins, MTQ resins, MDTQ resins, TD resins, TQ resins, and TDQ resins, which are composed of any combination of triorganosiloxy units (M units) (organo groups are methyl groups only, or methyl groups and vinyl groups or phenyl groups), diorganosiloxy units (D units) (organo groups are methyl groups only, or methyl groups and vinyl groups or phenyl groups), monoorganosiloxy units (T units) (organo groups are methyl groups, vinyl groups, or phenyl groups), and siloxy units (Q units). Depending on the combination of M units, D units, T units, and Q units, the branched organopolysiloxane can be liquid (e.g., oil-like) or solid (e.g., resin-like) at room temperature.

[0014] In one embodiment of the present invention, component (A) has a state of oil or crude rubber at room temperature. When the composition of one embodiment of the present invention is a solventless or low-solvent composition, from the viewpoint of coatability, component (A) preferably has a state of oil at room temperature. In this case, component (A) preferably has a viscosity at 25°C of 1 to 100,000 mPa·s, more preferably 10 to 50,000 mPa·s, and even more preferably 100 to 10,000 mPa·s. Furthermore, when the composition of one embodiment of the present invention is a solvent-based composition, component (A) preferably has a state of crude rubber at room temperature. In this case, at least a portion of component (A) preferably has a viscosity of more than 100,000 mPa s at 25°C, or a plasticity measured in accordance with the method specified in JIS K6249 (a 4.2 g spherical sample is subjected to a load of 1 kgf for 3 minutes at 25°C, the thickness is read to the nearest 1 / 100 mm, and this value is multiplied by 100) in the range of 50 to 200, more preferably in the range of 80 to 180, and even more preferably in the range of 100 to 150. In this specification, viscosity refers to a value measured at 25°C using a B-type viscometer.

[0015] In one embodiment of the present invention, the content of alkenyl groups in component (A) is preferably in the range of 0.001 to 10.0 mass%, more preferably in the range of 0.005 to 5.0 mass%, and even more preferably in the range of 0.01 to 3.0 mass%, relative to the mass of component (A). In particular, vinyl (CH ２ The content of the (═CH—) moiety (hereinafter referred to as the “vinyl group content”) is preferably in the range of 0.005 to 10.0 mass%, more preferably in the range of 0.01 to 5.0 mass%, even more preferably in the range of 0.10 to 2.0 mass%, and particularly preferably in the range of 0.30 to 1.0 mass%.

[0016] In one embodiment of the present invention, the content of component (A) is preferably in the range of 1.0 to 50.0 mass%, more preferably 5.0 to 40.0 mass%, and even more preferably 10.0 to 30.0 mass%, based on the total amount (100 mass%) of the composition.

[0017] 1.2 Component (B): Organopolysiloxane Component Component (B) is a component that provides the hot-melt properties of the composition of the present invention and adjusts the adhesive strength of the cured product obtained from the composition to a substrate. The composition of the present invention contains, as component (B), two or more organopolysiloxane components containing no aliphatic unsaturated bonds selected from the following components (B1) to (B3). A composition of one embodiment of the present invention contains component (B3) as component (B). Combinations of component (B) in the composition of one embodiment of the present invention include components (B1) and (B3), components (B2) and (B3), and components (B1) and (B2). Among these, a combination of components (B1) and (B3) is preferred from the standpoint of hot-melt properties. Note that, from the standpoint of preventing contact failure, the low-molecular-weight siloxane oligomers in component (B) may be reduced or eliminated.

[0018] In one embodiment of the present invention, the content of component (B) is preferably 70.0 to 95.0 mass%, more preferably 74.0 to 90.0 mass%, and even more preferably 75.0 to 85.0 mass%, based on the total amount (100 mass%) of the composition. By ensuring that the content of component (B) is within the above range, the adhesiveness of the cured product obtained from the composition of the present invention to the substrate surface can be improved. Furthermore, by using more than 100 mass parts of component (B) per 100 mass parts of component (A), the cured product can form a strong bond with the substrate surface, resulting in a permanent adhesion mode in which the cured layer undergoes cohesive failure upon peeling. In one embodiment of the present invention, the content of component (B) is preferably 100 to 500 mass parts, more preferably 200 to 450 mass parts, and even more preferably 250 to 450 mass parts per 100 mass parts of component (A).

[0019] <Component (B1)> Component (B1) is a compound having R １ ３ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and a siloxane unit (M unit) represented by SiO ４／２wherein the ratio of M units to 1 mole of Q units is in the range of 0.50 to 2.00. This ratio is preferably in the range of 0.50 to 1.50, more preferably in the range of 0.60 to 1.20, and even more preferably in the range of 0.80 to 1.10. By ensuring that this ratio is in the above range, it is possible to improve the adhesion of a cured product obtained from the composition of the present invention to a substrate, and also to improve the cohesive strength of the materials that make up the cured layer (cured product).

[0020] Component (B1) has the general unit formula: (R １ ３ SiO １／２ ) ａ (SiO ４／２ ) ｂ (In the formula, R １ each independently represents a monovalent organic group, a and b are each a positive number, a+b=1, and a / b=0.50 to 2.00. １ The monovalent organic group that can be selected as R is, for example, a monovalent hydrocarbon group. The monovalent hydrocarbon group may be, for example, a monovalent hydrocarbon group having 1 to 12 carbon atoms, and specific examples and a preferred embodiment thereof may be the same as those described above in "1.1 Component (A): Linear Organopolysiloxane." Component (B1) may be composed only of M units and Q units, or may be composed of R ２ SiO ２／２ units (D units), and / or RSiO ３／２ In the formula, R independently represents a monovalent organic group, and a specific example and a preferred embodiment thereof are R １ When component (B1) contains D units and / or T units, the total content of M units and Q units in component (B1) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more.

[0021] The organopolysiloxane resin of component (B1) preferably has a weight-average molecular weight (Mw) in the range of 2,000 to 50,000, as measured by gel permeation chromatography (GPC) relative to standard polystyrene. The lower limit of the weight-average molecular weight (Mw) is more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more. The upper limit of the weight-average molecular weight (Mw) is more preferably 30,000 or less, even more preferably 15,000 or less, and particularly preferably 10,000 or less. In particular, the combination of component (A) having the above-mentioned vinyl group content with component (B1) having the above-mentioned molecular weight can produce a cured product with a high shear storage modulus at room temperature and a high tensile stress at 500% strain.

[0022] Furthermore, component (B1) can be one from which high-molecular-weight components that tend to aggregate into a gel, increase the haze value, and reduce low-temperature curing properties have been removed in advance. Specifically, component (B1) contains an organopolysiloxane resin with a weight-average molecular weight (Mw) of 100,000 or more in an amount of less than 1 mass%, less than 0.5 mass%, less than 0.1 mass%, or 0 mass% of the total composition. This allows the cured product obtained from the composition of the present invention to have an organopolysiloxane cured layer with a low haze value.

[0023] Specifically, component (B1) may be any of the following: (MeSiO 1 / 2 ) 0.40 (SiO 4 / 2 ) 0.60 (HO 1 / 2 ) 0.10 (Me3SiO 1 / 2 ) 0.52 (SiO 4 / 2 ) 0.48 (HO 1 / 2 ) 0.01 (Me3SiO 1 / 2 ) 0.45 (SiO 4 / 2 ) 0.55 (MeO 1 / 2 ) 0.10 (Me3SiO 1 / 2 ) 0.25 (Me2PhSiO 1 / 2 ) 0.20 (SiO4 / 2 ) 0.55 (HO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.40 (MeSiO 2 / 2 ) 0.05 (SiO 4 / 2 ) 0.55 (HO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.40 (MeSiO 3 / 2 ) 0.05 (SiO 4 / 2 ) 0.55 (HO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.40 (MeSiO 2 / 2 ) 0.05 (MeSiO 3 / 2 ) 0.05 (SiO 4 / 2 ) 0.50 (HO 1 / 2 ) 0.05 (In each formula, Me represents a methyl group, Ph represents a phenyl group, MeO represents a methoxy group, and HO represents a silicon-bonded hydroxyl group. In order to represent the relative amount of hydroxyl groups to silicon atoms, the sum of the subscripts of the silicon-containing units is set to 1, and (HO) １／２ The subscript of the unit indicates the relative amount.)

[0024] In one embodiment of the present invention, when component (B1) is contained as component (B), the content of component (B1) is preferably in the range of 30.0 to 99.0 mass%, more preferably 50.0 to 90.0 mass%, and even more preferably 60.0 to 80.0 mass%, based on the total amount (100 mass%) of the composition.

[0025] <Component (B2)> Component (B2) is a linear or branched diorganopolysiloxane. In one embodiment of the present invention, component (B2) is a linear or branched diorganopolysiloxane that does not contain a carbon-carbon multiple bond in the molecule. In one embodiment of the present invention, component (B2) is more specifically a diorganopolysiloxane represented by the formula {R ２ ２ SiO ２／２} ｍ (In the formula, R２ In component (B2), R is a linear or branched diorganopolysiloxane having siloxane units (D units) represented by the formula: ２ Examples of monovalent organic groups that can be selected as m include monovalent hydrocarbon groups. The monovalent hydrocarbon group may be, for example, a monovalent hydrocarbon group having 1 to 12 carbon atoms, and specific examples and a suitable embodiment thereof may be the same as those described above in "1.1 Component (A): Linear Organopolysiloxane." The monovalent hydrocarbon group may also be a silanol group. m may be any number equal to or greater than 2, but from the standpoint of hot-melt properties, a number in the range of 5 to 5,000 is preferred, a number in the range of 10 to 3,000 is more preferred, and a number in the range of 10 to 2,000 is even more preferred.

[0026] The state of component (B2) at room temperature is either oily or rubbery, preferably rubbery. When component (B2) is rubbery, it is preferable that at least a portion of component (B2) has a viscosity of more than 1,000,000 mPa s at 25°C or a plasticity measured in accordance with the method specified in JIS K6249 (the measurement method is as described above) in the range of 50 to 200, more preferably 80 to 180, and even more preferably 130 to 180.

[0027] In one embodiment of the present invention, when component (B2) is contained as component (B), the content of component (B2) is preferably in the range of 1.0 to 30.0 mass%, more preferably 5.0 to 20.0 mass%, and even more preferably 7.0 to 15.0 mass%, based on the total amount (100 mass%) of the composition.

[0028] <Component (B3)> Component (B3) is an organopolysiloxane resin in which component (B1) and component (B2) are chemically bonded. In one embodiment of the present invention, when component (B) contains, for example, two types of components, component (B1) and component (B3), or two types of components, component (B2) and component (B3), component (B1) and component (B2) constituting component (B3) may be the same as or different from component (B1) or component (B2) contained separately from component (B3), respectively.

[0029] In one embodiment of the present invention, component (B3) is the following: (b3-1)R １ ３ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and a siloxane unit (M unit) represented by SiO ４／２ (b3-2) a resinous organosiloxane block containing a siloxane unit (Q unit) represented by the formula: {R ２ ２ SiO ２／２} ｍ (In the formula, R ２ wherein each independently represents a monovalent organic group, and m is a number of 2 or greater), and a resin-linear structure-containing organopolysiloxane block copolymer having a structure in which the following are linked by a chemical bond: a linear organosiloxane block having a siloxane unit (D unit) represented by the formula:

[0030] The method for linking the resinous organopolysiloxane that provides block X with the linear organosiloxane that provides block Y is not particularly limited, as long as it is a reaction that can chemically link the two blocks. Specific examples of such a reaction include a condensation reaction or a hydrosilylation reaction. In the case of a condensation reaction, blocks X and Y are linked via a siloxane bond, and in the case of a hydrosilylation reaction, blocks X and Y are linked via a silalkylene bond. In one embodiment of the present invention, from the viewpoint of durability, blocks X and Y are preferably linked via a siloxane bond. For more specific production methods of such resin-linear structure-containing organopolysiloxane block copolymers, see, for example, International Publication No. 2023 / 017746 (Patent Document 4).

[0031] In one embodiment of the present invention, the content ratio of component (b3-1) to component (b3-2) in component (B3) [component (b3-1):component (b3-2)] is preferably 99:1 to 1:99 by mass, more preferably 80:20 to 20:80, even more preferably 70:30 to 30:70, and particularly preferably 60:40 to 40:60.

[0032] In one embodiment of the present invention, when component (B3) is contained as component (B), the content of component (B3) is preferably in the range of 1.0 to 30.0 mass%, more preferably 2.0 to 20.0 mass%, and even more preferably 3.0 to 15.0 mass%, based on the total amount (100 mass%) of the composition.

[0033] In one embodiment of the present invention, when component (B) contains component (B1) and component (B3), the content of component (B3) relative to the total amount (100 parts by mass) of components (A) and (B1) is preferably in the range of 1.0 to 30.0 parts by mass, more preferably 2.0 to 20.0 parts by mass, and even more preferably 3.0 to 15.0 parts by mass.

[0034] 1.3 Component (C): Monofunctional or Polyfunctional Vinyl Monomer Component (C) is a radical-reactive component involved in a curing reaction by radical polymerization. The composition of the present invention contains a monofunctional or polyfunctional vinyl monomer as component (C). The monofunctional vinyl monomer is a monomer having one ethylenically unsaturated bond, such as a vinyl group, vinylene group, or vinylidene group, in the molecule. The polyfunctional vinyl monomer is a monomer having two or more ethylenically unsaturated bonds, such as a vinyl group, vinylene group, or vinylidene group, in the molecule. In one embodiment of the present invention, the monofunctional vinyl monomer may be a monofunctional (meth)acrylate monomer. In another embodiment of the present invention, the polyfunctional vinyl monomer may be a polyfunctional (meth)acrylate monomer. In this specification, "(meth)acrylate" refers to acrylate and / or methacrylate. Similarly, "(meth)acrylic" means acrylic and / or methacrylic, and "(meth)acryloyl" means acryloyl and / or methacryloyl.

[0035] <Monofunctional (meth)acrylate Monomer> Examples of the monofunctional (meth)acrylate monomer include a hydrocarbon group (including a saturated hydrocarbon group, an unsaturated hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc.)-containing (meth)acrylate, an amide group-containing (meth)acrylate, a hydroxyl group-containing (meth)acrylate, a fluorine-containing (meth)acrylate, an epoxy group-containing (meth)acrylate, a carboxyl group-containing (meth)acrylate, an ether bond-containing (meth)acrylate, and a silicon-containing (meth)acrylate.

[0036] Specific examples of the hydrocarbon group-containing (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 3,3,5-tricyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.

[0037] Specific examples of the amide group-containing (meth)acrylate include (meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, isobutoxymethoxy(meth)acrylamide, and N,N-dimethyl(meth)acrylamide.

[0038] Specific examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.

[0039] Specific examples of the fluorine-containing (meth)acrylate include trifluoropropyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, and perfluorooctylethyl (meth)acrylate.

[0040] Specific examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0041] Specific examples of the carboxyl group-containing (meth)acrylate include mono(2-acryloyloxyethyl) succinate, mono-2-(methacryloyloxy)ethyl phthalate, monohydroxyethyl phthalate acrylate, and ω-carboxy-polycaprolactone monoacrylate.

[0042] Specific examples of the ether bond-containing (meth)acrylate include tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, and diethylene glycol monomethyl ether (meth)acrylate.

[0043] Specific examples of the silicon-containing (meth)acrylate include (meth)acryloxypropyltrimethoxysilane.

[0044] <Polyfunctional (meth)acrylate Monomer> The polyfunctional (meth)acrylate monomer includes, for example, a (meth)acrylate having two (meth)acryloyl groups in the molecule, and a (meth)acrylate having three or more (meth)acryloyl groups in the molecule.

[0045] Specific examples of the (meth)acrylate having two (meth)acryloyl groups in the molecule include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, butylethylpropanediol di(meth)acrylate, 3-methyl-1,7-octanediol di(meth)acrylate, and 2-methyl-1,8-octanediol di(meth)acrylate. ethoxylated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, and 1,1,1-trishydroxymethylethane di(meth)acrylate.

[0046] Specific examples of the (meth)acrylate having three or more (meth)acryloyl groups in the molecule include trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, monopentaerythritol (meth)acrylate, dipentaerythritol (meth)acrylate, tripentaerythritol (meth)acrylate, and polypentaerythritol (meth)acrylate.

[0047] <Other Vinyl Monomers> Component (C) may contain a monofunctional or polyfunctional vinyl monomer other than the above-mentioned monofunctional or polyfunctional (meth)acrylate monomers. Such other monofunctional or polyfunctional vinyl monomers may be, for example, styrene-based monomers, vinyl ethers, vinyl amides, vinyl esters, carboxylic acid-based monomers, etc.

[0048] Specific examples of the monofunctional styrene-based monomer include alkyl-substituted styrenes such as styrene, 4-methylstyrene, and 4-ethylstyrene; halogen-substituted styrenes such as p-chlorostyrene and p-bromostyrene; etc. Specific examples of the polyfunctional styrene-based monofunctional monomers include 1,3-divinylbenzene, 1,4-divinylbenzene, etc.

[0049] Specific examples of monofunctional vinyl ethers include linear vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, trifluoroethyl vinyl ether, n-propyl vinyl ether, 2-methoxyethyl vinyl ether, and diethylene glycol ethyl vinyl ether; aliphatic ring-containing vinyl ethers such as cyclohexyl vinyl ether and 2-(vinyloxy)tetrahydropyran; aromatic ring-containing vinyl ethers such as phenyl vinyl ether, benzyl vinyl ether, and 4-methoxybenzyl vinyl ether; etc. Specific examples of polyfunctional vinyl ethers include linear vinyl ethers such as diethylene glycol divinyl ether, divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, triethylene glycol divinyl ether, and bis(vinyloxybutyl)succinate; and aliphatic ring-containing vinyl ethers such as 1,4-cyclohexanedimethanol divinyl ether.

[0050] Specific examples of vinylamides include monofunctional vinylamides such as N-vinylformamide, N-vinylacetamide, and N-vinylpyrrolidone. Specific examples of vinyl esters include monofunctional vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate, and vinyl stearate. Specific examples of carboxylic acid monomers include monofunctional carboxylic acid monomers such as (meth)acrylic acid, 2-(trifluoromethyl)acrylic acid, 6-acrylamidohexanoic acid, 4-carboxystyrene, itaconic acid, crotonic acid, fumaric acid, and maleic acid.

[0051] These monofunctional and polyfunctional vinyl monomers may be used alone or in combination of two or more types of monofunctional vinyl monomers. Similarly, one polyfunctional vinyl monomer may be used alone or in combination of two or more types of polyfunctional vinyl monomers. Furthermore, a monofunctional vinyl monomer and a polyfunctional vinyl monomer may be combined.

[0052] In one embodiment of the present invention, component (C) contains a monofunctional or polyfunctional vinyl monomer having 8 to 30 carbon atoms. The number of carbon atoms in the vinyl monomer is preferably 10 to 30, and more preferably 13 to 30. Among the above-mentioned vinyl monomers, 1,12-dodecanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. are particularly preferred.

[0053] In one embodiment of the present invention, the content of component (C) is preferably in the range of 0.01 to 10.0 mass%, more preferably 0.1 to 5.0 mass%, and even more preferably 0.3 to 2.0 mass%, based on the total amount (100 mass%) of the composition. By adjusting the content of component (C) within the above range, the non-flowability of the composition can be improved.

[0054] 1.4 Component (D): Radical Polymerization Initiator Component (D) is a component for initiating radical polymerization. Component (D) may be a photoradical polymerization initiator or a thermal radical polymerization initiator, but a photoradical polymerization initiator is preferred. The photoradical polymerization initiator is a component that promotes the photocuring reaction of the alkenyl group in component (A) and the vinyl monomer of component (C) by irradiation with high-energy rays such as ultraviolet rays. The photoradical polymerization initiator may be one that can promote the curing reaction not only by irradiation with high-energy rays such as ultraviolet rays, but also by irradiation with light in the visible light range.

[0055] Examples of the photoradical polymerization initiator include α-ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, bisacylphosphine oxides, monoacylphosphine oxides, anthraquinones, benzoic acid esters, and titanocenes.

[0056] Specific examples of the α-ketol compounds include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, and 1-hydroxycyclohexylphenyl ketone.

[0057] Specific examples of the acetophenone compounds include methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1.

[0058] Specific examples of the benzoin ether compounds include benzoin ethyl ether, benzoin isopropyl ether, anisoin methyl ether, and anisoin ethyl ether.

[0059] Specific examples of the ketal compounds include benzyl dimethyl ketal, etc. Specific examples of the aromatic sulfonyl chloride compounds include 2-naphthalenesulfonyl chloride, etc. Specific examples of the photoactive oxime compounds include 1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime, etc. Specific examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone, etc. Specific examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone, etc.

[0060] Specific examples of the bisacylphosphine oxides include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0061] Specific examples of the monoacylphosphine oxides include 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide.

[0062] Specific examples of the anthraquinones include anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone. Specific examples of the benzoic acid esters include ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester. Specific examples of the titanocenes include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium.

[0063] In addition to the above, the photoradical polymerization initiator may also be camphorquinone, halogenated ketone, phenyl disulfide 2-nitrofluorene, butyroin, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. The above-mentioned photoradical polymerization initiators may be used alone or in combination of two or more.

[0064] Commercially available acetophenone-based photopolymerization initiators suitable as component (C1) include Omnirad 907, 369, 369E, 379, and 651 manufactured by IGM Resins. Commercially available acylphosphine oxide-based photopolymerization initiators include Omnirad TPO, TPO-L, and 819 manufactured by IGM Resins. Commercially available oxime ester-based photopolymerization initiators include Irgacur OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919, ADEKA Arcles NCI-831, and NCI-831E manufactured by ADEKA Corporation, and TR-PBG-304 manufactured by Changzhou New Advanced Electronic Materials Co., Ltd.

[0065] In one embodiment of the present invention, the content of component (D) is preferably in the range of 0.01 to 10.0 mass%, more preferably 0.1 to 5.0 mass%, and even more preferably 0.3 to 3.0 mass%, based on the total amount (100 mass%) of the composition.

[0066] 1.5 Optional Components In addition to components (A) to (D), the composition of one embodiment of the present invention may contain other optional components as needed. Examples of such optional components include other optional organopolysiloxanes; photosensitizers; adhesion promoters; antioxidants such as phenols, quinones, amines, phosphorus, phosphites, sulfur, and thioethers; light stabilizers such as triazoles and benzophenones; flame retardants such as phosphate esters, halogens, phosphorus, and antimony; antistatic agents such as cationic surfactants, anionic surfactants, and nonionic surfactants; polymerization inhibitors; and ultraviolet absorbers. In addition to these components, other optional components include pigments, dyes, and inorganic fine particles (reinforcing fillers, dielectric fillers, conductive fillers, and thermally conductive fillers) that may be optionally surface-treated.

[0067] The composition of one embodiment of the present invention may or may not contain an organic solvent. The composition of one embodiment of the present invention is solid at room temperature or has poor fluidity, and therefore may be a substantially low-solvent or solvent-free composition. In this case, the unavoidable inclusion of a small amount of organic solvent is acceptable. In a substantially low-solvent or solvent-free composition, the organic solvent content may be less than 0.5 mass%, less than 0.1 mass%, less than 0.05 mass%, less than 0.01 mass%, or less than 0.001 mass%, based on the total amount (100 mass%) of the composition. Furthermore, the composition of another embodiment of the present invention may be temporarily mixed with an organic solvent as a diluent or dispersion medium, for example, when uniformly mixing various components or when molding into various shapes described below. Furthermore, a dispersion of the composition of one embodiment of the present invention dispersed in an organic solvent may be applied to mold into various shapes described below. In this case, it is preferable to finally remove the organic solvent by means of heat drying or the like. When the composition of one embodiment of the present invention is mixed with an organic solvent, the amount of the organic solvent is, for example, 1 to 100 parts by mass, preferably 1 to 50 parts by mass, and more preferably 1 to 25 parts by mass, relative to 100 parts by mass of the total amount of the composition of one embodiment of the present invention containing components (A) to (D).

[0068] Specific examples of organic solvents that can be used in one embodiment of the present invention include aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as heptane, hexane, octane, and isoparaffin; ester solvents such as ethyl acetate and isobutyl acetate; ether solvents such as diisopropyl ether and 1,4-dioxane; chlorinated aliphatic hydrocarbon solvents such as trichloroethylene, perchloroethylene, and methylene chloride; volatile oils; etc. Two or more of these organic solvents may be combined depending on the wettability of the substrate, etc.

[0069] 1.6 Properties of the Composition of the Present Invention The composition of the present invention is a hot-melt composition that is solid or non-flowable at room temperature and can be handled in the form of granules, pellets, sheets, films, and the like. The composition of one embodiment of the present invention is preferably one that, when molded into pellets, tablets, or the like, does not deform and / or flow at room temperature and in the absence of external force. Being non-flowable at room temperature provides good shape retention for the composition. Furthermore, in this case, the composition has low surface tack, allowing it to be easily handled even in an uncured state. Furthermore, the softening point of the composition of one embodiment of the present invention is preferably 100°C or lower. This softening point refers to the temperature at which, when a 22 mm-high piece of the composition is pressed down on a hot plate with a 100-gram load for 10 seconds, and the deformation of the composition is measured after the load is removed, the deformation in the height direction is 1 mm or more.

[0070] The composition of one embodiment of the present invention has a storage modulus (MPa) at 25°C, measured by the method described in the Examples below, of preferably 0.50 or more, more preferably 0.60 or more, even more preferably 0.70 or more, and preferably 3.50 or less, more preferably 3.40 or less, and even more preferably 3.30 or less. The composition of one embodiment of the present invention has a storage modulus (MPa) at 80°C, measured by the method described in the Examples below, of preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and preferably 0.10 or less, more preferably 0.09 or less, and even more preferably 0.08 or less.

[0071] The composition of one embodiment of the present invention has a complex viscosity (10 ３ The composition of one aspect of the present invention has a complex viscosity (10 Pa·s) at 80°C measured by the method described in the Examples below. ３The viscosity (Pa·s) is preferably 2.5 or more, more preferably 3.0 or more, and even more preferably 4.0 or more, and is preferably 50.0 or less, more preferably 40.0 or less, and even more preferably 30.0 or less.

[0072] 1.7 Production Method, Form, and Use of the Composition of the Present Invention The composition of one embodiment of the present invention can be produced by uniformly mixing components (A) to (D) and any optional components used as needed at room temperature using mechanical force such as a mixer. As described above, an organic solvent may be added as needed during this process. The composition of one embodiment of the present invention can be in the form of granules, pellets, sheets, films, and the like.

[0073] The composition of one embodiment of the present invention can be formed into a sheet or film by, for example, a method including the following steps: (I): applying the composition of one embodiment of the present invention onto a substrate; and (II): heating and drying the composition applied in (I) above.

[0074] In the above (I), when the composition of one embodiment of the present invention is applied to a substrate, the composition may be heated and melted, and then applied to the substrate in a fluid state. Alternatively, the composition of one embodiment of the present invention may be dispersed in an organic solvent, applied to the substrate in the form of a dispersion, and the organic solvent may be removed in the above (II). Molding into a sheet or film may be performed in the above (I), or may be performed in both the above (I) and (II). Note that, when a release layer is present on the substrate, the sheet or film that is one embodiment of the composition of the present invention can be obtained as part of the release laminate described below.

[0075] When the composition of one embodiment of the present invention is molded into a sheet or film, the average thickness may be 1 to 3000 μm, 5 to 2000 μm, or 10 to 1000 μm.

[0076] The composition of the present invention is a hot-melt curable organopolysiloxane composition containing the above-mentioned components, and has hot-melt properties. Furthermore, the composition of one embodiment of the present invention is excellent in handleability during melting (hot-melting), curability, transparency, and adhesiveness, and is therefore suitable for use in semiconductor components such as sealants for light-emitting or optical devices, adhesive materials, and light reflectors. More specifically, the composition is suitable for use as a sealant for semiconductors (including optical semiconductors); a sealant for power semiconductors such as SiC and GaN; and an adhesive, potting agent, protective agent, and coating agent for electrical and electronic applications.

[0077] Furthermore, a sheet or film that is an embodiment of the composition of the present invention has excellent moldability, gap-filling properties, and adhesive properties, and is therefore suitable for use as an encapsulant for semiconductors that are manufactured using press molding, compression molding, overmolding, or the like. The sheet or film is also suitable as a material for sealing or adhering large-area substrates using a vacuum laminator or the like. Furthermore, the sheet or film can also be used as a curable film adhesive or a stress buffer layer between two substrates with different linear expansion coefficients. Thus, the composition of one embodiment of the present invention may be an encapsulant intended for single-sided sealing, or may be an encapsulant intended for double-sided sealing that involves adhesion between two substrates.

[0078] Furthermore, a sheet or film, which is one embodiment of the composition of the present invention, can be peeled from the release film described below, placed at a desired position on a semiconductor or the like, and melted by heating to provide a cured layer on or between adherends that has gap-filling properties for irregularities and gaps on the semiconductor substrate. After the sheet or film is temporarily fixed, placed, or bonded to the adherend or between the adherends, the uncured composition can be cured by a radical polymerization reaction (e.g., a heat-curing reaction, a photocuring reaction, etc.) to form a cured product of the composition (including the form of a sheet or film) of one embodiment of the present invention, allowing the adherend to be bonded. Furthermore, because the sheet or film has hot-melt properties, heating the sheet or film before final curing softens or fluidizes it. For example, even if there are irregularities or gaps on the adherend's surface, the irregularities or gaps can be filled without gaps, forming an adhesive surface with the adherend. Examples of means for heating the sheet or film include various types of thermostatic baths, hot plates, electromagnetic heating devices, heating rolls, electric heating presses, diaphragm-type laminators, and roll laminators.

[0079] 2. Laminate and Method for Producing the Same

[0023] In one aspect, the present invention provides a laminate (hereinafter also referred to as "the laminate of the present invention") comprising the hot-melt curable organopolysiloxane composition described above in "1. Hot-melt curable organopolysiloxane composition." The laminate of the present invention comprises a composition of one embodiment of the present invention and a substrate having a release surface, attached to one or both sides of the sheet- or film-like composition. The laminate of one embodiment of the present invention is a three-layer laminate in which a sheet or film of one embodiment of the composition of the present invention is laminated between two sheet- or film-like substrates having release surfaces. The laminate of one embodiment of the present invention is a two-layer laminate in which a sheet or film of one embodiment of the composition of the present invention is laminated adjacent to one sheet or film-like substrate having a release surface. The sheet or film of one embodiment of the composition of the present invention is releasable from a sheet or film-like substrate having a release surface (generally also referred to as a release film; hereinafter, appropriately referred to as a "release film"). Furthermore, as described below, a cured product of the composition of one embodiment of the present invention is also releasable from the substrate. For this reason, the laminate of one embodiment of the present invention can also be called a peelable laminate. Note that, in the laminate of one embodiment of the present invention, the thickness of the release film is not particularly limited, and in this specification, sheets or films are collectively referred to as "release films" regardless of their thickness.

[0080] The three-layer laminate of one embodiment of the present invention can be produced, for example, by a method including the following. The two-layer laminate of one embodiment of the present invention can be produced in accordance with the method for producing a three-layer laminate. (A): Mixing the components of the composition of one embodiment of the present invention; (B): Kneading the mixture obtained in (A) above while heating and melting it; (C): Laminating the heated and melted mixture obtained in (B) above between two release films having at least one release surface so that the mixture contacts the release surface to form a laminate; (D): Pressuring the laminate obtained in (C) above between rolls to roll out the mixture placed between the two release films to form a sheet-like or film-like laminate; (E): Optionally, cutting the laminate obtained in (D) above.

[0081] In the above (A), the mixing method and the temperature during mixing are not particularly limited and can be carried out appropriately by a conventional method. The temperature during mixing may be, for example, heated to 50° C. or higher.

[0082] In the above (B), the method of kneading the mixture and the temperature of heat melting are not particularly limited. In one embodiment, the above (B) may be carried out by applying the mixture obtained in the above (A) dispersed in an organic solvent onto a release film, and removing the organic solvent by heating or the like before the above (C).

[0083] In the above (C), the method for laminating the mixture and the release film is not particularly limited. The release film that can be used in one embodiment of the present invention is preferably non-porous, and examples include polyester films, polyolefin films, polycarbonate films, and acrylic films. The release film has a release layer formed by treating one or both sides of a film containing the above materials to impart release properties. Such treatments are known in the art. The release layer is also called a release liner, separator, release layer, or release coating layer. The release layer can also be formed as a release layer having release coating properties, such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent. Furthermore, the substrate constituting the release film may have fine irregularities on its surface to reduce adhesion to the composition of one embodiment of the present invention, or a material that is less likely to adhere to a layer containing the composition of one embodiment of the present invention or a cured product thereof may be used.

[0084] In the above (D), the method of pressing and rolling is not particularly limited. For example, the sheet or film of the laminate of one embodiment of the present invention may be pressed and rolled so that the thickness thereof is 1 to 3,000 μm, 5 to 2,000 μm, or 10 to 1,000 μm. It is preferable that the sheet or film is flat. "Flat" means that the thickness of the obtained sheet or film is within a range of ±100 μm or less, preferably within a range of ±50 μm or less, and more preferably within a range of ±30 μm or less.

[0085] The cutting method of the above (E) is not particularly limited, and the obtained laminate may be cut to a desired size by a conventional method.

[0086] The three-layer laminate of one embodiment of the present invention obtained in this manner can be used, for example, by peeling off one of the two release films that can constitute the laminate, applying a sheet- or film-like member of the composition of one embodiment of the present invention in an uncured state that is not in contact with the release film to an adherend, and then peeling the other release film from the uncured sheet- or film-like member.

[0087] 3. Cured Product of the Composition of the Present Invention, and Method for Forming the Same, and Uses Thereof One aspect of the present invention provides a cured product of the composition described above in "1. Hot-melt Curable Organopolysiloxane Composition" (hereinafter also referred to as "the cured product of the present invention"). The cured product of the present invention can be produced by subjecting a composition of one embodiment of the present invention or a semi-cured product thereof (the semi-cured product will be described later) to a curing reaction (radical polymerization reaction) by irradiation with high-energy rays or heating. The cured product of one embodiment of the present invention can be produced by subjecting a composition of one embodiment of the present invention (or a semi-cured product thereof) to a photocuring reaction (photoradical polymerization reaction) by irradiation with high-energy rays. The cured product of one embodiment of the present invention may be in the form of a sheet or film. The form of the sheet and film is as described above in "1.7 Production Method, Form, and Uses of the Composition of the Present Invention."

[0088] High-energy rays that can be used in one embodiment of the present invention include, for example, ultraviolet rays, gamma rays, X-rays, α-rays, electron beams, and the like. Among these, ultraviolet rays, X-rays, and electron beams emitted from a commercially available electron beam irradiation device are preferred, and ultraviolet rays are more preferred from the viewpoint of practicality. Suitable sources of ultraviolet rays include high-pressure mercury lamps, medium-pressure mercury lamps, Xe—Hg lamps, and deep UV lamps, and the wavelength is preferably 280 to 400 nm, more preferably 300 to 400 nm. Furthermore, a light source having multiple emission bands may be used.

[0089] The amount of high-energy radiation varies depending on the type and amount of the photoradical polymerization initiator and the degree of the curing reaction. For example, in the case of ultraviolet light, the cumulative amount of radiation at a wavelength of 365 nm is 100 mJ / cm. ２ ~100 J / cm ２ It is preferable that the range is within the above range. Note that, for example, the high-energy radiation may be irradiated in a state in which the substrate or release film constituting the laminate of one embodiment of the present invention is present, as long as the substrate or release film does not absorb electromagnetic waves in the above wavelength range. In other words, as long as a certain amount of radiation can be achieved, the high-energy radiation may be irradiated through a cover material such as a substrate or release film.

[0090] When the curing reaction of one embodiment of the present invention is a photocuring reaction, the reaction does not require heating and can be cured at low temperatures, including room temperature. In this specification, "low temperature" refers to a temperature of 100°C or lower, and more specifically includes temperature ranges of 15°C to 100°C, 15°C to 80°C or lower, 15°C to 60°C, 15°C to 40°C, 15°C to 30°C, or 15°C to 25°C. When the curing reaction of the composition of one embodiment of the present invention (or a semi-cured product thereof) is allowed to proceed at a low temperature, the composition may be left standing at around room temperature (a temperature range that can be reached without heating or cooling, particularly including a temperature range of 20°C to 25°C), cooled to 15°C or higher and below room temperature, or heated to 100°C or higher and above room temperature. The time required for the curing reaction can be appropriately designed depending on the irradiation dose and temperature of high-energy rays such as ultraviolet rays. Alternatively, a semi-cured product that retains photocuring reactivity may be obtained by interrupting irradiation before a predetermined cumulative irradiation dose is reached. If desired, the semi-cured product can then be subjected to a further curing reaction.

[0091] The cured product of one embodiment of the present invention has practical resistance to yellowing under high temperature, high humidity, or ultraviolet exposure conditions, and has excellent transparency. For example, in a high temperature exposure test at 100°C or an accelerated weathering test in accordance with ASTM G 154 Cycle 1 (hereinafter referred to as a QUV test), the cured product has a thickness of 200 μm and shows a b ＊ The value is 2.0 or less, preferably 1.0 or less.

[0092] In particular, while known active energy ray-curable hot-melt silicone compositions capable of low-temperature curing (e.g., Patent Document 4, etc.) leave room for improvement in the yellowing resistance of the cured product, the cured product of one embodiment of the present invention can be rapidly cured at low temperatures, including room temperature, while still exhibiting practical yellowing resistance and high transparency. Therefore, the composition of one embodiment of the present invention and its cured product are suitable for applications such as sealing materials for optical materials and adhesive members. Examples of such optical materials include light-emitting semiconductor devices, which are light-emitting or optical devices, optical components for displays, and solar panel components. Furthermore, the composition of one embodiment of the present invention and its cured product are also suitable for applications such as sealing electronic materials, where transparency, light resistance, and heat resistance are important, and sealing substrates with poor heat resistance using a transparent cured product.

[0093] More specifically, the cured product of one embodiment of the present invention can be suitably used in semiconductor components. The cured product can be suitably used, for example, as an encapsulant for semiconductor elements and IC chips, and as adhesive materials such as pressure-sensitive adhesives, adhesives, and bonding members for semiconductor devices. Furthermore, the cured product of one embodiment of the present invention forms a permanent bond or bonded structure accompanied by cohesive failure of the cured product in peel mode, making it possible to bond substrates that block activation energy rays such as ultraviolet light. To improve the adhesion between the adherend and the cured product, the surface of the cured product or substrate may be subjected to surface treatments such as primer treatment, corona treatment, etching treatment, and plasma treatment. Furthermore, in the above cases, the surface of the cured product that is not in contact with the substrate can be designed to have adhesive properties for other substrates. That is, the surface of the cured product can also be used as a pressure-sensitive adhesive surface, a sticky surface, or an adhesive surface.

[0094] 4. Semiconductor Device and Method for Manufacturing Semiconductor Device One aspect of the present invention provides a semiconductor device comprising the cured product described above in "3. Cured Product of the Composition of the Present Invention, Method for Forming the Cured Product, and Uses thereof." Specific examples of the semiconductor device include those described above in "1.7 Method for Manufacturing, Forms, and Uses of the Composition of the Present Invention" and "3. Cured Product of the Composition of the Present Invention, Method for Forming the Cured Product, and Uses thereof."

[0095] Furthermore, as one aspect, the present invention provides a method for producing a semiconductor device (hereinafter also referred to as the "method for producing a semiconductor device of the present invention"), which includes a method for producing the composition of one aspect of the present invention in the form of a sheet or film, as described above in "1.7 Method for producing, form, and use of the composition of the present invention." Specific examples of the semiconductor device include those described above in "1.7 Method for producing, form, and use of the composition of the present invention" and "3. Cured product of the composition of the present invention, method for forming the same, and use thereof."

[0096] The method for producing a semiconductor device of the present invention is not particularly limited, and may be any method that includes at least (i) and (ii) of the method for producing a composition of the present invention in the form of a sheet or film at any stage in the manufacturing process of a semiconductor device. Furthermore, the method for producing a semiconductor device of one embodiment of the present invention may include the following (1) and (2): (1): bonding the composition of one embodiment of the present invention to a semiconductor device (including an optical semiconductor device) or a part or all of a substrate that is a precursor thereof; and (2): curing the composition by a photocuring reaction caused by irradiation with high-energy rays.

[0097] Furthermore, the method for manufacturing a semiconductor device according to one aspect of the present invention may include the following step (1') as a preliminary step to the step (1): (1'): causing the composition to flow by heating, and filling irregularities and voids in a substrate that is a semiconductor device (including an optical semiconductor device) or a precursor thereof.

[0098] In addition, when the above (1'), (1) and / or (2) are simultaneously carried out by carrying out (i) and (ii) in the method for producing the composition of the present invention in the form of a sheet or film, it is not necessarily necessary to carry out the above (1'), (1) and / or (2) separately.

[0099] The present invention will be further described below based on examples, but the present invention is not limited to the following examples.

[0100] Examples 1 to 3 and Comparative Examples 1 to 3 The following components were uniformly mixed in the proportions shown in Table 1 to prepare the curable organopolysiloxane compositions of Examples 1 to 3 and Comparative Examples 1 to 3 as toluene solutions with a solids concentration of 70%. Subsequently, in order to subject each composition to the adhesive strength evaluation test described below, it was coated onto a release film (manufactured by Nippa, FSC-6, thickness 50 μm) so that the thickness after curing would be 25 μm or 200 μm. The composition was then dried in an oven at 80°C for 10 minutes and cooled to room temperature. The release film was then placed over the composition surface to produce a release laminate with two release surfaces. In the table, "siloxane mass of composition" refers to the combined amount of component (A) and component (B) relative to the mass of the solids of the entire composition (components constituting the cured product, excluding the organic solvent). In the table, "resin / polymer ratio" refers to the ratio (R / P ratio) of the total mass R of component (B1) and component (B1) constituting component (B3) to the total mass P of component (A), component (B2), and component (B2) constituting component (B3).

[0101] <Component (A)> Dimethylsiloxane-methylvinylsiloxane copolymer crude rubber blocked at both ends with trimethylsiloxy groups (plasticity at 25°C = 130, vinyl group content: 0.70 mass%, containing two or more alkenyl groups in the molecule).

[0102] <Component (B)> Component (B1): Me in the molecule ３ SiO １／２ (wherein Me is a methyl group), and a siloxane unit (M unit) represented by the formula: ４／２ An organopolysiloxane resin (weight average molecular weight (Mw) measured by GPC using toluene as a solvent: 7000) containing siloxane units (Q units) represented by the following formula in a molar ratio of 1.0:1.0. Component (B2): A crude rubber-like polydimethylsiloxane (plasticity at 25°C: 170). Component (B3): A reaction product obtained by dehydration condensation of components (B1) and (B2) in a mass ratio (B1:B2) of 60:40.

[0103] <Component (C)> 1,12-dodecanediol di(meth)acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0104] <Component (D)> Component (D1): 2,2-dimethoxy-2-phenylacetophenone (product name: Omnirad 651, manufactured by IGM Resins) Component (D2): (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide (product name: Omnirad TPO-L, manufactured by IGM Resins).

[0105] [Storage Modulus and Complex Viscosity of Curable Organopolysiloxane Composition] A film-like composition (uncured product) with a thickness of 200 μm was placed in close contact between a shear rotation jig and a sample stage, and the temperature of the sample was raised from 25° C. to 100° C. at a rate of 3° C. / min using an Anton Paar MCR302, while applying shear stress to the sample (shear strain 0.05%, frequency 1 Hz), and the storage modulus and complex viscosity were measured.

[0106] [Adhesion strength and adhesion evaluation] The release film on one side of the prepared peelable laminate (thickness 25 μm) was peeled off, and the laminate was attached to PET (polyethylene terephthalate). Thereafter, ultraviolet light with a wavelength of 365 nm was irradiated from the other release film side of the laminate with an integrated light amount of 1,000 mJ / cm. ２ The composition was cured by irradiating the laminate so that the cured product (cured layer) surface was 25.4 mm (1 inch) wide. The release film was then peeled off, and the cured product (cured layer) surface was attached to a stainless steel plate (manufactured by Partec) using a roller to prepare a test specimen. The test specimen was stored at 25°C and 50% relative humidity (RH) for 1 hour, and the adhesive strength of the test specimen was measured at a tensile speed of 150 mm / min in accordance with the 180° peel test method in accordance with JIS Z 0237. The results are shown in Table 1. In Table 1, the unit gf / inch can be converted to N / 25 mm. The adhesiveness of the cured product was evaluated based on the fracture mode in the peel test. Specific examples include a case where peeling occurred at the interface between the cured product (cured layer) and the SUS plate, classified as "C," a case where the cured product (cured layer) itself underwent cohesive failure, classified as "A," and a case where the cured product (cured layer) itself underwent partial cohesive failure, classified as "B," and cases classified as "A" were judged to be acceptable.

[0107]

[0108] As shown in Table 1, the compositions of Examples 1 to 3 were solid or substantially non-flowable at room temperature (25°C), but exhibited a viscosity change of over 80% at 80°C, providing melt viscosities suitable for sealing and bonding. Furthermore, the cured products obtained by photoradical polymerization maintained high adhesion to substrates even after curing, demonstrating high practical utility. Furthermore, the compositions of Examples 1 to 3 exhibited a cohesive failure failure mode (i.e., "A") even after bonding the cured product to a substrate, demonstrating permanent adhesion. Therefore, they are suitable for use in bonding substrates that do not transmit ultraviolet light after curing. On the other hand, the cured products of the compositions of Comparative Examples 1 and 2, which contained only one type of component (B), exhibited a partial cohesive failure failure mode (i.e., "B"), resulting in inferior adhesion compared to Examples 1 to 3. Furthermore, when the content of component (B) was low and the resin / polymer ratio (R / P ratio) in the composition was 1.80 or less, as in Comparative Example 3, workability was poor and practical hot-melt properties could not be achieved.

[0109] Due to these properties, the composition of the present invention can exhibit excellent sealing performance and adhesive properties at 80°C when used in the manufacturing process of semiconductor devices, display devices, electronic devices, etc., which include substrates that are unstable at high temperatures (e.g., 100°C or higher). The composition of the present invention can also be cured at room temperature by irradiation with high-energy rays, resulting in a cured product with excellent appearance stability and transparency. Furthermore, the cured product has high adhesive strength and undergoes cohesive failure upon rupture, making it useful as a bonding layer capable of permanently bonding substrates. Alternatively, for example, a cured product of the composition of the present invention can be formed on only one side of a substrate, and the surface of the cured product can be used as an adhesive surface.

Claims

1. (A) A linear organopolysiloxane having two or more alkenyl groups in the molecule, (B) two or more organopolysiloxane components not containing aliphatic unsaturated bonds selected from the following components (B1) to (B3): (B1) A linear organopolysiloxane having two or more alkenyl groups in the molecule, １ ３ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and ４／２ (B2) a linear or branched diorganopolysiloxane; and (B3) an organopolysiloxane resin in which components (B1) and (B2) are linked by a chemical bond; (C) a monofunctional or polyfunctional vinyl monomer; and (D) a radical polymerization initiator; wherein the ratio of the total mass R of component (B1) constituting component (B3) to the total mass P of component (B2) constituting components (A), (B2), and (B3) (R / P ratio) is greater than 1.

80.

2. The composition according to claim 1, comprising component (B3).

3. The component (B3) is the following: (b3-1) R １ ３ SiO １／２ (In the formula, R １ each independently represents a monovalent organic group), and ４／２ (b3-2) a resinous organosiloxane block containing a siloxane unit (Q unit) represented by the formula: ２ ２ SiO ２／２ } ｍ (In the formula, R ２ each independently represents a monovalent organic group, and m is a number of 2 or more), 4. The composition according to claim 3, wherein in the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), the content ratio of components (b3-1) and (b3-2) [component (b3-1):component (b3-2)] is 99:1 to 1:99 by mass.

5. The composition according to claim 1, wherein component (B) comprises components (B1) and (B3), and the content of component (B3) relative to the total amount (100 parts by mass) of components (A) and (B1) is 1.0 to 30.0 parts by mass.

6. The composition according to claim 1, wherein component (C) comprises a monofunctional or polyfunctional vinyl monomer having 8 to 30 carbon atoms.

7. The composition of claim 1, wherein component (D) comprises a photoradical polymerization initiator.

8. A method for producing a sheet or film of a hot-melt curable organopolysiloxane composition, comprising: (i) applying the composition according to any one of claims 1 to 7 onto a substrate; and (ii) drying the applied composition by heating.

9. A laminate comprising: the hot melt type curable organopolysiloxane composition according to any one of claims 1 to 7; and a substrate having a release surface, attached to one or both sides of the composition in the form of a sheet or film.

10. The laminate according to claim 9, wherein the composition or the cured product of the composition is peelable from the substrate.

11. A cured product of the hot melt curable organopolysiloxane composition according to any one of claims 1 to 7.

12. The cured product according to claim 11, which is in the form of a sheet or film.

13. A semiconductor device comprising the cured product according to claim 11.

14. A method for manufacturing a semiconductor device, comprising the method according to claim 8.

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