JP2021160300A - Temporary-fixation composite - Google Patents

Abstract

To provide a temporary-fixation composite having a temporary-fixation layer and a substrate layer, the temporary-fixation composite with an extremely small dimensional change rate when exposed to high temperature, and having high anchorability between the temporary-fixation layer and the substrate layer.SOLUTION: A temporary-fixation composite includes a temporary-fixation layer, a substrate layer and a silicone adhesive layer composed of a silicone adhesive. The temporary-fixation layer is a foam layer or a rubber layer. The temporary-fixation layer and the substrate layer are laminated interposing an undercoat layer.SELECTED DRAWING: Figure 1

Description

The present invention relates to a temporary fixed complex.

In the manufacturing process of electronic circuit boards and the like, adhesive tapes for the purpose of temporarily fixing parts are required (for example, Patent Documents 1 to 3). Recently, as temporary fixing materials, foams with an acrylic pressure-sensitive adhesive layer and urethane foams have been proposed (for example, Patent Documents 4 and 5).

In the manufacturing process of an electronic circuit board or the like, a component may be mounted on the board by a solder reflow process. The solder reflow process usually has a thermal history in which the temperature gradually rises from around 50 ° C. and the maximum temperature becomes close to 300 ° C. By the solder reflow process, the solder balls existing between the substrate and the mounting component are melted and soldered.

Conventional adhesive tapes and temporary fixing materials used in the manufacturing process of electronic circuit boards and the like for the purpose of temporary fixing of parts cannot withstand high temperatures exposed in the solder reflow process, for example, solder. Large dimensional changes may occur before and after the reflow process, and the purpose of temporary fixing of parts may not be achieved with high reliability.

Further, many of the conventional adhesive tapes and temporary fixing materials for the purpose of temporarily fixing parts are provided with a temporary fixing layer and a base material layer that exhibit a temporary fixing function. However, the temporary fixing layer has a low anchoring property with the base material layer, and there is a problem that the temporary fixing layer tends to float or peel off.

Japanese Unexamined Patent Publication No. 2008-201899 Japanese Unexamined Patent Publication No. 2006-332419 Japanese Unexamined Patent Publication No. 2006-077072 Japanese Unexamined Patent Publication No. 2010-234536 Japanese Unexamined Patent Publication No. 2013-144788

An object of the present invention is a temporary fixing complex having a temporary fixing layer and a base material layer, which has an extremely small dimensional change rate when exposed to a high temperature, and has anchorability between the temporary fixing layer and the base material layer. Is to provide a temporary fixed complex with a high value.

The temporary fixed complex of the present invention is
A temporary fixing composite containing a temporary fixing layer, a base material layer, and a silicone-based pressure-sensitive adhesive layer formed of a silicone-based pressure-sensitive adhesive.
The temporary fixing layer is a foam layer or a rubber layer, and the temporary fixing layer is a foam layer or a rubber layer.
The temporary fixing layer and the base material layer are laminated via an undercoat layer.

In one embodiment, the undercoat layer has a thickness of 0.01 μm to 5 μm.

In one embodiment, the undercoat layer has a thickness of 0.1 μm to 3 μm.

In one embodiment, the undercoating agent constituting the undercoating layer is a silicone-based undercoating agent.

In one embodiment, the silicone-based undercoat is a peroxide-crosslinked silicone-based pressure-sensitive adhesive.

In one embodiment, the silicone-based undercoat is an addition-reaction silicone-based pressure-sensitive adhesive.

In one embodiment, the temporary fixing layer is a silicone-based foam layer.

In one embodiment, the thickness of the silicone-based pressure-sensitive adhesive layer is 1 μm to 100 μm.

In one embodiment, the thickness of the silicone-based pressure-sensitive adhesive layer is 5 μm to 90 μm.

In one embodiment, the thickness of the silicone-based pressure-sensitive adhesive layer is 8 μm to 80 μm.

According to the present invention, it is a temporary fixing complex having a temporary fixing layer and a base material layer, the dimensional change rate when exposed to a high temperature is extremely small, and the anchoring property between the temporary fixing layer and the base material layer is extremely small. It is possible to provide a temporary fixed complex having a high value.

It is the schematic sectional drawing of the temporary fixed complex by one Embodiment of this invention. It is a figure which shows the thermal history of the solder reflow process used in the measurement of a dimensional change rate.

≪≪Temporary fixed complex≫≫
The temporary fixing composite of the present invention includes a temporary fixing layer, a base material layer, and a silicone-based pressure-sensitive adhesive layer formed of a silicone-based pressure-sensitive adhesive. By adopting such a configuration, the temporary fixed complex of the present invention can have an extremely small dimensional change rate when exposed to a high temperature. The temporary fixing layer may be only one layer or two or more layers. The base material layer may be only one layer or two or more layers. The silicone-based pressure-sensitive adhesive layer may be only one layer or two or more layers.

The temporary fixing composite of the present invention is formed by laminating a temporary fixing layer and a base material layer via an undercoat layer. By laminating the temporary fixing layer and the base material layer via the undercoat layer in this way, the anchoring property between the temporary fixing layer and the base material layer can be improved.

The temporary fixing composite of the present invention is arbitrary as long as it contains a temporary fixing layer, an undercoat layer, a base material layer, and a silicone-based pressure-sensitive adhesive layer formed of a silicone-based pressure-sensitive adhesive, as long as the effects of the present invention are not impaired. It may contain other suitable layers. Such other layers may be only one layer or two or more layers.

In the temporary fixing composite of the present invention, a separator may be attached to the surface of the temporary fixing layer until it is used. When such a separator does not function as a support, it is preferably peeled off from the surface of the temporary fixing layer before the member to be temporarily fixed is placed on the temporary fixing composite of the present invention.

Therefore, in the temporary fixing composite of the present invention, the temporary fixing layer or the separator attached to the surface of the temporary fixing layer is preferably one of the outermost layers.

In the temporary fixing composite of the present invention, when the silicone-based pressure-sensitive adhesive layer is the outermost layer, a separator may be attached to the surface of the silicone-based pressure-sensitive adhesive layer until it is used. When such a separator does not function as a support, it is preferably peeled off from the surface of the silicone-based pressure-sensitive adhesive layer before use.

As shown in FIG. 1, one embodiment of the temporary fixing composite 100 of the present invention has a temporary fixing layer 10, an undercoat layer 20, a base material layer 30, and a silicone-based pressure-sensitive adhesive layer 40. In FIG. 1, the temporary fixing layer, the undercoat layer, the base material layer, and the silicone-based pressure-sensitive adhesive layer are directly laminated.

The total thickness of the temporary fixed complex of the present invention is preferably 10 μm to 4000 μm, more preferably 20 μm to 3000 μm, and further preferably 30 μm to 2000 μm in that the effects of the present invention can be more exhibited. Particularly preferably, it is 40 μm to 1000 μm.

The temporary fixed composite of the present invention is obtained in the MD direction when a sample cut into 100 mm × 100 mm is allowed to stand for 1 hour at a temperature of 23 ° C. and a humidity of 50% RH after passing through a solder reflow process having a peak temperature of 270 ° C. The dimensional change rate of is preferably 0.3% or less, more preferably 0.28% or less, further preferably 0.25%, particularly preferably 0.23%, and most preferably. It is 0.2% or less, and the dimensional change rate in the TD direction is preferably 0.3% or less, more preferably 0.28% or less, still more preferably 0.25%, and particularly preferably. It is 0.23%, most preferably 0.2% or less. If the dimensional change rate in the MD direction is within the above range and the dimensional change rate in the TD direction is within the above range, the temporary fixed composite of the present invention has an extremely high dimensional change rate when exposed to a high temperature. It can be a small foam complex.

The dimensional change rate in the MD direction and the dimensional change rate in the TD direction are calculated by the following formulas.

Dimensional change rate in MD direction (%) = [(Length in MD direction before passing through solder reflow process (mm) -After passing through solder reflow process, after standing at temperature 23 ° C. x humidity 50% RH for 1 hour MD direction length (mm)) / MD direction length before passing through the solder reflow process (mm)] x 100 (%)

Dimensional change rate in the TD direction (%) = [(Length in the TD direction before passing through the solder reflow process (mm) -After passing through the solder reflow process, after standing at a temperature of 23 ° C. x humidity of 50% RH for 1 hour TD direction length (mm)) / TD direction length before passing through the solder reflow process (mm)] x 100 (%)

≪Temporary fixed layer≫
As the thickness of the temporary fixing layer, any appropriate thickness can be adopted as long as the effect of the present invention is not impaired. The thickness of such a foam layer is preferably 10 μm to 3500 μm, more preferably 20 μm to 2500 μm, further preferably 30 μm to 1500 μm, and particularly preferably 40 μm to 950 μm. When the thickness of the temporary fixing layer is within the above range, the temporary fixing complex of the present invention can exhibit excellent temporary fixing property.

The temporary fixing layer is a foam layer or a rubber layer, and is preferably a foam layer in that the effects of the present invention can be more exhibited.

The foam layer preferably has cells (spherical bubbles). The cell (spherical bubble) does not have to be a strict true spherical bubble, and may be, for example, a substantially spherical bubble having a partial strain or a bubble composed of a space having a large strain.

The foam layer is preferably a foam layer having an open cell structure. Since the foam layer has an open cell structure, the member can be effectively temporarily fixed on the foam layer without biting air bubbles. More specifically, the foam layer has an open cell structure having through holes between adjacent cells. By providing an open cell structure in which the foam layer has through holes between adjacent cells, excellent air bubble removal property can be exhibited in combination with other features of the foam layer, and the member can be placed on the foam layer without biting bubbles. It can be effectively temporarily fixed, and when the temporary fixing is released, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be maintained.

To observe the existence of the open cell structure, use a low vacuum scanning electron microscope (“S-3400N scanning electron microscope”, manufactured by Hitachi High-Tech Fielding Co., Ltd.) to capture an enlarged image of the cross section of the foam layer, and through the hole in the cell wall. It can be done by confirming the presence or absence of.

The foam layer has an open cell ratio of preferably 90% or more, more preferably 90% to 100%, still more preferably 92% to 100%, still more preferably 95% to 100%. It is particularly preferably 99% to 100%, and most preferably substantially 100%. When the open cell ratio of the foam layer is within the above range, it is possible to exhibit better air bubble removal property in combination with other characteristics of the foam layer, and the member can be effectively placed on the foam layer without further biting bubbles. It can be temporarily fixed, and when the temporary fixing is released, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be further maintained.

The open cell ratio can be measured, for example, as follows. That is, by submerging the foam layer in water and leaving it under a reduced pressure of -750 mmHg for 3 minutes, the air in the bubbles is replaced with water, the mass of the absorbed water is measured, and the density of water is 1.0 g / cm. ^{The volume of water absorbed as 3} is calculated and calculated by the following formula.
Continuous bubble ratio (%) = {(volume of absorbed water) / (partial volume of bubbles)} x 100

The bubble partial volume is calculated by, for example, the following formula. Here, the resin density is a value obtained by measuring the density of the resin molded product produced by removing the emulsifier in the resin forming the foam layer.
Cell volume (cm ³ ) = {(mass of foam (foam sheet)) / (apparent density of foam (foam sheet))}-{(mass of foam (foam sheet)) / (resin density)}

The foamed layer has an average cell diameter of preferably 1 μm to 200 μm, more preferably 1.5 μm to 180 μm, still more preferably 2 μm to 170 μm, particularly preferably 2.5 μm to 160 μm, and most preferably. Is 3 μm to 150 μm. If the average cell diameter of the foamed layer is within the above range, it is possible to exhibit better air bubble removal property in combination with other characteristics of the foamed layer, and the member is effectively placed on the foamed layer without further biting bubbles. It can be temporarily fixed to the surface, and when the temporary fixing is released, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be further maintained.

The foam layer preferably has a cell diameter of 90% or more of all cells of 300 μm or less, more preferably 92% or more of all cells having a cell diameter of 300 μm or less, and further preferably 95% of all cells. The above cell diameter is 300 μm or less, particularly preferably 97% or more of all cells have a cell diameter of 300 μm or less, and most preferably substantially 100% of all cells have a cell diameter of 300 μm or less. Further, the foam layer is more preferably 90% or more of all cells having a cell diameter of 250 μm or less, further preferably 90% or more of all cells having a cell diameter of 200 μm or less, and particularly preferably all cells. 90% or more of the cell diameter is 180 μm or less, and most preferably 90% or more of all cells have a cell diameter of 150 μm or less. In the foamed layer, if the ratio of the cell diameter of 300 μm or less and the cell diameter of 90% or more of all the cells are within the above range, more excellent air bubble removal property can be exhibited in combination with other characteristics of the foamed layer, and even more bubbles can be exhibited. The member can be effectively temporarily fixed on the foam layer without biting, and when the temporary fixing is released, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be further maintained.

The maximum cell diameter in all cells of the foamed layer is preferably 300 μm or less, more preferably 250 μm or less, further preferably 200 μm or less, particularly preferably 180 μm or less, and most preferably 150 μm or less. be. In the foam layer, if the maximum cell diameter in all cells is within the above range, it is possible to exhibit better air bubble removal property in combination with other characteristics of the foam layer, and the member can be formed into a foam layer without further biting bubbles. It can be effectively temporarily fixed on the top, and when the temporary fixing is released, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be further maintained.

The minimum cell diameter in all cells of the foam layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 70 μm or less, particularly preferably 60 μm or less, and most preferably 50 μm or less. be. In the foam layer, if the minimum cell diameter in all cells is within the above range, it is possible to exhibit better air bubble removal property in combination with other characteristics of the foam layer, and the member can be formed into a foam layer without further biting bubbles. It can be effectively temporarily fixed on the top, and when the temporary fixing is released, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be further maintained.

As described above, the foamed layer preferably has an open cell structure, and preferably has a fine cell diameter as described above, so that excellent air bubble removal property can be exhibited and bubbles are not bitten. , The member can be effectively temporarily fixed on the foam layer, and when the temporary fixing is released, it can be peeled off without adhesive residue, which is suitable for the temporary fixing composite.

The average cell diameter can be determined, for example, by capturing an enlarged image of the cross section of the foam layer with a low vacuum scanning electron microscope (“S-3400N type scanning electron microscope”, manufactured by Hitachi High-Tech Science Systems Co., Ltd.) and analyzing the image. .. The number of cells to be analyzed is, for example, 20. The minimum cell diameter (μm) and the maximum cell diameter (μm) can be obtained by the same method.

The foam layer preferably has a surface opening. The surface opening referred to here means an opening having an average pore diameter of a certain size existing on the surface of the foamed layer. Since the foamed layer has a surface opening, the adsorption temporary fixing sheet of the present invention can effectively temporarily fix the member on the foamed layer without biting more air bubbles, and when the temporary fixing is released. It can be peeled off more easily without adhesive residue. It is presumed that this is because the surface opening acts as an appropriate suction cup, whereby the temporary fixing complex of the present invention having a foamed layer can more exhibit the excellent temporary fixing property as described above.

The aperture ratio of the surface opening is preferably 1% to 99%, more preferably 2% to 95%, still more preferably 3% to 90%, and particularly preferably 4% to 85%. , Most preferably 5% to 80%. When the opening ratio of the surface opening is within the above range, the temporary fixing composite of the present invention can effectively temporarily fix the member on the foam layer without biting more air bubbles, and the temporary fixing is released. It can be peeled off more easily without adhesive residue.

The average pore size of the surface opening is preferably 150 μm or less, more preferably 0.5 μm to 145 μm, further preferably 1.0 μm to 140 μm, particularly preferably 1.5 μm to 135 μm, and most preferably. Is 2.0 μm to 130 μm. When the average pore diameter of the surface opening is within the above range, the temporary fixing composite of the present invention can effectively temporarily fix the member on the foam layer without biting more air bubbles, and the temporary fixing is released. It can be peeled off more easily without adhesive residue.

The average pore size of the surface opening is determined by, for example, capturing an enlarged image of the surface of the foam layer with a low vacuum scanning electron microscope (“S-3400N type scanning electron microscope”, manufactured by Hitachi High-Tech Fielding Corporation) and analyzing the image. Can be done. The number of holes to be analyzed is, for example, 20.

The apparent density of the expanded layer is preferably ^{0.15g / cm 3 ~0.90g / cm 3} , more preferably from ^{0.20g / cm 3 ~0.85g / cm 3} , more preferably 0.25g / ^cm 3 was ～0.80G / cm ^3, particularly preferably from ^{0.30g / cm 3 ~0.75g / cm 3} . When the apparent density of the foamed layer is within the above range, the member can be effectively temporarily fixed on the foamed layer without biting more air bubbles in combination with other characteristics of the foamed layer, and the temporary fixing is released. In the case, it can be peeled off more easily without adhesive residue. Further, even if the thickness of the foam layer is reduced, the expression of these effects can be maintained.

The surface of the foam layer has an arithmetic mean surface roughness Ra of preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 9 μm, still more preferably 0.3 μm to 8.5 μm, and particularly. It is preferably 0.4 μm to 8 μm. Since the surface of the foam layer has an arithmetic average surface roughness Ra in such a range, the temporary fixing composite of the present invention has more sufficient shear adhesive force in the same direction as the surface, and has a sufficient shear adhesive force with respect to the surface. It can have a weaker adhesive force in the vertical direction.

As described above, a separator may be attached to the surface of the foam layer until it is used. When such a separator does not function as a support, it is preferably peeled off from the surface of the foam layer before the member to be temporarily fixed is placed on the foam composite of the present invention.

The thickness of the separator is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, further preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.

Examples of the separator include paper, a plastic film, a polytetrafluoroethylene (PTFE) film, and a plastic film whose surface is treated with silicone or fluorosilicone.

Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film. Examples thereof include polyurethane films, ethylene-vinyl acetate copolymer films, polyimide films, polyamide (nylon) films, and aromatic polyamide (aramid) films.

In particular, a plastic film that has not been surface-treated, such as silicone treatment or fluorinated silicone treatment, is attached to at least one surface of the foam layer as a separator in that the effects of the present invention can be further exhibited. Is preferable. As such a separator, a polyethylene terephthalate (PET) film which has not been surface-treated such as a silicone treatment or a fluorosilicone treatment is particularly preferable.

As the separator as described above, the arithmetic mean surface roughness Ra of the surface thereof is preferably 0.1 μm to 5 μm, more preferably 0.15 μm to 4.5 μm, and further preferably 0.2 μm to 4 μm. It is particularly preferably 0.22 μm to 3.5 μm. By adopting a separator having a surface with an arithmetic average surface roughness Ra in such a range, such a separator can be attached from the surface of the foam layer before the member to be temporarily fixed is placed on the foam composite of the present invention. By peeling, the temporary fixing composite of the present invention can have a more sufficient shear adhesive force in the same direction as the surface and a weaker adhesive force in the direction perpendicular to the surface.

One embodiment of the foam layer is a silicone-based foam layer. When the foamed layer is a silicone-based foamed layer, the effects of the present invention can be more exhibited.

The silicone-based foam layer is preferably formed by thermosetting the silicone resin composition.

The silicone resin composition preferably satisfies at least one requirement selected from the group consisting of the following (A) to (F).

That is, the silicone resin composition is preferably
(A) Contains an organopolysiloxane having at least two alkenyl groups in one molecule.
(B) For an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, the silicon atom-bonded hydrogen atom in the component (B) is 0 with respect to 1 mol of the alkenyl group in the component (A). Includes in an amount of 4 to 20 mol,
(C) Contains 100 parts by mass to 1000 parts by mass of a mixture composed of water and an inorganic thickener with respect to 100 parts by mass of the component (A).
(D) (D-1) A surfactant consisting of a nonionic surfactant having an HLB value of 3 or more and (D-2) a nonionic surfactant having an HLB value of less than 3 is (D-). 2) The mass ratio of the component (D-1) to the component is 0.1 parts by mass to 100 parts by mass.
(E) Includes a hydrosilylation reaction catalyst,
(F) Contains 0.001 part by mass to 5 parts by mass of the curing retardant with respect to 100 parts by mass of the component (A).
Meet at least one requirement selected from the group consisting of.

The component (A) is an organopolysiloxane having at least two alkenyl groups in one molecule, and is the main agent of the silicone resin composition.

Examples of the alkenyl group in the component (A) include a vinyl group, an allyl group, a hexenyl group and the like, and a vinyl group is preferable. Examples of the silicon atom-bonded organic group other than the alkenyl group in the component (A) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; a phenyl group and a tolyl group. Examples thereof include an aryl group such as a xsilyl group; an aralkyl group such as a benzyl group and a phenethyl group; a halogen-substituted alkyl group such as a 3,3,3-trifluoropropyl group; and a methyl group is preferable.

Specific examples of the component (A) include dimethylvinylsiloxy group-blocking dimethylpolysiloxane, dimethylvinylsiloxy group-blocking dimethylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-blocking methylvinylpolysiloxane, and trimethylsiloxy group. Examples thereof include a closed dimethylsiloxane / methylvinylsiloxane copolymer and a trimethylsiloxy group closed dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, preferably a diorganopolysiloxane having a substantially linear main chain. Is.

The component (B) is an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, and is a cross-linking agent for a silicone resin composition.

As the bond position of the silicon atom-bonded hydrogen atom in the component (B), any appropriate bond position can be adopted as long as the effect of the present invention is not impaired. Examples of such a binding position include a molecular chain terminal and / or a molecular chain side chain. Examples of the silicon atom-bonded organic group other than the hydrogen atom in the component (B) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; a phenyl group, a tolyl group and a xsilyl group. And the like; an aralkyl group such as a benzyl group and a phenethyl group; a halogen-substituted alkyl group such as a 3,3,3-trifluoropropyl group; and the like, preferably a methyl group.

Specific examples of the component (B) include dimethylhydrogensiloxy group-blocking dimethylpolysiloxane, dimethylhydrogensiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, and trimethylsiloxy group-blocking methylhydrogenpolysiloxane. , Trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, (CH ₃ ) ₃ siloxane unit represented by SiO _{1/2 and H (CH 3} ) ₂ siloxane unit represented by SiO _{1/2 and SiO 4 /} like organopolysiloxane composed of siloxane units represented by ₂ and the like, preferably, linear organopolysiloxanes.

The content of the component (B) is preferably in the range of 0.4 mol to 20 mol of the silicon atom-bonded hydrogen atom in the component (B) with respect to 1 mol of the alkenyl group in the component (A). It is an amount, more preferably an amount in the range of 1.5 mol to 20 mol, and further preferably an amount in the range of 1.5 mol to 10 mol. This is because when the number of moles of silicon atom-bonded hydrogen in the component (B) is within the above range, the compression set of the obtained foamed complex is improved.

The component (C) is a mixture of water and an inorganic thickener, and the water in the component (C) is removed from the silicone rubber obtained by cross-linking the silicone resin composition to obtain a silicone rubber sponge. It is a component of. Since the component (C) is stably dispersed in the component (A), the water in the component (C) is preferably ion-exchanged water.

The inorganic thickener in the component (C) is added to increase the viscosity of water, easily disperse the component (C) in the component (A), and stabilize the dispersed state of the component (C). .. The inorganic thickeners may be natural or synthetic, for example natural or synthetic smectite clays such as bentonite, montmorillonite, hectorite, saponite, saponite, biderite and nontronite; magnesium aluminum silicate; with these. A composite product with a water-soluble organic polymer such as a carboxyvinyl polymer; and the like; preferably, a smectite clay such as bentonite and montmorillonite. As such smectite clay, for example, a hydrothermal synthetic product, Sumecton SA (manufactured by Kunimine Kogyo Co., Ltd.), and a natural refined product, Wenger (manufactured by Hojun Co., Ltd.) are available. The pH of these smectite clays is preferably in the range of pH 5.0 to 9.0 from the viewpoint of maintaining the heat resistance of the foamed layer. The content of the inorganic thickener in the component (C) is preferably in the range of 0.1 part by mass to 10 parts by mass, more preferably 0.5 part by mass, with respect to 100 parts by mass of water. It is in the range of parts to 5 parts by mass.

The content of the component (C) is preferably in the range of 100 parts by mass to 1000 parts by mass, and more preferably in the range of 100 parts by mass to 800 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably in the range of 100 parts by mass to 500 parts by mass, particularly preferably in the range of 200 parts by mass to 500 parts by mass, and most preferably in the range of 200 parts by mass to 350 parts by mass. This is because a low-density foam layer can be formed when the content of the component (C) is not less than the lower limit of the above range, while a uniform and fine open cell structure is formed when the content is not more than the upper limit of the above range. This is because a foam layer having the above can be formed.

The surfactant of the component (D) is preferably a nonionic surfactant having a (D-1) HLB value of 3 or more and a nonionic surfactant having a (D-2) HLB value of less than 3. Consists of. Examples of the surfactant of the component (D) include glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene. Examples thereof include sorbitan fatty acid ester, polyoxyethylene / polyoxypropylene block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene fatty acid amide.

The component (D) is preferably composed of the component (D-1) and the component (D-2), and the mass ratio of the component (D-1) to the component (D-2) is preferably 0.1 or more. Yes, more preferably 1 or more, still more preferably 5 or more, still more preferably 8 or more, particularly preferably 10 or more, and most preferably 15 or more. The mass ratio of the component (D-1) to the component (D-2) is preferably 100 or less, more preferably 80 or less, still more preferably 70 or less, and particularly preferably 60 or less. , Most preferably 50 or less. This is because if the mass ratio is larger than the above lower limit, a low-density foam layer having a uniform and fine open cell structure can be formed, while if it is smaller than the above upper limit, (A). This is because the component (C) can be stably dispersed in the component and the component (B), and as a result, a foam layer having a uniform and fine open cell structure can be formed.

The content of the component (D) is preferably in the range of 0.1 parts by mass to 15 parts by mass, and more preferably in the range of 0.2 parts by mass to 3 parts by mass with respect to 100 parts by mass of the component (A). Is inside. This is because if the content of the component (D) is not less than the lower limit of the above range, a foam layer having a uniform and fine open cell structure can be formed, while if it is not more than the upper limit of the above range, heat resistance is reduced. This is because a foam layer having excellent properties can be formed.

The component (E) is a hydrosilylation reaction catalyst for accelerating the hydrosilylation reaction of the silicone resin composition, and examples thereof include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst, and a platinum-based catalyst is preferable. .. Examples of such component (E) include chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compound between chloroplatinic acid and olefins, vinylsiloxane or acetylene compound, platinum olefins, vinylsiloxane or acetylene compound. Coordinating compounds with, tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium and the like can be mentioned.

The content of the component (E) is an amount sufficient for cross-linking the silicone resin composition, and specifically, the content of the component (E) is relative to the total amount of the components (A) and (B). The amount of the catalyst metal is preferably in the range of 0.01 ppm to 500 ppm, more preferably in the range of 0.1 ppm to 100 ppm in terms of mass.

In order to adjust the curing rate and working usable time of the silicone resin composition, (F) a curing retarder may be contained. Examples of such component (F) include 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, 3-phenyl-1-butin-3-ol, and the like. Alkyne alcohols such as 1-ethynyl-1-cyclohexanol can be mentioned. The content of the component (F) is appropriately selected according to the method of use and the molding method of the silicone resin composition, and is generally preferably 0.001 part by mass to 100 parts by mass with respect to 100 parts by mass of the component (A). It is within the range of 5 parts by mass.

The silicone resin composition may further contain (G) reinforcing silica fine powder from the viewpoint of improving the strength of the obtained foamed layer. Such reinforcing silica fine powder, its BET specific surface area, preferably ^{50m 2} / ^g~350m 2 / g, more preferably ^{80m 2} / ^g~250m 2 / g. Examples of such reinforcing silica fine powder include fumed silica and precipitated silica. Further, these reinforcing silica fine powders may be surface-treated with organosilane or the like.

The content of the component (G) is preferably at most 20 parts by mass, more preferably at most 15 parts by mass, and further preferably at most 10 parts by mass with respect to 100 parts by mass of the component (A). be. The content of the component (G) is preferably at least 0.1 parts by mass with respect to 100 parts by mass of the component (A).

The silicone resin composition may contain pigments such as carbon black and red iron oxide as long as the object of the present invention is not impaired.

The silicone resin composition can be easily produced by uniformly mixing each of the above components or a composition containing various additives as necessary by a known kneading means. As the mixer used here, any suitable mixer can be used as long as the components (C) and (D) can be sufficiently dispersed in the component (A) as long as the effects of the present invention are not impaired. Can be adopted. Examples of such a mixer include a homomixer, a paddle mixer, a homodisper, a colloidal mill, a vacuum mixing / stirring mixer, a rotation / revolution mixer, and the like.

The foamed layer can be produced by any suitable method as long as the effects of the present invention are not impaired. As such a production method, for example, a resin composition for forming a foam layer (for example, a silicone resin composition) is coated on the separator A, and the coated resin composition is on the opposite side of the separator A. After placing the separator B on the surface and performing thermosetting, at least one selected from the separator A and the separator B is peeled off.

Examples of the separator A and the separator B include paper, a plastic film, a polytetrafluoroethylene (PTFE) film, and a plastic film whose surface is treated with silicone or fluorinated silicone. Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film. Polyurethane film, ethylene-vinyl acetate copolymer film, polyimide film, polyamide (nylon) film, aromatic polyamide (aramid) film and the like can be mentioned. A plastic film that has not been surface-treated such as a fluorosilicone treatment is preferable. As such a separator, a polyethylene terephthalate (PET) film which has not been surface-treated such as a silicone treatment or a fluorosilicone treatment is particularly preferable.

The thicknesses of the separator A and the separator B are preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm, respectively.

As an example of a method for producing a foamed layer, a case where the foamed layer is a silicone-based foamed layer will be described. When the foamed layer is another foamed layer, the following description of the production method may be read by replacing, for example, the silicone resin composition with a composition as a raw material for the other foamed layer.

In one embodiment of the method for producing a silicone-based foam layer, a silicone resin composition containing at least a thermosetting silicone resin and water is applied onto the separator A (hereinafter, this step is referred to as step (1)). Separator B is placed on the surface of the coated silicone resin composition opposite to the separator A (hereinafter, this step is referred to as step (2)), and the silicone resin composition is thermally cured (hereinafter, referred to as step (2)). , This step is referred to as step (3)), and at least one selected from the separator A and the separator B is peeled off and dried by heating (hereinafter, this step is referred to as step (4)) silicone-based foaming. Form a layer.

In another embodiment of the method for producing a silicone-based foam layer, a silicone resin composition containing at least a thermosetting silicone resin and water is applied onto the separator A (hereinafter, this step is referred to as step (1)). ), The separator B is placed on the surface of the coated silicone resin composition opposite to the separator A (hereinafter, this step is referred to as step (2)), and the silicone resin composition is thermally cured. (Hereinafter, this step is referred to as step (3)), at least one selected from the separator A and the separator B is peeled off and dried by heating (hereinafter, this step is referred to as step (4)) and supported. It is bonded to the body (hereinafter, this step is referred to as step (5)) to form a silicone-based foam layer.

When the separator A or separator B is used as it is as a support, an undercoating agent such as a silane coupling agent is applied to the surface of the support separator A or separator B in order to improve the anchoring property with the foam layer. Alternatively, surface treatment such as corona treatment or plasma treatment may be performed.

If there is a separator that is not removed during heating and drying in step (4), the release liner that can be used as the separator is preferably a base material (liner base material) of a polytetrafluoroethylene (PTFE) film, paper or plastic film. ) Is a release liner whose surface is treated with fluorosilicone. When there is a separator that is not removed during heating and drying in step (4), the surface of the base material (liner base material) of the polytetrafluoroethylene (PTFE) film, paper or plastic film is treated with fluorinated silicone. By using the peeling liner, peeling after heating and drying can be easily performed. Further, the separator A and the separator B may be provided with an adhesive layer.

The separator A used in the step (1) and the separator B used in the step (2) may be the same or different types. Further, the separator A used in the step (1) and the separator B used in the step (2) may have only one layer or two or more layers, respectively.

The silicone resin composition in contact with the surface of the separator A used in the step (1) and the separator B used in the step (2) depends on the degree of hydrophilicity / hydrophobicity of the surface of the separator B in contact with the silicone resin composition. The surface shape changes. For example, when a highly hydrophilic separator such as a polyethylene terephthalate (PET) film is used as the separator A or the separator B, many surface openings having a fine diameter should be present on the surface of the silicone resin composition in contact with the separator. Can be done. Further, when a highly hydrophobic separator such as a polyethylene terephthalate (PET) release liner treated with fluorinated silicone is used as the separator A or the separator B, the surface of the silicone resin composition in contact with the separator is fine. A small number of surface openings of diameter can be present. Therefore, when it is desired to develop high air permeability and high adsorptivity for the silicone-based foam layer, it is preferable to use a highly hydrophilic separator, which provides high water-stopping property and high dust resistance for the silicone-based foam layer. When it is desired to express it, it is preferable to use a highly hydrophobic separator. Further, when removability between the silicone-based foam layer and the separator is required, it is preferable to use a separator having high hydrophobicity. The degree of hydrophilicity / hydrophobicity can be defined by, for example, the contact angle with water. For example, a case where the contact angle with water is less than 90 degrees can be defined as hydrophilic, and a case where the contact angle with water is 90 degrees or more can be defined as hydrophobic.

In the step (3), the silicone resin composition is thermoset. The temperature of this thermosetting is preferably 50 ° C. or higher and lower than 100 ° C. in that the silicone resin composition can be heat-cured efficiently. If the thermosetting temperature is less than 50 ° C., the thermosetting may take too long. When the thermosetting temperature is 100 ° C. or higher, the moisture in the silicone resin composition that is sandwiched between the separator A and the separator B and is in a substantially sealed state volatilizes, resulting in coarsening and high density of the cells to be formed. There is a risk. What is formed from the silicone resin composition by the step (3) is referred to as a silicone-based foam layer precursor.

A state in which the water content in the silicone resin composition is not removed by performing a special thermosetting method in which the silicone resin composition is thermally cured in a substantially sealed state sandwiched between the separator A and the separator B as in the step (3). In cooperation with the subsequent step (4), it is possible to effectively obtain a silicone-based foam layer having an open cell structure and a fine cell diameter.

In the step (4), at least one selected from the separator A and the separator B is peeled off and dried by heating. By peeling off at least one selected from the separator A and the separator B, the substantially sealed state in the step (3) is released, and by heating and drying in this released state, the silicone system formed in the step (3) is released. Moisture is efficiently volatilized and removed from the foam layer precursor to obtain a silicone-based foam layer. The heating and drying temperature in the step (4) is preferably 120 ° C. to 250 ° C. from the viewpoint that the silicone-based foam layer can be effectively formed. If the heating and drying temperature in the step (4) is less than 120 ° C., drying and curing may take too long, and a silicone-based foam layer having an open cell structure and a fine cell diameter may not be obtained. .. If the heating and drying temperature in the step (4) exceeds 250 ° C., layer formation may become difficult due to shrinkage and expansion of the base material.

In the step (5), after the step (4), the silicone-based foam layer is formed by bonding with the support.

When the temporary fixing layer is a rubber layer, any suitable rubber layer can be adopted as long as the effect of the present invention is not impaired. The rubber layer is preferably a silicone-based rubber layer. If a silicone-based rubber layer is used as the rubber layer, the effects of the present invention can be further exhibited.

≪Base material layer≫
The temporary fixation complex of the present invention has any suitable base material layer as long as the effects of the present invention are not impaired.

As the thickness of the base material layer, any appropriate thickness can be adopted as long as the effects of the present invention are not impaired. The thickness of such a base material layer is preferably 2 μm to 500 μm, more preferably 5 μm to 450 μm, further preferably 10 μm to 400 μm, and particularly preferably 20 μm to 350 μm.

Examples of the base material layer include plastic film, paper, non-woven fabric, metal foil, metal mesh, glass, glass cloth and the like. The base material layer may be one layer or two or more layers. Further, in order to improve the anchoring property of the base material layer and the layer adjacent thereto, an undercoating agent such as a silane coupling agent is applied to the surface of the base material layer, or surface treatment such as corona treatment or plasma treatment is performed. You may.

Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film. Examples thereof include polyurethane films, ethylene-vinyl acetate copolymer films, polyimide films, polyamide (nylon) films, and aromatic polyamide (aramid) films. Among these plastic films, a polyimide film is preferable because the effects of the present invention can be more exhibited.

≪Undercoat layer≫
The thickness of the undercoat layer is not particularly limited, but is preferably 0.01 μm to 5 μm, and more preferably 0.1 μm to 3 μm.

The composition of the undercoat agent constituting the undercoat layer is not particularly limited, and known ones can be appropriately selected. In particular, a silicone-based undercoating agent is preferable because it can exhibit anchoring properties.

As the silicone-based undercoating agent, any suitable silicone-based undercoating agent can be adopted as long as the effects of the present invention are not impaired. As such a silicone-based undercoating agent, for example, a peroxide cross-linked silicone-based pressure-sensitive adhesive (peroxide-curable silicone-based), which is widely used in general, is used in that the effects of the present invention can be more exhibited. By forming the pressure-sensitive adhesive) or the addition-reaction type silicone-based pressure-sensitive adhesive with a thin thickness, it can be suitably used as a silicone-based undercoating agent.

When a peroxide-crosslinked silicone-based pressure-sensitive adhesive is used, the adhesion between the base material and the primer is excellent due to the generation of radicals due to heating.

When an addition reaction type silicone adhesive is used, it can be applied at a low temperature, expansion and contraction due to heating of the base material can be suppressed, and the appearance is excellent.

Commercially available products can be used as the peroxide-crosslinked silicone-based pressure-sensitive adhesive and the addition-reaction-type silicone-based pressure-sensitive adhesive. Specific examples of the peroxide-crosslinked silicone-based pressure-sensitive adhesive include KR manufactured by Shin-Etsu Chemical Co., Ltd. -3006A / BT, SH4280PSA manufactured by Dow Toray Co., Ltd. and the like can be mentioned. Specific examples of the addition reaction type silicone adhesive include X-40-3501 manufactured by Shin-Etsu Chemical Co., Ltd., BY24-712 manufactured by Dow Toray Co., Ltd., and TSE32X manufactured by GE Toshiba Silicone Co., Ltd.

≪Silicone adhesive layer≫
As the thickness of the silicone-based pressure-sensitive adhesive layer, any appropriate thickness can be adopted as long as the effects of the present invention are not impaired. The thickness of such a silicone-based pressure-sensitive adhesive layer is preferably 1 μm to 100 μm, more preferably 5 μm to 90 μm, still more preferably 8 μm to 80 μm, and particularly preferably 10 μm to 70 μm. When the thickness of the silicone-based pressure-sensitive adhesive layer is within the above range, the temporary fixing complex of the present invention can exhibit excellent temporary fixing property.

As the silicone-based pressure-sensitive adhesive forming the silicone-based pressure-sensitive adhesive layer, any suitable silicone-based pressure-sensitive adhesive may be adopted as long as the effects of the present invention are not impaired. Here, the "silicone-based pressure-sensitive adhesive forming the silicone-based pressure-sensitive adhesive layer" means a silicone-based pressure-sensitive adhesive used for forming the silicone-based pressure-sensitive adhesive layer. Generally, the pressure-sensitive adhesive layer is formed by a curing reaction or the like of a material composition that finally becomes the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer itself cannot be specified as a composition as a product. In this document, the silicone-based pressure-sensitive adhesive layer is defined by the expression "silicone-based pressure-sensitive adhesive layer formed from the silicone-based pressure-sensitive adhesive".

Typical examples of the silicone-based pressure-sensitive adhesive include a peroxide-curable silicone-based pressure-sensitive adhesive (sometimes referred to as a peroxide-crosslinked silicone-based pressure-sensitive adhesive) and an addition-reaction type silicone-based pressure-sensitive adhesive. Be done. The silicone-based pressure-sensitive adhesive may be only one type or two or more types.

<Peroxide curable silicone adhesive>
The peroxide-curable silicone-based pressure-sensitive adhesive typically includes silicone rubber, which is a long-chain polymer of polydimethylsiloxane, and a silicone resin having a three-dimensional structure. The peroxide-curable silicone-based pressure-sensitive adhesive may contain an organic peroxide such as benzoyl peroxide as a cross-linking agent because it is cured by cross-linking. The cross-linking agent may be only one kind or two or more kinds. In this case, in the peroxide-curable silicone-based pressure-sensitive adhesive, typically, radicals generated from the organic peroxide _{abstract hydrogen of three} Si-CH groups of the silicone rubber, and the generated SiC ₂ radicals are generated. It binds and the cross-linking reaction proceeds.

Examples of organic peroxides include benzoyl peroxides (t-butyl benzoate peroxide, 2,5-dimethyl-2,5-dibenzoyl peroxide hexane, dibenzoyl peroxide, 4,4'-dimethyldibenzoyl peroxide). , 3, 3'-dimethyldibenzoyl peroxide, 2, 2'-dimethyldibenzoyl peroxide, 2, 2', 4'-tetrachlorodibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide), Kumil peroxide, t-butyl cumyl peroxide, t-butyl peroxide, t-butylisobutyrate peroxide, t-butyl-2-ethylhexanoate peroxide, 2,2-bis t-butyloctane peroxide, Examples thereof include 1,1-bis peroxide t-butylcyclohexane. Among these, benzoyl peroxides are preferable from the viewpoint that the adhesive properties can be easily adjusted by changing the addition amount.

As the content of the organic peroxide in the peroxide-curable silicone-based pressure-sensitive adhesive, any appropriate blending amount can be adopted as long as the effect of the present invention is not impaired. Typically, the blending amount of the organic peroxide is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the solid content of the peroxide-curable silicone-based pressure-sensitive adhesive, and more preferably. It is 0.1 parts by mass to 5 parts by mass.

The peroxide-curable silicone-based adhesive may be applied to another layer (base material layer, etc.) via a primer layer containing an ultraviolet absorber, a light stabilizer, or the like, or may be applied to another layer (base layer, etc.). When the material layer or the like contains an ultraviolet absorber or the like, curing inhibition is less likely to occur, so that the curing ability can be further exhibited. Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a characteristic group of these compounds in the side chain (meth). Examples thereof include a polymer-type ultraviolet absorber obtained by polymerizing an acrylate. Examples of the light stabilizer include a hindered amine-based light stabilizer (HALS, etc.) and a hindered phenol-based light stabilizer. The ultraviolet absorber and the light stabilizer may be of only one type or two or more types, respectively.

The peroxide-curable silicone-based pressure-sensitive adhesive is, for example, a 30% by mass to 70% by mass organic solvent solution (a solution of a paraffin-based organic solvent such as hexane or a solution of an aromatic organic solvent such as toluene or xylene). Prepared or marketed as. That is, the peroxide-curable silicone-based pressure-sensitive adhesive is preferably a solution containing 30% by mass to 70% by mass of an organic solvent (typically, a coating liquid).

The silicone-based pressure-sensitive adhesive layer formed from the peroxide-curable silicone-based pressure-sensitive adhesive is obtained by applying a coating solution of the peroxide-curable silicone-based pressure-sensitive adhesive to an arbitrary suitable base material (base material layer, etc.). After the solvent is evaporated, it is heat-cured to form a silicone-based pressure-sensitive adhesive layer.

The temperature of heat curing when forming the silicone-based pressure-sensitive adhesive layer from the peroxide-curable silicone-based pressure-sensitive adhesive is preferably 130 ° C. to 200 ° C., more preferably 140 ° C. to 180 ° C. The time for heat curing when forming the silicone-based pressure-sensitive adhesive layer from the peroxide-curable silicone-based pressure-sensitive adhesive is preferably 1 minute to 15 minutes, and more preferably 3 minutes to 7 minutes.

Commercially available products of peroxide-curable silicone-based adhesives include, for example, YR3340, YR3286, PSA610-SM, XR37-B6722 manufactured by Momentive Performance Materials, SE4200, SH4280, and Shin-Etsu Chemical Co., Ltd. Examples thereof include KR-100, KR-101-10 (toluene solvent type), KR-120, KR-130, and X-40-3287 (isoparaffin solvent type) manufactured by the same company.

The peroxide-curable silicone-based pressure-sensitive adhesive may contain any suitable other components as long as the effects of the present invention are not impaired. Other components include, for example, organic solvents, flame retardants, tackifiers, UV absorbers, light stabilizers, antioxidants, antistatic agents, preservatives, fungicides, plasticizers, defoamers, colorants. , Fillers, wettability modifiers and the like.

<Addition reaction type silicone adhesive>
The addition-reactive silicone-based pressure-sensitive adhesive preferably contains a main agent, a cross-linking agent, and, if necessary, a curing catalyst. The addition reaction type silicone adhesive has an advantage that it can be used only by the primary curing at a low temperature and does not require the secondary curing at a high temperature. Therefore, when the addition reaction type silicone-based pressure-sensitive adhesive is adopted, the silicone-based pressure-sensitive adhesive layer can be manufactured at a relatively low temperature, which is excellent in energy economy.

The addition reaction type silicone-based pressure-sensitive adhesive usually contains a main agent consisting of a mixture of a silicone-based resin component and a silicone-based rubber component, a cross-linking agent containing a hydrosilyl group (SiH group), and a curing catalyst if necessary.

The silicone-based resin component is typically an organopolysiloxane having a network structure obtained by hydrolyzing organochlorosilane or organoalkoxysilane and then performing a dehydration condensation reaction. The silicone-based resin component may be only one kind or two or more kinds.

The silicone-based rubber component is typically a diorganopolysiloxane having a linear structure. The silicone-based rubber component may be only one type or two or more types.

In both the silicone-based resin component and the silicone-based rubber component, examples of the organogroup include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. Organo groups are partly like vinyl group, hexenyl group, allyl group, butenyl group, pentenyl group, octenyl group, (meth) acryloyl group, (meth) acryloylmethyl group, (meth) acryloylpropyl group, cyclohexenyl group. It may be substituted with an unsaturated group.

In the addition reaction type silicone-based pressure-sensitive adhesive, cross-linking proceeds by the addition reaction of an unsaturated group and a hydrosilyl group to form a network structure, and the tackiness is developed. The number of unsaturated groups such as vinyl groups is preferably 0.05 to 3.0, more preferably 0.1 to 2.5, relative to 100 organogroups. By setting the number of unsaturated groups to 100 organogroups to 0.05 or more, it is possible to prevent the reactivity with the hydrosilyl group from being lowered and becoming difficult to cure, and to impart an appropriate adhesive force. .. By setting the number of unsaturated groups to 3.0 or less with respect to 100 organogroups, it is possible to prevent the crosslink density of the adhesive from increasing and the adhesive force and cohesive force from increasing, which adversely affect the adherend surface. ..

Examples of the organopolysiloxane include KS-3703 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (the number of vinyl groups is 0.6 for every 100 methyl groups) and BY23-753 manufactured by Dow Toray Co., Ltd. (vinyl). The number of groups is 0.1 for 100 methyl groups), BY24-162 (the number of vinyl groups is 1.4 for 100 methyl groups), SD4560PSA, SD4570PSA, SD4580PSA. , SD4584PSA, SD4585PSA, SD4587L, SD4592PSA and the like.

Examples of the silicone-based rubber component include KS-3800 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (the number of vinyl groups is 7.6 for 100 methyl groups) and BY24-162 manufactured by Dow Toray Co., Ltd. The number of vinyl groups is 1.4 for 100 methyl groups), BY24-843 (has no unsaturated group), SD-7292 (the number of vinyl groups is 1.4 for 100 methyl groups). The number is 5.0).

The cross-linking agent may be only one kind or two or more kinds. Examples of the cross-linking agent include a siloxane-based cross-linking agent (silicone-based cross-linking agent). Examples of the siloxane-based cross-linking agent include polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule. In such a polyorganohydrogensiloxane, various organic groups may be bonded to the silicon atom to which the hydrogen atom is bonded in addition to the hydrogen atom. Examples of such an organic group include an alkyl group such as a methyl group and an ethyl group; an aryl group such as a phenyl group; an alkyl halide group; and the like. As such an organic group, a methyl group is preferable from the viewpoint of synthesis and handling. The skeleton structure of the polyorganohydrogensiloxane may have any of linear, branched, and cyclic skeleton structures, and is preferably linear.

The cross-linking agent has preferably 0.5 or more and 10 or less hydrogen atoms bonded to silicon atoms with respect to one unsaturated group such as a vinyl group of a silicone-based resin component and a silicone-based rubber component. More preferably, the number is 1 or more and 2.5 or less.

The curing catalyst is typically used to promote the hydrosilylation reaction between the unsaturated group in the silicone-based resin component and the silicone-based rubber component and the Si—H group in the cross-linking agent. The curing catalyst may be only one type or two or more types.

Examples of the curing catalyst include platinum-based catalysts, that is, platinum chloride acid, an alcohol solution of platinum chloride acid, a reaction product of platinum chloride acid and an alcohol solution, a reaction product of platinum chloride acid and an olefin compound, and platinum chloride acid. Examples thereof include a reaction product of and a vinyl group-containing siloxane compound, a platinum-olefin complex, a platinum-vinyl group-containing siloxane complex, and a platinum-phosphorus complex. Specific examples of such a curing catalyst are described in, for example, JP-A-2006-28311 and JP-A-10-147758. Specific examples of commercially available products include SRX-212 manufactured by Dow Toray Co., Ltd. and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.

The content ratio of the curing catalyst is preferably 5 mass ppm to 2000 mass ppm, more preferably 10 mass ppm to 500 mass ppm, based on the total amount of the silicone-based resin component and the silicone-based rubber component as the platinum content. be.

In the addition reaction type silicone-based pressure-sensitive adhesive, the adhesive strength is exhibited even at room temperature, but the cross-linking reaction between the silicone-based resin component and the silicone-based rubber component by the cross-linking agent is promoted by heating or irradiating with active energy rays. However, it is preferable from the viewpoint of stability of adhesive strength.

When the cross-linking reaction is promoted by heating, the heating temperature is preferably 60 ° C. to 140 ° C., more preferably 80 ° C. to 130 ° C.

When irradiating an active energy ray to promote a cross-linking reaction, an active energy ray having an energy quantum in an electromagnetic wave or a charged particle beam, that is, an active light such as an ultraviolet ray or an electron beam can be used. When cross-linking by irradiating with an electron beam, a photopolymerization initiator is not required, but when cross-linking by irradiating with active light such as ultraviolet rays, it is preferable to have a photopolymerization initiator present. As the photopolymerization initiator when irradiated with ultraviolet rays, any suitable photopolymerization initiator can be adopted as long as the effects of the present invention are not impaired. Examples of such photopolymerization initiators include benzoins, benzophenones, acetophenones, α-hydroxyketones, α-aminoketones, α-diketones, α-diketone dialkyl acetals, anthraquinones, thioxanthones and the like. Can be mentioned. The photopolymerization initiator may be only one kind or two or more kinds. The amount of the photopolymerization initiator used is preferably 0.01 parts by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the main agent and the cross-linking agent composed of a mixture of the silicone-based resin component and the silicone-based rubber component. , More preferably 0.05 parts by mass to 20 parts by mass.

When irradiating with active energy rays to promote the cross-linking reaction, any appropriate irradiation conditions can be adopted as the irradiation conditions as long as the effects of the present invention are not impaired.

The addition reaction type silicone-based pressure-sensitive adhesive may contain any suitable other components as long as the effects of the present invention are not impaired. Other components include, for example, organic solvents, flame retardants, tackifiers, UV absorbers, light stabilizers, antioxidants, antistatic agents, preservatives, fungicides, plasticizers, defoamers, colorants. , Fillers, wettability modifiers and the like.

≪≪Manufacturing method of foam complex≫≫
The foamed complex of the present invention can be produced by any suitable method.

When the foamed composite of the present invention is formed by directly laminating the temporary fixing layer, the undercoat layer, the base material layer, and the silicone-based pressure-sensitive adhesive layer as shown in FIG. 1, the manufacturing method thereof is, for example, a base material. An undercoat layer is formed on one side of the layer, an adhesive layer is formed on the other side, a separator is attached to the adhesive side, and then a silicone resin composition containing a thermosetting silicone resin and water is applied to the undercoat surface. A separator is placed on the surface opposite to the coated silicone resin composition, the silicone resin composition is thermoset, and the peeled separator is heat-dried to form a silicone-based foam. Examples include a method of forming a layer.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods in the examples and the like are as follows. In addition, when it is described as "part", it means "mass part" unless there is a special note, and when it is described as "%", it means "mass%" unless there is a special note.

<Measurement of thickness>
3D measurement With a laser microscope (LEXT OLS4000, manufactured by Olympus Co., Ltd.), a glass plate (micro slide glass S, manufactured by Matsunami Glass Ind. Co., Ltd.) with high precision and a setting of 10 times the objective lens is used for measurement (for example, A suction temporary fixing sheet) was placed, and a 3D image from the surface of the glass plate to the top of the object to be measured was measured, and the height was taken as the thickness.

<Measurement of apparent density>
The object to be measured was punched with a punching blade type of 50 mm × 50 mm, and the volume of the object to be measured was calculated from these values using the above-mentioned values of <measurement of thickness>.
Next, the mass of the object to be measured was measured with a precision balance having a minimum scale of 0.01 g or more. From these values, the apparent density (g / cm ³ ) of the object to be measured was calculated.

<Measurement of Arithmetic Mean Surface Roughness Ra>
3D measurement 3D image is measured with a laser microscope (LEXT OLS4000, manufactured by Olympus Corporation) with high accuracy and 10x objective lens setting, and the arithmetic mean roughness Ra is calculated according to JIS B0601 (1994). rice field.

<Measurement of dimensional change rate>
(Dimensional change rate in MD direction)
The temporary fixing complex was cut out to a size of 100 mm × 100 mm, and the adhesive layer located on the outermost layer (the separator was peeled off if it was attached) was attached to a SUS403BA plate to prepare a measurement sample. Then, using a caliper, three points in the length direction (width and length of the positions of both ends and the center) were measured to the second decimal place, and the average value was calculated.
Subsequently, the measurement sample was passed through a solder reflow process with a thermal history as shown in FIG. 2, allowed to stand at 23 ° C. × 50% RH for 1 hour, and then calipers were placed at the same position measured before the reflow. It was used to measure up to the second decimal place, and the average value was calculated.
The dimensional change rate in the MD direction was calculated by the following formula.
Dimensional change rate in MD direction (%) = [(Length in MD direction before passing through solder reflow process (mm) -After passing through solder reflow process, after standing at temperature 23 ° C. x humidity 50% RH for 1 hour MD direction length (mm)) / MD direction length before passing through the solder reflow process (mm)] x 100 (%)
The case where the dimensional change rate in the MD direction was 0.3% or less was evaluated as ◯, and the case where the dimensional change rate in the MD direction was 0.3% or more was evaluated as x.
(Dimensional change rate in the TD direction)
The temporary fixing complex was cut out to a size of 100 mm × 100 mm, and the adhesive layer located on the outermost layer was attached to a SUS403BA plate to prepare a measurement sample. Then, using a caliper, three points in the horizontal direction (width and length of the positions of both ends and the center) were measured to the second decimal place, and the average value was calculated.
Subsequently, the measurement sample was passed through a solder reflow process having a thermal history as shown in FIG. 4, and then allowed to stand at 23 ° C. × 50% RH for 1 hour. It was used to measure up to the second decimal place, and the average value was calculated.
The dimensional change rate in the TD direction was calculated by the following formula.
Dimensional change rate in the TD direction (%) = [(Length in the TD direction before passing through the solder reflow process (mm) -After passing through the solder reflow process, after standing at a temperature of 23 ° C. x humidity of 50% RH for 1 hour TD direction length (mm)) / TD direction length before passing through the solder reflow process (mm)] x 100 (%)
The case where the dimensional change rate in the TD direction was 0.3% or less was evaluated as ◯, and the case where the dimensional change rate in the TD direction was 0.3% or more was evaluated as x.

<Measurement of anchoring force>
Silicone adhesive (SH4280, manufactured by Dow Toray Co., Ltd., peroxide cross-linking) is applied to the surface of the temporary fixing layer (which is peeled off if a separator is attached) located at the outermost layer of the temporary fixing composite. ) / PET base material (25 μm), the silicone-based adhesive side of the laminate was pressure-bonded once with a 2 kg roller, and then cut to a width of 20 mm. After curing for 30 minutes, the fracture morphology when peeled at a tension angle of 90 degrees and a peeling speed of 150 mm / min was evaluated.
Fracture form in which the temporary fixing layer is coagulated and broken, and the load when the temporary fixing layer is interfacially broken between the temporary fixing layer and the silicone-based adhesive of the laminated body without cohesive failure is 2N / 20 mm or more. The case of the form was marked with ◯. The case where the load was less than 2N / 20 mm when the temporary fixing layer was interfacially broken between the temporary fixing layer and the silicone-based pressure-sensitive adhesive layer of the laminated body without cohesive failure was evaluated as x.

[Production Example 1]: Production of Silicone Rubber Layer (1) Addition reaction type silicone adhesive (SD4592, SRX-212 manufactured by Dow Toray Co., Ltd.) is diluted with n-heptane to a solid content concentration of 0.3%. Then, it was formed on one side of the glass epoxy base material so as to have a dry thickness of 1 μm. On the opposite side, a silicone-based pressure-sensitive adhesive layer formed from a peroxide-curable silicone-based pressure-sensitive adhesive (SH4280 manufactured by Dow Toray Co., Ltd.) is formed, and a PET separator treated with fluorinated silicone is applied to the pressure-sensitive adhesive layer. It was pasted on. Next, a thermosetting silicone resin (Dow Toray Co., Ltd., RBL-9200) was applied to the surface of the primer, and a PET film (Toray Co., Ltd., Lumirror, thickness 38 μm) was applied on the surface of the coated silicone resin composition. ) Was affixed to the silicone resin composition, and the PET film was peeled off and dried by heating to produce a silicone rubber layer (1).

[Production Example 2]: Production of Silicone Foam Layer (1) Dimethylpolysiloxane with vinyl group content of 0.28% by mass: Methylhydro with 83.45 parts by mass and silicon atom-bonded hydrogen atom content of 0.7% by mass Genpolysiloxane: 6.40 parts by mass (amount of silicon atom-bonded hydrogen atom in this methylhydrogenpolysiloxane is 5 mol with respect to 1 mol of vinyl group in the above dimethylpolysiloxane), smectite clay (water-based addition) Agent, Organic Polymer Composite Purified Bentnite, manufactured by Hojun Co., Ltd.): 0.85 parts by mass, ion-exchanged water: 99.16 parts by mass, fumed silica with BET specific surface area of 225 m2 / g surface-treated with hexamethyldisilazane: 6.50 parts by mass, Bengala (trade name: Biferrox, manufactured by Bayer): 2.40 parts by mass, nonionic surfactant (sorbitan fatty acid ester, trade name: Leodor SP-O10V, HLB 4.3 manufactured by Kao): 0.98 parts by mass, nonionic surfactant (sorbitan fatty acid ester, trade name: Leodor SP-O30V, HLB 1.8 manufactured by Kao Co., Ltd.): 0.045 parts by mass, 1-ethynyl-1-cyclohexanol: 0.02 1,3-Divinyltetramethyldisiloxane solution of 1,3-divinyltetramethyldisiloxane complex of platinum (platinum metal content: about 4000 ppm): 0.22 parts by mass, Rentaro Awatori (manufactured by Shinky) ) For 15 minutes, then the emulsion was dried under reduced pressure at room temperature for 5 minutes to defoam, and a resin composition was obtained.
The obtained resin composition is applied onto a fluorosilicone-treated PET film (Nipper sheet PET38x1-SS4A, manufactured by Nipper) using an applicator, and then covered with a PET film (Lumirer S10, manufactured by Toray Industries, Inc.). The resin composition was cured by heating in a hot air oven at 85 ° C. for 6 minutes. After curing, the PET film was peeled off and further heat-dried at 200 ° C. for 3 minutes to produce a silicone-based foam layer (1) having ^{an apparent density of 0.5 g / cm 3 and a thickness of 0.2 mm.}

[Example 1]: Temporary fixed complex (1)
Silicone rubber layer (1) (thickness = 0.2 μm) / silicone undercoat layer (1) (thickness = 1 μm) / glass epoxy base material layer (manufactured by Risho Kogyo, BG3520, thickness = 100 μm) / peroxide curable silicone A temporary fixing composite (1), which is a laminate of a silicone-based pressure-sensitive adhesive layer (thickness = 50 μm) formed from a based pressure-sensitive adhesive (SH4280, manufactured by Dow Toray Co., Ltd.), was obtained.
The results are shown in Table 1.

[Example 2]: Temporary fixed complex (2)
Except that the outermost silicone-based pressure-sensitive adhesive layer was replaced with a silicone-based pressure-sensitive adhesive layer (thickness = 75 μm) formed from an addition-reaction type silicone-based pressure-sensitive adhesive (SD4592, manufactured by Dow Toray Co., Ltd.), the same as in Example 1. Perform in the same manner, silicone rubber layer (1) (thickness = 0.2 μm) / silicone undercoat layer (1) (thickness = 1 μm) / glass epoxy base material layer (manufactured by Risho Kogyo, BG3520, thickness = 100 μm) / addition A temporary fixing composite (2), which is a laminate of a silicone-based pressure-sensitive adhesive layer (thickness = 50 μm) formed from a reactive silicone-based pressure-sensitive adhesive (SD4592, manufactured by Dow Toray Co., Ltd.), was obtained.
The results are shown in Table 1.

[Example 3]: Temporary fixed complex (3)
Examples except that the silicone-based rubber layer (1) was replaced with the silicone-based foam layer (1) and the glass epoxy base material layer was replaced with the polyimide base material layer (manufactured by Toray DuPont, Capton 300H, thickness = 75 μm). Perform in the same manner as in 1, Silicone foam layer (1) (thickness = 0.2 μm) / silicone undercoat layer (1) (thickness = 1 μm) / polyimide base material layer (manufactured by Toray DuPont, Capton 300H, thickness = 75 μm) ) / Temporary fixed composite (3), which is a laminate of silicone-based pressure-sensitive adhesive layers (thickness = 50 μm) formed from a polyimide-curable silicone-based pressure-sensitive adhesive (SH4280, manufactured by Dow Toray Co., Ltd.) was obtained.
The results are shown in Table 1.

[Example 4]: Temporary fixed complex (4)
Example 3 and Example 3 except that the outermost silicone-based pressure-sensitive adhesive layer was replaced with a silicone-based pressure-sensitive adhesive layer (thickness = 50 μm) formed from an addition-reaction type silicone-based pressure-sensitive adhesive (SD4592, manufactured by Dow Toray Industries, Inc.). Do the same, silicone-based foam layer (1) (thickness = 0.2 μm) / silicone undercoat layer (1) (thickness = 1 μm) / polyimide base material layer (manufactured by Toray DuPont, Capton 300H, thickness = 75 μm) / A temporary fixing composite (4), which is a laminate of a silicone-based pressure-sensitive adhesive layer (thickness = 50 μm) formed from an addition-reaction type silicone-based pressure-sensitive adhesive (SD4592, manufactured by Dow Toray Industries, Inc.), was obtained.
The results are shown in Table 1.

[Comparative Example 1]: Temporary fixed complex (C1)
The same procedure as in Example 1 was performed except that the silicone undercoat layer (1) was not provided, and the silicone rubber layer (1) (thickness = 0.2 μm) / glass epoxy base material layer (manufactured by Risho Kogyo, BG3520, thickness). = 100 μm) / Temporary fixed composite (C1), which is a laminate of silicone-based pressure-sensitive adhesive layers (thickness = 50 μm) formed from peroxide-curable silicone-based pressure-sensitive adhesive (SH4280, manufactured by Dow Toray Co., Ltd.), is obtained. rice field.
The results are shown in Table 1.

[Comparative Example 2]: Temporary fixed complex (C2)
The same procedure as in Example 2 was performed except that the silicone undercoat layer (1) was not provided, and the silicone rubber layer (1) (thickness = 0.2 μm) / glass epoxy base material layer (manufactured by Risho Kogyo, BG3520, thickness). = 100 μm) / A temporary fixing composite (C2), which is a laminate of a silicone-based pressure-sensitive adhesive layer (thickness = 50 μm) formed from an addition-reaction type silicone-based pressure-sensitive adhesive (SD4592, manufactured by Dow Toray Co., Ltd.), was obtained.
The results are shown in Table 1.

[Comparative Example 3]: Temporary fixed complex (C3)
The same procedure as in Example 3 was carried out except that the silicone undercoat layer (1) was not provided, and the silicone-based foam layer (1) (thickness = 0.2 μm) / polyimide base material layer (manufactured by Toray DuPont, Capton 300H, Temporary fixing composite (C3), which is a laminate of silicone-based pressure-sensitive adhesive layers (thickness = 50 μm) formed from a peroxide-curable silicone-based pressure-sensitive adhesive (SH4280, manufactured by Dow Toray Industries, Inc.). Obtained.
The results are shown in Table 1.

[Comparative Example 4]: Temporary fixed complex (C4)
The same procedure as in Example 4 was carried out except that the silicone undercoat layer (1) was not provided, and the silicone-based foam layer (1) (thickness = 0.2 μm) / polyimide base material layer (manufactured by Toray DuPont, Kapton 300H, A temporary fixing composite (C4), which is a laminate of a silicone-based pressure-sensitive adhesive layer (thickness = 50 μm) formed from an addition-reaction type silicone-based pressure-sensitive adhesive (SD4592, manufactured by Dow Toray Industries, Inc.), was obtained. ..
The results are shown in Table 1.

The temporary fixing complex of the present invention can be suitably used, for example, for temporary fixing of parts in a manufacturing process of an electronic circuit board or the like.

10 Temporary fixing layer 20 Undercoat layer 30 Base material layer 40 Silicone adhesive layer 100 Temporary fixing composite

Claims (10)

A temporary fixing composite containing a temporary fixing layer, a base material layer, and a silicone-based pressure-sensitive adhesive layer formed of a silicone-based pressure-sensitive adhesive.
The temporary fixing layer is a foam layer or a rubber layer, and the temporary fixing layer is a foam layer or a rubber layer.
The temporary fixing layer and the base material layer are laminated via an undercoat layer.
Temporary fixed complex. The temporary fixed complex according to claim 1, wherein the undercoat layer has a thickness of 0.01 μm to 5 μm. The temporary fixing complex according to claim 2, wherein the undercoat layer has a thickness of 0.1 μm to 3 μm. The temporary fixing complex according to any one of claims 1 to 3, wherein the undercoating agent constituting the undercoating layer is a silicone-based undercoating agent. The temporary fixing composite according to claim 4, wherein the silicone-based undercoating agent is a peroxide-crosslinked silicone-based pressure-sensitive adhesive. The temporary fixing composite according to claim 4, wherein the silicone-based undercoating agent is an addition-reaction type silicone-based pressure-sensitive adhesive. The temporary fixing composite according to any one of claims 1 to 6, wherein the temporary fixing layer is a silicone-based foam layer. The temporary fixing complex according to any one of claims 1 to 7, wherein the silicone-based pressure-sensitive adhesive layer has a thickness of 1 μm to 100 μm. The temporary fixing complex according to claim 8, wherein the silicone-based pressure-sensitive adhesive layer has a thickness of 5 μm to 90 μm. The temporary fixing complex according to claim 9, wherein the silicone-based pressure-sensitive adhesive layer has a thickness of 8 μm to 80 μm.

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