WO2025135092A1 - Hot-melt-type curable organopolysiloxane composition - Google Patents

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 ₃SiO_1/2 (in the formula, R¹s each represent a monovalent organic group) and a siloxane unit (Q unit) represented by SiO_4/2, 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 type curable organopolysiloxane composition

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 including the cured product, and a method for producing a semiconductor device.

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 such curable organopolysiloxane compositions are less susceptible to discoloration than other organic materials, and also suffer less deterioration in physical properties, making them suitable as optical materials and sealants for semiconductor devices.
Examples of hot-melt type curable organopolysiloxane compositions include those described in Patent Documents 1 to 4.

International Publication No. 2023/042743 International Publication No. 2023/017746 International Publication No. 2015/194158 International Publication No. 2017/068762

Under these circumstances, there was a demand for new hot melt type curable organopolysiloxane compositions.

The present invention provides the following hot melt curable organopolysiloxane composition and the like.
[1]
(A) a linear organopolysiloxane having two or more alkenyl groups in the molecule;
(B) Two or more types of organopolysiloxane components not containing aliphatic unsaturated bonds selected from the following components (B1) to (B3):
(B1) an organopolysiloxane resin containing in its molecule siloxane units (M units) represented by R ¹ ₃ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 , the mass ratio of M units to 1 mole of Q units being in the range of 0.50 to 2.00;
(B2) a linear or branched diorganopolysiloxane, and (B3) an organopolysiloxane resin in which component (B1) and component (B2) are linked by a chemical bond.
(C) a monofunctional or polyfunctional vinyl monomer, and (D) a radical polymerization initiator.
Including,
A hot-melt curable organopolysiloxane composition, in which the ratio (R/P ratio) of the total mass R of component (B1) and component (B3) constituting component (B1) to the total mass P of component (A), component (B2), and component (B2) constituting component (B3) is greater than 1.80.
[2]
The composition according to [1], further comprising component (B3).
[3]
The component (B3) is the following:
(b3-1) a resinous organosiloxane block containing siloxane units (M units) represented by R ¹ ₃ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 , and (b3-2) a linear organosiloxane block having siloxane units (D units) represented by {R ² ₂ SiO _2/2 } _m (wherein R ² independently represents a monovalent organic group and m is a number of 2 or more);
The composition according to [1] or [2], which is a resin-linear structure-containing organopolysiloxane block copolymer having a structure in which the following are linked by a chemical bond:
[4]
The composition according to [3], wherein in the resin-linear structure-containing organopolysiloxane block copolymer of component (B3), the content ratio of component (b3-1) to component (b3-2) [component (b3-1):component (b3-2)] is 99:1 to 1:99 in terms of mass ratio.
[5]
The composition according to any one of the items [1] to [4], wherein component (B) contains 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 any one of items [1] to [5], wherein component (C) contains a monofunctional or polyfunctional vinyl monomer having 8 to 30 carbon atoms.
[7]
The composition according to any one of items [1] to [6], wherein component (D) contains a photoradical polymerization initiator.
[8]
(i) applying the composition according to any one of items [1] to [7] onto a substrate; and (ii) drying the applied composition by heating;
2. A method for producing a sheet or film of a hot melt curable organopolysiloxane composition comprising:
[9]
[1] to [7], and
a substrate having a release surface and attached to one or both sides of the composition in the form of a sheet or film;
A laminate comprising:
[10]
The laminate according to [9], wherein the composition or a 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 [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 manufacturing a semiconductor device, comprising the method according to [8].

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 a substrate. 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 a substrate. 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, has high adhesion to a substrate, and can provide a cured product that has good adhesion to a substrate.

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

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 its molecule; (B) two or more types of organopolysiloxane components containing no carbon-carbon multiple bonds selected from the following components (B1) to (B3): (B1) an organopolysiloxane resin containing siloxane units (M units) represented by R ¹ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 in its molecule, wherein the substance ratio 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.
In the composition of the present invention, 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) 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, and 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 (for example, 15 to 30°C, preferably 20 to 25°C. The same applies hereinafter unless a specific temperature is specified), resulting in reduced workability. Also, if the R/P ratio is too low, a hot melt type composition having flowability at room temperature cannot be obtained.
The lower limit of the R/P ratio is 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 the 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).
In this specification, "non-fluidity" means that the composition does not deform and/or flow in the absence of an external force. The 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.
In this specification, "adhesion" includes 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 unevenness of the adherend and hardens to fix the interface. Chemical adhesion includes adhesion called primary bonding, in which the composition and the adherend are bonded by chemical interaction (covalent bond, etc.). Physical adhesion includes adhesion called secondary bonding, in which the composition spreads over the adherend surface and adheres closely due to physical interaction (van der Waals force, etc.).
Each component constituting the composition of the present invention will be described in detail below.

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 the alkenyl group having 2 to 12 carbon atoms include a vinyl group, a propenyl group (including an allyl group), a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group. These groups also include structural isomers.
In one aspect 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 a vinyl group, an allyl group, and a hexenyl group, and particularly preferably a vinyl group or a hexenyl group.
The bonding position of the alkenyl group in component (A) may be, for example, at the molecular chain terminals and/or at the molecular chain side chains; however, component (A) preferably has an alkenyl group bonded to a silicon atom at a site other than the molecular chain terminals, and more preferably has an alkenyl group at a molecular chain side chain.

In component (A), the silicon-bonded groups other than alkenyl groups may be monovalent hydrocarbon groups 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 group include methyl, ethyl, propyl groups such as n-propyl and isopropyl, butyl groups such as n-butyl, isobutyl, s-butyl and t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. These groups also include structural isomers.
Specific examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
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, bromine atoms, etc., and specific examples include a chloromethyl group, a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group.
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.

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.

Specific examples of linear organopolysiloxanes include dimethylsiloxane-methylvinylsiloxane copolymers blocked at both molecular chain ends with trimethylsiloxy groups, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers blocked at both molecular chain ends with trimethylsiloxy groups, dimethylpolysiloxanes blocked at both molecular chain ends with dimethylvinylsiloxy groups, methylphenylpolysiloxanes blocked at both molecular chain ends with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers blocked at both molecular chain ends with dimethylvinylsiloxy groups, and dimethylpolysiloxane-methylvinylsiloxane copolymers blocked at both molecular chain ends with dimethylvinylsiloxy groups. trimethylphenylpolysiloxane copolymer, dimethylsiloxane-methylvinylsiloxane copolymer with both molecular chain ends blocked by dimethylphenylsiloxy groups, dimethylpolysiloxane with both molecular chain ends blocked by methylvinylphenylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer with both molecular chain ends blocked by trimethylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer with both molecular chain ends blocked by dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer with both molecular chain ends blocked by dimethylphenylsiloxy groups, etc.

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, methyl groups and vinyl groups or phenyl groups), diorganosiloxy units (D units) (organo groups are methyl groups only, 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 organopolysiloxanes can be liquid (e.g., oil-like) or solid (e.g., resin-like) at room temperature.

In one embodiment of the present invention, the property of component (A) at room temperature is oil-like or rubber-like.
When the composition of one embodiment of the present invention is a solventless or low-solvent composition, from the viewpoint of coatability, the property of component (A) at room temperature is preferably oily. In this case, the viscosity of component (A) at 25° C. is preferably 1 to 100,000 mPa·s, more preferably 10 to 50,000 mPa·s, and even more preferably 100 to 10,000 mPa·s.
In addition, when the composition according to one embodiment of the present invention is a solvent-based composition, it is preferable that component (A) has a raw rubber-like property at room temperature. In this case, at least a part of component (A) 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 thickness measured by applying a load of 1 kgf to a 4.2 g spherical sample at 25° C. for 3 minutes, reading the thickness to the nearest 1/100 mm, and multiplying this value 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, the viscosity refers to a value measured at 25° C. using a Brookfield viscometer.

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, the content of vinyl (CH ₂ ═CH—) moieties in the aliphatic unsaturated carbon-carbon bond-containing group (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%.

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.

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 of the present invention to a substrate.
The composition of the present invention contains, as component (B), two or more types of organopolysiloxane components containing no aliphatic unsaturated bonds selected from the following components (B1) to (B3).
The 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 component (B1) and component (B3), component (B2) and component (B3), and component (B1) and component (B2).
Among these, the combination of component (B1) and component (B3) is preferred from the viewpoint of hot melt properties.
From the standpoint of preventing contact failure, etc., the low molecular weight siloxane oligomers in component (B) may be reduced or eliminated.

In one embodiment of the present invention, the content of component (B) is preferably in the range of 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 setting the content of component (B) within the above range, the adhesion of the cured product obtained from the composition of the present invention to the surface of a substrate can be improved.
In addition, by using more than 100 parts by mass of component (B) per 100 parts by mass of component (A), the cured product forms a strong bond with the substrate surface, and the cured layer may be subjected to cohesive failure during peeling, resulting in a permanent adhesion mode. In one embodiment of the present invention, the content of component (B) is preferably 100 to 500 parts by mass, more preferably 200 to 450 parts by mass, and even more preferably 250 to 450 parts by mass per 100 parts by mass of component (A).

<Component (B1)>
Component (B1) is an organopolysiloxane resin containing in its molecule siloxane units (M units) represented by R ¹ ₃ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 , with the substance ratio of M units to 1 mole of Q units being in the range of 0.50 to 2.00. This substance 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 setting the substance amount ratio within the above range, the adhesion of the cured product obtained from the composition of the present invention to a substrate can be improved, and the cohesive force of the substances constituting the cured layer (cured product) can be improved.

Component (B1) is preferably an organopolysiloxane resin represented by the general unit formula: (R ¹ ₃ SiO _1/2 ) _a (SiO _4/2 ) _b (wherein R ¹ independently represents a monovalent organic group, a and b are each positive numbers, a+b=1, and a/b=0.50 to 2.00).
In component (B1), the monovalent organic group that may be selected as ^R1 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 suitable embodiment thereof may be the same as those described above in "1.1 Component (A): Linear organopolysiloxane."
Component (B1) may be composed of only M units and Q units, or may contain _{R2SiO2 /2} units (D units) and/or RSiO3 _/2 units (T units). In the formula, R independently represents a monovalent organic group, and specific examples and a preferred embodiment thereof may be the same as those of ^R1 .
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 mass % or more, more preferably 80 mass % or more, even more preferably 95 mass % or more, and particularly preferably 99 mass % or more.

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) in terms of 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 and component (B1) having the above-mentioned molecular weight can give a cured product with a high shear storage modulus at room temperature and a high tensile stress at 500% strain.

Furthermore, component (B1) can be one from which high molecular weight components that tend to easily aggregate into a gel, increase the haze value, and reduce low-temperature curing properties have been removed in advance. Specifically, component (B1) contains organopolysiloxane resins 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 entire 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.

Specifically, component (B1) may be any of the following:
(Me ₃ SiO _1/2 ) _0.40 (SiO _4/2 ) _0.60 (HO _1/2 ) _0.10
(Me ₃ SiO _1/2 ) _0.52 (SiO _4/2 ) _0.48 (HO _1/2 ) _0.01
(Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.55 (MeO _1/2 ) _0.10
(Me ₃ SiO _1/2 ) _0.25 (Me ₂ PhSiO _1/2 ) _0.20 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (Me ₂ SiO _2/2 ) _0.05 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (MeSiO _3/2 ) _0.05 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (Me ₂ SiO _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 express the relative amount of hydroxyl groups to silicon atoms, the sum of the subscripts of the silicon-containing units is set to 1, and the subscript of the (HO) _1/2 unit indicates the relative amount.)

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.

<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 linear or branched diorganopolysiloxane having a siloxane unit (D unit) represented by {R ² ₂ SiO _2/2 } _m (wherein R ² independently represents a monovalent organic group, and m is a number of 2 or more).
In component (B2), the monovalent organic group that may be selected as ^R2 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 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.
Furthermore, m may be any number equal to or greater than 2, but from the standpoint of hot melt properties, it is preferably a number in the range of 5 to 5,000, more preferably a number in the range of 10 to 3,000, and even more preferably a number in the range of 10 to 2,000.

The properties of component (B2) at room temperature are oil-like or raw rubber-like, but raw rubber-like is preferred. When raw rubber-like, at least a portion of component (B2) has a viscosity of more than 1 million mPa·s at 25°C, or the plasticity measured in accordance with the method specified in JIS K6249 (the measurement method is as described above) is preferably in the range of 50 to 200, more preferably in the range of 80 to 180, and even more preferably in the range of 130 to 180.

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.

<Component (B3)>
Component (B3) is an organopolysiloxane resin in which component (B1) and component (B2) are linked by chemical bonds. In one embodiment of the present invention, when component (B) contains, for example, two kinds of components (B1) and (B3), or two kinds of components (B2) and (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).

In one embodiment of the present invention, component (B3) is
(b3-1) a resinous organosiloxane block containing siloxane units (M units) represented by R ¹ ₃ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 , and (b3-2) a linear organosiloxane block having siloxane units (D units) represented by {R ² ₂ SiO _2/2 } _m (wherein R ² independently represents a monovalent organic group and m is a number of 2 or more);
The resin-linear structure-containing organopolysiloxane block copolymer has a structure in which the above-mentioned are linked by a chemical bond.
The explanation for component (b3-1) is the same as that for “component (B1)” above. The explanation for component (b3-2) is the same as that for “component (B2)” above.
In one embodiment of the present invention, the block related to component (b3-1) (hereinafter referred to as "block X") and the block related to component (b3-2) (hereinafter referred to as "block Y") may be linked via a siloxane bond or a silalkylene bond.

The method for linking the resinous organopolysiloxane that gives block X with the linear organosiloxane that gives 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 by a siloxane bond, and in the case of a hydrosilylation reaction, blocks X and Y are linked by a silalkylene bond.
In one embodiment of the present invention, from the viewpoint of durability, it is preferable that blocks X and Y are linked via a siloxane bond.
For a more specific method for producing such a resin-linear structure-containing organopolysiloxane block copolymer, see, for example, International Publication No. 2023/017746 (Patent Document 4).

In one embodiment of the present invention, the content ratio of component (b3-1) and 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.

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.

In one embodiment of the present invention, when component (B) contains components (B1) and (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.

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

<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.

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.

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

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.

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

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

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

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.

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

<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.

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. acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, ethoxylated cyclohexane dimethanol 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.

Specific examples of (meth)acrylates 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, glycerol 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.

<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 monomers, vinyl ethers, vinyl amides, vinyl esters, carboxylic acid monomers, etc.

Specific examples of the monofunctional styrene monomer include: styrene; alkyl-substituted styrenes such as 4-methylstyrene and 4-ethylstyrene; halogen-substituted styrenes such as p-chlorostyrene and p-bromostyrene; and the like.
Specific examples of polyfunctional styrene-based monofunctional compounds include 1,3-divinylbenzene, 1,4-divinylbenzene, and the like.

Specific examples of monofunctional vinyl ethers include chain 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; and aromatic ring-containing vinyl ethers such as phenyl vinyl ether, benzyl vinyl ether, and 4-methoxybenzyl vinyl ether.
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.

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.
The carboxylic acid monomer includes, for example, 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.

As for these monofunctional and polyfunctional vinyl monomers, one type of monofunctional vinyl monomer may be used alone, or two or more types of monofunctional vinyl monomers may be used in combination.
Similarly, one type of polyfunctional vinyl monomer may be used alone, or two or more types of polyfunctional vinyl monomers may be used in combination.
Furthermore, a monofunctional vinyl monomer and a polyfunctional vinyl monomer may be combined.

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

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.

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 region.

Photoradical polymerization initiators include, for example, 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.

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.

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.

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

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

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(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

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

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-pyrrol-1-yl)ethyl)phenyl]titanium.

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

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 Strong Electronic New Materials Co., Ltd.

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.

1.5 Optional Components The composition according to one embodiment of the present invention may contain other optional components, if necessary, in addition to the components (A) to (D). Examples of such optional components include other optional organopolysiloxanes; photosensitizers; adhesion promoters; antioxidants such as phenols, quinones, amines, phosphorus, phosphite, sulfur, or thioethers; light stabilizers such as triazoles or benzophenones; flame retardants such as phosphates, halogens, phosphorus, or antimony; antistatic agents such as cationic surfactants, anionic surfactants, or nonionic surfactants; polymerization inhibitors; ultraviolet absorbers; and the like. 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 surface-treated.

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 may be a substantially low-solvent or solvent-free composition because it is solid at room temperature or has poor fluidity. In this case, it is acceptable to unavoidably contain a small amount of organic solvent. In a substantially low-solvent or solvent-free composition, the content of the organic solvent 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.
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 various components are uniformly mixed, or when the composition is molded into various shapes described below. Furthermore, the composition of one embodiment of the present invention may be molded into various shapes described below by coating a dispersion obtained by dispersing the composition in an organic solvent. In this case, it is preferable to finally remove the organic solvent by a means such as heating and drying. 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, when the total amount of the composition of one embodiment of the present invention including the components (A) to (D) is taken as 100 parts by mass.

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; and the like. Two or more of these organic solvents may be combined depending on the wettability of the substrate.

1.6 Properties of the Composition of the Present Invention The composition of the present invention is a hot-melt type composition that is solid or non-flowable at room temperature and can be handled in the form of granules, pellets, sheets, films, etc.
The composition according to 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 in the absence of external force.
When the composition is non-flowable at room temperature, the shape retention of the composition is good, and in this case, the surface tackiness is low, so that the composition can be easily handled even in an uncured state.
The softening point of the composition according to one embodiment of the present invention is preferably equal to or lower than 100° C. Such a softening point means a temperature at which, when a 22 mm-high composition is pressed from above on a hot plate with a load of 100 grams for 10 seconds, and the amount of deformation of the composition is measured after the load is removed, the amount of deformation in the height direction is 1 mm or more.

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, 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, even more preferably 0.08 or less.

The composition of one embodiment of the present invention has a complex viscosity ( ¹⁰ Pa·s) at 25°C, measured by the method described in the Examples below, of preferably 150.0 or more, more preferably 155.0 or more, even more preferably 160.0 or more, and also preferably 800.0 or less, more preferably 700.0 or less, even more preferably 600.0 or less.
The composition of one embodiment of the present invention has a complex viscosity ( ¹⁰ Pa·s) at 80°C, measured by the method described in the Examples below, of preferably 2.5 or more, more preferably 3.0 or more, and even more preferably 4.0 or more, and also preferably 50.0 or less, more preferably 40.0 or less, and even more preferably 30.0 or less.

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 the mechanical force of a mixer or the like. In this case, an organic solvent may be added as needed, as described above.
The composition according to one embodiment of the present invention can be in the form of granules, pellets, sheets, films, or the like.

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

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 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, and applied to the substrate in the form of a dispersion, and the organic solvent may be removed in the above (II).
The molding into a sheet or film may be carried out during the above step (I), or during both steps (I) and (II).
When a release layer is present on the substrate, a sheet or film which is one embodiment of the composition of the present invention can be obtained as a part of a peelable laminate which will be described later.

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.

The composition of the present invention is a hot-melt type curable organopolysiloxane composition containing the above-mentioned components, and has hot-melt properties. Furthermore, the composition of one aspect of the present invention has excellent handleability when molten (hot melt), curability, transparency, adhesion, etc., and can therefore be suitably used as a sealant for light-emitting or optical devices, adhesive material, light reflector, and other semiconductor materials. More specifically, it is suitable 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.

In addition, the sheet or film, which is one embodiment of the composition of the present invention, has excellent formability, gap-filling properties, and adhesion, and is therefore suitable for use as a sealant for semiconductors using press molding, compression molding, overmolding, and the like. The sheet or film is also suitable as a material for sealing or adhering large-area substrates using a vacuum laminator, etc. Furthermore, the sheet or film can also be used as a curable film adhesive or a stress buffer layer between two types of substrates with different linear expansion coefficients. In this way, the composition of one embodiment of the present invention may be a sealant intended for single-sided sealing, or may be a sealant intended for double-sided sealing involving adhesion between two substrates.

Furthermore, a sheet or film which is one embodiment of the composition of the present invention can be peeled off from a 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 which has gap-filling properties for unevenness and gaps on the semiconductor substrate.
In this manner, the sheet or film can be temporarily fixed, positioned, or bonded onto or between adherends, and then 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 of one embodiment of the present invention (including in the form of a sheet or film) and adhere the adherend.
In addition, since the sheet or film has hot-melt properties, the sheet or film can be softened or fluidized by heating it before final curing, and even if there are irregularities or gaps on the bonding surface of the adherend, the irregularities or gaps can be filled without leaving any gaps, forming an adhesive surface with the adherend.
Examples of the means for heating the sheet or film include various types of thermostatic chambers, hot plates, electromagnetic heating devices, heating rolls, electric heating presses, diaphragm-type laminators, roll laminators, and the like.

2. Laminate and Manufacturing Method Thereof One aspect of the present invention provides a laminate (hereinafter also referred to as the "laminate of the present invention") containing the hot melt curable organopolysiloxane composition described above in "1. Hot melt curable organopolysiloxane composition." The laminate of the present invention includes the composition of one aspect of the present invention and a substrate having a release surface, which is attached to one or both sides of the composition in the form of a sheet or film.
The laminate of one embodiment of the present invention is a three-layer laminate in which a sheet or film which is one embodiment of the composition of the present invention is laminated between two sheet or film-like substrates having a release surface.
The laminate of one embodiment of the present invention is a two-layer laminate in which a sheet or film which is 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 the composition of the present invention can be peeled off from a sheet or film-like substrate having a release surface (generally also referred to as a release film. In this specification, it is appropriately referred to as a "release film"). In addition, as described later, the cured product of the composition of one embodiment of the present invention can also be peeled off from the substrate. Therefore, the laminate of one embodiment of the present invention can also be called a peelable laminate.
In the laminate of one embodiment of the present invention, the thickness of the release film is not particularly limited, and in this specification, a sheet or film is collectively referred to as a "release film" regardless of its thickness.

The three-layer laminate according to one embodiment of the present invention can be produced, for example, by a method including the following: The two-layer laminate according to one embodiment of the present invention can be produced according to the method for producing the three-layer laminate.
(A): mixing the components of the composition of one embodiment of the present invention;
(B): Kneading the mixture obtained in (A) while heating and melting it;
(C): forming a laminate by laminating the heat-melted mixture obtained in (B) between two release films having at least one release surface such that the mixture is in contact with the release surface;
(D): Pressing the laminate obtained in (C) between rolls to roll out the mixture disposed between two release films to form a sheet- or film-like laminate;
(E): Optionally, cutting the laminate obtained in (D) above.

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

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

In the above (C), the method of 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 includes, for example, polyester film, polyolefin film, polycarbonate film, or acrylic film. 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 may also be 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 capability, 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 formed on its surface to reduce the adhesive strength to the composition of one embodiment of the present invention, or may be made of a material that does not easily adhere to a layer containing the composition of one embodiment of the present invention or a cured product thereof.

In (D) above, the method of pressing and rolling is not particularly limited. For example, pressing and rolling may be performed so that the thickness of the sheet or film of the laminate of one embodiment of the present invention is 1 to 3000 μm, 5 to 2000 μm, or 10 to 1000 μm. It is preferable that the sheet or film is flat. Flat means that the thickness of the obtained sheet or film is within the range of ±100 μm or less, preferably within the range of ±50 μm or less, and more preferably within the range of ±30 μm or less.

The cutting method for (E) above is not particularly limited, and the obtained laminate can be cut to the desired size by conventional methods.

The three-layer laminate of one embodiment of the present invention thus obtained can be used, for example, by peeling off one of the two release films that may 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 off the other release film from the uncured sheet- or film-like member.

3. Cured Product of the Composition of the Present Invention, 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 the 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. Regarding the form of the sheet or film, the same applies as described above in "1.7 Production method, form and use of the composition of the present invention."

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

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 preferably in the range of 100 mJ/cm ² to 100 J/cm ² .
In addition, the high-energy ray 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-mentioned wavelength range. In other words, as long as a certain amount of irradiation can be achieved, the high-energy ray may be irradiated through a cover material such as a substrate or release film.

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 a low temperature range including room temperature. In this specification, "low temperature" refers to a temperature of 100°C or less, more specifically, includes a temperature range of 15°C to 100°C, 15°C to 80°C or less, 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 in a low temperature region, 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 to 25° C.), may be cooled to a temperature of 15° C. or higher and below room temperature, or may be heated to a temperature of room temperature or higher and 100° C. or lower.
The time required for the curing reaction can be appropriately designed according to the irradiation amount and temperature of high energy rays such as ultraviolet rays. In addition, a semi-cured product that retains photocuring reactivity may be obtained by interrupting the irradiation before a predetermined cumulative irradiation amount is reached. The semi-cured product can then be subjected to further curing reaction as desired.

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 b ^* value after 500 hours when the thickness of the cured product is 200 μm is 2.0 or less, preferably 1.0 or less.

In particular, while known active energy ray-curable hot-melt silicone compositions capable of low-temperature curing (such as those described in the above-mentioned Patent Document 4) leave room for improvement in terms of 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 having practical yellowing resistance and high transparency. For this reason, the composition of one embodiment of the present invention and its cured product can be suitably used in applications such as sealing materials for optical materials and adhesive members.
The optical materials include, for example, light-emitting semiconductor devices that are light-emitting or optical devices, optical members for displays, members for solar panels, and the like.
Furthermore, the composition according to one embodiment of the present invention and a cured product thereof can also be suitably used for applications such as encapsulation of electronic materials in which transparency, light resistance, and heat resistance are important, and encapsulation of substrates having poor heat resistance with a transparent cured product.

More specifically, the cured product according to one embodiment of the present invention can be suitably used as a semiconductor member, for example, as a sealing material for semiconductor elements, IC chips, and the like, and as an adhesive member such as a pressure-sensitive adhesive, adhesive, or bonding member for semiconductor devices.
Furthermore, since the cured product of one embodiment of the present invention forms a permanent bond or bond accompanied by cohesive failure of the cured product in the peel mode, it is also possible to bond substrates that block activation energy rays such as ultraviolet rays.
Here, in order to improve the adhesion between the adherend and the cured product, the surface of the cured product or the substrate may be subjected to a surface treatment such as a primer treatment, a corona treatment, an etching treatment, a plasma treatment, etc. Furthermore, in the above case, the surface of the cured product that is not in contact with the substrate may be designed to have adhesion to other substrates. That is, the surface of the cured product may be used as a pressure-sensitive adhesive surface, a sticky surface, or an adhesive surface.

4. Semiconductor device and method for manufacturing a semiconductor device One aspect of the present invention provides a semiconductor device comprising the cured product described in "3. Cured product of the composition of the present invention, method for forming same, and use thereof" above.
Specific examples of the semiconductor device include those described above in "1.7 Production method, form, and use of the composition of the present invention" and "3. Cured product of the composition of the present invention, and method for forming the same, and use thereof."

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 a composition of one embodiment of the present invention in the form of a sheet or film, as described above in "1.7 Production Method, Form, and Use of the Composition of the Present Invention."
Specific examples of the semiconductor device include those described above in "1.7 Production method, form, and use of the composition of the present invention" and "3. Cured product of the composition of the present invention, and method for forming the same, and use thereof."

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

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'): The composition is heated to cause it to flow, and irregularities and voids in a substrate that is a semiconductor device (including an optical semiconductor device) or a precursor thereof are filled.

In addition, when the above (1'), (1) and/or (2) are carried out simultaneously by carrying out (i) and (ii) in the manufacturing method of 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.

The present invention will be further explained below based on examples, but the present invention is not limited to the following examples.

Examples 1 to 3, Comparative Examples 1 to 3
The components below were mixed uniformly in the compositions 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%. Then, 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, dried in an oven at 80° C. for 10 minutes, cooled to room temperature, and then the release film was placed over the composition surface to produce a release laminate having two release surfaces.
In the table, "mass of siloxane in composition" means the total amount of component (A) and component (B) relative to the mass of the solid content of the entire composition (components that constitute the cured product, excluding organic solvents).
In addition, in the table, "resin/polymer ratio" means the ratio (R/P ratio) of the total mass R of component (B1) constituting component (B3) to the total mass P of component (A), component (B2), and component (B2) constituting component (B3).

<Component (A)>
Dimethylsiloxane-methylvinylsiloxane copolymer raw rubber capped at both ends with trimethylsiloxy groups (plasticity at 25° C.: 130, vinyl group content: 0.70% by mass, having two or more alkenyl groups in the molecule).

<Component (B)>
Component (B1): An organopolysiloxane resin containing siloxane units (M units) represented by _{Me3SiO1 /2} (wherein Me is a methyl group) and siloxane units (Q units) represented by SiO4 _/2 in a molar ratio of 1.0:1.0 within the molecule (weight average molecular weight (Mw) measured by GPC using toluene as a solvent = 7,000).
Component (B2): Raw rubber-like polydimethylsiloxane (plasticity at 25°C = 170).
Component (B3): A reaction product obtained by dehydration condensation of component (B1) and component (B2) in a mass ratio (B1:B2) of 60:40.

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

<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).

[Storage Modulus and Complex Viscosity of Curable Organopolysiloxane Composition]
A film-like composition (non-cured product) with a thickness of 200 μm was placed in close contact between a shear rotation jig and a sample stage, and a shear stress was applied to the sample (shear strain 0.05%, frequency 1 Hz) while 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, to measure the storage modulus and complex viscosity.

[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, the laminate was irradiated with ultraviolet light having a wavelength of 365 nm from the other release film side so that the cumulative light amount was 1,000 mJ/ ^cm2 , and the composition was cured.
The cured laminate was cut to a width of 25.4 mm (1 inch), the release film was removed, and the cured product (cured layer) was attached to a SUS 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.
In addition, the adhesiveness of the cured product was evaluated based on the fracture mode in the peel test. Specific examples were classified as "C" when peeling occurred at the interface between the cured product (cured layer) and the SUS plate, "A" when the cured product (cured layer) itself underwent cohesive failure, and "B" when the cured product (cured layer) itself underwent partial cohesive failure, with "A" being judged as acceptable.

As shown in Table 1, the compositions according to Examples 1 to 3 were solid or substantially non-fluid at room temperature (25° C.), but had a melt viscosity suitable for sealing and adhesion due to a viscosity change of more than 80% at 80° C. Furthermore, the cured products obtained by the photoradical polymerization reaction had high adhesive strength to substrates even after curing, and were highly practical.
Furthermore, the compositions of Examples 1 to 3 showed a cohesive failure mode (i.e., "A") even after the cured product was bonded to a substrate, and exhibited 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 according to Comparative Examples 1 and 2, which contained only one type of component (B), showed a fracture mode of partial cohesive failure (i.e., "B"), and the adhesive properties were inferior to those of 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, the workability was poor and practical hot melt properties could not be achieved.

Due to these properties, the composition of the present invention can exhibit excellent sealing performance and adhesiveness at 80°C when used in the manufacturing process of semiconductor devices, display devices, electronic devices, etc., which contain substrates that are not stable at high temperatures (e.g., 100°C or higher). In addition, the composition of the present invention can be cured at room temperature by irradiation with high-energy rays, and a cured product with excellent appearance stability and transparency is obtained. Furthermore, since the cured product has high adhesive strength and undergoes cohesive failure when broken, it is useful as a bonding layer capable of permanently bonding substrates. In addition, 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 (14)

(A) a linear organopolysiloxane having two or more alkenyl groups in the molecule;
(B) Two or more types of organopolysiloxane components not containing aliphatic unsaturated bonds selected from the following components (B1) to (B3):
(B1) an organopolysiloxane resin containing in its molecule siloxane units (M units) represented by R ¹ ₃ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 , the mass ratio of M units to 1 mole of Q units being in the range of 0.50 to 2.00;
(B2) a linear or branched diorganopolysiloxane, and (B3) an organopolysiloxane resin in which component (B1) and component (B2) are linked by a chemical bond.
(C) a monofunctional or polyfunctional vinyl monomer, and (D) a radical polymerization initiator.
Including,
A hot-melt curable organopolysiloxane composition, in which the ratio (R/P ratio) of the total mass R of component (B1) and component (B3) constituting component (B1) to the total mass P of component (A), component (B2), and component (B2) constituting component (B3) is greater than 1.80. The composition according to claim 1, comprising component (B3). Component (B3) is the following:
(b3-1) a resinous organosiloxane block containing siloxane units (M units) represented by R ¹ ₃ SiO _1/2 (wherein R ¹ independently represents a monovalent organic group) and siloxane units (Q units) represented by SiO _4/2 , and (b3-2) a linear organosiloxane block having siloxane units (D units) represented by {R ² ₂ SiO _2/2 } _m (wherein R ² independently represents a monovalent organic group and m is a number of 2 or more);
The composition according to claim 2, which is a resin-linear structure-containing organopolysiloxane block copolymer having a structure in which the are linked by a chemical bond. The composition according to claim 3, in which the content ratio of component (b3-1) to component (b3-2) [component (b3-1):component (b3-2)] in the resin-linear structure-containing organopolysiloxane block copolymer of component (B3) is 99:1 to 1:99 by mass. The composition according to claim 1, wherein component (B) contains 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. The composition according to claim 1, in which component (C) contains a monofunctional or polyfunctional vinyl monomer having 8 to 30 carbon atoms. The composition of claim 1, wherein component (D) includes a photoradical polymerization initiator. (i) applying the composition according to any one of claims 1 to 7 onto a substrate, and (ii) drying the applied composition by heating;
2. A method for producing a sheet or film of a hot melt curable organopolysiloxane composition comprising: The hot melt type curable organopolysiloxane composition according to any one of claims 1 to 7,
a substrate having a release surface and attached to one or both sides of the composition in the form of a sheet or film;
A laminate comprising: The laminate according to claim 9, wherein the composition or the cured product of the composition is peelable from the substrate. A cured product of the hot melt curable organopolysiloxane composition according to any one of claims 1 to 7. The cured product according to claim 11, which is in the form of a sheet or film. A semiconductor device comprising the cured product according to claim 11. A method for manufacturing a semiconductor device, comprising the method according to claim 8.