JP2021045953A - Method for producing curable silicone sheet having hot melt property - Google Patents

Abstract

To provide a method for efficiently producing a curable silicone sheet having hot melt properties, excellent flatness and uniformity, and which may be substantially filler-less, and a method for producing a laminate that comprises the curable silicone sheet.SOLUTION: There is provided a method for producing a curable silicone sheet having hot melt properties, which comprises the steps of: 1 removing an organic solvent from a solution in which a solid organo-polysiloxane resin or the like is dispersed or dissolved at a temperature of 150°C or higher to obtain a hot-melt solid content; 2 adding all curing agents to the hot-melt solid content obtained in the step 1 and then kneading while heating and melting the same at a temperature of 120°C or lower; 3 laminating the heated and melted mixture obtained in the step 2 between films having at least one peeling surface; and 4 stretching the laminate obtained in the step 3 between rolls to form a curable silicone sheet having a specific film thickness.SELECTED DRAWING: Figure 2

Description

The present invention is a manufacturing method capable of obtaining a curable silicone sheet having a hot melt property which is simple and excellent in flatness and uniformity, and a curable property having a hot melt property which can be obtained by the manufacturing method. It relates to a laminate having a structure in which silicone sheets are laminated between films having at least one peeled surface.

The curable silicone composition is used in a wide range of industrial fields because it cures to form a cured product having excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. A cured product of such a curable silicone composition is generally less likely to discolor than other organic materials, and has a small decrease in physical properties, so that it is also suitable as a sealing agent for optical materials and semiconductor devices.

The applicant proposes a hot-melt curable granular silicone composition and a reactive silicone composition for molding in Patent Document 1 and Patent Document 2. These silicone compositions are made of a so-called phenyl silicone resin, and have the advantages of being excellent in hot melt property and being excellent in hardness and strength of the cured product as compared with the methyl silicone resin.

Furthermore, in Patent Documents 3 to 5, the Applicants used an inorganic filler containing no coarse particles in the curable granular silicone composition, thereby providing toughness and durability especially at high temperatures and gap fillability at the time of melting. , It is proposed that the light reflectance etc. can be improved.

On the other hand, these curable granular silicone compositions are required to be applied to various semiconductor applications including power semiconductors, and these curable granular silicone compositions are used as a uniform hot-melt curable silicone sheet. May be required. However, when an attempt is made to mold the curable granular silicone composition into a sheet by a usual method, the curable silicone sheet is liable to be damaged or defective, and a simple method can be used to obtain a hot melt property having excellent flatness and uniformity. There has been a demand for a means for obtaining a curable silicone sheet having.

On the other hand, Patent Document 6 describes a combination of components containing a silicone resin, an organopolysiloxane, a silane cross-linking agent, a catalyst and a solvent, and supplies this combination to an extruder to remove volatile substances to provide a condensation-curing hot melt silicone. A method for obtaining an adhesive composition and a method for molding the composition between release liners are described, but nothing is described particularly for a thermosetting type hot melt silicone composition, and the method is thermosetting. When an attempt is made to mold a sex silicone composition or the like into a sheet, the curable silicone sheet may be damaged or defective. Further, when the production method is applied at a high temperature, a curing reaction may proceed particularly in a thermosetting type hot melt silicone composition, and a sheet material having hot melt properties may not be obtained.

In addition to this, the above-mentioned curable silicone composition contains a high concentration of inorganic filler due to its nature, but the use of the hot-melt curable silicone composition is diversifying year by year, and the inorganic filler is used. Transparent and uniform curable silicone sheets that are small in quantity or substantially free of inorganic fillers may also be applied to applications involving semiconductors. Therefore, it is not necessary to use an inorganic filler or a curable granular silicone, the film thickness of the curable silicone sheet is precisely controlled, and a transparent hot-melt curable silicone sheet containing no voids or defects can be easily produced. There is a need for a way to do this.

International Publication No. 2016/136243 Pamphlet Japanese Unexamined Patent Publication No. 2014-09322 International Publication No. 2018/030286 Pamphlet International Publication No. 2018/030287 Pamphlet International Publication No. 2018/030288 Pamphlet Japanese Patent Publication No. 2011-525444

An object of the present invention is to have hot melt property, excellent handling workability and curing properties, excellent flatness and uniformity, and if necessary, curability excellent in transparency without containing a functional filler. An object of the present invention is to provide a method for efficiently producing a silicone sheet. Furthermore, an object of the present invention is to provide a laminate containing the curable silicone sheet and a method for producing the same.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by a method for producing a curable silicone sheet having hot melt property, which comprises the following steps, and arrived at the present invention.
Step 1: The organic solvent is removed from a solution in which a solid organopolysiloxane resin at room temperature and optionally a chain diorganopolysiloxane are dispersed or dissolved in an organic solvent at a temperature of 150 ° C. or higher. Step 2: Obtaining hot-melting solids Step 2: After adding all the curing agents to the hot-melting solids obtained in Step 1, kneading while heating and melting at a temperature of 120 ° C. or lower 3 : The mixture obtained in step 2 after heating and melting is laminated between films having at least one peeling surface. Step 4: The laminate obtained in step 3 is stretched between rolls to have a specific film thickness. The process of molding a curable silicone sheet

In the above method for producing a curable silicone sheet,
The melt viscosity of the mixture after heating and melting obtained in step 2 measured by an elevated flow tester at 150 ° C. is in the range of 1 to 1,000 Pas.
In step 3, the step of laminating the mixture after heating and melting between films having at least one peeling surface ejects the mixture after heating and melting while molding the mixture into a film or a string using a die and a nozzle. Then, it is a step of laminating between films having at least one peeling surface.
Further, a manufacturing method including a step of cooling the entire laminate obtained in the step 3 or adjusting the temperature between 80 and 120 ° C. as a pre-step of the step 4 or in the step 4 is preferable. In particular, the production method is useful in that when the melt viscosity of the mixture after heating and melting is low, the mixture can be tentatively molded by a die.

In the above method for producing a curable silicone sheet,
The softening point of the entire mixture obtained in step 2 is 200 ° C. or lower.
Step 2 is a step of heating the mixture obtained in step 1 to a temperature equal to or higher than the softening point of the mixture.
In step 3, the step of laminating the mixture after heating and melting between films having at least one peeling surface ejects the mixture after heating and melting in a solid state and has a film having at least one peeling surface. A manufacturing method that is a step of laminating between them is preferable.
When the film thickness of the laminate containing the mixture discharged in the solid state is adjusted in step 4, the film thickness adjusting roll preferably further has a temperature adjusting function, and the roll having the temperature adjusting function is provided. A manufacturing method that stabilizes the film thickness of the obtained curable silicone sheet by stretching is preferable. In particular, the production method is useful in that when the melt viscosity of the mixture after heating and melting is high, it can be molded into a sheet shape without performing temporary molding.

In the above method for producing a curable silicone sheet, steps 2 to 4 are continuous steps, and the time from the start of step 2 to the end of step 4 may be 30 minutes or less. In particular, steps 3 and 4 may be continuous and integrated steps, for example, the mixture after heating and melting obtained in step 2 has two peeled surfaces immediately below between the rolls. It may be laminated by being discharged or applied between the films, and at the same time, it may be stretch-molded to a specific film thickness by adjusting the gap between the rolls. As described above, the manufacturing method having the steps in which the steps 3 and 4 are substantially integrated is included in the scope of the above-mentioned manufacturing method.

The above-mentioned method for producing a curable silicone sheet may further include a step of cutting a laminate containing the curable silicone sheet obtained in step 4.

In the above method for producing a curable silicone sheet, in step 3, the step of laminating the mixture after heating and melting obtained in step 2 between films having at least one peeling surface is a step of laminating the mixture after heating and melting. Using a die selected from a T-type die and a strand die, and a nozzle selected from a single nozzle and a multi-nozzle, the film is ejected while being molded into a film or string shape, and laminated between films having at least one peeling surface. It may be a process.

In the above method for producing a curable silicone sheet, the organopolysiloxane resin in step 1 contains at least 20 mol% of the siloxane unit (R is an aryl group) represented by _{RSiO 3/2} or SiO _{4/2 as the total siloxane unit.} It is an organopolysiloxane resin containing the above, and the chain diorganopolysiloxane contains at least 90 mol% or more of the siloxane unit (R ^{2 is a methyl group) represented by RR 2} SiO _2/2. It may be an organopolysiloxane.

In the above method for producing a curable silicone sheet, the mixture obtained in step 2 is cured by curing.
The storage elastic modulus (G') at 25 ° C. is 2000 MPa or less.
The storage elastic modulus (G') at 150 ° C. is 100 MPa or less.
It is preferable to give a cured product having a peak value of loss tangent (tan δ) represented by storage elastic modulus / loss elastic modulus (G'/ G'') at a frequency of 1.0 Hz of 0.40 or more.

In the above method for producing a curable silicone sheet,
The mixture obtained in step 2 is cured by curing.
(1) The maximum torque value measured by MDR (Moving Die Ratio) at the molding temperature from room temperature to 200 ° C. is less than 50 dBN · m, and (2) When the maximum torque value is reached, the storage torque value / It is preferable to give a cured product in which the value of the loss tangent (tan δ) represented by the ratio of the loss torque values is less than 0.2.

In the above method for producing a curable silicone sheet, the mixture obtained in step 2 may have a functional filler content of less than 5.0% by mass in the entire mixture. In particular, the production method of the present invention is suitable as a production method for a curable silicone sheet that does not substantially contain a functional filler, has excellent transparency, and does not contain voids or defects.

In the above method for producing a curable silicone sheet, the curable silicone sheet may be a curable silicone sheet for compression molding, vacuum lamination, or press molding, and in particular, curing for compression molding or vacuum lamination. It is preferably a sex silicone sheet.

In the above method for producing a curable silicone sheet, the curable silicone sheet may be a hot melt film adhesive.

In the above method for producing a curable silicone sheet, the curable silicone sheet may be a substantially flat curable silicone sheet having a thickness of 10 to 2000 μm.

Another object of the present invention is to contain an organopolysiloxane resin, a curing agent, and optionally a chain of diorganopolysiloxane, and have a substantially flat hot melt property having a thickness of 10 to 2000 μm. It is solved by a laminate comprising a structure in which a curable silicone sheet having a functional filler content of less than 5.0% by mass is laminated between films having at least one peeling surface. Both of the films may have a peeling surface, and are preferable.

The peeled body is a peeling coating obtained by curing a curable organopolysiloxane composition containing one or more types of organopolysiloxane having a fluorine-containing substituent bonded to a silicon atom in one molecule. It is a layer, and the thickness of at least one of the films having the peeled surface is preferably 50 μm or more. The fluorine substituent is preferably one or more kinds of fluorine-containing substituents selected from a fluoroalkyl group and a perfluoropolyether group. Further, the curable organopolysiloxane is preferably one or more kinds of organopolysiloxanes containing a fluorine-containing substituent bonded to a silicon atom and a curing-reactive functional group in one molecule.

The method for producing the laminate preferably includes the method for producing the curable silicone sheet in the step.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for efficiently producing a curable silicone sheet having excellent flatness and uniformity. The curable silicone sheet is made of a curable silicone composition, has hot melt properties, is excellent in handling workability and curable properties, and is preferably excellent in gap fill property at the time of melting and excellent in stress relaxation. A flexible cured product can be formed. Further, in the curable silicone sheet of the present invention, by changing the type of the functional inorganic filler in the curable silicone composition, the cured product is provided with a low linear expansion rate, thermal conductivity, light reflectivity, and the like. On the other hand, it is also possible to design a composition that does not substantially contain a functional filler, and to impart excellent transparency to the composition. Furthermore, according to the present invention, it is possible to provide a laminate containing the curable silicone sheet, such as a peelable laminate containing a hot melt film adhesive, and a method for producing the same.

It is a figure which shows the partial structure (up to the part of the extrusion machine) of the manufacturing apparatus of the curable silicone sheet of Example 1. It is a figure which shows the whole structure (the whole part including the sheet formation) of the manufacturing apparatus of the curable silicone sheet of Example 1.

[Manufacturing method of curable silicone sheet]
The curable silicone sheet according to the present invention has a hot-melt property, and it is essential that it contains an organopolysiloxane resin and a curing agent, and may contain a chain-like organopolysiloxane if necessary. Characteristically, the production method of the present invention includes the following steps 1 to 4.
Step 1: The organic solvent is removed from a solution in which a solid organopolysiloxane resin at room temperature and optionally a chain diorganopolysiloxane are dispersed or dissolved in an organic solvent at a temperature of 150 ° C. or higher. Step 2: Obtaining hot-melting solids Step 2: After adding all the curing agents to the hot-melting solids obtained in Step 1, kneading while heating and melting at a temperature of 120 ° C. or lower 3 : The mixture obtained in step 2 after heating and melting is laminated between films having at least one peeling surface. Step 4: The laminate obtained in step 3 is stretched between rolls to have a specific film thickness. The process of molding a curable silicone sheet

Here, "having a hot melt property" means that the softening point is in the range of 50 ° C. to 200 ° C. and has the property of softening or flowing by heating. Further, the curable silicone sheet according to the present invention may have a hot melt property as a mixture regardless of the hot melt property of the organopolysiloxane resin which is a constituent of the curable silicone sheet. The curable silicone sheet according to the present invention may contain a functional filler, but may have a structure that does not substantially contain a functional filler, and is preferable.

In the following description, "room temperature" means 25 ° C.

[Step 1]
The above step 1 is a step of mixing a hot-melt silicone component excluding a curing agent, that is, an organopolysiloxane resin and optionally a chain-like organopolysiloxane, and these components are dispersed or dissolved in an organic solvent. This is a step of removing the organic solvent from the solution at a high temperature of 150 ° C. or higher. Each of these components will be described later. It should be noted that this step is particularly suitable for producing a curable silicone sheet having a low content of the functional filler or substantially no functional filler and having excellent transparency and uniformity.

The mixture given in step 1 contains an organopolysiloxane resin that is solid at room temperature and optionally a chain of diorganopolysiloxane, and the mixture as a whole has hot melt properties, but at this stage the curing agent. Since it does not contain thermosetting, it does not have thermosetting property. Therefore, even if it is handled at a high temperature of 150 ° C. or higher in order to remove the organic solvent in step 1, the finally obtained curable silicone sheet has hot melt property and curability. Is not impaired. The mixture is non-fluid at 25 ° C. Here, the non-fluidity means that it does not deform or flow in a no-load state, and preferably, when molded into a sheet, it does not deform or flow in a state of 25 ° C. and no load. .. Such non-fluidity can be evaluated, for example, by placing the molded composition on a hot plate at 25 ° C. and substantially not deforming or flowing even when no load or a constant load is applied. When it is non-fluid at 25 ° C., it has good shape retention at that temperature and can be treated as a solid.

The softening point of the mixture given in step 1 is 200 ° C. or lower, preferably 150 ° C. or lower. Such a softening point is pressed on a hot plate with a load of 100 grams for 10 seconds from above, and when the amount of deformation of the composition is measured after removing the load, the amount of deformation in the height direction is 1 mm or more. It means the temperature that becomes.

The softening point of the mixture given in step 1 is 200 ° C. or lower, and by heating the entire mixture to a temperature equal to or higher than the softening point of the mixture in step 2 described later, the mixture is heated and melted to give a constant fluidity. be able to. By molding the softened product or melt, a curable silicone sheet having hot melt property can be obtained.

In step 1, the organopolysiloxane resin solid at room temperature and optionally the chain diorganopolysiloxane are used in the form of a solution dispersed or dissolved in an organic solvent. Organopolysiloxane resin, which is solid at room temperature, is non-fluid by itself at room temperature, and chain diorganopolysiloxane, which is an optional component, is semi-solid with liquid or plasticity at room temperature, but is organic. When dispersed or dissolved in a solvent, these components can be handled in a uniform solution system, and by removing the organic solvent, an organopolysiloxane resin and optionally a chain diorganopoly can be used. A hot-melting solid component containing siloxane can be easily obtained. In the step 1, any component other than the curing agent (may contain a functional filler, but is substantially not contained) as long as it does not adversely affect the removal of the organic solvent and the curing reaction at a high temperature does not proceed. Is particularly preferable). Further, the mixture which is a hot-melting solid component obtained in step 1 excluding the curing agent is sometimes called "compound" in the actual manufacturing process.

A typical step of dispersing or dissolving an organopolysiloxane resin solid at room temperature, optionally a chain of diorganopolysiloxane, and any other component (excluding a curing agent) in an organic solvent is typical. Is a step of using a mixing or stirring device using mechanical force. The organopolysiloxane resin and chain diorganopolysiloxane used in the present invention are soluble in organic solvents. Further, the organopolysiloxane resin is industrially generally synthesized in a state of being dissolved in an organic solvent. Therefore, it is relatively easy to physically and uniformly mix the solution of the organopolysiloxane resin dissolved in the organic solvent with the above-mentioned chain organopolysiloxane in a solution system. The mixing or stirring device using mechanical power is not particularly limited, but a kneader, a Banbury mixer, a loss mixer, a hobart mixer, a dental mixer, a planetary mixer, a kneader mixer, a homo mixer, and a paddle having a heating / cooling function are not particularly limited. Examples thereof include batch type devices such as mixers, line mixers, homodispers, propeller stirrers, vacuum kneaders, high-speed dispersers, lab plast mills and Henschel mixers.

A hot-melt solid content can be obtained by removing the organic solvent while heat-treating the above mixture containing the organic solvent at a temperature of 150 ° C. or higher, preferably 200 ° C. or higher. Here, the removal of the organic solvent is preferably carried out while performing uniform mixing, and can be carried out in the above-mentioned mixing or stirring device using mechanical force provided with heat treatment means. In particular, it is particularly preferable to use a continuous heating and kneading device such as a single-screw extruder, a twin-screw extruder, or a continuous kneader having a heating function. Preferably, the above mixture containing the organic solvent is treated with a continuous heat-kneading device such as an extruder heated to 200 ° C. or higher to remove the organic solvent and continuously recover as a hot-melt solid. It is possible to do.

If the purpose is simply to remove the organic solvent, it is sufficient to treat the above mixture at about 150 to 200 ° C., but in the present invention, it is particularly treated at a temperature of 200 ° C. or higher. It is possible to remove as much as possible the volatile components derived from the organopolysiloxane resin and the like, which will be described later, from this mixture. Therefore, step 1 is preferably a step of removing volatile components derived from an organic solvent and other organopolysiloxane resin at a temperature of 200 ° C. or higher. In particular, by removing these volatile components in step 1, the physical properties of the cured product obtained by curing the obtained curable silicone sheet having hot melt property may be further improved.

In step 1, the treatment for removing the volatile components derived from the organic solvent and other organopolysiloxane resin or the like may be under a reduced pressure condition of 1 atm or less (preferably under vacuum reduced pressure) under 1 atm of normal pressure. It may be. In particular, in step 1, a continuous heating and kneading device such as an extruder may be used, and the inside thereof may be depressurized to 1 atm or less, or may be used at normal pressure.

[Step 2]
In step 2, all the curing agents are added to the mixture of the organopolysiloxane resin that is non-fluid at 25 ° C. and the chain-like organopolysiloxane obtained in step 1, and then kneaded while heating at a temperature below a certain level. In order to knead each raw material in the presence of a curing agent without advancing the curing reaction and finally obtain a curable silicone sheet having hot melt property, temperature control in the process is important. Become an element. Further, by suppressing the heat history after the start of the step 2, particularly the time of exposure to a high temperature for a short time, the curability of the finally obtained curable silicone sheet can be maintained or improved. In addition, in order to remove air bubbles described later from the composition, step 2 is preferably performed under degassing conditions by a degassing mechanism such as a vacuum pump.

Step 2 can be carried out in the batch type apparatus described in Step 1 and can also be carried out in a mixing or stirring apparatus provided with a temperature control mechanism, preferably a degassing mechanism, but a number of additives are continuously added. From the viewpoint that it can be charged separately, it is preferable to use a continuous heat kneading device such as a single-screw extruder, a twin-screw extruder, and a continuous kneader. In particular, it is preferable to use a twin-screw extruder equipped with a temperature control mechanism and a degassing mechanism.

In step 1, which is a pre-step of step 2, a hot-meltable mixture (compound) heated to 150 ° C. or higher is obtained. The mixture is a hot-melt solid, non-fluid at room temperature and free of organic solvents and other volatile components. Further, since the mixture has fluidity at a temperature of 150 ° C. or higher, the kneading device in step 2, preferably a twin-screw extruder or the like, is used as it is unless a special cooling operation or the like is performed after step 1. It is possible to supply (feed) to a continuous heating and kneading device. On the other hand, when the step 1 and the step 2 are separated, the obtained hot-meltable mixture (compound) is reheated and melted while being supplied to the kneader used in the step 2. This method will be described later. The use of bulk melters can be mentioned.

In step 2, the means for supplying (feeding) the hot-melting solid content to the heat-kneading apparatus is not particularly limited, but the purpose is to maintain the temperature control means (specifically, the tank having the heating / cooling mechanism and the temperature). By using a metering pump having (the jacket mentioned above), it is possible to supply (feed) a constant amount of hot-melt solids per unit time to a continuous heat-kneading device such as a twin-screw extruder. .. If the temperature of the solid content is controlled to be equal to or higher than the softening point, preferably 150 ° C. or higher in the metering pump, the hot-melt solid content is supplied to the heat-kneading apparatus in a fluid state of being heated and melted ( (Feed).

In step 2 of the present invention, in particular, by using a bulk melter manufactured by Nordson, a constant amount of hot-melt solid content per unit time can be easily applied to a continuous heat-kneading device such as a twin-screw extruder. Can be supplied.

Step 2 of the present invention includes a step of adding a curing agent to the above-mentioned hot-melting solid content. Preferably, in a continuous heat-kneading apparatus such as a twin-screw extruder, the hot-melt solid content (organopolysiloxane resin solid at room temperature and optionally chain organopolysiloxane) obtained in step 1 is contained. The mixture) is extruded into the kneading device while maintaining its fluidity, and at that time, a fixed amount of the curing agent is fed into the device from another line per unit time, so that the process The hot-melting solid content obtained in 1 and the curing agent are kneaded at a constant mass ratio.

Next, a mixture of the organopolysiloxane resin and optionally a chain of organopolysiloxane is extruded while flowing in the extruder, and the curing agent is quantitatively fed from another line using a metering pump to start melt kneading. To do. The metering pump into which the curing agent is charged may be used by appropriately selecting a gear pump, a plunger pump, a press pump, etc. depending on the amount and viscosity of the curing agent, and is particularly limited as long as it has a quantitative supply property. It's not a thing.

The curing agent supply line in step 2 may be divided into one or two or more supply lines. For example, the curable silicone sheet having hot meltability according to the present invention is a hydrosilylation reaction-curable silicone composition, and the organopolysiloxane resin obtained in step 1 and optionally a linear organopolysiloxane are used. When the mixture is an organopolysiloxane mixture containing a carbon-carbon double bond such as an alkenyl group, the curing agent is a combination of an organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom in the molecule and a hydrosilylation reaction catalyst. Can be mentioned. In this case, the hot-meltable solid content obtained in step 1 is supplied to the kneading apparatus in step 2 in a state of being heated and melted via the supply line, and the curing agent is supplied in the kneading apparatus in step 2. A component containing an organohydrogenpolysiloxane can be supplied by line 1, and then a component containing a hydrosilylation reaction catalyst can be supplied by line 2 of a curing agent. In particular, when using a continuous heat kneading device, by taking two or more hardener supply lines in step 2 and using a metering pump, not only is it unnecessary to perform operations such as uniform mixing of the hardener in advance. Since the temperature control described later becomes easy, it is extremely advantageous from the viewpoint of quality control of the curable silicone sheet having hot melt property, especially in large-scale industrial production.

In the above example, at the point where the organohydrogenpolysiloxane or the like is supplied to the hot melt solid content from the curing agent supply line 1 (referred to as “supply point 1”), the mixture serves as a hydrosilylation reaction catalyst. Due to the lack, the thermosetting reaction does not proceed even at high temperatures. Therefore, from the supply point 1 to the point where the sharing of the other curing agent is completed, the organohydrogenpolysiloxane or the like and the hot-melt solid content are kneaded at a temperature exceeding 120 ° C. (for example, 150 ° C.). can do. On the other hand, in the composition beyond the point where the hydrosilylation reaction catalyst is supplied from the curing agent supply line 2 (referred to as “supply point 2”), the thermosetting reaction proceeds at a high temperature. From this, when the operation of step 2 is performed by a continuous heat kneading device such as a twin-screw extruder, the temperature is set so that the thermosetting reaction does not proceed after the supply point 2 of the curing agent for the hot-melting solid content. It is necessary to control the temperature, and specifically, the temperature in the continuous heat-kneading apparatus after the supply point 2 is preferably controlled at 120 ° C. or lower, more preferably 100 ° C. or lower.

The temperature in the kneading apparatus after the point where the supply of one or more curing agents is completed needs to be 120 ° C. or lower, more preferably 100 ° C. or lower. Since the composition after the addition of the curing agent has thermosetting property at a high temperature, the composition has a softening point of 120 ° C. or higher, preferably 100 ° C., regardless of whether it is a batch type or a continuous type. If the temperature is not kept below the temperature, the thermosetting reaction proceeds and the whole is completely cured, making it difficult to obtain the curable silicone sheet which is the object of the present invention. The temperature range is preferably a temperature range of 80 ° C. to 120 ° C., particularly preferably a temperature range of 80 ° C. to 100 ° C.

When the step 2 is carried out particularly in a continuous heat-kneading device, the hot-melting solid content obtained in the step 1 is supplied into the device in a state of fluidity at a high temperature and extruded into the device. After the point at which the supply of the curing agent from one or more supply lines is completed and the composition acquires thermosetting property, the temperature in the kneading apparatus needs to be equal to or lower than the lower limit. Since the hot-melt solid content in step 1 is heated to 150 ° C. or higher, the temperature inside the apparatus is 120 ° C. or lower, preferably 100 ° C. or lower, particularly preferably 80 ° C. to 100 ° C. by the above point. It is one of the features in the manufacturing method of the present invention that the temperature is controlled so as to be.

In step 2, the curing retarder described later may be supplied together with an organohydrogenpolysiloxane or may be supplied together with a hydrosilylation reaction catalyst. In particular, from the viewpoint of improving the transparency and curability of the curable silicone sheet of the present invention, the organopolysiloxane is combined with the organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom in the molecule before the supply of the hydrosilylation reaction catalyst. It is preferably added to the mixture of resin and optionally linear organopolysiloxane and kneaded. Specifically, it is particularly preferable to supply the organohydrogenpolysiloxane and the curing retarder from the curing agent supply line 1 at the supply point 1. By going through such a step, the compound, the organohydrogenpolysiloxane, and the curing retarder can be uniformly kneaded at a high temperature, and an unintended curing reaction after the addition of the hydrosilylation reaction catalyst may be suppressed. In addition, it may be possible to suppress unintended reactions, coloring, and inactivation of the hydrosilylation reaction catalyst and the curing retarder.

Preferably, the step 2 includes a step of degassing and kneading the hot-melting solid content and the curing agent of the step 1 while heating and melting under the above temperature conditions. In this step 2, air is entrained when each component is mixed, and bubbles appear on the sheets produced in steps 3 and subsequent steps, which adversely affects the quality and heat-melting characteristics of the curable silicone sheet having hot-melt property. Since there is a high possibility, kneading while degassing is particularly preferable for obtaining a curable silicone sheet having excellent transparency. The degree of degassing can be appropriately adjusted by entraining air during kneading (that is, the amount of air bubbles), but it is preferable to degas under reduced pressure to less than 1 atm. It should be noted that this degree of decompression degassing can be easily realized by connecting a known degassing / depressurizing pump such as a vacuum pump to the kneading device used in step 2, and appropriately depending on the degree of defoaming. The internal pressure may be adjusted.

[Mixture fluidity and temporary molding process]
When the mixture obtained in step 1 has a low heat-melt viscosity and high fluidity, it can be laminated on a release film after being temporarily molded in advance in step 3 described later, and is preferable. If the melt viscosity of the mixture after heating and melting obtained in step 2 as measured by an elevated flow tester at 150 ° C. is in the range of 1 to 1,000 Pas, temporary molding can be performed in step 3.

On the other hand, when the heat-melt viscosity of the mixture obtained in step 1 is high and the fluidity is poor, the mixture obtained in step 1 is melt-kneaded at a temperature equal to or higher than the softening point in step 2 to obtain a uniform composition. After obtaining the morphology, it may be laminated on the release film in step 3 without performing temporary molding.

[Step 3]
Step 3 is a step of laminating the mixture after heating and melting obtained in Step 2 between films having at least one peeling surface, and is a preliminary step for pressure molding in Step 4. Therefore, the step 3 and the subsequent step, the step 4, can be integrated, and if necessary, the step 3 and the step 4 can be substantially performed at the same time. By forming a laminate in which the mixture obtained in step 2 is sandwiched between films, pressure molding by roll stretching can be performed on the film to obtain a sheet-shaped molded product, and the film is peeled off after molding. Only the film can be removed from the sheet-like molded product using the surface.

The mixture after heating and melting obtained in step 2 is laminated between two films. Although it depends on the usage pattern of the obtained curable silicone sheet, it is preferable that both of the two films have a peeling surface, and in step 3, the mixture obtained in step 2 is laminated between the peeling surfaces of each film. Is particularly preferable. By adopting such a laminated form, a laminated sheet that can be peeled from both sides, in which a thin layer curable silicone sheet is sandwiched between the peelable films, is obtained through pressure molding in step 4 and subsequent arbitrary cutting. It can be obtained, and at the time of use, the films on both sides can be peeled off to expose only the curable silicone sheet without fear of damaging the formed curable silicone sheet.

The base material of the film used in step 3 is not particularly limited, and is not particularly limited. Sheet paper, cardboard paper, clay coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin film / sheet, natural fiber cloth, synthetic fiber. Examples include cloth, artificial leather cloth, and metal foil. In particular, synthetic resin films and sheets are preferable, and examples of the synthetic resin include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and nylon. When heat resistance is particularly required, a film made of a heat-resistant synthetic resin such as polyimide, polyetheretherketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide, or polyethersulphon is suitable. On the other hand, in applications where visibility is required such as display devices, transparent substrates, specifically transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN are suitable. Further, it may be a multi-layer film in which two or more types of films are laminated. In this case, it is preferable that the side in contact with the obtained curable silicone sheet is a functional film having excellent optical characteristics and the like.

The thickness of the film is not particularly limited, but when the melt viscosity of the obtained melt-kneaded product is high, the film is exposed to considerable pressure in a high temperature state in the stretching step by roll in step 4, so that high heat resistance is obtained. When the film is not used, if the film is too thin, wrinkles and the like may occur during stretching. Therefore, the film thickness is 50 μm or more, preferably 75 μm or more, preferably 75 to 300 μm, more preferably 75 to 75. It is preferably 200 μm.

The film preferably comprises at least one release layer, which is in contact with the mixture obtained in step 2. As a result, the hot-meltable curable silicone sheet that has been pressure-molded can be easily peeled off from the film through the steps 3 and 4. The release layer is sometimes called a release liner, a separator, a release layer or a release coating layer, and preferably removes a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, a fluorosilicone-based release agent, or the like. The peeling layer having a coating ability, physically fine irregularities may be formed on the surface of the base material, or the base material itself which is hard to adhere to the hot meltable curable silicone sheet according to the present invention may be used.

As will be described later, the curable silicone sheet having hot melt property according to the present invention is laminated between two films. When the silicone sheet is used, usually both films are peeled off and used, but the silicone sheet may be cured by peeling off only one film and leaving the film on one side. In this case, it is preferable to select a film that can be easily peeled off even after the silicone sheet has been cured.

The release surface on the film is preferably a release coating layer obtained by a fluorosilicone-based release agent from the viewpoint of releaseability to the curable silicone sheet. Here, the fluorosilicone-based release agent is a curable organopolysiloxane composition containing one or more types of organopolysiloxane having a fluorine-containing substituent bonded to a silicon atom in one molecule, and is particularly intramolecular. It is preferable to use a curable organopolysiloxane composition containing an organopolysiloxane containing at least one fluorine-containing substituent selected from a fluoroalkyl group and a perfluoropolyether group. The organopolysiloxane containing a fluorine-containing substituent may further have a curing reactive group such as an alkenyl group in the same molecule, and an organopolysiloxane containing two or more different fluorine-containing substituents may be combined. It may be used in a specific mixing ratio.

For example, the release coating layer obtained by the fluorosilicone-based release agent that can be used in the present invention may be a release coating layer obtained by curing the following compositions (i) to (iv).
(I) Curable organopolysiloxane composition containing two or more types of organopolysiloxanes having different fluoroalkyl groups and having curing reactive groups in the molecule (ii) Different perfluoropolyether groups Curable organopolysiloxane composition containing two or more types of organopolysiloxanes and having a cure-reactive group in the molecule (iii) Organopoly having a fluoroalkyl group and a cure-reactive group in the molecule Curable organopolysiloxane composition containing siloxane and an organopolysiloxane having a perfluoropolyether group and a curing reactive group in the molecule (iv) Selected from fluoroalkyl and perfluoropolyether groups in the molecule 1 A curable organopolysiloxane composition containing an organopolysiloxane containing more than one type of fluorine-containing substituent, having no curing-reactive group, and having a property of being mixed with other curing-reactive components.

In the present invention, practically, the peeling surface on the film is a peeling coating layer obtained by a fluorosilicone-based release agent, and specifically, a fluorosilicone-based coating containing a perfluorobutyl ethyl group is preferable. Examples of film products that have undergone such a release coating treatment include Takaline Corporation's FL1-01, FL1-02, FL1-03, FL2-01, Nippa Corporation's FSA6, FSB6, FSC6, and I'm Co., Ltd. Examples include FB and FE. For fluorosilicone-based coatings using a curable organopolysiloxane composition containing an organopolysiloxane having a fluorine-containing substituent such as a perfluorobutylethyl group at the side chain or end, selection and peeling of the crosslinked structure and crosslink density The desired peeling property can be designed depending on the thickness of the layer, and in the practice of the present invention, a peeling coating film having an appropriate peeling force may be selected from the above-mentioned commercially available products to give the desired peeling property. Such a film may be appropriately designed and used.

When the above-mentioned two-layer or more multi-layer film is used, it is possible to produce a multi-layer laminate of a curable silicone sheet and a functional film by using the above-mentioned releaseable film on both sides as the outermost exterior. .. By selecting the type of functional film, it is possible to provide a hot melt silicone sheet having various additional functions such as optical properties and barrier properties. The exact same production process can be used to produce a multi-layered sheet.

At least one of the films may further have a functional layer. The functional layer is a layer provided in contact with one surface of the above-mentioned hot-meltable curable silicone sheet, and may form a multi-layer laminate together with the curable silicone composition layer. The functional layer has a function that is not found in a layer formed by curing a curable silicone sheet having hot melt property, or is formed by curing a curable hot melt silicone composition layer or a curable hot melt silicone composition. The layer may be made of a material exhibiting properties preferable to those of the layer, and may be a layer for imparting a desired function to one surface of the multi-layer laminate. The function of the functional layer is not limited to a specific function, but is lower tack, higher elastic modulus, and lower contamination than, for example, a curable hot melt silicone composition layer or a cured product layer formed by curing the composition. Functions selected from property and high water repellency and / or oil repellency can be mentioned. The multi-layer laminate of the present invention is sealed by using as the functional layer a curable hot-melt silicone composition layer or a functional layer having a lower tack or a higher elastic modulus than the layer formed by curing the layer. When a curable hot-melt silicone composition layer is adhered to a substrate, for example, a semiconductor precursor substrate to prepare a substrate sealed with silicone, the stickiness of the surface of the sealing layer can be reduced. It can be handled, which improves the ease of handling and the stain resistance of the surface. The functional layer is a layer made of a material having a lower tack than the curable hot melt silicone composition, a layer made of a material having a higher elasticity than the cured product formed by curing the curable hot melt silicone composition, and curability. Curable when cured with the hot melt silicone composition A layer made of a curable material that has a higher elasticity than the cured product formed by curing the hot melt silicone composition, and has water repellency and / or oil repellency. a layer of material, and the optically functional layer, e.g., light scattering layer, the light diffusion layer, the high refractive index layer, a low refractive index layer, and the light of a specific wavelength from and whether Ranaru group selectively permeable layers It is preferably a layer selected from the group consisting of selected layers.

The material used for the functional layer may be a silicone-based material different from the above-mentioned curable hot-melt silicone composition, or a non-silicone-based material. Further, the material used for the functional layer may be a non-curable material or a curable material. As the material used for the functional layer, any material having the above-mentioned properties can be used. When the material used for the functional layer is a curable material, it is particularly preferable that the material is cured under the conditions for curing the curable hot-melt silicone composition of the multi-layer laminate. Examples of the material used for the functional layer include, but are not limited to, plastic films, silicone resins, and silicone elastomers.

Desirable for improving adhesion between a functional layer (eg, a layer made of a plastic film, a silicone resin, a silicone elastomer, etc., which has properties such as low tack or high elasticity) and a curable hot melt silicone composition layer. To the extent that the technical effect of the present invention is not impaired, the surface of the functional layer is subjected to surface treatment by an oxidation method, an unevenness method, or a primer treatment, and then the above-mentioned curable hot-melt silicone is applied. The composition layer may be laminated. Here, examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, and the like, and the unevenness method includes unevenness treatment. For example, a sandblasting method, a thermal spraying method, and the like can be mentioned. For these surface treatment methods, a suitable method can be selected according to the type of functional layer and the required adhesion, but the effect obtained by the surface treatment, particularly the effect of improving the adhesion is high, and the operation is simple. Therefore, the corona discharge treatment method can be mentioned as a preferable method. The surface treatment may improve the contact interface adhesion after lamination, particularly the adhesion of the curable hot melt silicone composition layer before the curing reaction. For example, a plastic film, a silicone elastomer (cured product) or a silicone resin is selected as a functional layer, and the surface thereof is subjected to the above surface treatment, primer treatment, etc., and then a curable hot melt silicone composition layer is formed by heating and melting. Forming a multi-layer laminate by forming is included in a preferred embodiment of the present invention.

By optional option, as the functional layer used in step 3, plastic film, silicone resin, and silicone elastomer can be preferably mentioned as described above, and in particular, plastic which may optionally have a release layer on the surface. A product in which a functional layer made of a cured product of a silicone resin or a cured product of a silicone elastomer is formed on the surface of a film substrate or the like can be preferably exemplified. These functional layers are formed by, for example, applying a curable silicone resin composition or a curable silicone elastomer composition on a plastic film substrate which may optionally have a release layer on the surface and curing the coating. , Easy to prepare. The applicable curing method is not particularly limited because it depends on the curing system, and examples thereof include drying by removing the solvent, heat drying, moisture curing at room temperature, and irradiation with high energy rays such as ultraviolet rays.

In step 3, the mixture obtained in step 2 is optionally tentatively molded and then laminated between the two films. The step is not particularly limited, but in step 3, the step of laminating the mixture after heating and melting between the films is not particularly limited, and (i) the step is on the first release film provided with the release surface. After the mixture after heating and melting from No. 2 is discharged or applied, the second release film is brought into contact with the surface of the mixture opposite to the surface in contact with the first release film to obtain the first release film. It may be a step of interposing, that is, sandwiching the mixture after heating and melting between the second release films, or (ii) step 2 between the first release film having the release surface and the second release film. It may be a step of interposing the mixture after heating and melting between the two release films by discharging or applying the mixture after heating and melting from the film. In (ii), the first and second release films are brought close to each other by an appropriate means such as two rolls, and the mixture from step 2 is discharged or coated at a place where the two release films are close to each other to prepare the mixture. A method of sandwiching the gap between two release films at the same time or almost at the same time can be exemplified.

The mixture obtained in step 2 may be supplied by being discharged or applied onto the release layer of one film, and a laminate may be formed by laminating the release layer of the other film from the mixture. , The laminate may be formed by supplying the mixture by continuously discharging or applying the mixture between the two films. At this time, in the continuous manufacturing process of the curable silicone sheet, each film is transported to the supply position of the mixture in step 2 via a rotary roll, and a laminating operation is performed between the films. The diameter and width of the rotary roll are not particularly limited, but it is desirable that the structure allows uniform pressurization in the width direction. The pressurizing method is not particularly limited, but an air cylinder or a hydraulic type is preferable.

The amount of the mixture obtained in step 2 in step 3 supplied between the films can be designed according to the production speed and scale. As an example, a supply amount of 1 to 10 kg / hour can be supplied between the films of the mixture obtained in step 2, but it goes without saying that the supply amount is not limited to this. However, in step 3, the amount of the mixture obtained in step 2 to be laminated between the films needs to be determined according to the average thickness of the curable silicone sheet designed in step 4, and is rolled in step 4. It needs to be thick enough to be processed.

When the heat-melt viscosity of the mixture obtained in step 1 is low and the fluidity is high, in step 3, the mixture obtained after heat-melting in step 2 is in the form of a film or a string (narrow diameter) using a die and a nozzle. It is preferable that the film is discharged while being molded into a rod-shaped molded product (including a rod-shaped molded product discharged from the hole) and laminated between the films. Here, the die is used for temporarily molding the mixture, and the type and thickness at the time of temporary molding are not particularly limited, but a T-type die or a strand die having a structure capable of heating is used. It can be temporarily molded into a substantially sheet shape having a thickness in the range of 100 to 2000 μm (= 2 mm), and is preferable. Further, if necessary, a die in which the discharge port of these T-type dies or strand dies is deformed to be flat with respect to the discharge surface (horizontal direction) may be used.

When the heat-melt viscosity of the mixture obtained in step 2 is low and the fluidity is high, after the above-mentioned temporary molding, the entire laminate obtained in step 3 is cooled or temperature-controlled as a pre-step of step 4 or in step 4. It is preferable to include a step. This is because the pressure molding in the step 4 is effectively performed by cooling the heated melt to make it solid. The cooling step is not particularly limited, but the mixture supplied or laminated on the film by a cooling roll, cold air, or the like is cooled in the range of -50 ° C to room temperature by using a cooling means such as air cooling or a cooling solvent. It can be done by doing.

On the other hand, when the heat-melt viscosity of the mixture obtained in step 2 is high and the fluidity is low, if the entire laminate is cooled in step 3, the viscosity of the mixture becomes too high and it is difficult to control the film thickness. Therefore, it is preferable to include a step of adjusting the temperature of the entire laminate between 80 and 120 ° C. as a pre-step or step 4 of step 4. The details of temperature control will be described in step 4.

[Step 4]
Step 4 is a step of stretching the laminate obtained in the above step 3 between the rolls to form a curable silicone sheet having a specific film thickness, and pressurizing and stretching the mixture obtained in step 2 from the film. This is a step of molding into a uniform curable silicone sheet. The number of sets of rolling rolls may be single or plural.

The rolling process in step 4 can be performed on the laminated body obtained in step 3 by using a known rolling method such as roll rolling. In particular, in the case of roll rolling, there is an advantage that a curable silicone sheet having a desired thickness can be designed by adjusting the gap between the rolls. For example, the average thickness between the rolls is in the range of 10 to 2000 μm. By rolling with the gap adjusted to be constant, it is possible to obtain a curable silicone sheet having excellent flatness and extremely few defects on the sheet surface and inside the sheet. More specifically, in the case of roll rolling, it is particularly preferable that the gap between the rolls is adjusted in the range of 1.5 to 4.0 times the average thickness of the target organopolysiloxane cured film.

By stretching in step 4, a substantially flat curable silicone sheet having a thickness of 10 to 2000 μm can be obtained. By roll-stretching the mixture after heating and melting in step 2 in the form of being laminated between the peelable films in step 3, it contains a curable silicone sheet having hot melt property, which has low defects and excellent handling workability by peeling. A peelable laminate can be obtained. Further, by attaching a film thickness meter, the film thickness can be measured for the laminate obtained in step 3, the film thickness can be easily adjusted, and the film thickness can be controlled.

[Temperature control in step 4]
In step 4, when the laminate obtained in step 3 is stretched between rolls, the roll further has a temperature control function, and the temperature of the entire laminate is controlled during roll rolling, and heating or cooling is performed as necessary. Is preferable. By controlling the temperature, the gap between the rolls can be kept stable, and the flatness and uniformity (uniformity of film thickness) of the obtained hot-meltable curable silicone sheet can be improved. The specific range of temperature control can be appropriately designed according to the heat resistance of the film, the thickness of the curable silicone sheet (design thickness), its reactivity, etc., but is generally within the range of 5 to 120 ° C. is there.

When the melt viscosity of the mixture after heating and melting obtained in step 2 is high, if the temperature of the mixture is significantly lowered at the time of laminating with a roll, the viscosity of the mixture becomes too high and it becomes difficult to control the film thickness. Sometimes. In order to avoid this, when the heat-melt viscosity of the mixture is high, it is necessary to supply the mixture to a rotary roll without lowering the temperature of the mixture. Take measures such as heating the roll itself to a temperature range of 80 to 120 ° C. and narrowing the distance between the die and the roll, which is the outlet of a continuous heating and kneading device such as a twin-screw extruder, as much as possible. As a result, the mixture can be supplied to the rotary roll at a temperature substantially the same as the outlet temperature of the heat-kneading apparatus, and it is possible to prevent the viscosity from increasing.

On the other hand, if the temperature of the mixture or the temperature of the roll itself significantly exceeds 120 ° C., there is a concern that the reaction of the heat-curable mixture will proceed, or if the heat resistance of the film used is low, the film will wrinkle during stretching. Precise temperature control is required at this step because there is a concern that it will enter.

[Control of the time from the start of process 2 to the end of process 4]
From the viewpoint of industrial mass production from the steps 2 to 4, it is preferable that the steps are continuous, but when a thermosetting composition is handled as a hot-meltable composition, as described above, a certain point of the step 2 ( When exposed to a high temperature for a long time from the supply point 2), the curing reaction of the composition can proceed, which may adversely affect the curability of the finally obtained hot-meltable curable silicone sheet. In order to prevent this, temperature control during kneading is important, but further, the time from the completion of steps 2 to 4 to the start of cooling of the obtained silicone sheet is short, specifically, It is preferably within 30 minutes, preferably within 15 minutes, and even more preferably within 5 minutes. In the manufacturing process, if the time of exposure to high temperature is within the above range, even if a silicone sheet made of a thermosetting composition is produced, the reaction does not proceed and a sheet having excellent hot melt property is produced. Is possible.

[Integration or integration of process 3 and process 4]
Steps 3 and 4 may be continuous and integrated steps, for example, the mixture after heating and melting obtained in step 2 is discharged between the films having at least one peeling surface directly under the rolls. It may be laminated by being applied, and at the same time, it may be stretch-molded to a specific film thickness by adjusting the gap between the rolls. As described above, a manufacturing method having a step in which the steps 3 and 4 are substantially integrated is also included in the scope of the above-mentioned manufacturing method.
That is, in steps 3 and 4, the mixture obtained in step 2 is discharged or applied between two release films, and the mixture is between the two release films, for example, between two long release films. The step of sandwiching the film, the two release films obtained thereby, and the laminate consisting of the above-mentioned mixture interposed between them are continuously passed between the rolls to stretch-mold the mixture between the release films, and a predetermined value is obtained. The step of adjusting the film thickness to obtain the desired laminate may be continuously and integrally performed. A method of integrally performing such steps 3 and 4 is also included in the above-mentioned manufacturing method.

[Cutting process]
By step 4, a peelable laminate in which a hot-meltable curable silicone sheet is interposed between the release films can be obtained, and optionally, a step of cutting the laminate containing the curable silicone sheet is performed. May have. This makes it possible to obtain a peelable laminate containing a hot-meltable curable silicone sheet of a desired size. The cutting device is not limited, but a device capable of continuously cutting in the width direction and the length direction is preferable, and it is desirable that the line speed can be adjusted. It can be cut continuously by using a sheet cutter manufactured by Soltec Industry Co., Ltd. If the cutting device has a foreign matter inspection machine, foreign matter can be detected, marked and removed before cutting.

[Pass line after rotary roll]
Further, according to the step 4, a peelable laminate in which a hot-melt curable silicone sheet is interposed between the peelable films is obtained, and the peelable film is coated with a fluorosilicone system. When used, the adhesion to the silicone sheet tends to be very weak, and the film may peel off from the silicone sheet depending on the pass line after step 4. If an extreme U-shaped pass line is present, the film is likely to peel off from the silicone sheet, so that the pass line is preferably straight after the rotary roll to be stretched. For this reason, it is better to avoid winding with a winding device or the like before the cutting process, and it is preferable to continuously cut to a desired size in the cutting process.

[Arbitrary process for quality control, etc.]
In step 4, a peelable laminate in which a hot-meltable curable silicone sheet is interposed between the peelable films is obtained. After that, a step for the purpose of quality control (for example, characteristic value) A step of measuring and controlling the presence or absence of foreign matter) may be included, and is preferable. The step is preferably performed by a foreign matter detecting device provided with an optical measuring means such as a camera or a video.

[Laminate]
The laminate obtained by the above steps is a substantially flat, curable silicone having a hot melt property having a thickness of 10 to 2000 μm, which contains at least an organopolysiloxane resin, optionally a chain of organopolysiloxane and a curing agent. The sheet is a laminated body having a structure in which the sheets are laminated between films having at least one peeling surface. The film may both have a peeling surface, and is preferable.

[Curable silicone sheet]
The curable silicone sheet obtained by the production method of the present invention contains at least an organopolysiloxane resin, optionally a chain of organopolysiloxane, and a curing agent, and may further contain a functional filler and other components. It is a silicone composition, has hot melt properties, can be used as a heat-meltable pressure-sensitive adhesive, and forms a cured silicone product with excellent heat resistance and stress relaxation by curing. In particular, the curable silicone sheet is excellent in moldability, gap fill property and adhesive strength / adhesive strength, and can be used as a die attach film or a film adhesive. It can also be suitably used as a curable silicone sheet that forms a sealing layer by compression molding, press molding, or vacuum lamination. Regardless of the application, the curable silicone sheet is a sheet-like product having hot melt properties, and therefore can be suitably applied to adhesion or sealing of a large area.

Specifically, the curable silicone sheet obtained by the production method of the present invention is a film that is peeled off from a peelable film and then placed at a desired site such as a semiconductor to take advantage of the gap fill property for irregularities and gaps. An adhesive layer is formed on the adherends to temporarily fix, arrange, and bond the adherends, and further, the curable silicone sheet is heated to 150 ° C. or higher to form the adhesive layer between the adherends. It may be adhered by a cured product of a curable silicone sheet. The peelable film may be peeled off after the curable silicone sheet is heated to form a cured product, and such use is preferable when it is used as a layer for sealing a substrate such as a semiconductor. The timing of peeling may be selected according to the application and method of use of the curable silicone sheet.

Since the curable silicone sheet is hot-meltable, it can be softened or fluidized by heating the sheet before final curing. For example, even if the adherend surface of the adherend has irregularities, there are no gaps. And gaps can be filled to form an adhesive surface. As the heating means for the curable silicone sheet, for example, various constant temperature baths, hot plates, electromagnetic heating devices, heating rolls, and the like can be used. For more efficient bonding and heating, for example, an electric press, a diaphragm type laminator, a roll laminator, or the like is preferably used.

As described above, the curable silicone sheet according to the present invention is excellent in gap fill property at the time of melting and flexibility of the cured product at room temperature to high temperature. It can be extremely suitably used for a molding method including a coating step (so-called mold underfill method) in which filling is performed all at once. Further, the present composition is a coating that covers the surface of a semiconductor wafer substrate on which a single or a plurality of semiconductor elements are mounted and is overmolded so that the gaps between the semiconductor elements are filled with the cured product due to the above characteristics. It can be suitably used for a molding method including a step (so-called wafer molding).

In the above steps, a compression molding machine, an injection molding machine, an auxiliary ram type molding machine, a slide type molding machine, a double ram type molding machine, a low pressure filling molding machine, a heat press, a vacuum laminator and the like can be used. In particular, the curable silicone sheet according to the present invention can be suitably used for the purpose of obtaining a cured product by press molding, compression molding, and vacuum lamination.

As a condition for thermosetting the curable silicone sheet, the optimum temperature can be selected according to the curing system. In the case of a hydrosilylation reaction, the temperature is preferably 150 ° C. or higher, and in the case of organic peroxide curing, the temperature is preferably 170 ° C. or higher.

Since it is suitable as a protective member for semiconductors and the like, it is preferable that the type D durometer hardness of the cured product obtained by curing the curable silicone sheet according to the present invention at 25 ° C. is 20 or more. The hardness of this type D durometer is determined by a type D durometer according to JIS K 6253-1997 "Hardness test method for vulcanized rubber and thermoplastic rubber".

Further, since it is suitable as a sealing material for semiconductors for flexible applications that require flexibility, the bending elongation of the cured product measured by the method specified in JIS K 6911-1995 "General Test Method for Thermosetting Plastics". Is preferably 2% or more, or 4% or more.

[Use of curable silicone sheet according to the present invention]
The curable silicone sheet according to the present invention has a hot melt property, and is excellent in gap fill property at the time of melting (hot melt), handling workability, and curability. Therefore, a sealant or underfill agent for semiconductors. Encapsulants and underfill agents for power semiconductors such as SiC and GaN; Encapsulants and photoreflectors for opto-semiconductors such as light emitting diodes, photodiodes, phototransistors, laser diodes; Adhesives for electricity and electronics , Suitable as a potting agent, a protective agent, and a coating agent. Further, since this composition has hot melt properties, it is also suitable as a material for press molding, compression molding, or molding by vacuum lamination. In particular, it is preferably used as a sealing agent for semiconductors that use a mold underfill method or a wafer molding method at the time of molding.

In particular, the curable silicone sheet according to the present invention can be used for encapsulating a large area of a semiconductor substrate (including a wafer or an optical semiconductor substrate). Further, the sheet formed by molding the curable silicone composition of the present invention into a sheet forms a die attach film, seals a flexible device, and adheres two different substrates, for example, a large-area substrate to a panel or panel to each other. It can be used for stress relaxation layers and the like.

[Use of the cured product of the curable silicone sheet according to the present invention]
The application of the cured product of the present invention is not particularly limited, but the composition of the present invention has hot melt properties, is excellent in moldability and gap fill characteristics, and the cured product has the above-mentioned flexibility at room temperature. It has high stress relaxation characteristics, bending elongation, etc. Therefore, the cured product obtained by curing the present composition can be suitably used as a member for a semiconductor device, a sealing material for a semiconductor element including an optical semiconductor, an IC chip, and a light reflecting material for an optical semiconductor device. , It can be suitably used as an adhesive / bonding member for semiconductor devices and an adhesive / bonding member for display panels.

The semiconductor device provided with the member made of the cured product is not particularly limited, but is particularly preferably a power semiconductor device, an optical semiconductor device, and a semiconductor device mounted on a flexible circuit board.

[Curable Silicone Composition]
The curable silicone sheet of the present invention comprises a curable silicone composition containing (A1) an organopolysiloxane resin solid at room temperature, optionally (A2) a chain diorganopolysiloxane, and (B) a curing agent. It's okay. Hereinafter, each component and optional components of the composition will be described.

The component (A1) is the main agent of the present composition, and is an organopolysiloxane resin in a solid state at room temperature, which is cured by the curing agent (C). Here, at least a part of the component (A1) preferably has a curing-reactive functional group, and is selected from a condensation-reactive group, a hydrosilylation-reactive group, a radical-reactive group and a peroxide-curable group. Although it is one or more kinds of functional groups, a hydrosilylation-reactive group and a radical-reactive group are preferable, and a curing-reactive functional group containing a carbon-carbon double bond is particularly preferable.

The hydrosilylation-reactive group in the component (A1) includes a vinyl group, an allyl group, a butenyl group, a penthenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group and the like. 2 to 20 alkenyl groups and silicon atom-bonded hydrogen atoms are exemplified. As the hydrosilylation-reactive group, an alkenyl group is preferable. The alkenyl group may be linear or branched, preferably a vinyl group or a hexenyl group. The component (A1) preferably has at least two hydrosilylation-reactive groups in one molecule.

Examples of the group bonded to the silicon atom other than the hydrosilylation-reactive group in the component (A1) include an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , A halogen-substituted aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group, and a hydroxyl group are exemplified. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; phenyl group and trill group. , Aryl groups such as xylyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group; aralkyl groups such as phenethyl group and phenylpropyl group; and some or all of the hydrogen atoms bonded to these groups are chlorine atoms. , A group substituted with a halogen atom such as a bromine atom; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group is exemplified. In particular, phenyl groups and hydroxyl groups are preferable.

The radically reactive group in the component (A1) includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Alkyl group having 1 to 20 carbon atoms; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc. Alkenyl groups; acrylic-containing groups such as 3-acryloxypropyl group and 4-acryloxybutyl group; methacryl-containing groups such as 3-methacryloxypropyl group and 4-methacryloxybutyl group; and silicon atom-bonded hydrogen atoms are exemplified. Will be done. The radical reactive group is preferably an alkenyl group. The alkenyl group may be linear or branched, preferably a vinyl group or a hexenyl group. The component (A1) preferably has at least two radical reactive groups in one molecule.

Examples of the group bonded to the silicon atom other than the radical reactive group in the component (A1) include a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen-substituted aryl group having 6 to 20 carbon atoms. Groups, aralkyl groups having 7 to 20 carbon atoms, alkoxy groups, and hydroxyl groups are exemplified, and groups similar to the above are exemplified. In particular, phenyl groups and hydroxyl groups are preferable. In particular, the component (A1) preferably contains 10 mol% or more of all organic groups in the molecule as an aryl group, particularly a phenyl group.

In the present invention, the component (A1) preferably contains an organopolysiloxane resin having a curing-reactive functional group, but the organopolysiloxane resin may be hot-meltable as a whole molecule. It may be an organopolysiloxane resin having no hot melt property as a whole molecule. However, when the organopolysiloxane resin does not have hot melt properties, it is preferably a mixture with a chain (linear or branched) organopolysiloxane which is a component (A2). Further, an organopolysiloxane resin which does not have a curing reactive functional group and does not have a hot melt property as a whole molecule may be used in combination, and is preferable.

That is, at least a part or all of the component (A1)
(A1-1) A hot-melt organopolysiloxane resin having a softening point of 30 ° C. or higher and having a curing-reactive functional group containing at least one carbon-carbon double bond in the molecule may be used. ..

On the other hand, the organopolysiloxane resin as the component (A1) may be an organopolysiloxane resin that does not have hot melt properties by itself.
(A1-2-1) The molecule as a whole does not have hot melt properties, does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and is represented by _{SiO 4/2.} An organopolysiloxane resin containing at least 20 mol% or more of siloxane units, and (A1-2-2) molecule as a whole having no hot melt property and at least one carbon-carbon double in the molecule. One or more selected from organopolysiloxane resins having a curing reactive functional group including a bond and containing at least 20 mol% or more of the siloxane unit represented by _{SiO 4/2, or these.} It is particularly preferable that it is a mixture of. However, since these organopolysiloxane resins do not have hot melt properties by themselves,
(A2) A semi-solid linear or branched organopolysiloxane having liquid or plasticity at 25 ° C. and having a curing reactivity containing at least two carbon-carbon double bonds in the molecule. It needs to be a mixture of those with functional groups.

Particularly preferably, it is composed of a mixture of (A1-2-1) component, (A1-2-2) component and (A2) component, and the entire mixture is a solid content having hot melt property.
Hereinafter, these components will be described.

[(A1-1) component]
The component (A1-1) itself has a hot-melt property and has a curing-reactive functional group containing at least one carbon-carbon double bond in the molecule. Therefore, the curing agent (B) described later. Hardens with. Such a (A1-1) component is
(A ₁ ) Resin-like organopolysiloxane,
(A ₂ ) An organopolysiloxane crosslinked product obtained by cross-linking at least one type of organopolysiloxane.
(A ₃ ) Block copolymer consisting of a resinous organosiloxane block and a chain organosiloxane block,
Alternatively, an organopolysiloxane resin composed of a mixture of at least two of these is preferable. These are soluble in organic solvents and are industrially synthesized in organic solvents.

The component (A ₁ ) is a resin-like organopolysiloxane having a hydrosilylation-reactive group and / or a radical-reactive group, and is a hot-melt resin-like organopoly having many T units or Q units and having an aryl group. It is preferably siloxane. Such (A ₁ ) components include triorganosyloxy units (M units) (organo groups are only methyl groups, methyl groups and vinyl groups or phenyl groups), and diorganosyloxy units (D units) (organo). The groups are only methyl groups, methyl groups and vinyl groups or phenyl groups), monoorganosyloxy units (T units) (organo groups are methyl groups, vinyl groups, or phenyl groups) and siloxy units (Q units). ), MQ resin, MDQ resin, MTQ resin, MDTQ resin, TD resin, TQ resin, TDQ resin are exemplified. The component (A ₁ ) has at least two hydrosilylation-reactive groups and / or radical-reactive groups in the molecule, and 10 mol% or more of all the organic groups in the molecule are aryl groups, particularly phenyl. It is preferably a group.

Since the _{component (A 2} ) is formed by cross-linking at least one kind of organopolysiloxane, cracks are less likely to occur when the component (C) is cured by the curing agent, and the curing shrinkage can be reduced. Here, "crosslinking" means connecting the organopolysiloxane as a raw material by a hydrosilylation reaction, a condensation reaction, a radical reaction, a high energy ray reaction, or the like. Examples of the hydrosilylation-reactive group and the radical-reactive group (including the high-energy ray-reactive group) include the same groups as described above, and examples of the condensation-reactive group include a hydroxyl group, an alkoxy group, and an acyloxy group. Will be done.

The unit constituting the component (A ₂ ) is not limited, and siloxane units and sylalkylene group-containing siloxane units are exemplified, and since sufficient hardness and mechanical strength are imparted to the obtained cured product, the same molecule It is preferable to have a resin-like polysiloxane unit and a chain-like polysiloxane unit. That is, the _{component (A 2} ) is preferably a crosslinked product of a resin-like (resin-like) organopolysiloxane and a chain-like (including linear or branched-chain) organopolysiloxane. (A ₂₎ in the component, a resinous organopolysiloxane structure - by introducing a chain organopolysiloxane structure, (A ₂₎ with component exhibits good hot-melt properties, the curing agent (C), good Shows good curability.

(A ₂ ) component is
(1) A resinous organopoly in the molecule undergoes a hydrosilylation reaction between an organopolysiloxane having at least two alkenyl groups in one molecule and an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule. Siloxane-chain organopolysiloxane structure linked by alkylene bond (2) At least two organopolysiloxanes having at least two radical-reactive groups in one molecule undergo a radical reaction with an organic peroxide. , Resin-like organopolysiloxane structure in the molecule-Chain-chain organopolysiloxane structure linked by siloxane bond or alkylene bond (3) Resin-like organopoly in the molecule through the condensation reaction of at least two types of organopolysiloxane. Siloxane structure-A chain of organopolysiloxane structures linked by a siloxane (-Si-O-Si-) bond. Since such a _{component (A 2} ) has a structure in which an organopolysiloxane portion having a resin structure-chain structure is linked by an alkylene group or a new siloxane bond, the hot melt property is remarkably improved.

In the above (1) and (2), _{examples of the alkylene group contained in the component (A 2} ) are alkenyl groups having 2 to 20 carbon atoms such as an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. These may be linear or branched, preferably an ethylene group or a hexylene group.

The crosslinked product of the resinous organopolysiloxane and the chain-like (including linear or branched chain-like) organopolysiloxane is composed of, for example, the following siloxane unit and sylalkylene group-containing siloxane unit.
M unit: R ¹ R ² ₂ Siloxane unit represented by SiO _1/2,
D unit: R ¹ R ² siloxane unit represented by SiO _2/2,
R ³ M / R ³ D unit: R ³ _1/2 R ² ₂ Siloxane group-containing siloxane unit represented by SiO _1/2 ^{and Sylalkylene group represented by R 3} _1/2 R ² SiO _2/2 At least one siloxane unit selected from the contained siloxane units, and T / Q units: at least one siloxane selected from the siloxane unit represented ^{by R 2} SiO _3/2 and the siloxane unit represented by SiO _4/2. unit

In the formula, R ¹ is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. A halogen-substituted aryl group having a number of 6 to 20 or an aralkyl group having a carbon number of 7 to 20 is exemplified, and the same group as described above is exemplified. R ¹ is preferably a methyl group, a vinyl group, or a phenyl group. However, of all the siloxane units, it is preferred that at least two of R ¹ is an alkenyl group.

Further, in the formula, R ² is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen-substituted alkyl group having 6 to 20 carbon atoms. It is an aryl group or an aralkyl group having 7 to 20 carbon atoms, and a group similar to ^{R 1 is exemplified.} R ² is a methyl group, a phenyl group are preferred.

Further, in the formula, R ³ is a linear or branched alkylene group having 2 to 20 carbon atoms bonded to a silicon atom in another siloxane unit. Examples of the alkylene group include the same groups as described above, and an ethylene group and a hexylene group are preferable.

The M unit is _{a siloxane unit that constitutes the terminal of the component (A 2} ), and the D unit is a siloxane unit that constitutes a linear polysiloxane structure. It is preferable that there is an alkenyl group on these M units or D units, particularly M units. On the other hand, the R ³ M unit and the R ³ D unit are siloxane units that are bonded to silicon atoms in other siloxane units via silalkylene bonds and to silicon atoms in other siloxane units via oxygen atoms. Is. The T / Q unit is a branched siloxane unit that gives a resin-like structure to polysiloxane, and the _{component (A 2} ) is ^{represented by R 2} SiO _3/2 , a siloxane unit, and / or SiO _4/2. It preferably contains a siloxane unit. In particular, since the hot melt property of the component _{(A 2} ) is improved and the content of the aryl group in the component _{(A 2 ) is adjusted, the component (A 2} ) is a siloxane represented by ^{R 2} SiO _3/2. It is preferable to contain a unit, and in particular, it is preferable to contain a siloxane unit in which ^{R 2 is a phenyl group.}

The R ³ M / R ³ D unit is one of the characteristic structures of the component _{(A 2} ), and represents a structure in which silicon atoms are crosslinked via an alkylene group of ^{R 3.} Specifically, it is selected from an alkylene group-containing siloxane unit represented by ^{R 3} _1/2 R ² ₂ SiO _1/2 and an alkylene group-containing siloxane unit represented by R ³ _1/2 R ² SiO _2/2. It is preferable that at least one kind of siloxane unit is used, and at least two of all the siloxane units constituting the component _{(A 2) are these alkylene group-containing siloxane units.} The preferred bonding form between the siloxane units having an alkylene group of R ^{3 is as described above, and the number of R 3} between two alkylene group-containing siloxane units has a binding value of "1 /" similar to oxygen in the M unit. It is expressed as "2". Assuming that ^{the number of R 3} is 1, [O _1/2 R ² ₂ SiR ³ SiR ² ₂ O _1/2 ], [O _1/2 R ² ₂ SiR ³ SiR ² O _2/2 ] and [O _2/2 R ² SiR ³ SiR ² O _2/2 ] contains at least one or more selected from the structural units of the siloxane represented by [A ₂ ] in the component (A 2), and each oxygen atom (O) is the above-mentioned M. , D, T / Q to bond to the silicon atom contained in the unit. By having such a structure, the _{component (A 2} ) can be relatively easily designed to have a chain polysiloxane structure composed of D units and a resin-like polysiloxane structure containing T / Q units in the molecule. , It is remarkably excellent in its physical properties.

In the above (1), an organopolysiloxane having at least two alkenyl groups in one molecule and an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule are referred to as [the number of moles of alkenyl groups] /. It can be obtained by conducting a hydrosilylation reaction at a reaction ratio of [number of moles of silicon atom-bonded hydrogen atom]> 1.

In (2) above, at least two types of organopolysiloxane having at least two radical-reactive groups in one molecule are organically peroxidized in an amount insufficient for all the radical-reactive groups in the system to react. It can be obtained by radical reaction with an object.

In the above (1) and (2), the _{component (A 2} ) is a hydrosilylation reaction or a radical reaction between an organopolysiloxane having a resinous siloxane structure and an organopolysiloxane having a chain siloxane structure.

For example, the _{component (A 2} ) is
( ^AR ) In the molecule, ^{a siloxane unit represented by R 2} SiO _3/2 (in the formula, R ² is a group similar to the above) and / or a siloxane unit represented by _{SiO 4/2.} At least one resinous organopolysiloxane containing and having an alkenyl group having 2 to 20 carbon atoms or a silicon atom-bonded hydrogen atom or a radically reactive group, and ^{R 2} ₂ SiO ^{in the (AL} ) molecule. siloxane units (wherein, R ^2, said a is the same group.) represented by _2/2 contains, and, by the above (a ^R) component and a hydrosilylation reaction or radical reactable groups At least one chain organopolysiloxane having an alkenyl group having 2 to 20 carbon atoms or a silicon atom-bonded hydrogen atom.
It is (A ^R) component or (A ^L) organopolysiloxane hydrosilylation reactive group and / or a radical reactive group in component obtained by reacting a ratio designed to remain after the reaction.

In the above (1), when ^{at least a part of the (AR} ) component is a resinous organopolysiloxane having an alkenyl group having 2 to 20 carbon atoms, at least a part of the ( ^AL ) component is a silicon atom-bonded hydrogen. It is preferably a chain organopolysiloxane having an atom.

Similarly, when ^{at least a part of the (AR} ) component is a resinous organopolysiloxane having a silicon atom-bonded hydrogen atom, at least a part of the ( ^AL ) component has an alkenyl group having 2 to 20 carbon atoms. It is preferably a chain organopolysiloxane.

Such (A ₂ ) component is
Component (a ₁ ): Organic peroxide of an organopolysiloxane having at least two alkenyl groups having 2 to 20 carbon atoms in a molecule composed of the following _{component (a 1-1} ) and / or the following component (a _1-2). Radical reaction with a substance, or with the component _{(a 1),}
(A ₂ ) Organohydrogenpolysiloxane,
In the presence of a catalyst for hydrosilylation reaction, the molar ratio of silicon atom-bonded hydrogen atoms in the component _{(a 2} ) to the alkenyl group having 2 to 20 carbon atoms contained in the component _{(a 1) is 0.} It is preferable that the hydrosilylation reaction is carried out in an amount of .2 to 0.7 mol.

The component (a _1-1 ) is a polysiloxane having a relatively large amount of branching units, and the average unit formula:
(R ⁴ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁴ SiO _3/2 ) _c (SiO _4/2 ) _d (R ⁵ O _1/2 ) _e
It is an organopolysiloxane having at least two alkenyl groups in one molecule represented by. In the formula, R ⁴ is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. A halogen-substituted aryl group having a number of 6 to 20 or an aralkyl group having a carbon number of 7 to 20 is exemplified, and a group similar to that of ^{R 1 is exemplified.} R ⁴ is preferably a methyl group, a vinyl group or a phenyl group. Provided that at least two R ⁴ is an alkenyl group. Further, since the hot melt is good, it is preferred that all R ⁴ of 10 mol% or more, or more than 20 mol% are phenyl groups. In the above formula, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkyl group similar to the above can be exemplified.

In the formula, a is a number in the range of 0 to 0.7, b is a number in the range of 0 to 0.7, c is a number in the range of 0 to 0.9, and d is a number in the range of 0 to 0.9. A number in the range of 7, e is a number in the range of 0 to 0.1, c + d is a number in the range of 0.3 to 0.9, a + b + c + d is 1, preferably a is 0 to 0. Numbers in the range of 0.6, b is the number in the range of 0 to 0.6, c is the number in the range of 0 to 0.9, d is the number in the range of 0 to 0.5, and e is the number in the range of 0 to 0.5. The number in the range of 0 to 0.05, c + d is the number in the range of 0.4 to 0.9, and a + b + c + d is 1. This is because when a, b, and c + d are numbers within the above ranges, the hardness and mechanical strength of the obtained cured product are excellent.

Examples of such (a _1-1 ) components include the following organopolysiloxanes. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
(ViMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 (HO _1/2 ) _0.02
(ViMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75
(ViMe ₂ SiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80
(ViMe ₂ SiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.38 (SiO _4/2 ) _0.47 (HO _1/2 ) _0.01
(ViMe ₂ SiO _1/2 ) _0.13 (Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.42 (HO _1/2 ) _0.01
(ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.85 (HO _1/2 ) _0.01
(Me ₂ SiO _2/2 ) _0.15 (MeViSiO _2/2 ) _0.10 (PhSiO _3/2 ) _0.75 (HO _1/2 ) _0.04
(MeViPhSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.05
(ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.75 (SiO _4/2 ) _0.10 (HO _1/2 ) _0.02
(Ph ₂ SiO _2/2 ) _0.25 (MeViSiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.04
(Me ₃ SiO _1/2 ) _0.20 (ViMePhSiO _1/2 ) _0.40 (SiO _4/2 ) _0.40 (HO _1/2 ) _0.08

The component (a _1-2 ) is a polysiloxane having a relatively large amount of chain siloxane units, and the average unit formula:
(R ⁴ ₃ SiO _1/2 ) _a' (R ⁴ ₂ SiO _2/2 ) _b' (R ⁴ SiO _3/2 ) _c' (SiO _4/2 ) _d' (R ⁵ O _1/2 ) _e'
It is an organopolysiloxane having at least two alkenyl groups having 2 to 20 carbon atoms in one molecule represented by. In the formula, R ⁴ and R ⁵ are the same groups as described above.

In the formula, a'is a number in the range of 0.01 to 0.3, b'is a number in the range of 0.4 to 0.99, and c'is a number in the range of 0 to 0.2. , D'is a number in the range 0-0.2, e'is a number in the range 0-0.1, and c'+ d'is a number in the range 0-0.2, a'+ b '+ C'+ d'is 1, preferably a'is a number in the range 0.02 to 0.20, b'is a number in the range 0.6 to 0.99, and c'is 0 to 0. Numbers in the range of 0.1, d'is the number in the range 0-0.1, j'is the number in the range 0-0.05, and c'+ d'is 0-0.1. The number in the range, a'+ b'+ c'+ d', is 1. This is because if a', b', c', and d'are numbers within the above ranges, toughness can be imparted to the obtained cured product.

Examples of such a _{component (a 1-2} ) include the following organopolysiloxane. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
ViMe ₂ SiO (MePhSiO) ₁₈ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.10 (MePhSiO _2/2 ) _0.90
ViMe ₂ SiO (MePhSiO) ₃₀ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.063 (MePhSiO _2/2 ) _0.937
ViMe ₂ SiO (MePhSiO) ₁₅₀ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.013 (MePhSiO _2/2 ) _0.987
ViMe ₂ SiO (Me ₂ SiO) ₁₈ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.10 (Me ₂ SiO _2/2 ) _0.90
ViMe ₂ SiO (Me ₂ SiO) ₃₀ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.063 (Me ₂ SiO _2/2 ) _0.937
ViMe ₂ SiO (Me ₂ SiO) ₃₅ (MePhSiO) ₁₃ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.04 (Me ₂ SiO _2/2 ) _0.70 (MePhSiO _2/2 ) _0.26
ViMe ₂ SiO (Me ₂ SiO) ₁₀ SiMe ₂ Vi, that is, (ViMe ₂ SiO _1/2 ) _0.17 (Me ₂ SiO _2/2 ) _0.83
(ViMe ₂ SiO _1/2 ) _0.10 (MePhSiO _2/2 ) _0.80 (PhSiO _3/2 ) _0.10 (HO _1/2 ) _0.02
(ViMe ₂ SiO _1/2 ) _0.20 (MePhSiO _2/2 ) _0.70 (SiO _4/2 ) _0.10 (HO _1/2 ) _0.01
HOME ₂ SiO (MeViSiO) ₂₀ SiMe ₂ OH
Me ₂ ViSiO (MePhSiO) ₃₀ SiMe ₂ Vi
Me ₂ ViSiO (Me ₂ SiO) ₁₅₀ SiMe ₂ Vi

The component (a _1-1 ) is preferably used from the viewpoint of imparting hardness and mechanical strength to the obtained cured product. The component (a _1-2 ) can be added as an optional component from the viewpoint of imparting toughness to the obtained cured product, but when a cross-linking agent having many chain siloxane units is used in _{the following component (a 2), there.} May be substituted. In any case, the mass ratio of the component having many branched siloxane units to the component having many chain siloxane units is within the range of 50:50 to 100: 0, or within the range of 60:40 to 100: 0. It is preferable to have. This is because when the mass ratio of the component having many branched siloxane units and the component having many chain siloxane units is a value within the above range, the hardness and mechanical strength of the obtained cured product are good. is there.

When the _{component (a 1} ) is radically reacted with an organic peroxide, the component (a _1-1 ) and the component (a _1-2 ) are reacted in the range of 10:90 to 90:10, and (a 1-1) is reacted in the range of 10:90 to 90:10. a ₂ ) It is not necessary to use the component.

The component (a _{2 ) is a component for cross-linking the component (a 1-1} ) and / or the component (a _1-2 ) in the hydrosilylation reaction, and has at least two silicon atom-bonded hydrogen atoms in one molecule. It is an organopolysiloxane containing an individual. Examples of the group bonded to the silicon atom other than the hydrogen atom in the component (a ₂ ) include an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. Examples thereof include a halogen-substituted aryl group having a number of 6 to 20, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group, an epoxy group-containing group, or a hydroxyl group, and the same groups as described above are exemplified.

Such a _{component (a 2} ) is not limited, but preferably the average composition formula:
^{_{R 6 k H m SiO (4}} -k-m) / 2
It is an organohydrogenpolysiloxane represented by. In the formula, R ⁶ is an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen-substituted aryl group having 6 to 20 carbon atoms, or a carbon number of carbon atoms. It is an aralkyl group of 7 to 20, ^{and a group similar to that of R 1} is exemplified, preferably a methyl group or a phenyl group.

Further, in the formula, k is a number in the range of 1.0 to 2.5, preferably a number in the range of 1.2 to 2.3, and m is a number in the range of 0.01 to 0.9. Preferably, it is a number in the range of 0.05 to 0.8, and k + m is a number in the range of 1.5 to 3.0, preferably a number in the range of 2.0 to 2.7.

The component (a ₂ ) may be a resin-like organohydrogenpolysiloxane having many branched siloxane units, or may be a chain-organohydrogenpolysiloxane having many chain-like siloxane units. Specifically, the _{component (a 2} ) is _{an organohydrogenpolysiloxane represented by the following (a 2-1} ), an organohydrogenpolysiloxane represented by the following (a _2-2 ), or a mixture thereof. Is exemplified.

The component (a _2-1 ) is based on the average unit formula:
[R ⁷ ₃ SiO _1/2 ] _f [R ⁷ ₂ SiO _2/2 ] _g [R ⁷ SiO _3/2 ] _h [SiO _4/2 ] _i (R ⁵ O _1/2 ) _j
It is a resinous organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom represented by. In the formula, R ⁷ is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen-substituted aryl group having 6 to 20 carbon atoms. , An aralkyl group having 7 to 20 carbon atoms, or a hydrogen atom, and a group similar to that of ^{R 1 is exemplified.} In the above formula, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the same groups as those exemplified.

In the formula, f is a number in the range of 0 to 0.7, g is a number in the range of 0 to 0.7, h is a number in the range of 0 to 0.9, and i is a number in the range of 0 to 0.9. A number in the range of 7, j is a number in the range of 0 to 0.1, h + i is a number in the range of 0.3 to 0.9, f + g + h + i is 1, preferably f is 0 to 0. Numbers in the range of 0.6, g is the number in the range of 0 to 0.6, h is the number in the range of 0 to 0.9, i is the number in the range of 0 to 0.5, j is the number in the range of 0 to 0.5. The number in the range of 0 to 0.05, h + i is the number in the range of 0.4 to 0.9, and f + g + h + i is 1.

The component (a _2-2 ) is based on the average unit formula:
(R ⁷ ₃ SiO _1/2 ) _f' (R ⁷ ₂ SiO _2/2 ) _g' (R ⁷ SiO _3/2 ) _h' (SiO _4/2 ) _i' (R ⁵ O _1/2 ) _j'
It is an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule represented by. In the formula, R ⁷ and R ⁵ are the same groups as described above.

In the formula, f'is a number in the range of 0.01 to 0.3, g'is a number in the range of 0.4 to 0.99, and h'is a number in the range of 0 to 0.2. , I'is a number in the range 0-0.2, j'is a number in the range 0-0.1, and h'+ i'is a number in the range 0-0.2, f'+ g '+ H'+ i'is 1, preferably f'is a number in the range 0.02 to 0.20, g'is a number in the range 0.6 to 0.99, and h'is 0 to 0. A number in the range of 0.1, i'is a number in the range of 0 to 0.1, j'is a number in the range of 0 to 0.05, and h'+ i'is a number in the range of 0 to 0.1. The number in the range, f'+ g'+ h'+ i', is 1.

As described above, in the _{component (a 2} ), the resin-like organopolysiloxane having many branched siloxane units imparts hardness and mechanical strength to the cured product, and the obtained organopolysiloxane has many chain siloxane units. since those that confer toughness to the cured product, it is preferable to use _{(a 2)} as the component _{(a 2-1)} as appropriate components and _{(a 2-2)} component. Specifically, when _{(a 1)} is less branched siloxane units in the _{component, (a 2) (a 2-1} ) mainly it is preferred to use component as the component in _{(a 1)} component When the number of chain siloxane units is small, it is preferable to mainly use the component _{(a 2-2). (A 2) component, (a 2-1)} component and _{(a 2-2)} component weight ratio of 50: 50 to 100: 0 in the range of, or 60: 40 to 100: in the range of from 0 Is preferable.

Examples of such component (a ₂ ) include the following organopolysiloxane. In the formula, Me and Ph represent a methyl group and a phenyl group, respectively.
Ph ₂ Si (OSiMe ₂ H) ₂ , that is, Ph _0.67 Me _1.33 H _0.67 SiO _0.67
HMe ₂ SiO (Me ₂ SiO) ₂₀ SiMe ₂ H, that is, Me _2.00 H _0.09 SiO _0.95
HMe ₂ SiO (Me ₂ SiO) ₅₅ SiMe ₂ H, that is, Me _2.00 H _0.04 SiO _0.98
PhSi (OSiMe ₂ H) ₃ , that is, Ph _0.25 Me _1.50 H _0.75 SiO _0.75
(HMe ₂ SiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4 , that is, Ph _0.40 Me _1.20 H _0.60 SiO _0.90

The amount of the component (a ₂ ) added is such that the molar ratio of the silicon atom-bonded hydrogen atom in the component _{(a 2} ) to the alkenyl group in the component _{(a 1) is 0.2 to 0.7.} Yes, preferably the amount is 0.3 to 0.6. This is because when the _{amount of the component (a 2} ) added is within the above range, the initial hardness and mechanical strength of the obtained cured product are good.

The organic peroxide used for radical reaction of the component (a ₁ ) is not limited, and the organic peroxide exemplified by the component (C) below can be used. When a radical reaction, _{(a 1) component, (a 1-1)} component and _{(a 1-2)} component weight ratio of 10: 90 to 90: is preferably a mixture of 10, on a weight basis. The amount of the organic peroxide added is not limited, but is within the range of 0.1 to 5 parts by mass, within the range of 0.2 to 3 parts by mass, or 0 with respect to 100 parts by mass of the component _{(a 1).} It is preferably in the range of .2 to 1.5 parts by mass.

Further, the hydrosilylation reaction catalyst used for the hydrosilylation reaction between the component (a ₁ ) and the component (a ₂ ) is not limited, and the hydrosilylation reaction catalyst exemplified by the component (C) below can be used. .. The amount of the hydrosilylation reaction catalyst added is _{0.01 to 0.01 to the total amount of the (a 1} ) component and the (a ₂ ) component, with the platinum-based metal atom in the hydrosilylation reaction catalyst in mass units. The amount is preferably in the range of 500 ppm, in the range of 0.01 to 100 ppm, or in the range of 0.01 to 50 ppm.

The above (A ₃ ) is a _{condensation reaction of the following (a 3} ) component and the following (a ₄ ) component with a condensation reaction catalyst.

The component (a ₃ ) is based on the average unit formula:
(R ⁸ ₃ SiO _1/2 ) _p (R ⁸ ₂ SiO _2/2 ) _q (R ⁸ SiO _3/2 ) _r (SiO _4/2 ) _s (R ⁹ O _1/2 ) _t
It is a condensation-reactive organopolysiloxane represented by. In the formula ^{, each of R 8} independently has an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. A halogen-substituted aryl group having a number of 6 to 20 or an aralkyl group having a carbon number of 7 to 20 is exemplified, and the same group as described above is exemplified. Further, R ⁹ in the formula is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 5 carbon atoms, and an alkoxy group such as a methoxy group or an ethoxy group; an acyloxy group is exemplified. The component (a ₃ ) has at least one silicon atom-bonded hydroxyl group, a silicon atom-bonded alkoxy group, or a silicon atom-bonded acyloxy group in one molecule. Moreover, in one molecule, at least two R ⁸ is an alkenyl group, it is preferably 10 mol% or more of total R ^8, or more than 20 mol% are phenyl groups.

In the formula, p is a number in the range of 0 to 0.7, q is a number in the range of 0 to 0.7, r is a number in the range of 0 to 0.9, and s is a number in the range of 0 to 0.7. The number in the range, t is the number in the range of 0.01 to 0.10, r + s is the number in the range of 0.3 to 0.9, p + q + r + s is 1, preferably p is 0 to 0. Numbers in the range of 0.6, q is the number in the range 0-0.6, r is the number in the range 0-0.9, s is the number in the range 0-0.5, t is The number is in the range of 0.01 to 0.05, and r + s is the number in the range of 0.4 to 0.9. This is because when p, q, and r + s are numbers within the above ranges, they are flexible at 25 ° C., non-fluid, have low surface adhesiveness, and have sufficiently low melt viscosity at high temperatures. This is because hot melt silicone can be obtained.

The component (a ₄ ) is based on the average unit formula:
(R ⁸ ₃ SiO _1/2 ) _p' (R ⁸ ₂ SiO _2/2 ) _q' (R ⁸ SiO _3/2 ) _r' (SiO _4/2 ) _s' (R ⁹ O _1/2 ) _t'
It is a condensation-reactive organopolysiloxane represented by. In the formula, R ⁸ and R ⁹ are the same groups as described above. The component (a ₄ ) has at least one silicon atom-bonded hydroxyl group, a silicon atom-bonded alkoxy group, or a silicon atom-bonded acyloxy group in one molecule. In the formula, p'is a number in the range of 0.01 to 0.3, q'is a number in the range of 0.4 to 0.99, and r'is a number in the range of 0 to 0.2. , S'is a number in the range 0-0.2, t'is a number in the range 0-0.1, and r'+ s'is a number in the range 0-0.2, p'+ q '+ R'+ s'is 1, preferably p'is a number in the range 0.02 to 0.20, q'is a number in the range 0.6 to 0.99, and r'is 0 to 0. A number in the range of 0.1, s'is a number in the range of 0 to 0.1, t'is a number in the range of 0 to 0.05, and r'+ s'is a number in the range of 0 to 0.1. It is a number within the range. This is because when p', q', r', and s'are within the above ranges, they are flexible at 25 ° C., non-fluid, have low surface adhesiveness, and melt at high temperatures. This is because a hot-meltable silicone having a sufficiently low viscosity can be obtained.

The catalyst for the condensation reaction for the condensation reaction of the component (a ₃ ) and the component (a ₄ ) is not limited, and for example, dibutyltin dilaurate, dibutyltin diacetate, tin octenoate, dibutyltin dioctate, tin laurate, etc. Organic tin compounds; Organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, dibutoxybis (ethylacetoacetate); Other acidic compounds such as hydrochloric acid, sulfuric acid and dodecylbenzene sulfonic acid; Alkaline compounds such as ammonia and sodium hydroxide; 1 Amine compounds such as, 8-diazabicyclo [5.4.0] undecene (DBU) and 1,4-diazabicyclo [2.2.2] octane (DABCO) are exemplified, preferably organic tin compounds and organic titanium. It is a compound.

Further, (A ₃₎ component is a block copolymer consisting of resinous organosiloxane block and chain organosiloxane block. Such _{(A 3)} component, Torishirokishi preferably, disiloxy unit of 40 to 90 mol% of the formula ^{_{[R 1 2 SiO 2/2],}} 10~60 mol% of the formula ^[R 1 SiO _3/2] It consists of units and preferably contains 0.5-35 mol% silanol groups [≡SiOH]. Here, R ¹ is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. A halogen-substituted aryl group having a number of 6 to 20 or an aralkyl group having 7 to 20 carbon atoms, and the same group as described above is exemplified. In one molecule, at least two of R ¹ is an alkenyl group. Further, the disiloxy unit _^[R 1 _{2 SiO 2/2]} forms a linear block having 100-300 amino disiloxy unit on average per one linear block, the Torishirokishi units ^[R 1 SiO _{3 / 2} ] forms non-linear blocks having a molecular weight of at least 500 g / mol, at least 30% of the non-linear blocks are bonded to each other, and each linear block is associated with at least one non-linear block. A resinous organosiloxane that is attached via a −Si—O—Si− bond, has a mass average molecular weight of at least 20000 g / mol, and contains at least one alkenyl group of 0.5-4.5 mol%. It is a block copolymer.

The component (A ₃ ) is a _{condensation reaction of (a 5} ) a resinous organosiloxane or a resinous organosiloxane block copolymer with (a ₆ ) a chain organosiloxane and, if necessary, a (a ₇ ) siloxane compound. Is prepared.

The component (a ₅ ) is based on the average unit formula:
[R ¹ ₂ R ² SiO _1/2 ] _i [R ¹ R ² SiO _2/2 ] _ii [R ¹ SiO _3/2 ] _iii [R ² SiO _3/2 ] _iv [SiO _4/2 ] _v
It is a resinous organosiloxane represented by. In the formula, R ¹ is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. A halogen-substituted aryl group having a number of 6 to 20 or an aralkyl group having a carbon number of 7 to 20 is exemplified, and the same group as described above is exemplified. Further, in the formula, R ² is independently an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen-substituted alkyl group having 6 to 20 carbon atoms. It is an aryl group or an aralkyl group having 7 to 20 carbon atoms, and a group similar to ^{R 1 is exemplified.}

Further, in the formula, i, ii, iii, iv, and v represent the molar fraction of each syroxy unit, i is a number from 0 to 0.6, and ii is a number from 0 to 0.6. , Iii is a number from 0 to 1, iv is a number from 0 to 1, v is a number from 0 to 0.6, where ii + iii + iv + v> 0 and i + ii + iii + iv + v≤1. Further, the _{component (a 5} ) preferably contains 0 to 35 mol% silanol group [≡SiOH] in one molecule.

The component (a ₆ ) has a general formula:
_{^{R 1 3-α (X)}} α SiO (R 1 2 SiO) β Si (X) α R 1 3-α
It is a linear organosiloxane represented by. In the formula, R ¹ is the same as described above, and the same group as described above is exemplified. In the above formula, X ^{is, -OR 5, F, Cl,} Br, I, -OC (O) R 5, -N (R 5) 2 or -ON = ^CR _{5 2} (where,, ^{R 5} is It is a hydrolyzable group selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Further, in the formula, α is 1, 2, or 3 independently, and β is an integer of 50 to 300.

The component (a ₇ ) has a general formula:
R ¹ R ² ₂ SiX
It is a siloxane compound represented by. In the formula, R ¹ , R ² , and X are the same groups as described above.

The catalyst for the condensation reaction for the condensation reaction of the component (a ₅ ) and the component (a ₆ ) and / or the component (a ₇ ) is not limited, and for example, dibutyltin dilaurate, dibutyltin diacetate, tin octate, dibutyl. Organic tin compounds such as tin dioctate and tin laurate; organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate and dibutoxybis (ethylacetacetate); other acidic compounds such as hydrochloric acid, sulfuric acid and dodecylbenzene sulfonic acid; ammonia and water. Alkaline compounds such as sodium oxide; amine compounds such as 1,8-diazabicyclo [5.4.0] undecene (DBU) and 1,4-diazabicyclo [2.2.2] octane (DABCO) are exemplified.

The component (A1-1) exhibits hot melt properties, and specifically, it is preferably solid (non-fluid) at 25 ° C. and has a melt viscosity at 100 ° C. of 8000 Pa · s or less. Non-fluidity means that it does not flow under no load. For example, the softening point of a hot melt adhesive by the ring ball method specified in JIS K 6863-1994 "Test method for softening point of hot melt adhesive". The state below the softening point measured by the test method is shown. That is, in order to be non-fluid at 25 ° C, the softening point needs to be higher than 25 ° C.

The component (A1-1) preferably has a melt viscosity at 100 ° C. of 8000 Pa · s or less, 5000 Pa · s or less, or 10 to 3000 Pa · s. When the melt viscosity at 100 ° C. is within the above range, the adhesion after hot melting and cooling to 25 ° C. is good.

[Organic solvent]
The organic solvent used for the synthesis and dissolution of the components of Step 1 and (A1-1) is not limited, but aliphatic hydrocarbons such as n-hexane, cyclohexane and n-heptane; aromatics such as toluene, xylene and mesityrene Hydrocarbons; ethers such as tetrahydrofuran and dipropyl ether; silicones such as hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether; acetone, Examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone.

[(A1-2-1) component]
The component (A1-2-1) of the present invention is a non-hot melt organopolysiloxane resin containing a carbon-carbon double bond in the molecule and having no curing reactive functional group. The component is soluble in organic solvents and is industrially synthesized in organic solvents.

The component (A1-2-1) does not have hot-melt property as a whole molecule, does not have a curing-reactive functional group containing a carbon-carbon double bond in the molecule, and is represented by SiO _4/2 . It is an organopolysiloxane resin fine particle containing at least 20 mol% or more of the siloxane unit to be produced, and this component is used as a part of the component (A1) in a linear or branched chain form as the component (A2). It is a component that realizes the hot melt property of the composition as a whole when used in combination with the organopolysiloxane of the above in a predetermined quantitative range.

The component (A1-2-1) is an organopolysiloxane resin in a solid state in a solvent-free state without having a hot-melt property as a whole molecule. Here, having no hot-melt property means that the resin as a component (A1-2-1) does not exhibit heat-melting behavior by itself, and specifically, it has a softening point and a melting viscosity. Means not.

Preferably, the functional group bonded to the silicon atom in the component (A1-2-1) is a methyl group, and 70 mol% or more of the functional groups bonded to all the silicon atoms is preferably a methyl group. , 80 mol% or more is more preferably a methyl group, and 88 mol% or more is particularly preferably a methyl group. In such a range, the component (A1-2-1) can be designed as a component which is not hot-meltable and has particularly excellent color resistance and the like at high temperature of the cured product. The component (A) may contain a small amount of hydroxyl group or alkoxy group.

Since the component (A1-2-1) does not have a curing reactive group having a carbon-carbon double bond in the molecule, it does not form a cured product by itself, but the composition as a whole has a hot melt property. Has an improving and reinforcing effect on cured products.

The component (A1-2-1) is a solid organopolysiloxane resin fine particle in a solvent-free state, and the siloxane unit _{represented by SiO 4/2} , which is a branched siloxane unit in the molecule, is at least the total siloxane unit. It is characterized by containing 20 mol% or more. Preferably, the siloxane unit is at least 40 mol% or more of the total siloxane unit, and is particularly preferably in the range of 50 mol% or more, particularly 50 to 65 mol%.

Preferably, the component (A1-2-1) has the following average unit formula:
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (R ² O _{1/2) e}
(In the formula, each R ¹ independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond; each R ² is a hydrogen atom or 1 to 10 carbon atoms. It is an alkyl group having an atom; a, b, c, d and e are numbers satisfying the following: 0.10 ≦ a ≦ 0.60, 0 ≦ b ≦ 0.70, 0 ≦ c ≦ 0. 80, 0.20 ≦ d ≦ 0.65, 0 ≦ e ≦ 0.05, and a + b + c + d = 1)
It is a non-hot melt organopolysiloxane resin represented by.

In the above average unit formula, each R ¹ independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond, such as a monovalent hydrocarbon group such as methyl, ethyl, propyl, butyl and pentyl. , Hexyl, heptyl, or similar alkyl groups; phenyl, trill, xylyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and chloromethyl, 3-chloropropyl, 3,3,3-trifluoro Propyl, or a similar alkyl halide group. Here, it is preferable that 70 mol% or more of the total R ¹ in one molecule is an alkyl group having 1 to 10 carbon atoms such as a methyl group, and 88 mol% or more is a methyl group in terms of industrial production. And from the viewpoint of the technical effect of the invention, it is particularly preferable. On the other hand, ^{it is preferable that R 1} does not substantially contain an aryl group such as a phenyl group. When a large amount of an aryl group such as a phenyl group is contained, the component (A1-2-1) itself becomes hot-meltable, and the color resistance of the cured product at high temperature may be deteriorated.

In the formula, R ² is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms. Alkyl group of R ² include methyl, ethyl, propyl, butyl, exemplified by pentyl or hexyl. Functional group ^R 2 _{O 1/2} containing the ^{R 2} corresponds to a hydroxyl group or an alkoxy group (a2-1-1) in the component.

In the formula, a is a number indicating the ratio of the siloxane unit of ^{the general formula: R 1} ₃ SiO _1/2. This number satisfies 0.1 ≦ a ≦ 0.60, preferably 0.15 ≦ a ≦ 0.55. When a is equal to or higher than the lower limit of the above range, the composition containing this component can realize good hot melt performance as a whole composition. On the other hand, if a is not more than the upper limit of the above range, the mechanical strength (hardness, etc.) of the obtained cured product does not become too low.

Wherein, b is the general ^formula: is a number that indicates the ratio of siloxane units _R 1 _{2 SiO 2/2.} This number satisfies 0 ≦ b ≦ 0.70, preferably 0 ≦ b ≦ 0.60. When b is not more than the upper limit of the range, the composition containing this component can realize good hot melt performance as a whole composition, and a granular composition with less stickiness can be obtained at room temperature. In the present invention, b may be 0 and is preferable.

In the formula, c is a number indicating the ratio of the siloxane unit of the ^{general formula: R 1} SiO _3/2. This number satisfies 0 ≦ c ≦ 0.70, preferably 0 ≦ c ≦ 0.60. When c is not more than the upper limit of the range, the composition containing this component can realize good hot melt performance as a whole composition, and a granular composition with less stickiness can be obtained at room temperature. In the present invention, c may be 0 and is preferable.

In the formula, d is _{a number indicating the ratio of the siloxane unit of SiO 4/2} , and it is necessary that 0.20 ≦ d ≦ 0.65, and 0.40 ≦ d ≦ 0.65. Is preferable, and 0.50 ≦ d ≦ 0.65 is particularly preferable. Within the numerical range, the composition containing this component can perform good hot-melt performance as a whole composition, has excellent mechanical strength of the obtained cured product, and is not sticky as a whole composition, and has handleability. A good composition can be realized.

In the formula, e is ^{a number indicating the ratio of the unit of the general formula: R 2} O _1/2 , and the unit means a hydroxyl group or an alkoxy group bonded to a silicon atom that can be contained in the organopolysiloxane resin. This number satisfies 0 ≦ e ≦ 0.05, preferably 0 ≦ e ≦ 0.03. When e is not more than the upper limit of the range, a material that realizes good hot melt performance as a whole composition can be obtained. Finally, the sum of a, b, c and d, which is the sum of each siloxane unit, is equal to 1.

[(A1-2-2) component]
The component (A1-2-2) of the present invention is a solid organopolysiloxane resin in a solvent-free state, does not have hot melt properties as a whole molecule, and has at least one carbon-carbon dicarbonate in the molecule. It is an organopolysiloxane resin having a curing reactive functional group including a heavy bond and containing at least 20 mol% or more of siloxane units represented by _{SiO 4/2 in total siloxane units.} The component is soluble in organic solvents and is industrially synthesized in organic solvents.

Here, having no hot-melt property means that the organopolysiloxane resin, which is a component (A1-2-2), does not exhibit heat-melting behavior by itself. Specifically, it has a softening point and a melt viscosity. Means not have. Such physical properties are not particularly structurally limited, but the functional group in the organopolysiloxane resin is a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly a methyl group or the like having 1 to 10 carbon atoms. It is a functional group selected from the alkyl groups of the above, and preferably does not substantially contain an aryl group such as a phenyl group. When a large amount of phenyl group or the like is contained, the component may be hot-meltable, and the effect of reinforcing the cured product peculiar to the _{SiO 4/2 group may be reduced.}

Unlike the component (A1-2-1), the component (A1-2-2) has a cure-reactive functional group containing at least one carbon-carbon double bond in the molecule, and itself has a curing-reactive functional group. It participates in the curing reaction together with the curing agent and forms a cured product. Such a curing reactive group is a hydrosilylation-reactive or organic peroxide-curable functional group, and forms a cured product by a cross-linking reaction with other components. Such a curing reactive group is an alkenyl group or an acrylic group, for example, an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and a heptenyl group; 3-methacryl. Examples thereof include an acrylic group-containing monovalent organic group such as a loxypropyl group and a 3-acryloxypropyl group, and a vinyl group or a hexenyl group is particularly preferable.

Preferably, the functional group bonded to the silicon atom in the component (A1-2-2) is a group selected from an alkenyl group such as a methyl group and a vinyl group, and 70 of the functional groups bonded to all the silicon atoms. It is preferable that mol to 99 mol% is a methyl group, 80 to 99 mol% is more preferably a methyl group, 88 to 99 mol% is a methyl group, and other functional groups bonded to silicon atoms are vinyl. It is particularly preferable that it is an alkenyl group such as a group. In such a range, the component (A1) can be designed as a component which is not hot-meltable and has particularly excellent color resistance and the like at high temperature of the cured product. The component (A1-2-2) may contain a small amount of hydroxyl group or alkoxy group.

The component (A1-2-2) is a solid organopolysiloxane resin in a solvent-free state, and the siloxane unit _{represented by SiO 4/2} , which is a branched siloxane unit in the molecule, is at least 20 of all siloxane units. It is characterized by containing mol% or more. Preferably, the siloxane unit is at least 40 mol% or more of the total siloxane unit, and is particularly preferably in the range of 50 mol% or more, particularly 50 to 65 mol%.

Preferably, the component (A1-2-2) contains the following average unit formula:
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (R ² O _{1/2) e}
(In the formula, each R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, except that ^{1 to 12 mol% of all R 1 in} one molecule is an alkenyl group; each R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers satisfying the following: 0.10 ≦ a ≦ 0.60, 0 ≦ b ≦ 0.70, 0 ≦ c ≦ 0.80, 0 ≦ d ≦ 0.65, 0 ≦ e ≦ 0.05, where c + d> 0.20 and a + b + c + d = 1)
It is a non-hot melt organopolysiloxane resin represented by.

In the above average unit formula, each R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or a similar alkyl group; Vinyl, allyl, butenyl, pentenyl, hexenyl, or similar alkenyl groups; phenyl, trill, xsilyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and chloromethyl, 3-chloropropyl, 3,3 , 3-Trifluoropropyl, or a similar alkyl halide group. Further, 1 to 12 mol% of the total R ¹ in one molecule is an alkenyl group, and preferably 2 to 10 mol% ^{of the total R 1 in one molecule is an alkenyl group.} If the content of the alkenyl group is less than the lower limit of the above range, the mechanical strength (hardness, etc.) of the obtained cured product may be insufficient. On the other hand, when the content of the alkenyl group is not more than the upper limit of the above range, the composition containing this component can realize good hot melt performance as a whole composition. It is preferable that each R ¹ is a functional group selected from an alkyl group having 1 to 10 carbon atoms such as a methyl group and an alkenyl group such as a vinyl group and a hexenyl group, and from the viewpoint of the technical effect of the invention, R 1 is R. ¹ is preferably substantially free of aryl groups such as phenyl. When a large amount of aryl groups such as phenyl groups are contained, the component itself may become hot-meltable and the technical effect of the present invention may not be achieved, and in the cured product, curing peculiar to _{SiO 4/2 groups.} The effect of reinforcing an object may be reduced.

In the formula, R ² is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms. Alkyl group of R ² include methyl, ethyl, propyl, butyl, exemplified by pentyl or hexyl. Functional group ^R 2 _{O 1/2} containing the ^{R 2} corresponds to a hydroxyl group or an alkoxy group in the component.

In the formula, a is a number indicating the ratio of the siloxane unit of the ^{general formula: R 1} ₃ SiO _1/2. This number satisfies 0.1 ≦ a ≦ 0.60, preferably 0.15 ≦ a ≦ 0.55. When a is equal to or higher than the lower limit of the above range, the composition containing this component can realize good hot melt performance as a whole composition. On the other hand, if a is not more than the upper limit of the above range, the mechanical strength (hardness, elongation, etc.) of the obtained cured product is not too low.

Wherein, b is the general ^formula: is a number that indicates the ratio of siloxane units _R 1 _{2 SiO 2/2.} This number satisfies 0 ≦ b ≦ 0.70, preferably 0 ≦ b ≦ 0.60. When b is not more than the upper limit of the range, the composition containing this component can realize good hot melt performance as a whole composition, and a composition having less stickiness at room temperature can be obtained.

In the formula, c is a number indicating the ratio of the siloxane unit of the ^{general formula: R 3} SiO _3/2. This number satisfies 0 ≦ c ≦ 0.80, preferably 0 ≦ c ≦ 0.75. When c is not more than the upper limit of the range, the composition containing this component can realize good hot melt performance as a whole composition, and a tack-free composition having less stickiness at room temperature can be obtained. In the present invention, c may be 0 and is preferable.

In the formula, d is _{a number indicating the ratio of the siloxane unit of SiO 4/2} , and it is necessary that 0.00 ≦ d ≦ 0.65 and 0.20 ≦ d ≦ 0.65. Is preferable, and 0.25 ≦ d ≦ 0.65 is particularly preferable. This is because, within the numerical range, the composition containing this component can realize good hot melt performance as a whole composition, and the obtained cured product has sufficient flexibility.

In the present invention, c or d may be 0, but it is necessary that c + d> 0.20. If the value of c + d is less than the above lower limit, good hot melt performance cannot be realized as a whole composition, and the technical effect of the present invention may not be sufficiently achieved.

In the formula, e is ^{a number indicating the ratio of the unit of the general formula: R 2} O _1/2 , and the unit means a hydroxyl group or an alkoxy group bonded to a silicon atom that can be contained in the organopolysiloxane resin. This number satisfies 0 ≦ e ≦ 0.05, preferably 0 ≦ e ≦ 0.03. When e is not more than the upper limit of the range, a material that realizes good hot melt performance as a whole composition can be obtained. Finally, the sum of a, b, c and d, which is the sum of each siloxane unit, is equal to 1.

Preferably, the component (A1) of the present invention is
(A1-2-1) The molecule as a whole does not have hot melt properties, does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and is represented by _{SiO 4/2.} 100 parts by mass of an organopolysiloxane resin containing at least 20 mol% or more of siloxane units, and (A2-2-2) the molecule as a whole does not have hot melt properties, and at least one carbon in the molecule- 0 to 600 parts by mass of an organopolysiloxane resin having a curing reactive functional group containing a carbon double bond and containing at least 20 mol% or more of siloxane units represented by _{SiO 4/2 in total siloxane units.} It is particularly preferred to be a mixture.

[(A2) component]
The component (A2) is one of the main components of the composition used together with the component (A1), and is a semi-solid linear or branched organopolysiloxane having liquid or plasticity at 25 ° C. It has a cure-reactive functional group containing at least two carbon-carbon double bonds in the molecule. Such a curing-reactive chain organopolysiloxane is, in particular, the above-mentioned solid organopolysiloxane resin, which can be mixed with the component (A1-2-1) or the component (A1-2-2). , The whole mixture develops hot melt properties.

The component (A2) is soluble in an organic solvent like the component (A1), and can be uniformly mixed with the component (A1) in a solution system.

The component (A2) preferably has a curing reactive group having a carbon-carbon double bond in the molecule, and such a curing reactive group is hydrosilylation-reactive, radical-reactive or organic peroxide curing. It is a sex functional group and forms a cured product by a cross-linking reaction with other components. Such a curing reactive group is an alkenyl group or an acrylic group, and the same group as described above is exemplified, and a vinyl group or a hexenyl group is particularly preferable.

The component (A2) is a semi-solid linear or branched organopolysiloxane having liquid or plasticity at 25 ° C. (room temperature), and by mixing with the solid (A1) component at room temperature. , The composition as a whole exhibits hot melt properties. Its structure consists of a small number of branched siloxane units (eg, T units represented by ^{the general formula: R 4} SiO _3/2 ^{(R 4} is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently)). _{Alternatively,} it may be a branched organopolysiloxane having (Q unit represented by SiO 4/2), but it is preferable.
(A2-1) The following structural formula:
R ⁴ ₃ SiO (SiR ⁴ ₂ O) _k SiR ⁴ ₃
(In the formula, each R ⁴ is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, except ^{that at least 2 of R 4 in} one molecule are alkenyl groups, and k is 20 to 10 (The number of 000)
It is a linear diorganopolysiloxane represented by. Preferably, a linear diorganopolysiloxane having one alkenyl group at each end of the molecular chain is preferable.

In the formula, each R ⁴ is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or similar alkyl groups; vinyl, allyl, Butenyl, pentenyl, hexenyl, or similar alkenyl groups; phenyl, trill, xsilyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and chloromethyl, 3-chloropropyl, 3,3,3-tri Fluoropropyl, or a similar alkyl halide group. Furthermore, at least two alkenyl groups R ⁴ in one molecule, preferably vinyl groups. It is preferable that each R ⁴ is a functional group selected from an alkenyl group such as an alkyl group and vinyl group, hexenyl group having 1 to 10 carbon atoms such as a methyl group, of all the R ^4, at least two There is an alkenyl group, it is preferred that the remaining R ⁴ are methyl groups. From the viewpoint of the technical effect of the invention, ^{it is preferable that R 4} does not substantially contain an aryl group such as a phenyl group. When a large amount of aryl groups such as phenyl groups are contained, the color resistance of the cured product at high temperatures may deteriorate. Particularly preferably, one having an alkenyl group such as a vinyl group at each end of the molecular chain and the other R ⁴ being a methyl group is preferable.

In the formula, k is a number of 20 to 10,000, preferably 30 to 9,000, particularly preferably 45 to 8,000. When k is equal to or higher than the lower limit of the above range, a granular composition with less stickiness can be obtained at room temperature. On the other hand, when k is not more than the upper limit of the above range, good hot melt performance can be realized as the whole composition.

[Mixture containing non-hot melt organopolysiloxane resin]
When the component (A1-2-1) or the component (A1-2-2), which is the above-mentioned non-hot melt organopolysiloxane resin, is used as the component (A1) of the present invention, (A1-2-1) The amount of the component (A2) used is in the range of 3 to 100 parts by mass, preferably in the range of 4 to 75 parts by mass, based on 100 parts by mass of the sum of the component (A1-2-2) and the component (A1-2-2). The range of ~ 50 parts by mass is particularly preferable.

[Removal of volatile low molecular weight components]
As described above, as the component (A), an organopolysiloxane resin (specifically, a component A1-2-1, _{2) having a high content of a specific branched siloxane unit (SiO 4/2) is used.} In the case, a volatile low molecular weight component is generated in the production process and mixed in the resin. The volatile low molecular weight component is specifically _{a component mainly composed of an M 4} Q structure, and is an organocon consisting of an M unit (R ³ ₃ SiO _1/2 ) and a Q unit (SiO _4/2 ). Appears as a by-product when polymerizing a polysiloxane resin. The structure has the effect of significantly reducing the hardness of the cured product of the composition of the present invention. The organopolysiloxane resin is the presence polymerization of highly compatible organic solvents, but obtain a solid form of organopolysiloxane resin by removing the organic solvent by drying under reduced pressure or the like, M 4 _Q structures are of the It is highly intersoluble with the organopolysiloxane resin and cannot be removed under dry conditions such as removing organic solvents. It has been known that this structure can be removed by exposing it to a temperature of 200 ° C. or higher for a short time, but if it is integrally molded with a base material such as a semiconductor and then exposed to a high temperature to remove it, the volume of the cured product is reduced and the volume is remarkable. The hardness increases, the dimensions of the molded product change, and warpage occurs. _{Further, when a large amount of siloxane unit represented by SiO 4/2} is contained in the network of the cured silicone product, the one having a high hardness of the cured product tends to be extremely brittle, resulting in embrittlement. Occur. Therefore, in order to apply to the application of the present invention prior to the molding process of the substrate, that is, it is necessary to remove the structure or the like of M _{4 Q} at the point of feedstock.

Therefore, it is preferable to remove the low molecular weight component from these organopolysiloxane resin components as much as possible at an arbitrary step before entering the above step 2. Specifically, it is necessary that the mass reduction rate when these organopolysiloxane resin components are exposed at 200 ° C. for 1 hour is 2.0% by mass or less, and 1.5% by mass or less. It is preferably 1.0% by mass or less, and more preferably 1.0% by mass or less.

The type of volatile low molecular weight component is not particularly limited, but the organopolysiloxane resin of the present invention contains a large number of branched siloxane units (Q units) represented by _{SiO 4/2 , and thus R 3} SiO. by reaction with _1/2 represented by siloxane units (M units), M 4 _Q is the volatile siloxane component is likely-produced expressed as volatile to the volatile siloxane component as the main component in the present invention It is particularly preferable that the above-mentioned mass reduction rate is realized by removing the low-molecular-weight component having sex from the organopolysiloxane resin.

Since the component (A1) in the above step 1 is a solution dissolved or dispersed in an organic solvent,
On the other hand, after mixing these organopolysiloxane resins in the presence of a solvent, the solvent is removed by heating with an extruder or the like. At this time, by treating at a temperature of 200 ° C. or higher, the organopolysiloxane resin is contained in the organopolysiloxane resin. It is possible to remove low molecular weight components at the same time.

[(B) component]
The component (B) is a curing agent for curing the component (A), and is not limited as long as the component (A) can be cured. When the component (A) has an alkenyl group, the component (B) is an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule and a catalyst for a hydrosilylation reaction (A). When the component) contains an alkenyl group and contains a catalyst for a hydrosilylation reaction, the component (B) may be only an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule. A hydrosilylation reaction catalyst may be used in combination. When the component (A) has an alkenyl group, the component (B) may be an organic peroxide, and an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule may be used in combination. Good. On the other hand, when the component (A) has a silicon atom-bonded hydrogen atom, the component (B) is an organopolysiloxane having at least two alkenyl groups in one molecule and a catalyst for the hydrosilylation reaction (A). When the component) has a silicon atom-bonded hydrogen atom and contains a hydrosilylation reaction catalyst, the component (B) may be only an organopolysiloxane having at least two alkenyl groups in one molecule. A catalyst for hydrosilylation reaction may be used in combination.

Examples of the organopolysiloxane in the component (B) include the alkenyl group-containing organopolysiloxane represented by _{the above (a 1} ) and / or the above (a _{2 ), or the above (a 3} ) and / or the above (a ₄ ). An example is an organopolysiloxane containing a silicon atom-bonded hydrogen atom represented by.

When organopolysiloxane is used as the component (B), its content is not limited, but in order for the composition to cure, the number of silicon atom-bonded hydrogen atoms is 0 with respect to 1 mol of the alkenyl group in the composition. The amount is preferably in the range of .5 to 20 mol, or preferably in the range of 1.0 to 10 mol.

Examples of the catalyst for the hydrosilylation reaction include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst, and a platinum-based catalyst is preferable because it can remarkably accelerate the curing of the present composition. Examples of the platinum-based catalyst include platinum fine powder, platinum chloride acid, an alcohol solution of platinum chloride acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, a platinum-carbonyl complex, and these platinum-based catalysts are made of silicone resin and polycarbonate. Examples of catalysts are dispersed or encapsulated in a thermoplastic resin such as a resin or an acrylic resin, and a platinum-alkenylsiloxane complex is particularly preferable. Examples of this alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Examples thereof include alkenylsiloxanes in which some of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups and the like, and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups and the like. In particular, since the platinum-alkenylsiloxane complex has good stability, it is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. In addition, a fine-grained platinum-containing hydrosilylation reaction catalyst dispersed or encapsulated in a thermoplastic resin may be used from the viewpoint of improving handling workability and pot life of the composition. As the catalyst for promoting the hydrosilylation reaction, a non-platinum metal catalyst such as iron, ruthenium, or iron / cobalt may be used.
Although the production method of the present invention takes a short time, a certain temperature is applied to the composition during the kneading process. Therefore, from the viewpoint of storage stability of the composition, fine particles dispersed or encapsulated with a thermoplastic resin. A platinum-containing hydrosilylation reaction catalyst in the form may be used, and it is preferable.

The amount of the catalyst for the hydrosilylation reaction to be added is an amount in which the metal atom is in the range of 0.01 to 500 ppm in mass unit, an amount in the range of 0.01 to 100 ppm, or an amount of the metal atom with respect to the component (A). The amount is preferably in the range of 0.01 to 50 ppm.

Examples of organic peroxides include alkyl peroxides, diacyl peroxides, esters peroxide, and carbonates peroxide.

Examples of alkyl peroxides include dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and 2, , 5-Dimethyl-2,5-di (tert-butylperoxy) hexin-3, tert-butylcumyl, 1,3-bis (tert-butylperoxyisopropyl) benzene, 3,6,9-triethyl-3, 6,9-trimethyl-1,4,7-triperoxonan is exemplified.

Examples of diacyl peroxides include benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide.

Examples of the peroxide esters include 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, tert-butylperoxyneodecanoate, and tert-butylperoxy. Neoheptanoate, tert-butylperoxypivalate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxyl-2- Ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, tert-amylperoxy-3,5,5- Examples thereof include trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate and di-butylperoxytrimethyladipate.

Examples of carbonate peroxides include di-3-methoxybutylperoxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, diisopropylperoxycarbonate, tert-butylperoxyisopropylcarbonate, and di (4-tert-butylcyclohexyl). ) Peroxydicarbonate, disetylperoxydicarbonate, dimyristylperoxydicarbonate are exemplified.

The organic peroxide preferably has a half-life of 10 hours and a temperature of 90 ° C. or higher, or 95 ° C. or higher. Examples of such organic peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, t-butyl cumyl peroxide, and 2,5-dimethyl-2,5-di (). tert-butylperoxy) hexane, 1,3-bis (tert-butylperoxyisopropyl) benzene, di- (2-t-butylperoxyisopropyl) benzene, 3,6,9-triethyl-3,6,9- Examples thereof are trimethyl-1,4,7-triperoxonan.

The content of the organic peroxide is not limited, but is within the range of 0.05 to 10 parts by mass or the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). Is preferable.

In addition, the composition may contain hot-melt fine particles other than the component (A), a curing retarder, and an adhesion-imparting agent as other optional components as long as the object of the present invention is not impaired. However, when the curable silicone sheet of the present invention is transparent, it is preferable that it does not substantially contain hot-melt fine particles other than the component (A).

Examples of the curing retarder include 2-methyl-3-butin-2-ol, 3,5-dimethyl-1-hexin-3-ol, 2-phenyl-3-butin-2-ol, and 1-ethynyl-1-. Alkyne alcohols such as cyclohexanol; enein compounds such as 3-methyl-3-pentene-1-in, 3,5-dimethyl-3-hexene-1-in; tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahexenylcyclo Alkyne group-containing low molecular weight siloxanes such as tetrasiloxane; alkynyloxysilanes such as methyl-tris (1,1-dimethylpropynyloxy) silane and vinyl-tris (1,1-dimethylpropynyloxy) silane are exemplified. The content of this curing retarder is not limited, but is preferably in the range of 10 to 10,000 ppm by mass with respect to the present composition. As described above, when the curing retarder is added to the raw material mixture of the curable silicone sheet of the present invention, in step 2, at the supply point 1 before the addition of the hydrosilylation reaction catalyst, a part of the curing agent is used. It is preferably added as a mixture with a certain organohydrogenpolysiloxane.

As the adhesion-imparting agent, an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule is preferable. Examples of this alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. Further, as a group bonded to a silicon atom other than the alkoxy group in the organic silicon compound, a halogen-substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkyl halide group; Glycydoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and the like. Epoxycyclohexylalkyl groups; epoxyalkyl groups such as 3,4-epoxybutyl group, 7,8-epoxyoctyl group; acrylic group-containing monovalent organic groups such as 3-methacryloxypropyl group; hydrogen atoms are exemplified. The organosilicon compound preferably has an alkenyl group or a group capable of reacting with a silicon atom-bonded hydrogen atom in the present composition, and specifically, preferably has a silicon atom-bonded hydrogen atom or an alkenyl group. Further, since good adhesiveness can be imparted to various base materials, it is preferable that this organosilicon compound has at least one epoxy group-containing monovalent organic group in one molecule. Examples of such organosilicon compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate include linear, linear with partial branches, branched chain, cyclic, and network, and in particular, linear, branched, and network. It is preferable to have. Examples of the organic silicon compound include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; silicon atoms in one molecule. Silicon atom-bonded hydroxy in one molecule with a siloxane compound having at least one bonded alkenyl group or silicon atom-bonded hydrogen atom and at least one silicon atom-bonded alkoxy group, and a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group. A mixture of a siloxane compound having at least one group and at least one silicon atom-bonded alkenyl group, a reaction mixture of an amino group-containing organoalkoxysilane and an epoxy group-containing organoalkoxysilane, and having at least two alkoxysilyl groups in one molecule. and, and silicon during their silyl groups - organic compounds that contain bonds other than oxygen bonds, the general _{^{formula: R a n Si (OR b}} ) 4-n
(In the formula, ^Ra is a monovalent epoxy group-containing organic group, R ^b is an alkyl group or a hydrogen atom having 1 to 6 carbon atoms, and n is a number in the range of 1 to 3).
Epoxy group-containing silane represented by or a partially hydrolyzed condensate thereof, reaction mixture of vinyl group-containing siloxane oligomer (including those having a chain or cyclic structure) and epoxy group-containing trialkoxysilane, methylpolysilicate, ethylpoly Examples thereof include silicates and epoxy group-containing ethylpolysilicates. The adhesive is preferably a low-viscosity liquid, and its viscosity is not limited, but is preferably in the range of 1 to 500 mPa · s at 25 ° C. The content of the adhesive is not limited, but is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the present composition.

In the present invention, a reaction mixture of an amino group-containing organoalkoxysilane and an epoxy group-containing organoalkoxysilane is exemplified as a particularly suitable adhesion-imparting agent. Such a component is a component that improves the initial adhesiveness to various substrates that are in contact during curing, particularly the low temperature adhesiveness to an unwashed adherend. In addition, depending on the curing system of the curable silicone composition containing the present adhesion accelerator, it may also act as a cross-linking agent. Such a reaction mixture is disclosed in Japanese Patent Application Laid-Open No. 52-8854 and Japanese Patent Application Laid-Open No. 10-195085.

Examples of the alkoxysilane having an amino group-containing organic group constituting such a component include aminomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and N. -(2-Aminoethyl) aminomethyltributoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ani Linopropyltriethoxysilane is exemplified.

Examples of the epoxy group-containing organoalkoxysilane include 3-glycidoxyprolyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2-( 3,4-Epoxide cyclohexyl) ethylmethyldimethoxysilane is exemplified.

The ratio of the alkoxysilane having an amino group-containing organic group to the alkoxysilane having an epoxy group-containing organic group is preferably in the range of (1: 1.5) to (1: 5) in terms of molar ratio. It is particularly preferable that it is in the range of (1: 2) to (1: 4). This component (e1) is easily synthesized by mixing an alkoxysilane having an amino group-containing organic group as described above and an alkoxysilane having an epoxy group-containing organic group and reacting them at room temperature or under heating. be able to.

｛式中、Ｒ¹はアルキル基、アルケニル基またはアルコキシ基であり、Ｒ²は同じかまたは異なる一般式：

（式中、Ｒ⁴はアルキレン基またはアルキレンオキシアルキレン基であり、Ｒ⁵は一価炭化水素基であり、Ｒ⁶はアルキル基であり、Ｒ⁷はアルキレン基であり、Ｒ⁸はアルキル基、アルケニル基、またはアシル基であり、ａは０、１、または２である。）
で表される基からなる群から選択される基であり、Ｒ³は同じかまたは異なる水素原子もしくはアルキル基である。｝
で表されるカルバシラトラン誘導体を含有することが特に好ましい。このようなカルバシラトラン誘導体として、以下の構造で表される１分子中にケイ素原子結合アルコキシ基またはケイ素原子結合アルケニル基を有するカルバシラトラン誘導体が例示される。

（式中、Ｒcはメトキシ基、エトキシ基、ビニル基、アリル基およびヘキセニル基から選ばれる基） In particular, in the present invention, when the alkoxysilane having an amino group-containing organic group and the alkoxysilane having an epoxy group-containing organic group are reacted by the method described in JP-A No. 10-195085, particularly, an alcohol exchange reaction is carried out. General formula:

{In the formula, R ¹ is an alkyl group, an alkenyl group or an alkoxy group, and R ² is the same or different general formula:

(In the formula, R ⁴ is an alkylene group or an alkyleneoxyalkylene group, R ⁵ is a monovalent hydrocarbon group, R ⁶ is an alkyl group, R ⁷ is an alkylene group, R ⁸ is an alkyl group, It is an alkenyl group or an acyl group, and a is 0, 1, or 2).
It is a group selected from the group consisting of the groups represented by, and R ³ is the same or different hydrogen atom or alkyl group. }
It is particularly preferable to contain a carbacilatran derivative represented by. Examples of such a carbacilatran derivative include a carbacilatran derivative having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule represented by the following structure.

(In the formula, Rc is a group selected from a methoxy group, an ethoxy group, a vinyl group, an allyl group and a hexenyl group)

式中のＲ¹は同じかまたは異なる水素原子もしくはアルキル基であり、特に、Ｒ¹としては、水素原子、またはメチル基が好ましい。また、上式中のＲ²は水素原子、アルキル基、および一般式：−Ｒ⁴−Ｓｉ(ＯＲ⁵)_xＲ⁶ _(3-x)で表されるアルコキシシリル基含有有機基からなる群から選択される同じかまたは異なる基であり、但し、Ｒ²の少なくとも１個はこのアルコキシシリル基含有有機基である。Ｒ²のアルキル基としては、メチル基等が例示される。また、Ｒ²のアルコキシシリル基含有有機基において、式中のＲ⁴は二価有機基であり、アルキレン基またはアルキレンオキシアルキレン基が例示され、特に、エチレン基、プロピレン基、ブチレン基、メチレンオキシプロピレン基、メチレンオキシペンチレン基であることが好ましい。また、式中のＲ⁵は炭素原子数１〜１０のアルキル基であり、好ましくは、メチル基、エチル基である。また、式中のＲ⁶は置換もしくは非置換の一価炭化水素基であり、好ましくは、メチル基である。また、式中のｘは１、２、または３であり、好ましくは、３である。 Further, in the present invention, a silatlan derivative represented by the following structural formula may be used as an adhesive-imparting agent.

^{R 1} in the formula is the same or different hydrogen atom or alkyl group, and in particular, R ¹ is preferably a hydrogen atom or a methyl group. In addition, R ² in the above formula consists of a group consisting of a hydrogen atom, an alkyl group, and an alkoxysilyl group-containing organic group represented by the ^{general formula: −R 4} −Si (OR ⁵ ) _x R ⁶ _(3-x). The same or different groups of choice, except that ^{at least one of R 2} is this alkoxysilyl group-containing organic group. Examples of the alkyl group of R ^{2 include a methyl group.} Further, among the alkoxysilyl group-containing organic groups of ^{R 2 , R 4} in the formula is a divalent organic group, and an alkylene group or an alkyleneoxyalkylene group is exemplified, and in particular, an ethylene group, a propylene group, a butylene group, and a methyleneoxy group. It is preferably a propylene group or a methyleneoxypentylene group. Further, R ⁵ in the formula is an alkyl group having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group. Further, R ⁶ in the formula is a substituted or unsubstituted monovalent hydrocarbon group, preferably a methyl group. Further, x in the formula is 1, 2, or 3, preferably 3.

Examples of such an alkoxysilyl group-containing organic group of R ^{2 include the following groups.}
− (CH2) 2Si (OCH3) 3- (CH2) 2Si (OCH3) 2CH3
− (CH2) 3Si (OC2H5) 3- (CH2) 3Si (OC2H5) (CH3) 2
−CH2O (CH2) 3Si (OCH3) 3
−CH2O (CH2) 3Si (OC2H5) 3
−CH2O (CH2) 3Si (OCH3) 2CH3
−CH2O (CH2) 3Si (OC2H5) 2CH3
−CH2OCH2Si (OCH3) 3-CH2OCH2Si (OCH3) (CH3) 2

^{R 3} in the above formula is selected from the group consisting of a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group having 1 to 10 carbon atoms, a glycidoxyalkyl group, an oxylanylalkyl group, and an asyloxyalkyl group. at least one group that is, as the monovalent hydrocarbon group R ^3, is exemplified an alkyl group such as a methyl group, the alkoxy group R ^3, a methoxy group, an ethoxy group, a propoxy group are exemplified, Examples of the glycidoxyalkyl group of R ³ include a 3-glycidoxypropyl group, and examples of the ^{oxylanyl alkyl group of R 3} include a 4-oxylanyl butyl group and an 8-oxylanyl octyl group. Examples of the asyloxyalkyl group of R ³ include an acetoxypropyl group and a 3-methacryloxypropyl group. In particular, R ³ is preferably an alkyl group, an alkenyl group, or an alkoxy group, more preferably an alkyl group or an alkenyl group, and a group selected from a methyl group, a vinyl group, an allyl group, and a hexenyl group. Is particularly preferably exemplified.

Further, the composition has heat resistance of iron oxide (bengala), cerium oxide, cerium dimethyl silanolate, fatty acid cerium salt, cerium hydroxide, zirconium compound and the like as other optional components as long as the object of the present invention is not impaired. Agent; In addition, a dye, a pigment other than white, a flame retardant-imparting agent, and the like may be contained.

The above composition reflects light by using an inorganic filler such as a white pigment, a thermally conductive filler, a conductive filler, and a phosphor in combination with the organopolysiloxane resin fine particles as the component (A) or a mixture containing the same. It has excellent gap-filling property at the time of melting (hot melt) with the functionality of improving rate and thermal conductivity, and the cured product is flexible from room temperature to high temperature, specifically, 25 ° C to 150 ° C, and stress It has excellent relaxation characteristics and is not easily damaged even if it is bent or otherwise deformed at room temperature.

[About the content of functional filler]
The production method of the present invention is particularly suitable for producing a curable silicone sheet composed of a curable silicone composition having a low content or substantially no content of a functional filler and having excellent transparency and uniformity. is there. Examples of the functional filler include inorganic fillers, organic fillers, and mixtures thereof, but they are transparent even when used in an amount of less than 5% by mass, more preferably less than 1% by mass, of the entire curable silicone sheet. A curable silicone sheet having excellent properties and uniformity and having hot melt properties can be obtained.

[Use of multi-component curable silicone composition]
As described above, the production method of the present invention includes a process of separately adding an organopolysiloxane resin (and optionally a chain diorganopolysiloxane) and a curing agent in steps 1 and 2. Therefore, at least, it is preferable to use a composition containing two or more components as a raw material, in which a component containing an organopolysiloxane resin and a component containing a curing agent are separately stored and used. Further, when the curable silicone sheet of the present invention is thermosetting reactive, particularly hydrosilylation reactive curable, I) component part containing an organopolysiloxane resin (and optionally a chain diorganopolysiloxane), II). A three-component or higher multi-component curable silicone composition containing at least a component part containing an organohydrogenpolysiloxane as a cross-linking agent, preferably a curing retarder, and III) a component part containing a hydrosilylation reaction catalyst. It is preferably used as a raw material. The component part containing the organopolysiloxane resin (and optionally the chain diorganopolysiloxane) may be a solution system containing an organic solvent, and is preferable. Further, III) the component part containing the hydrosilylation reaction catalyst may be a solution system in which the hydrosilylation reaction catalyst is dispersed in a siloxane solvent, and is preferable.

[Storage modulus of cured product]
Specifically, the cured product obtained by curing the above composition has a storage elastic modulus (G') value of 2000 MPa or less at 25 ° C. and a storage elastic modulus (G') value at 150 ° C. It is 100 MPa or less. Such a cured product is flexible at both room temperature (25 ° C.) and high temperature (150 ° C.), has excellent adhesion and followability to a substrate such as a semiconductor substrate, and is a flexible semiconductor substrate that has been introduced in recent years. Even in the case of a semiconductor element sealing application that is premised on deformation as described above, the occurrence of defects such as breakage or peeling of the sealed semiconductor element and voids is suppressed. The storage elastic modulus (G') at 25 ° C. may be 1500 MPa or less, 1000 MPa or less, and the storage elastic modulus at 150 ° C. is particularly high in applications that require high elongation and followability to deformation. The value of (G') may be 50 MPa or less or 40 MPa or less.

[Peak value and peak temperature of loss tangent (tan δ) of cured product]
Further, the cured product obtained by curing the composition of the present invention is defined by the ratio of the storage elastic modulus (G') to the loss modulus (G'') at a frequency of 1.0 Hz, that is, G'/ G''. The peak value of the loss tangent (tan δ) to be formed needs to be 0.40 or more, preferably 0.50 or more, and particularly preferably in the range of 0.50 to 0.80. If the peak value of the tan δ is less than 0.40, warpage or breakage of the molded product may occur, especially in the form of a thin film or when integrally molded with an aluminum lead frame or the like. The peak temperature that gives the peak value of tan δ is not particularly limited, but is preferably in the range of 30 to 200 ° C., and particularly preferably in the range of 40 to 150 ° C.

In the composition of the present invention, a cured product having excellent stress relaxation ability is formed by setting the peak value of tan δ to 0.4 or more, but the above components are particularly preferably selected. Thereby, a high tan δ can be realized even in a composition having a relatively large content of the inorganic filler. Such a cured product realizes an excellent low warpage ability in a large-area batch encapsulation process for semiconductors, which has been introduced in recent years.

Further, in the composition of the present invention, the mixture of the organopolysiloxane resin fine particles, the curing agent and the functional filler is cured by curing.
(1) The maximum torque value measured by MDR (Moving Die Ratio) at the molding temperature from room temperature to 200 ° C. is less than 50 dBN · m, and (2) When the maximum torque value is reached, the storage torque value / It is particularly preferable to give a cured product in which the value of the loss tangent (tan δ) represented by the ratio of the loss torque values is less than 0.2.

In particular, (1) the maximum torque value measured by MDR set to 150 ° C., which is a general molding temperature, is less than 50 dBN · m, and (2) the storage torque value / loss when the maximum torque value is reached. It is particularly preferable that the value of the loss tangent (tan δ) represented by the ratio of the torque values is less than 0.2. As long as the above curing behavior is satisfied and the physical property value of MDR at a specific temperature (for example, 150 ° C.) is satisfied, the curable silicone composition for transfer molding of the present invention is desired from room temperature to 200 ° C. It goes without saying that the molding temperature (for example, a molding temperature other than 150 ° C.) can be selected as desired and can be used.

The above maximum torque value will be described. In the present invention, the torque value refers to a cured product obtained by curing (= vulcanizing) the composition, and refers to JIS K 6300-2 "Unvulcanized rubber-Physical properties-Part 2: Vibration type vulcanization tester". It is a torque value obtained by measurement by MDR in accordance with "How to obtain vulcanization characteristics by", and the maximum torque value is a torque value measured in 600 seconds after vulcanization at a molding temperature, preferably 150 ° C. The maximum value. Here, when the maximum torque value at the molding temperature of the cured product is less than 50 dN · m, it means that the cured product after molding is soft even at a high temperature, that is, the cured product has low modulus and flexibility, and has a low elastic modulus. It means that the stress relaxation characteristics are excellent, and in the present invention, the maximum torque value at the molding temperature of the cured product may be less than 40 dBN · m, preferably less than 35 dBN · m, and 5 to 5 The range of 30 dN · m is particularly preferable. This is because within this range, sufficient stress relaxation characteristics of the cured product can be realized, and it is possible to achieve compatibility with the loss tangent (tan δ) described later. On the other hand, if the maximum torque value at the molding temperature of the cured product exceeds the above upper limit, the cured product is excessively hard and stress relaxation property cannot be realized. In some cases.

Next, the conditions of loss tangent (tan δ) of the composition in the present invention will be described. Loss tangent (tan δ) is measured by reading the value of loss tangent (tan δ) represented by the ratio of storage torque value / loss torque value when the maximum torque value is reached by the above measurement using MDR. Is the value to be. Here, when the loss tangent (tan δ) of the composition is less than 0.2, it means that the rubber elasticity of the cured product obtained by curing the composition is low and the surface thereof is moderately hard. Therefore, the cured product is difficult to adhere / adsorb to the mold at the time of mold release in the molding process, and is excellent in mold removal property. From the viewpoint of demoldability, the loss tangent (tan δ) of the cured product when the maximum torque value is reached is preferably in the range of 0.01 to 0.19, preferably in the range of 0.03 to 0.18. It is particularly preferable to have. On the other hand, when the loss tangent (tan δ) of the composition exceeds 0.2, the rubber elasticity of the obtained cured product becomes high and the surface becomes sticky, so that the cured product adheres to the mold at the time of mold release. / It becomes easy to adsorb, it is difficult to separate from the mold smoothly, and the mold releasability may be insufficient.

For the cured product, (1) the condition of the maximum torque value and (2) the condition of the value of the loss tangent (tan δ) expressed by the ratio of the storage torque value / the loss torque value when the maximum torque value is reached. The curable silicone sheet is excellent in stress relaxation characteristics of the cured product, is less likely to cause warpage or defects of the cured product, and realizes good mold removal property.

The method for producing a hot-meltable curable silicone sheet of the present invention will be described in detail with reference to Examples and Comparative Examples. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively. The softening point of the curable granular silicone composition constituting the curable silicone sheet was measured by the following method.

[Softening point of curable silicone composition]
The curable silicone composition was molded into cylindrical pellets having a diameter of 14 mm × 22 mm. The pellet was placed on a hot plate set at 25 ° C. to 100 ° C. and pressed under a load of 100 grams for 10 seconds from above to remove the load, and then the amount of deformation of the pellet was measured. The temperature at which the amount of deformation in the height direction was 1 mm or more was defined as the softening point.

Hereinafter, an organopolysiloxane resin containing a hydrosilylation reaction catalyst is prepared by the method shown in the reference example, the presence or absence of hot melt property is evaluated based on the presence or absence of softening point / melt viscosity, and the organopolysiloxane resin fine particles are further prepared. did. In the reference example, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane used for the platinum complex which is a hydrosilylation reaction catalyst is described as "1,3-divinyltetramethyldisiloxane". ..

[Reference Example 1: Preparation of a mixture of hot-meltable organopolysiloxane resin and linear organopolysiloxane]
White solid at 25 ° C, average unit formula:
(Me ₂ ViSio _1/2 ) _0.05 (Me ₃ SiO _1/2 ) _0.39 (SiO _4/2 ) _0.56 (HO _1/2 ) _0.02
Organopolysiloxane resin represented by (vinyl group content = 1.9% by mass) 3.25 kg
White solid at 25 ° C, average unit formula:
(Me ₃ SiO _1/2 ) _0.44 (SiO _4/2 ) _0.56 (HO _1/2 ) _0.02
Organopolysiloxane resin represented by (vinyl group content = 0% by mass) 3.05 kg
And formula:
ViMe ₂ SiO (Me ₂ SiO) ₈₀₀ SiViMe ₂
Dimethylvinylsiloxy group-blocking dimethylpolysiloxane at both ends of the molecular chain (vinyl group content = 0.09% by mass) 2.85 kg,
Was dissolved in 4.00 kg of xylene in a pail using a three-one motor. The obtained solution was fed to a biaxial extruder whose maximum temperature reached was set to 230 ° C., and xylene and low molecular weight organopolysiloxane components were removed under the condition of a vacuum degree of −0.08 MPa. The transparent mixture 1 of the above was obtained, and it was received on a barrel pail and cooled as it was to be solidified. When the amount of volatile components of this mixture was measured under the condition of 200 ° C. × 1 hour, it was 0.7 wt%.

[Reference Example 2: Non-hot melt organopolysiloxane resin fine particles]
In a 1 L flask, in white solid form at 25 ° C., average unit formula:
(Me ₃ SiO _1/2 ) _0.44 (SiO _4/2 ) _0.56 (HO _1/2 ) _0.02
270.5 g of 55 mass% -xylene solution of organopolysiloxane resin represented by, and 1,3-divinyltetramethyldisiloxane solution of 1,3-divinyltetramethyldisiloxane complex of platinum (platinum metal content = Approximately 4000 ppm) 0.375 g was added and stirred uniformly at room temperature (25 ° C.) to prepare a xylene solution of an organopolysiloxane resin containing 10 ppm by mass as a platinum metal. Further, this organopolysiloxane resin did not soften / melt even when heated to 200 ° C. and did not have hot melt properties.

The xylene solution of the organopolysiloxane resin prepared above was atomized at 50 ° C. by a spray method using a spray dryer while removing xylene to prepare spherical non-hot melt organopolysiloxane resin fine particles. When these fine particles were observed with an optical microscope, the particle size was 5 to 10 μm, and the average particle size was 7.4 μm.

[Example 1]
The hot-meltable mixture 1 obtained in Reference Example 1 was put into a twin-screw extruder at 170 ° C. using a bulk melter for a barrel pail (VersaPail melter manufactured by Nordson) from line 1 to 9.30 kg shown in FIG. The amount of / hr was fed.
next,
formula:
Me ₃ SiO (MeHSiO) ₇ (Me ₂ SiO) _6.5 SiMe ₃
Organohydrogenpolysiloxane represented by 0.20 kg / hr,
formula:
HMe ₂ SiO (Me ₂ SiO) ₁₇ SiMe ₂ H
Organohydrogenpolysiloxane represented by 0.50 kg / hr,
1-ethynyl-1-cyclohexanol (amount of mass unit 1000 ppm with respect to this composition),
The mixture consisting of was fed from line 2 shown in FIG. The set temperature of the charging part was 150 ° C.
continue,
ViMe ₂ SiO (Me ₂ SiO) ₈₀₀ SiViMe ₂
Dimethylvinylsiloxy group-blocking dimethylpolysiloxane at both ends of the molecular chain (vinyl group content = 0.09% by mass) 1.5 kg / hr,
1,3-Divinyltetramethyldisiloxane solution of 1,3-divinyltetramethyldisiloxane complex of platinum (amount of platinum metal 4.0 ppm by mass with respect to this composition),
The mixture was fed from line 3 in FIG. 1 (the set temperature of the charging section was 80 ° C.), the degree of vacuum in the extruder was −0.08 MPa, and degassing, melting and kneading was performed. The outlet temperature of the twin-screw extruder is 80 ° C., and the mixture is in the form of a semi-solid softened product, and the supply amount is 5 kg / hr on a 125 μm thick peelable film (FL2-01, manufactured by Takaline Corporation). It was supplied so as to be, and laminated between two release films. Subsequently, the laminate was stretched between rolls whose temperature was controlled at 90 ° C. to obtain a laminate in which a hot-meltable curable silicone sheet having a thickness of 300 μm was laminated between two release films. It was formed and the whole was cooled by air cooling. It took about 2 minutes to stretch from line 2 with a roll. The overall configuration of the manufacturing apparatus is shown in FIG.

When the peelable film was separated from the obtained laminate, a flat, homogeneous, tack-free, transparent hot-meltable curable silicone sheet having no bubbles could be obtained, and the softening temperature was 80 ° C.

[Comparative Example 1]
Non-hot melt organopolysiloxane resin fine particles (vinyl group content = 0% by mass) obtained in Reference Example 2 6.98 kg,
formula:
ViMe ₂ SiO (Me ₂ SiO) ₈₀₀ SiViMe ₂
Dimethylvinylsiloxy group-blocking dimethylpolysiloxane at both ends of the molecular chain (vinyl group content = 0.09% by mass) 2.9 kg,
formula:
Me ₃ SiO (MeHSiO) ₇ (Me ₂ SiO) _6.5 SiMe ₃
Organohydrogenpolysiloxane represented by 0.20 kg,
{Amount of silicon atom-bonded hydrogen atom in the above-mentioned organohydrogenpolysiloxane is 1.4 mol with respect to 1 mol of vinyl group in dimethylpolysiloxane, which is a blockage of dimethylvinylsiloxy groups at both ends of the molecular chain},
When 1-ethynyl-1-cyclohexanol (amount having a mass unit of 1000 ppm with respect to this composition was put into a medium-sized crusher all at once and stirred at room temperature (25 ° C.) for 1 minute, it became a sticky mass in places. No uniform mixture was obtained.

The obtained mass was transferred to a barrel pail, and an attempt was made to feed the obtained mass to a twin-screw extruder at 100 ° C. using the same bulk melter (VersaPail melter manufactured by Nordson) as in Example 1, but the pusher was used without melting. Could not feed.

[Comparative Example 2]
Non-hot melt organopolysiloxane resin fine particles (vinyl group content = 0% by mass) obtained in Reference Example 2 6.98 kg,
formula:
ViMe ₂ SiO (Me ₂ SiO) ₈₀₀ SiViMe ₂
Dimethylvinylsiloxy group-blocking dimethylpolysiloxane at both ends of the molecular chain (vinyl group content = 0.09% by mass) 2.9 kg,
formula:
Me ₃ SiO (MeHSiO) ₇ (Me ₂ SiO) _6.5 SiMe ₃
Organohydrogenpolysiloxane represented by 0.20 kg,
{Amount of silicon atom-bonded hydrogen atom in the above-mentioned organohydrogenpolysiloxane is 1.4 mol with respect to 1 mol of vinyl group in dimethylpolysiloxane, which is a blockage of dimethylvinylsiloxy groups at both ends of the molecular chain},
When 1-ethynyl-1-cyclohexanol (amount having a mass unit of 1000 ppm with respect to this composition was put into a medium-sized crusher all at once and stirred at room temperature (25 ° C.) for 1 minute, it became a sticky mass in places. No uniform mixture was obtained.

When the obtained mass was transferred for a barrel pail and fed to a twin-screw extruder at 170 ° C. using the same hot melter (VersaPail melter manufactured by Nordson) as in Example 1, curing started in the middle and the feed could be performed. There wasn't.

[Summary]
According to Reference Example 1, a compound containing a hot-meltable organopolysiloxane resin containing no curing agent was obtained, and the mixture was mixed with the curing agent by a temperature-controlled biaxial extruder to perform degassing, melting and kneading. By laminating between the peelable films, a hot-meltable curable silicone sheet could be industrially and continuously produced in a short time. In the production method, a curable silicone sheet that does not substantially contain a functional filler, has excellent transparency and uniformity, and has no surface tack (adhesion) can be obtained.

On the other hand, even if an attempt is made to mix other components such as a curing agent after obtaining non-hot meltable organopolysiloxane resin fine particles using a similar raw material, the raw materials cannot be mixed uniformly, resulting in poor melting or curing. Due to the progress of the reaction, continuous production by a twin-screw extruder was difficult.

Figure 1
1: Bulk melter
2: Twin-screw extruder with T-type die
3-a: Pump
3-b: Pump
3-c: Vacuum pump
4-a: Line 1
4-b: Line 2
4-c: Line 3

Figure 2
1: Bulk melter
2: Twin-screw extruder with T-type die
3-a: Pump
3-b: Pump
3-c: Vacuum pump
4-a: Release sheet
4-b: Release sheet
5-a: Stretching roll (optionally further provided with temperature control function)
5-b: Stretching roll (optionally further provided with temperature control function)
6: Film thickness meter
7-a: Tensile roll
7-b: Tensile roll
8: Foreign matter inspection machine
9: Sheet cutter

Claims (16)

A method for producing a curable silicone sheet having hot melt property, which comprises the following steps.
Step 1: The organic solvent is removed from a solution in which a solid organopolysiloxane resin at room temperature and optionally a chain diorganopolysiloxane are dispersed or dissolved in an organic solvent at a temperature of 150 ° C. or higher. Step 2: Obtaining hot-melting solids: After adding all the curing agents to the hot-melting solids obtained in step 1, 1
Step 3: Kneading while heating and melting at a temperature of 20 ° C. or lower Step 3: The mixture after heating and melting obtained in Step 2 is laminated between films having at least one peeling surface Step 4: Obtained in Step 3. A process of stretching a laminate between rolls to form a curable silicone sheet having a specific film thickness. The melt viscosity of the mixture after heating and melting obtained in step 2 measured by an elevated flow tester at 150 ° C. is in the range of 1 to 1,000 Pas.
In step 3, the step of laminating the mixture after heating and melting between films having at least one peeling surface ejects the mixture after heating and melting while molding the mixture into a film or a string using a die and a nozzle. Then, it is a step of laminating between films having at least one peeling surface.
Further, as a pre-step of step 4 or in step 4, the step of cooling the entire laminate obtained in step 3 or adjusting the temperature between 80 and 120 ° C. is included.
The method for producing a curable silicone sheet having a hot melt property according to claim 1. The softening point of the entire mixture obtained in step 2 is 200 ° C. or lower.
Step 2 is a step of heating the mixture obtained in step 1 to a temperature equal to or higher than the softening point of the mixture.
In step 3, the step of laminating the mixture after heating and melting between films having at least one peeling surface ejects the mixture after heating and melting in a solid state and has a film having at least one peeling surface. It is a process of laminating between
The method for producing a curable silicone sheet having a hot melt property according to claim 1. The curable silicone sheet having hot melt property according to claim 1, wherein steps 2 to 4 are continuous steps, and the time from the start of step 2 to the end of step 4 is within 30 minutes. Production method. Further, the step of cutting the laminate containing the curable silicone sheet obtained in step 4 is included.
The method for producing a curable silicone sheet having hot melt property according to any one of claims 1 to 4. In step 3, the step of laminating the mixture after heating and melting obtained in step 2 between films having at least one peeling surface is a die in which the mixture after heating and melting is selected from a T-type die and a strand die. Any of claims 1 to 5, which is a step of discharging while molding into a film or string using a nozzle selected from a single nozzle and a multi-nozzle, and laminating between films having at least one peeling surface. The method for producing a curable silicone sheet having hot melt property according to item 1. The organopolysiloxane resin in step 1 is an organopolysiloxane resin containing at least 20 mol% or more of siloxane units (R is an aryl group) represented by _{RSiO 3/2} or SiO _{4/2, and is a chain.} The diorganopolysiloxane is a diorganopolysiloxane containing at least 90 mol% or more of siloxane units (R ^{2 is a methyl group) represented by RR 2} SiO _2/2.
The method for producing a curable silicone sheet having a hot melt property according to any one of claims 1 to 6. The mixture obtained in step 2 is cured by curing.
The storage elastic modulus (G') at 25 ° C. is 2000 MPa or less.
The storage elastic modulus (G') at 150 ° C. is 100 MPa or less.
It is characterized by giving a cured product having a peak value of loss tangent (tan δ) represented by storage elastic modulus / loss elastic modulus (G'/ G'') at a frequency of 1.0 Hz of 0.40 or more.
The method for producing a curable silicone sheet having hot melt property according to any one of claims 1 to 7. The mixture obtained in step 2 is cured by curing.
(1) The maximum torque value measured by MDR (Moving Die Ratio) at the molding temperature from room temperature to 200 ° C. is less than 50 dBN · m, and (2) When the maximum torque value is reached, the storage torque value / It is characterized by giving a cured product having a loss tangent (tan δ) value expressed by a ratio of loss torque values of less than 0.2.
The method for producing a curable silicone sheet having a hot melt property according to any one of claims 1 to 8. The curable silicone sheet having hot melt property according to any one of claims 1 to 9, wherein the mixture obtained in step 2 has a functional filler content of less than 5.0% by mass in the entire mixture. Production method. The production of a curable silicone sheet having a hot melt property according to any one of claims 1 to 10, wherein the curable silicone sheet is a curable silicone sheet for compression molding, press molding, or vacuum lamination. Method. The method for producing a curable silicone sheet having a hot melt property according to any one of claims 1 to 10, wherein the curable silicone sheet is a hot melt film adhesive. The method for producing a curable silicone sheet having hot melt property according to any one of claims 1 to 10, wherein the curable silicone sheet is a substantially flat curable silicone sheet having a thickness of 10 to 2000 μm. .. A substantially flat, curable silicone sheet having a hot melt property with a thickness of 10 to 2000 μm and a functional filler content of less than 5.0% by mass between films having at least one peeled surface. A laminated body having a laminated structure. The peeled surface is a peeling coating layer obtained by curing a curable organopolysiloxane composition containing one or more types of organopolysiloxane having a fluorine-containing substituent bonded to a silicon atom in one molecule. The laminate according to claim 14, wherein at least one of the films having faces has a thickness of 50 μm or more. The method for producing a laminate according to claim 14 or 15, which comprises the method for producing a curable silicone sheet having hot melt property according to any one of claims 1 to 13.

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