CN214830077U

CN214830077U - Temporary fixation complex

Info

Publication number: CN214830077U
Application number: CN202120665189.1U
Authority: CN
Inventors: 伊关亮; 德山英幸; 斋藤诚; 金田充宏
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2020-04-01
Filing date: 2021-04-01
Publication date: 2021-11-23
Anticipated expiration: 2031-04-01
Also published as: CN113493659A; TW202140712A; JP2021160300A

Abstract

The utility model provides a temporary fixing composite, which is a temporary fixing composite having a temporary fixing layer and a base material layer, the dimensional change rate of which is extremely small when exposed to high temperature, and the difference between the temporary fixing layer and the base material layer is very small. High anchorage. The temporary fixing composite of the present invention comprises a temporary fixing layer, a base material layer and a silicone-based adhesive layer formed by a silicone-based 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 composite is formed by laminating the temporary fixing layer and the base material layer via a primer layer.

Description

Temporary fixation complex

Technical Field

The utility model relates to a temporary fixation complex.

Background

In a manufacturing process of an electronic circuit board or the like, an adhesive tape is required for the purpose of temporary fixing of parts or the like (for example, patent documents 1 to 3). Recently, as temporary fixing materials, foams with an acrylic pressure-sensitive adhesive layer and urethane-based foams have been proposed (for example, patent documents 4 and 5).

In a manufacturing process of an electronic circuit board or the like, components are sometimes mounted on the board through a reflow process. The reflow step generally has a thermal history in which the temperature gradually rises from about 50 ℃ and the maximum temperature approaches 300 ℃. In the reflow step, solder balls present between the substrate and the mounting member are melted and soldered.

Conventional adhesive tapes and temporary fixing materials used in the production process of electronic circuit boards and the like for the purpose of temporary fixing of components and the like cannot withstand high temperatures that are exposed in the reflow process, and for example, significant dimensional changes occur before and after the reflow process, and the purpose of temporary fixing of components and the like cannot be achieved with good reliability.

Further, many conventional pressure-sensitive adhesive tapes and temporary fixing materials for the purpose of temporary fixing of components and the like include a temporary fixing layer and a base material layer that exhibit a temporary fixing function. However, the following problems exist: the temporary fixing layer has low anchoring properties with the base material layer, and the temporary fixing layer is likely to float or peel.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2008-201899

Patent document 2: japanese laid-open patent publication No. 2006-332419

Patent document 3: japanese patent laid-open publication No. 2006-077072

Patent document 4: japanese patent laid-open No. 2010-234536

Patent document 5: japanese patent laid-open publication No. 2013-144788

SUMMERY OF THE UTILITY MODEL

Problem to be solved by utility model

The utility model aims at providing a temporary fixation complex body with temporary fixation layer and substrate layer, the size change rate of temporary fixation complex body when exposing in high temperature is minimum to, the anchoring nature of temporary fixation layer and substrate layer is high.

Means for solving the problems

The temporary fixing composite of the utility model is a temporary fixing composite comprising a temporary fixing layer, a substrate layer and an organic silicon adhesive layer formed by organic silicon adhesive,

the temporary fixing layer is a foaming layer or a rubber layer,

the temporary fixing composite is formed by laminating the temporary fixing layer and the base material layer through an undercoat layer.

In one embodiment, the thickness of the primer layer is 0.01 to 5 μm.

In one embodiment, the thickness of the primer layer is 0.1 to 3 μm.

In one embodiment, the primer constituting the primer layer is a silicone primer.

In one embodiment, the silicone primer is a peroxide-crosslinking silicone adhesive.

In one embodiment, the silicone-based primer is an addition reaction type silicone-based adhesive.

In one embodiment, the temporary fixing layer is a foamed layer.

In one embodiment, the foamed layer has an open cell structure.

In one embodiment, the foamed layer has an open cell ratio of 90% or more.

In one embodiment, the foamed layer has an average cell diameter of 1 to 200 μm.

In one embodiment, 90% or more of all cells in the foamed layer have a cell diameter of 300 μm or less.

In one embodiment, the foamed layer has surface openings.

In one embodiment, the aperture ratio of the surface opening is 1% to 99%.

In one embodiment, the surface opening has an average pore diameter of 150 μm or less.

In one embodiment, the foamed layer has an apparent density of 0.15g/cm³～0.90g/cm³。

In one embodiment, the arithmetic average surface roughness Ra of the surface of the foamed layer is 0.1 to 10 μm.

In one embodiment, a separator is attached to a surface of the foamed layer.

In one embodiment, the surface of the separator has an arithmetic average surface roughness Ra of 0.1 to 5 μm.

In one embodiment, the temporary fixing layer is a silicone 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 to 80 μm.

Effect of the utility model

According to the utility model discloses, can provide the temporary fixation complex body that has temporary fixation layer and substrate layer, this temporary fixation complex body is minimum when exposing in high temperature's dimensional change rate to, the anchor nature of temporary fixation layer and substrate layer is high.

Drawings

Fig. 1 is a schematic cross-sectional view of a temporary fixation composite according to an embodiment of the present invention.

Fig. 2 is a diagram showing a thermal history of a reflow process used for measuring the dimensional change rate.

Description of the reference numerals

10 temporary fixing layer

20 base coat

30 base material layer

40 silicone-based adhesive layer

100 temporary fixation of composite

Detailed Description

"temporary fixed Complex

The utility model discloses a temporary fixation complex contains temporary fixation layer, substrate layer and is the organosilicon adhesive layer that is formed by organosilicon adhesive. The temporary fixing composite of the present invention is constituted by such a constitution, and the dimensional change rate when exposed to high temperature is extremely small. The temporary fixing layer may be only 1 layer or 2 or more layers. The base material layer may be 1 layer only, or may be 2 or more layers. The silicone adhesive layer may be only 1 layer, or 2 or more layers.

The utility model discloses a temporary fixation complex body is that temporary fixation layer and substrate layer carry out range upon range of with the help of the under coat and form. By laminating the temporary fixing layer and the base material layer via the undercoat layer in this manner, the anchoring properties between the temporary fixing layer and the base material layer are improved.

The utility model discloses a temporary fixation complex body as long as contain temporary fixation layer, under coat, substrate layer and the organosilicon adhesive linkage that is formed by organosilicon adhesive linkage, just can be in not haring the utility model discloses the within range of effect contains other layers of arbitrary suitable. Such other layers may be only 1 layer or 2 or more layers.

In the temporary fixing composite of the present invention, a spacer may be attached to the surface of the temporary fixing layer until use. When such a separator does not function as a support body, it is preferable that the separator is 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 spacer attached to the surface of the temporary fixing layer is preferably an outermost layer.

In the temporary fixing composite of the present invention, when the silicone adhesive layer is the outermost layer, the separator may be attached to the surface of the silicone adhesive layer until the use. When such a separator does not function as a support, it is preferably peeled 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 includes 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 and the primer layer, and the base layer and the silicone-based pressure-sensitive adhesive layer are directly laminated.

From the viewpoint of further exhibiting the effect of the present invention, the total thickness of the temporary fixation composite of the present invention is preferably 10 to 4000 μm, more preferably 20 to 3000 μm, still more preferably 30 to 2000 μm, and particularly preferably 40 to 1000 μm.

In a sample obtained by cutting the temporary anchoring composite of the present invention into pieces of 100mm × 100mm, when the sample is left for 1 hour at a temperature of 23 ℃ × humidity 50% RH after the reflow process at a peak temperature of 270 ℃, the dimensional change rate in the MD direction is preferably 0.3% or less, more preferably 0.28% or less, further preferably 0.25% or less, particularly preferably 0.23% or less, and most preferably 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, further preferably 0.25% or less, particularly preferably 0.23% or less, and 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 fixation composite of the present invention can be a foamed composite in which the dimensional change rate is extremely small when exposed to high temperature.

The dimensional change rate in the MD direction and the dimensional change rate in the TD direction are obtained by the following equations.

Dimension change rate (%) in MD ═ length (mm) in MD before reflow process [ ("length (mm) in MD after reflow process and after standing at temperature 23℃ × humidity 50% RH for 1 hour ]/length (mm) in MD before reflow process [ (]) 100 ]

Dimension change rate (%) in TD direction [ (% TD direction length (mm) before reflow process) [ (TD direction length (mm) after 1 hour of standing at temperature 23℃ × humidity 50% RH) after reflow process ]/(% TD direction length (mm) before reflow process) ] × 100 ]

Temporary fixing layer

As the thickness of the temporary fixing layer, any appropriate thickness can be adopted within the range not impairing the effects of the present invention. The thickness of such a foamed layer is preferably 10 to 3500. mu.m, more preferably 20 to 2500. mu.m, still more preferably 30 to 1500. mu.m, and particularly preferably 40 to 950. mu.m. If the thickness of the temporary fixing layer is within the above range, the temporary fixing composite of the present invention can exhibit excellent temporary fixing property.

The temporary fixing layer is preferably a foamed layer or a rubber layer, and is preferably a foamed layer from the viewpoint of further exhibiting the effects of the present invention.

The foamed layer preferably has cells (spherical bubbles). It should be noted that the cells (spherical cells) may not be strictly spherical cells, and may be, for example, roughly spherical cells in which deformation is partially present, including cells having a space with significant deformation.

The foamed layer is preferably a foamed layer having an open cell structure. By providing the foam layer with an open cell structure, the member can be effectively temporarily fixed to the foam layer without trapping cells. More specifically, the foamed layer has an open cell structure having through-holes between adjacent cells. By providing the foamed layer with an open cell structure having through-holes between adjacent cells, in addition to other characteristics of the foamed layer, excellent bubble releasing properties can be exhibited, the member can be more effectively temporarily fixed to the foamed layer without entrapping bubbles, and the member can be more easily peeled without adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be maintained.

The presence or absence of the open cell structure can be observed by obtaining 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 field) and confirming the presence or absence of through holes in the cell wall.

The open cell ratio of the foamed layer is preferably 90% or more, more preferably 90% to 100%, further preferably 92% to 100%, further preferably 95% to 100%, particularly preferably 99% to 100%, most preferably substantially 100%. If the open cell ratio of the foamed layer is in the above range, in addition to other characteristics of the foamed layer, more excellent cell release properties can be exhibited, the member can be more effectively temporarily fixed to the foamed layer without trapping cells, and the member can be more easily peeled without leaving adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be further maintained.

The continuous bubble rate can be measured, for example, as follows. That is, the foamed layer was immersed in water and left under a reduced pressure of-750 mmHg for 3 minutes to replace the air in the bubbles with water, and the mass of the absorbed water was measured to set the density of the water to 1.0g/cm³The volume of water absorbed was calculated and calculated by the following equation.

Continuous bubble rate (%) { (volume of water absorbed)/(bubble partial volume) } × 100

The bubble portion volume is calculated by, for example, the following equation. Here, the resin density is a value obtained by measuring the density of a resin molded article prepared by removing an emulsifier from a resin forming a foamed layer.

Partial volume of air bubbles (cm)³) { (mass of foam (foamed sheet))/(apparent density of foam (foamed sheet)) } - { (mass of foam (foamed sheet))/(resin density) }

The average cell diameter of the foamed layer is preferably 1 to 200. mu.m, more preferably 1.5 to 180. mu.m, still more preferably 2 to 170. mu.m, particularly preferably 2.5 to 160. mu.m, and most preferably 3 to 150. mu.m. If the average cell diameter in the foamed layer is within the above range, in addition to other characteristics of the foamed layer, more excellent bubble removability can be exhibited, the member can be more effectively temporarily fixed to the foamed layer without entrapping bubbles, and the member can be more easily peeled without adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be further maintained.

The foamed layer preferably has a cell diameter of not less than 90% of the total cells of not more than 300 μm, more preferably not less than 92% of the total cells of not more than 300 μm, still more preferably not less than 95% of the total cells of not more than 300 μm, particularly preferably not less than 97% of the total cells of not more than 300 μm, and most preferably not more than 300 μm of substantially 100% of the total cells of cell diameter. Further, the foamed layer more preferably has a cell diameter of 250 μm or less in 90% or more of the total cells, still more preferably has a cell diameter of 200 μm or less in 90% or more of the total cells, particularly preferably has a cell diameter of 180 μm or less in 90% or more of the total cells, and most preferably has a cell diameter of 150 μm or less in 90% or more of the total cells. If the proportion of the cell diameter of 300 μm or less in the foamed layer and the cell diameter of 90% or more of the total cells are in the above range, in addition to other characteristics of the foamed layer, more excellent cell releasing property can be exhibited, the member can be more effectively temporarily fixed to the foamed layer without trapping cells, and the member can be more easily peeled without adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be further maintained.

The maximum cell diameter of 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. If the maximum cell diameter of all the cells of the foamed layer is in the above range, in addition to other characteristics of the foamed layer, more excellent bubble-releasing properties can be exhibited, the member can be more effectively temporarily fixed to the foamed layer without entrapping the bubbles, and the member can be more easily peeled without adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be further maintained.

The minimum cell diameter of all cells of the foamed 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. If the minimum cell diameter of all the cells of the foamed layer is within the above range, in addition to other characteristics of the foamed layer, more excellent bubble-releasing properties can be exhibited, the member can be more effectively temporarily fixed to the foamed layer without entrapping the cells, and the member can be more easily peeled without adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be further maintained.

As described above, the foamed layer preferably has an open cell structure, and the cell diameter is preferably fine as described above, so that excellent air bubble releasing properties can be exhibited, the member can be effectively temporarily fixed to the foamed layer without trapping air bubbles, and the member can be peeled without leaving adhesive residue when the temporary fixation is released, and thus the foamed layer is suitable for temporarily fixing a composite.

The average cell diameter can be determined by, for example, obtaining an enlarged image of a cross section of the foamed layer by using a low vacuum scanning electron microscope ("S-3400N type scanning electron microscope", manufactured by Hitachi High-Tech Science systems Co., Ltd.), and performing image analysis. The number of cells to be analyzed is, for example, 20. The minimum cell diameter (. mu.m) and the maximum cell diameter (. mu.m) can be determined by the same method.

The foamed layer preferably has surface openings. The surface opening referred to herein means: an opening having an average pore diameter of a certain size is present on the surface of the foam layer. Through making the foaming layer have the surface opening, the utility model discloses an adsorb interim stationary blade can be fixed the component on the foaming layer more effectively temporarily and not wrap up in and press from both sides the bubble, can peel off and not the cull more easily when removing interim fixed. This is presumably because the temporary fixing composite of the present invention having a foamed layer can further exhibit excellent temporary fixing properties as described above by functioning as an appropriate suction pad.

The aperture ratio of the surface opening is preferably 1% to 99%, more preferably 2% to 95%, still more preferably 3% to 90%, particularly preferably 4% to 85%, most preferably 5% to 80%. If the opening ratio of the surface opening portion is in the above range, the temporary fixing composite of the present invention can temporarily fix the member to the foaming layer more effectively without entrapping air bubbles, and can be peeled off more easily without adhesive residue when releasing the temporary fixation.

The average pore diameter of the surface openings is preferably 150 μm or less, more preferably 0.5 to 145. mu.m, still more preferably 1.0 to 140. mu.m, particularly preferably 1.5 to 135. mu.m, most preferably 2.0 to 130. mu.m. If the average pore diameter of the surface opening portion is within the above range, the temporary fixing composite of the present invention can more effectively temporarily fix the member on the foaming layer without trapping air bubbles, and can be more easily peeled without adhesive residue when releasing the temporary fixation.

The average pore diameter of the surface opening can be determined by obtaining a magnified image of the surface of the foam layer by a low vacuum scanning electron microscope ("S-3400N type scanning electron microscope", manufactured by Hitachi High-Tech field Co., Ltd.), and analyzing the image. The number of wells to be analyzed is, for example, 20.

The apparent density of the foamed layer is preferably 0.15g/cm³～0.90g/cm³More preferably 0.20g/cm³～0.85g/cm³More preferably 0.25g/cm³～0.80g/cm³Particularly preferably 0.30g/cm³～0.75g/cm³. If the apparent density of the foamed layer is within the above range, the member can be more effectively temporarily fixed to the foamed layer without entrapping air bubbles in addition to other characteristics of the foamed layer, and can be more easily peeled without adhesive residue when the temporary fixation is released. Further, even if the thickness of the foamed layer is reduced, the effects can be maintained.

The arithmetic average surface roughness Ra of the surface of the foamed layer is preferably 0.1 to 10 μm, more preferably 0.2 to 9 μm, still more preferably 0.3 to 8.5 μm, and particularly preferably 0.4 to 8 μm. By providing the surface of the foamed layer with the arithmetic average surface roughness Ra in this range, the temporary fixing composite of the present invention can have a more sufficient shear adhesion in the same direction as the surface and a weaker adhesion in the direction perpendicular to the surface.

As described above, the separator may be attached to the surface of the foamed layer until use. When such a separator does not function as a support, it is preferable that the separator is 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 to 500. mu.m, more preferably 3 to 450. mu.m, still more preferably 5 to 400. mu.m, and particularly preferably 10 to 300. mu.m.

Examples of the separator include paper, a plastic film, a Polytetrafluoroethylene (PTFE) film, and a plastic film having a surface treated with silicone or fluorinated silicone.

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

In particular, from the viewpoint of further exhibiting the effects of the present invention, a plastic film which has not been subjected to surface treatment such as silicone treatment or fluorinated silicone treatment is preferably attached as a separator to at least one surface of the foamed layer. As such a separator, a polyethylene terephthalate (PET) film which is not subjected to surface treatment such as silicone treatment or fluorinated silicone treatment is particularly preferable.

The separator as described above preferably has an arithmetic average surface roughness Ra of 0.1 to 5 μm, more preferably 0.15 to 4.5 μm, still more preferably 0.2 to 4 μm, and particularly preferably 0.22 to 3.5 μm on the surface. By using a separator having a surface with arithmetic average surface roughness Ra in such a range, the temporary fixation composite of the present invention can be made to have more sufficient shear adhesion force in the same direction as the surface and weaker adhesion force in the direction perpendicular to the surface by peeling off the separator from the surface of the foam layer before placing a member intended to be temporarily fixed on the foam composite of the present invention.

One embodiment of the foamed layer is a silicone-based foamed layer. The effect of the present invention can be further exhibited by making the foaming layer an organic silicon foaming layer.

The silicone-based foamed layer is preferably formed by heat curing of the silicone resin composition.

The silicone resin composition preferably satisfies at least 1 condition selected from the group consisting of the following (a) to (F).

That is, the silicone resin composition preferably satisfies at least 1 condition selected from the group consisting of the following conditions.

(A) Comprises an organopolysiloxane having at least 2 alkenyl groups in one molecule;

(B) an organopolysiloxane that contains in one molecule hydrogen atoms to which silicon atoms are bonded, in an amount such that the number of silicon atom-bonded hydrogen atoms in component (B) is 0.4 to 20 moles per 1 mole of alkenyl groups in component (a);

(C) 100 to 1000 parts by mass of a mixture comprising water and an inorganic thickener per 100 parts by mass of component (A);

(D) a surfactant comprising (D-1) 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, in a mass ratio of (D-1) to (D-2) of 0.1 to 100 parts by mass;

(E) comprising a hydrosilylation reaction catalyst;

(F) the curing retarder is contained in an amount of 0.001 to 5 parts by mass per 100 parts by mass of the component (A).

(A) The component (A) is an organopolysiloxane having at least 2 alkenyl groups in one molecule, which is the main agent of the silicone resin composition.

Examples of the alkenyl group in the component (a) include vinyl, allyl, hexenyl, 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 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; halogen-substituted alkyl groups such as 3,3, 3-trifluoropropyl groups, etc., preferably methyl groups.

Specific examples of the component (A) include dimethylvinylsiloxy-terminated dimethylpolysiloxane, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymer, trimethylsiloxy-terminated methylvinylpolysiloxane, trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymer, trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, and the component (A) is preferably a diorganopolysiloxane having a substantially linear main chain.

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

The bonding position of the hydrogen atom bonded with the silicon atom in the component (B) may be any suitable bonding position within a range not impairing the effects of the present invention. Examples of such a bonding position include a molecular chain end and/or a molecular chain side chain. Examples of the silicon atom-bonded organic group other than a hydrogen atom in the component (B) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; halogen-substituted alkyl groups such as 3,3, 3-trifluoropropyl groups, etc., preferably methyl groups.

Specific examples of the component (B) include dimethylhydrogensiloxy-terminated dimethylpolysiloxane, dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer, trimethylsiloxy-terminated methylhydropolysiloxane, trimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer, and a Copolymer of (CH) with a group represented by formula (I)₃)₃SiO_1/2Siloxane units and H (CH) as shown₃)₂SiO_1/2Siloxane units and SiO_4/2The organopolysiloxane formed of the siloxane unit is preferably a linear organopolysiloxane.

(B) The content of component (B) is an amount in which the silicon atom-bonded hydrogen atoms in component (B) are preferably in the range of 0.4 to 20 mol, more preferably in the range of 1.5 to 20 mol, and still more preferably in the range of 1.5 to 10 mol, based on 1 mol of alkenyl groups in component (a). 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 resulting foam composite is improved.

(C) Component (C) is a mixture of water and an inorganic thickener, and is a component for removing water in component (C) from the silicone rubber obtained by crosslinking the silicone resin composition to prepare a silicone rubber sponge. Since the component (C) is stably dispersed in the component (a), the water in the component (C) is preferably ion-exchanged water.

(C) The inorganic thickener in the component (a) is blended to increase the viscosity of water, to facilitate the dispersion of the component (C) in the component (a), and to stabilize the dispersion state of the component (C). Examples of the inorganic thickener include natural or synthetic smectite clays such as bentonite, montmorillonite, hectorite, saponite, sauconite, beidellite, and smectite; magnesium aluminum silicate; the clay is preferably a smectite clay such as bentonite or montmorillonite, for example, a composite of these with a water-soluble organic polymer such as a carboxyvinyl polymer. As such a smectite clay, for example, SUMECTON SA (manufactured by KUNIMINE INDUSTRIES Inc.) which is a hydrothermal synthetic product and ベンゲル (manufactured by HOJUN Inc.) which is a natural purified product can be obtained. The pH of these smectite clays is preferably in the range of pH5.0 to 9.0 from the viewpoint of maintaining the heat resistance of the foamed layer. The content of the inorganic thickener in component (C) is preferably in the range of 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of water.

(C) The content of the component (b) is preferably in the range of 100 to 1000 parts by mass, more preferably in the range of 100 to 800 parts by mass, still more preferably in the range of 100 to 500 parts by mass, particularly preferably in the range of 200 to 500 parts by mass, and most preferably in the range of 200 to 350 parts by mass, relative to 100 parts by mass of the component (a). This is because: when the content of the component (C) is not less than the lower limit of the above range, a foamed layer having a low density can be formed, and on the other hand, the following are included: when the content is not more than the upper limit of the above range, a foamed layer having a uniform and fine interconnected cell structure can be formed.

(D) The surfactant of component (A) is preferably composed of (D-1) 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. Examples of the surfactant of component (D) include glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid amides.

(D) Component (B) preferably comprises component (D-1) and component (D-2), and the mass ratio of component (D-1) to component (D-2) is preferably 0.1 or more, more preferably 1 or more, further preferably 5 or more, further 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, particularly preferably 60 or less, and most preferably 50 or less. This is because: if the mass ratio is greater than the lower limit, a low-density foamed layer having a uniform and fine open cell structure can be formed, but on the other hand, the reason is that: if the amount is less than the upper limit, the component (C) can be stably dispersed in the components (A) and (B), and as a result, a foamed layer having a uniform and fine interconnected cell structure can be formed.

(D) The content of component (b) is preferably in the range of 0.1 to 15 parts by mass, more preferably 0.2 to 3 parts by mass, per 100 parts by mass of component (a). This is because: when the content of the component (D) is not less than the lower limit of the above range, a foamed layer having a uniform and fine interconnected cell structure can be formed, and on the other hand, the following is because: when the content is not more than the upper limit of the above range, a foamed layer having excellent heat resistance can be formed.

(E) The component (c) is a hydrosilylation catalyst for promoting 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 the component (E) include chloroplatinic acid, alcohol-modified chloroplatinic acid; a complex compound of chloroplatinic acid with an olefin, vinylsiloxane or acetylene compound; coordination compounds of platinum with olefinic, vinylsiloxane or acetylene compounds; tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) rhodium chloride, and the like.

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

The silicone resin composition may contain (F) a curing retarder for adjusting the curing speed and the working usable time. Examples of the component (F) include alkynols such as 3-methyl-1-butyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3-ol, and 1-ethynyl-1-cyclohexanol. (F) The content of the component (b) may be appropriately selected depending on the method of using the silicone resin composition and the method of molding, and is generally preferably in the range of 0.001 to 5 parts by mass relative to 100 parts by mass of the component (a).

The silicone resin composition may further contain (G) a reinforcing fine silica powder from the viewpoint of improving the strength of the resulting foamed layer. The BET specific surface area of the reinforcing fine silica powder is preferably 50m²/g～350m²(ii)/g, more preferably 80m²/g～250m²(ii) in terms of/g. Examples of the reinforcing fine silica powder include fumed silica and precipitated silica. These reinforcing fine silica powders may be surface-treated with organic silane or the like.

(G) The content of the component (b) 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, relative to 100 parts by mass of the component (a). The content of the component (G) is preferably at least 0.1 part by mass per 100 parts by mass of the component (A).

The silicone resin composition may contain a pigment such as carbon black or indian red in a range not to impair the object of the present invention.

The silicone resin composition can be easily produced by uniformly mixing the above-mentioned components or a composition in which various additives are added as needed by a known kneading means. As the stirrer used herein, any suitable stirrer may be used as long as it can sufficiently disperse the component (C) and the component (D) in the component (a), within a range not impairing the effects of the present invention. Examples of such a stirrer include a homogenizing stirrer, a paddle stirrer, a homogenizing distributor, a colloid mill, a vacuum mixing stirrer, and a rotation and revolution stirrer.

The foamed layer may be produced by any appropriate method within a range not impairing the effects of the present invention. As such a production method, for example, a resin composition (for example, a silicone resin composition) forming a foamed layer is applied to a separator a, a separator B is placed on a surface of the applied resin composition on the opposite side to the separator a, and after heat curing, at least 1 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 having a surface treated with silicone or fluorinated silicone. Examples of the plastic film include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, a polyimide film, a polyamide (nylon) film, an aromatic polyamide (aromatic polyamide) film, and the like, and particularly, from the viewpoint of further exhibiting the effects of the present invention, a plastic film which is not subjected to a surface treatment such as a silicone treatment or a fluorinated silicone treatment is preferable. The separator is particularly preferably a polyethylene terephthalate (PET) film which is not subjected to surface treatment such as silicone treatment or fluorinated silicone treatment.

The thickness of each of the separator A and the separator B is preferably 1 μm to 500. mu.m, more preferably 3 μm to 450. mu.m, still more preferably 5 μm to 400. mu.m, and particularly preferably 10 μm to 300. mu.m.

As an example of the method for producing the 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, for example, the following explanation of the production method can be understood by replacing the silicone resin composition with a composition that is a raw material of the other foamed layer.

In one embodiment of the method for producing a silicone-based foamed layer, a silicone resin composition containing at least a thermosetting silicone resin and water is applied to a separator a (hereinafter, this step is referred to as step (1)), a separator B is placed on the surface of the applied silicone resin composition on the side opposite to the separator a (hereinafter, this step is referred to as step (2)), the silicone resin composition is thermally cured (hereinafter, this step is referred to as step (3)), and at least 1 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)), thereby forming a silicone-based foamed layer.

In another embodiment of the method for producing a silicone-based foamed layer, a silicone resin composition containing at least a thermosetting silicone resin and water is applied to a separator a (hereinafter, this step is referred to as step (1)), a separator B is placed on the surface of the applied silicone resin composition on the side opposite to the separator a (hereinafter, this step is referred to as step (2)), the silicone resin composition is thermally cured (hereinafter, this step is referred to as step (3)), at least 1 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 the silicone-based foamed layer is formed by bonding to a support (hereinafter, this step is referred to as step (5)).

When the separator a and the separator B are used as the support as they are, the surfaces of the separator a and the separator B serving as the support may be coated with an undercoat agent such as a silane coupling agent, or subjected to surface treatment such as corona treatment or plasma treatment, in order to improve the anchoring property to the foamed layer.

In the case of a separator that is not removed during the heat drying in step (4), the release liner that can be used as the separator is preferably a release liner in which the surface of a substrate (liner substrate) of a Polytetrafluoroethylene (PTFE) film, paper, or plastic film is treated with a fluorinated silicone. In the case of the separator having a separator that is not removed during the heat drying in step (4), the separator can be easily peeled after the heat drying by using a release liner in which the surface of a substrate (liner substrate) of a Polytetrafluoroethylene (PTFE) film, paper or plastic film is treated with a fluorinated silicone. Further, an adhesive layer may be provided on the separators a and B.

The separator a used in the step (1) may be the same as or different from the separator B used in the step (2). The separator a used in step (1) and the separator B used in step (2) may be 1 layer or more, respectively, or may include 2 or more layers.

The surface shape of the silicone resin composition in contact with the surface changes depending on the degree of hydrophilicity/hydrophobicity of the surface of the separator a used in step (1) and the surface of the separator B used in step (2) in contact with the silicone resin composition. For example, when a highly hydrophilic separator such as a polyethylene terephthalate (PET) film is used as the separators a and B, a large number of surface openings having a fine diameter can be present on the surface of the silicone resin composition in contact with the separator. In addition, for example, when a highly hydrophobic separator such as a polyethylene terephthalate (PET) release liner treated with a fluorinated silicone is used as the separators a and B, a small number of surface openings having a fine diameter can be present on the surface of the silicone resin composition in contact with the separator. Therefore, when it is desired to exhibit high air permeability and high adsorptivity to the silicone foamed layer, a separator having high hydrophilicity is preferably used, and when it is desired to exhibit high water-stopping property and high dust-proofing property to the silicone foamed layer, a separator having high hydrophobicity is preferably used. When removability of the silicone foamed layer and the separator is required, the separator having high hydrophobicity is preferably used. 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 is defined as hydrophilic, and a case where the contact angle with water is 90 degrees or more is defined as hydrophobic.

In the step (3), the silicone resin composition is thermally cured. From the viewpoint of efficiently thermally curing the silicone resin composition, the temperature for the thermal curing is preferably 50 ℃ or higher and less than 100 ℃. When the temperature for the heat curing is lower than 50 ℃, the heat curing may be too time-consuming. When the temperature for thermosetting is 100 ℃ or higher, moisture in the silicone resin composition in a substantially closed state sandwiched between the separator a and the separator B is volatilized, and thus, there is a possibility that the formed cells are coarsened and densified. The silicone resin composition formed in step (3) is referred to as a silicone-based foam layer precursor.

By performing a special thermosetting method in which the silicone resin composition is thermally cured in a substantially closed state sandwiched between the separator a and the separator B as in the step (3), the silicone resin composition is thermally cured in a state in which the moisture in the silicone resin composition is not removed, and by the synergistic action with the subsequent step (4), a silicone-based foamed layer having a continuous cell structure and a fine cell diameter can be effectively obtained.

In the step (4), at least 1 selected from the separator a and the separator B is peeled off and then heated and dried. The substantially sealed state in the step (3) is released by peeling at least 1 selected from the separator a and the separator B, and the released state is dried by heating, so that moisture is efficiently volatilized from the silicone-based foaming layer precursor formed in the step (3) and removed, thereby obtaining the silicone-based foaming layer. The heating and drying temperature in the step (4) is preferably 120 to 250 ℃ from the viewpoint of efficiently forming the silicone-based foamed layer. When the heating and drying temperature in the step (4) is less than 120 ℃, drying and curing may be too time-consuming, and a silicone-based foamed layer having an open cell structure and fine cell diameters may not be obtained. If the heating and drying temperature in step (4) exceeds 250 ℃, the layer may be difficult to form due to shrinkage or expansion of the substrate.

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

When the temporary fixing layer is the rubber layer, any appropriate rubber layer can be adopted within the range of the effect of the utility model. The rubber layer is preferably a silicone rubber layer. If the silicone rubber layer is used as the rubber layer, the effects of the present invention can be further exhibited.

Substrate layer

The utility model discloses a temporary fixation complex body can be at the harm not the utility model discloses the within range of effect has arbitrary appropriate substrate layer.

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

Examples of the substrate layer include plastic films, papers, nonwoven fabrics, metal foils, metal meshes, glass, and glass cloths. The base material layer may have 1 layer or 2 or more layers. In order to improve the anchoring property between the base material layer and the layer adjacent thereto, the surface of the base material layer may be coated with an undercoating agent such as a silane coupling agent, or subjected to surface treatment such as corona treatment or plasma treatment.

Examples of the plastic film include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, a polyimide film, a polyamide (nylon) film, and an aromatic polyamide (aromatic polyamide) film. Among these plastic films, polyimide films are preferable from the viewpoint of further exhibiting the effects of the present invention.

Primer layer

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

The composition of the primer constituting the undercoat layer is not particularly limited, and can be appropriately selected from known primers. In particular, a silicone-based primer is preferable from the viewpoint of being able to exhibit anchoring properties.

As the silicone-based primer, any suitable silicone-based primer can be used within a range in which the effects of the present invention are not impaired. Such a silicone-based primer can be suitably used as a silicone-based primer by forming a generally used peroxide crosslinking silicone-based adhesive (peroxide-curable silicone-based adhesive) or an addition reaction silicone-based adhesive in a small thickness, for example, from the viewpoint of further exhibiting the effects of the present invention.

When the peroxide-crosslinking silicone adhesive is used, the adhesion between the base material and the primer is excellent along with the generation of radicals by heating.

When the addition reaction type silicone adhesive is used, the coating can be performed at a low temperature, the expansion and contraction of the substrate due to heating can be suppressed, and the appearance and the like are excellent.

Commercially available products can be used as the peroxide-crosslinkable silicone adhesive and the addition-reactive silicone adhesive, and specific examples of the peroxide-crosslinkable silicone adhesive include KR-3006A/BT, manufactured by shin-Etsu chemical Co., Ltd., SH4280PSA, manufactured by Dow-Toray Co., Ltd. Specific examples of the addition reaction type silicone-based adhesive include X-40-3501 manufactured BY shin-Etsu chemical Co., Ltd., BY24-712 manufactured BY Dow-Toray Co., Ltd., TSE32X manufactured BY GE TOSHIBA SILICONES Co., Ltd.

Silicone-based adhesive layer

The thickness of the silicone adhesive layer may be any appropriate thickness within a range not impairing the effects of the present invention. The thickness of the silicone adhesive layer is preferably 1 μm to 100. mu.m, more preferably 5 μm to 90 μm, still more preferably 8 μm to 80 μm, and particularly preferably 10 μm to 70 μm. If the thickness of the silicone-based adhesive layer is within the above range, the temporary fixing composite of the present invention can exhibit excellent temporary fixing properties.

As the silicone adhesive forming the silicone adhesive layer, any suitable silicone adhesive can be used within the range not impairing the effects of the present invention. Here, the "silicone adhesive forming the silicone adhesive layer" refers to a silicone adhesive for forming the silicone adhesive layer. In general, the pressure-sensitive adhesive layer is formed by a curing reaction or the like of a material composition that finally forms the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer itself cannot be defined as a composition of an object, and therefore, in the present specification, the expression "a silicone-based pressure-sensitive adhesive layer formed of a silicone-based pressure-sensitive adhesive" is used for the silicone-based pressure-sensitive adhesive layer.

Representative examples of the silicone-based adhesive include a peroxide-curable silicone-based adhesive (also referred to as a peroxide-crosslinkable silicone-based adhesive in some cases), an addition-reactive silicone-based adhesive, and the like. The number of the silicone-based binders may be only 1, or may be 2 or more.

< peroxide-curable Silicone-based adhesive >

Typically, the peroxide curable silicone-based adhesive contains a silicone rubber as a long-chain polymer of polydimethylsiloxane and a silicone resin of a three-dimensional structure. The peroxide-curable silicone adhesive may contain an organic peroxide such as benzoyl peroxide as a crosslinking agent for curing by crosslinking. The number of the crosslinking agents may be only 1, or may be 2 or more. In this case, the peroxide-curable silicone adhesive is typically produced from an organic peroxideThe raw radicals will abstract the Si-CH of the silicone rubber₃Radical hydrogen, SiCH produced₂The radicals are bonded to each other to perform a crosslinking reaction.

Examples of the organic peroxide include benzoyl peroxides (t-butyl peroxybenzoate, 2, 5-dimethyl-2, 5-dibenzoylhexane diperoxide, dibenzoyl peroxide, 4,4 '-dimethyldibenzoyl peroxide, 3' -dimethyldibenzoyl peroxide, 2 ', 4, 4' -tetrachlorodibenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide), cumene peroxide, t-butylcumyl peroxide, t-butyl isobutyrate, t-butyl peroxy-2-ethylhexanoate, 2-di-t-butyloctane diperoxide, 1-di-t-butylcyclohexane diperoxide, and the like. Among these, benzoyl peroxides are preferable from the viewpoint of facilitating adjustment of the adhesive properties by changing the amount of addition.

The content of the organic peroxide in the peroxide-curable silicone adhesive can be any appropriate amount within a range that does not impair the effects of the present invention. Typically, the amount of the organic peroxide to be blended is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the solid content of the peroxide-curable silicone adhesive.

When the curable silicone adhesive is applied to another layer (e.g., a base material layer) through a primer layer containing an ultraviolet absorber, a light stabilizer, or the like, or when the other layer (e.g., the base material layer) contains an ultraviolet absorber or the like, the peroxide-curable silicone adhesive is less likely to cause inhibition of curing, and therefore, the curable ability can be further exhibited. Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and polymer-type ultraviolet absorbers obtained by polymerizing (meth) acrylates having characteristic groups of these compounds in side chains. Examples of the light stabilizer include hindered amine light stabilizers (such as HALS) and hindered phenol light stabilizers. The number of the ultraviolet absorber and the number of the light stabilizer may be only 1 or 2 or more, respectively.

The peroxide-curable silicone adhesive is prepared as an organic solvent solution (e.g., a solution of an alkane-based organic solvent such as hexane, or a solution of an aromatic organic solvent such as toluene or xylene) of 30 to 70 mass% or is commercially available. That is, the peroxide-curable silicone adhesive is preferably a solution (typically a coating solution) containing 30 to 70 mass% of an organic solvent.

The silicone adhesive layer formed of the peroxide-curable silicone adhesive is formed by applying a coating liquid of the peroxide-curable silicone adhesive to an arbitrary appropriate substrate (base material layer or the like), evaporating a solvent, and then heating and curing the coating liquid.

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

Examples of commercially available peroxide-curable silicone adhesives include YR3340, YR3286, PSA610-SM, and XR37-B6722 available from Momentive Performance Materials, Inc.; SE4200, SH4280 by Dow-Toray company; KR-100, KR-101-10 (solvent-type toluene), KR-120, KR-130, and X-40-3287 (solvent-type isoparaffin) manufactured by shin-Etsu chemical industries, Ltd.

The peroxide-curable silicone adhesive may contain any other suitable component within a range not impairing the effects of the present invention. Examples of the other components include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, preservatives, mildewcides, plasticizers, antifoaming agents, colorants, fillers, and wettability modifiers.

< addition reaction type Silicone adhesive >

The addition reaction type silicone adhesive preferably contains a main agent, a crosslinking agent, and if necessary, a curing catalyst. The addition reaction type silicone adhesive has the following advantages: can be used only by primary curing at low temperature, and does not need secondary curing at high temperature. Therefore, when the addition reaction type silicone adhesive is used, the silicone adhesive layer can be produced at a relatively low temperature, and the energy economy is excellent.

The addition reaction type silicone-based adhesive generally contains: a main agent comprising a mixture of a silicone resin component and a silicone rubber component, a crosslinking agent containing a hydrosilyl group (SiH group), and if necessary, a curing catalyst.

Typically, the silicone resin component is an organopolysiloxane having a network structure obtained by hydrolyzing an organochlorosilane or organoalkoxysilane and then performing a dehydration condensation reaction. The silicone resin component may be only 1 type, or may be 2 or more types.

Typically, the silicone rubber component is a diorganopolysiloxane having a linear structure. The number of silicone rubber components may be only 1, or may be 2 or more.

In the silicone resin component and the silicone rubber component, examples of the organic group include methyl, ethyl, propyl, butyl, phenyl, and the like. The organic group may be partially substituted with an unsaturated group such as a vinyl group, a hexenyl group, an allyl group, a butenyl group, a pentenyl group, an octenyl group, a (meth) acryloyl group, a (meth) acryloylmethyl group, a (meth) acryloylpropyl group, or a cyclohexenyl group.

In addition reaction type silicone adhesives, crosslinking proceeds by addition reaction of unsaturated groups and hydrosilyl groups to form a network structure, and adhesion is exhibited. The number of unsaturated groups such as vinyl groups is preferably 0.05 to 3.0, more preferably 0.1 to 2.5, per 100 organic groups. By setting the number of unsaturated groups to 0.05 or more relative to 100 organic groups, it is possible to prevent the reactivity with hydrosilyl groups from decreasing and curing becomes difficult, and it is possible to impart a suitable adhesive force. By setting the number of unsaturated groups to 3.0 or less relative to 100 organic groups, it is possible to prevent the adhesive from being adversely affected by an increase in crosslinking density, adhesive force, and cohesive force of the adhesive.

Examples of the organopolysiloxane include KS-3703 (the number of vinyl groups is 0.6 relative to 100 methyl groups) manufactured by shin-Etsu chemical industries, Inc.; BY23-753 (number of vinyl groups is 0.1 relative to 100 methyl groups), BY24-162 (number of vinyl groups is 1.4 relative to 100 methyl groups), SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, SD4592PSA, and the like, manufactured BY Dow-Toray.

Examples of the silicone rubber component include KS-3800 (the number of vinyl groups is 7.6 based on 100 methyl groups) manufactured by shin-Etsu chemical industries, Inc.; BY24-162 (number of vinyl groups is 1.4 per 100 methyl groups), BY24-843 (unsaturated group-free), SD-7292 (number of vinyl groups is 5.0 per 100 methyl groups) manufactured BY Dow-Toray, Inc.

The number of the crosslinking agents may be only 1, or may be 2 or more. Examples of the crosslinking agent include a silicone crosslinking agent (silicone crosslinking agent). Examples of the silicone-based crosslinking agent include polyorganohydrogensiloxanes having 2 or more hydrogen atoms bonded to silicon atoms in the molecule. In such polyorganohydrogensiloxanes, 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 organic groups include alkyl groups such as methyl and ethyl; aryl groups such as phenyl; haloalkyl, and the like. Such an organic group is preferably a methyl group from the viewpoint of synthesis and handling. The skeleton structure of the polyorganohydrogensiloxane may have any of a linear, branched, and cyclic skeleton structure, and is preferably linear.

In the crosslinking agent, the number of hydrogen atoms bonded to silicon atoms is preferably 0.5 or more and 10 or less, and more preferably 1 or more and 2.5 or less, relative to 1 unsaturated group such as a vinyl group in the silicone resin component and the silicone rubber component.

Typically, the curing catalyst is used to promote the hydrosilylation reaction between the unsaturated groups in the silicone resin component and the silicone rubber component and the Si — H groups in the crosslinking agent. The curing catalyst may be 1 type or 2 or more types.

Examples of the curing catalyst include platinum-based catalysts, i.e., chloroplatinic acid, alcohol solutions of chloroplatinic acid, reactants of chloroplatinic acid and alcohol solutions, reactants of chloroplatinic acid and olefin compounds, reactants of chloroplatinic acid and vinyl-containing siloxane compounds, platinum-olefin complexes, platinum-vinyl-containing siloxane complexes, and platinum-phosphorus complexes. Specific examples of such curing catalysts are described in, for example, Japanese patent application laid-open Nos. 2006-28311 and 10-147758. Specific examples of commercially available products include SRX-212 manufactured by Dow-Toray, and PL-50T manufactured by shin-Etsu chemical industries.

The content of the curing catalyst is preferably 5 to 2000 mass ppm, more preferably 10 to 500 mass ppm, in terms of platinum component, relative to the total amount of the silicone resin component and the silicone rubber component.

The addition reaction type silicone-based adhesive exhibits adhesive force even at normal temperature, but from the viewpoint of stability of adhesive force, it is preferable that: the crosslinking reaction of the silicone resin component and the silicone rubber component by the crosslinking agent is promoted by heating or irradiation with active energy rays.

The heating temperature for accelerating the crosslinking reaction by heating is preferably 60 to 140 ℃ and more preferably 80 to 130 ℃.

When the crosslinking reaction is promoted by irradiation with an active energy ray, an active energy ray having an energy quantum among electromagnetic waves or charged particle beams, that is, an active light such as ultraviolet rays, an electron beam, or the like can be used. When crosslinking is performed by irradiation of electron beams, a photopolymerization initiator is not required, but when crosslinking is performed by irradiation of active light such as ultraviolet light, a photopolymerization initiator is preferably present. As the photopolymerization initiator when ultraviolet rays are irradiated, any suitable photopolymerization initiator can be used within a range not impairing the effects of the present invention. Examples of such photopolymerization initiators include benzoins, benzophenones, acetophenones, α -hydroxyketones, α -aminoketones, α -diketones, α -diketodialkylacetals, anthraquinones, and thioxanthones. The number of photopolymerization initiators may be only 1, or may be 2 or more. The amount of the photopolymerization initiator used is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the total amount of the main agent and the crosslinking agent, which is a mixture of the silicone resin component and the silicone rubber component.

As the irradiation conditions for promoting the crosslinking reaction by irradiating the active energy ray, any appropriate irradiation conditions may be adopted within the range not impairing the effects of the present invention.

The addition reaction type silicone adhesive may contain any other suitable component within a range not impairing the effects of the present invention. Examples of the other components include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, preservatives, mildewcides, plasticizers, antifoaming agents, colorants, fillers, and wettability modifiers.

Method for producing foam composite

The foamed composite of the present invention can be produced by any suitable method.

When the foam composite of the present invention is obtained by directly laminating the temporary fixing layer, the primer layer, the base layer, and the silicone adhesive layer as shown in fig. 1, examples of the production method include the following methods: the silicone resin composition is thermally cured by applying a silicone resin composition comprising a thermosetting silicone resin and water to the surface of the primer, placing a separator on the surface opposite to the applied silicone resin composition, and then heating and drying the separator, thereby forming a silicone foamed layer.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples at all. The test and evaluation methods in examples and the like are as follows. In the case of "part(s)", unless otherwise specified, "part(s) by mass" means "part(s)" and in the case of "%" means "% by mass" means "part(s) by mass" means "unless otherwise specified.

< measurement of thickness >

An object to be measured (for example, an adsorption temporary fixing sheet) is placed on a glass plate (Micro Slide glass S, manufactured by songbais industries) with high accuracy and with an objective lens set at 10 times by a 3D measuring laser microscope (LEXT OLS4000, manufactured by olympus), and a 3D image from the surface of the glass plate to the uppermost portion of the object to be measured is measured and the height thereof is taken as the thickness.

< measurement of apparent Density >

The object to be measured was punched out with a 50mm × 50mm punching die, and the volume of the object to be measured was calculated from the values of the thickness using the values of the above < measurement of thickness >.

Next, the mass of the object to be measured is measured by a balance with a minimum scale of 0.01g or more. From these values, the apparent density (g/cm) of the object to be measured was calculated³)。

< measurement of arithmetic average surface roughness Ra >

The 3D image was measured with a 3D measuring laser microscope (LEXT OLS4000, product of olympus) at a high accuracy and with an objective lens at a magnification of 10, and the arithmetic average roughness Ra was determined according to JIS B0601 (1994).

< measurement of dimensional Change ratio >

(rate of change in dimension in MD)

The temporary fixing composite was cut into 100mm × 100mm, and the adhesive layer located at the outermost layer (obtained by peeling the separator when attached) was attached to a SUS403BA plate as a measurement sample. Thereafter, the second decimal place was measured at 3 points in the longitudinal direction (the length in the width direction of the positions of both end portions and the central portion) using a vernier caliper, and the average value was obtained.

Next, the measurement sample was subjected to 1 reflow process through a thermal history as shown in fig. 2, and then left to stand at 23℃ × 50% RH for 1 hour, and then measured to the second decimal place with a vernier caliper at the same position measured before reflow, and the average value thereof was obtained.

The dimension change rate in the MD direction is calculated by the following equation.

Dimension change rate (%) in MD ═ length in MD (mm) before reflow process [ ("length in MD (mm) before reflow process) —" length in MD (mm) after standing for 1 hour at temperature 23℃ × humidity 50% RH after reflow process ]/("length in MD (mm) before reflow process) ] × 100 (%)

The case where the dimensional change rate in the MD direction was 0.3% or less was indicated as "o", and the case where the dimensional change rate was 0.3% or more was indicated as "x".

(rate of change in dimension in TD direction)

The temporary fixing composite was cut into 100mm × 100mm, and the adhesive layer located at the outermost layer was attached to a SUS403BA board as a measurement sample. Thereafter, the second decimal place was measured at 3 points in the width direction (the length in the width direction of the position of both end portions and the central portion) using a vernier caliper, and the average value was obtained.

The dimension change rate in the TD direction is calculated by the following formula.

Dimension change rate (%) in TD direction [ (% TD direction length (mm) before reflow process) -TD direction length (mm) after standing for 1 hour at temperature 23℃ × humidity 50% RH after reflow process ]/TD direction length (mm) before reflow process ] × 100 (%)

The case where the dimensional change rate in the TD direction was 0.3% or less was designated as "o", and the case where the dimensional change rate was 0.3% or more was designated as "x".

< measurement of anchoring force >

On the surface of the temporary fixing layer (obtained by peeling off the separator when the separator is attached) located at the outermost layer of the temporary fixing composite, the silicone adhesive side in the laminate of silicone adhesive (SH4280, manufactured by Dow-Toray, peroxide crosslinking)/PET substrate (25 μm) was pressure-bonded by reciprocating 1 time with a 2kg roller, and then cut into a width of 20 mm. After aging for 30 minutes, the fracture morphology at the time of peeling under the conditions of a stretching angle of 90 degrees and a peeling rate of 150 mm/min was evaluated.

The case of a failure mode in which the temporary securing layer was cohesively broken and a failure mode in which the temporary securing layer was not cohesively broken and the load at the time of interfacial failure between the temporary securing layer and the silicone-based adhesive of the laminate was 2N/20mm or more was described as ∘. The failure mode in which the temporary securing layer was not cohesively broken but the load at the time of interfacial failure between the temporary securing layer and the silicone-based pressure-sensitive adhesive layer of the laminate was less than 2N/20mm was represented by x.

[ production example 1 ]: production of silicone rubber layer (1)

An addition reaction type silicone adhesive (SD4592, SRX-212, manufactured by Dow-Toray Co., Ltd.) was diluted with n-heptane to a solid content concentration of 0.3%, and formed on one surface of the glass epoxy substrate so that the dry thickness became 1 μm. On the opposite side, a silicone adhesive layer made of a peroxide-curable silicone adhesive (SH4280, manufactured by Dow-Toray) was formed, and a PET separator subjected to a fluorinated silicone treatment was attached to the adhesive layer. Subsequently, a thermosetting silicone resin (RBL-9200, manufactured by Dow-Toray) was applied to the surface of the primer, a PET film (Lumirror, 38 μm thick, manufactured by Toray) was attached to the surface of the applied silicone resin composition, the silicone resin composition was thermally cured, and the PET film was peeled off, and the resultant was dried by heating, thereby producing the silicone rubber layer (1).

[ production example 2 ]: production of Silicone foam layer (1)

Using あわとり tera (THINKY MIXER) (manufactured by THINKY corporation), the following were emulsified for 15 minutes, and then the emulsion was dried under reduced pressure at room temperature for 5 minutes to be defoamed, to obtain a resin composition: 83.45 masses of dimethylpolysiloxane having a vinyl group content of 0.28 mass%(ii) Methylhydrogenpolysiloxane 6.40 parts by mass (the amount of the silicon atom-bonded hydrogen atoms in the methylhydrogenpolysiloxane was 5 mol per 1 mol of vinyl groups in the dimethylpolysiloxane), smectite clay (aqueous additive, organic polymer composite purified bentonite, manufactured by HOJUN Co., Ltd.) 0.85 part by mass, ion-exchanged water 99.16 parts by mass, BET specific surface area of 225 m/g, surface-treated with hexamethyldisilazane²6.50 parts by mass of fumed silica, 2.40 parts by mass of India red pigment (trade name: Bayferrox, manufactured by Bayer Co.), 0.98 parts by mass of nonionic surfactant (sorbitan fatty acid ester, trade name: RHEODOL SP-O10V, manufactured by King of HLB4.3), 0.045 parts by mass of nonionic surfactant (sorbitan fatty acid ester, trade name: RHEODOL SP-O30V, manufactured by King of HLB1.8), 0.02 parts by mass of 1-ethynyl-1-cyclohexanol, and 0.22 parts by mass of 1, 3-divinyltetramethyldisiloxane solution of 1, 3-divinyltetramethyldisiloxane complex of platinum (platinum metal content: about 4000 ppm).

The obtained resin composition was coated on a fluorosilicone-treated PET film (NIPPER SHEET PET38x1-SS4A, manufactured by NIPPER Co., Ltd.) using an applicator, and the PET film (Lumiror S10, manufactured by Toray Co., Ltd.) was covered from above, and heated in a hot air oven at 85 ℃ for 6 minutes to cure the resin composition. After curing, the PET film was peeled off, and further heated and dried at 200 ℃ for 3 minutes to give a sheet having an apparent density of 0.5g/cm³And a silicone-based foam layer (1) having a thickness of 0.2 mm.

[ example 1 ]: temporary fixed complex (1)

A temporary fixed composite (1) was obtained, which was a laminate of a silicone adhesive layer (thickness: 50 μm) formed from a silicone rubber layer (1) (thickness: 0.2 μm)/a silicone primer layer (1) (thickness: 1 μm)/a glass epoxy substrate layer (manufactured by richhang industries, BG3520, thickness: 100 μm)/a peroxide-curable silicone adhesive (SH4280, manufactured by Dow-Toray).

The results are shown in Table 1.

[ example 2 ]: temporary fixed complex (2)

A temporary fixed composite (2) was obtained in the same manner as in example 1 except that the outermost silicone adhesive layer was replaced with a silicone adhesive layer (thickness: 75 μm) formed from an addition reaction type silicone adhesive (SD4592, manufactured by Dow-Toray), and a laminate of a silicone adhesive layer (thickness: 50 μm) formed from a silicone rubber layer (1) (thickness: 0.2 μm)/a silicone undercoat layer (1) (thickness: 1 μm)/a glass epoxy substrate layer (manufactured by richhang industries, BG3520, thickness: 100 μm)/an addition reaction type silicone adhesive (SD4592, manufactured by Dow-Toray) was obtained.

The results are shown in Table 1.

[ example 3 ]: temporary fixed complex (3)

A temporary fixation composite (3) which is a laminate of silicone adhesive layers (thickness: 50 μm) formed of a silicone foamed layer (1) (thickness: 0.2 μm)/a silicone primer layer (1) (thickness: 1 μm)/a polyimide substrate layer (Dupont-Toray, KAPTON 300H, thickness: 75 μm)/a peroxide-curable silicone adhesive (SH4280, Dow-Toray) was obtained in the same manner as in example 1 except that the silicone rubber layer (1) was replaced with the silicone foamed layer (1) and the glass epoxy base material layer was replaced with a polyimide substrate layer (thickness: 75 μm).

The results are shown in Table 1.

[ example 4 ]: temporary fixed complex (4)

A temporary fixed composite (4) was obtained in the same manner as in example 3, except that the outermost silicone adhesive layer was replaced with a silicone adhesive layer (thickness: 50 μm) formed from an addition reaction type silicone adhesive (SD4592, manufactured by Dow-Toray), and a laminate of silicone adhesive layers (thickness: 50 μm) formed from a silicone foamed layer (1) (thickness: 0.2 μm)/a silicone undercoat layer (1) (thickness: 1 μm)/a polyimide base layer (manufactured by Dupont-Toray, KAPTON 300H, thickness: 75 μm)/an addition reaction type silicone adhesive (SD4592, manufactured by Dow-Toray) was obtained.

The results are shown in Table 1.

[ comparative example 1 ]: temporary fixed complex (C1)

A temporary fixed composite (C1) which was a laminate of silicone adhesive layers (thickness: 50 μm) formed from silicone rubber layer (1) (thickness: 0.2 μm)/glass epoxy substrate layer (manufactured by litha industries, BG3520, thickness: 100 μm)/peroxide-curable silicone adhesive (SH4280, manufactured by Dow-Toray) was obtained in the same manner as in example 1, except that silicone primer layer (1) was not provided.

The results are shown in Table 1.

[ comparative example 2 ]: temporary fixed complex (C2)

A temporary fixed composite (C2) which was a laminate of a silicone adhesive layer (thickness: 50 μm) formed from a silicone rubber layer (1) (thickness: 0.2 μm)/a glass epoxy substrate layer (manufactured by litha industries, BG3520, thickness: 100 μm)/an addition reaction type silicone adhesive (SD4592, manufactured by Dow-Toray) was obtained in the same manner as in example 2, except that the silicone primer layer (1) was not provided.

The results are shown in Table 1.

[ comparative example 3 ]: temporary fixed complex (C3)

A temporary fixed composite (C3) which was a laminate of silicone-based pressure-sensitive adhesive layers (thickness 50 μm) formed from a silicone-based foamed layer (1) (thickness 0.2 μm)/polyimide substrate layer (Dupont-Toray, KAPTON 300H, thickness 75 μm)/peroxide-curable silicone-based pressure-sensitive adhesive (SH4280, Dow-Toray) was obtained in the same manner as in example 3, except that the silicone undercoat layer (1) was not provided.

The results are shown in Table 1.

[ comparative example 4 ]: temporary fixed complex (C4)

A temporary fixed composite (C4) which was a laminate of a silicone adhesive layer (thickness: 50 μm) formed from a silicone foamed layer (1) (thickness: 0.2 μm)/a polyimide base material layer (Dupont-Toray, KAPTON 300H, thickness: 75 μm)/an addition reaction type silicone adhesive (SD4592, Dow-Toray) was obtained in the same manner as in example 4, except that the silicone undercoat layer (1) was not provided.

The results are shown in Table 1.

[ Table 1]

Industrial applicability

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

Claims

1. A temporary fixing composite comprising a temporary fixing layer, a base material layer and a silicone adhesive layer formed of a silicone adhesive,

the temporary fixing layer is a foaming layer or a rubber layer,

2. A temporary fixation composite as claimed in claim 1, wherein the primer layer has a thickness of 0.01 to 5 μm.

3. A temporary fixation composite as claimed in claim 2, wherein the primer layer has a thickness of 0.1 to 3 μm.

4. The temporary fixing composite according to claim 1, wherein the primer constituting the primer layer is a silicone-based primer.

5. The temporary fixation composite according to claim 4, wherein the silicone-based primer is a peroxide-crosslinking silicone-based adhesive.

6. The temporary fixation composite as claimed in claim 4, wherein the silicone-based primer is an addition reaction type silicone-based adhesive.

7. A temporary fixation composite as claimed in claim 1, wherein the temporary fixation layer is a foamed layer.

8. A temporary fixation composite as claimed in claim 7, wherein the foamed layer is a foamed layer having an open cell structure.

9. A temporary fixing composite according to claim 8, wherein the foam layer has an open cell ratio of 90% or more.

10. The temporary fixing composite according to claim 7, wherein the average cell diameter of the foamed layer is 1 to 200 μm.

11. The temporary fixing composite according to claim 7, wherein 90% or more of all cells of the foamed layer have a cell diameter of 300 μm or less.

12. A temporary fixation composite as claimed in claim 7, wherein the foam layer has surface openings.

13. A temporary fixing composite according to claim 12, wherein the aperture ratio of the surface opening portion is 1% to 99%.

14. A temporary fixation composite as claimed in claim 12, wherein the surface openings have an average pore size of 150 μm or less.

15. The temporary fixation composite of claim 7, wherein the foamed layer has an apparent density of 0.15g/cm³～0.90g/cm³。

16. The temporary fixing composite according to claim 7, wherein the arithmetic average surface roughness Ra of the surface of the foam layer is 0.1 to 10 μm.

17. A temporary fixation composite as claimed in claim 7, wherein a separator is attached to the surface of the foam layer.

18. A temporary fixing composite according to claim 17, wherein an arithmetic average surface roughness Ra of the surface of the separator is 0.1 μm to 5 μm.

19. A temporary fixation composite as claimed in claim 1, wherein the temporary fixation layer is a silicone-based foam layer.

20. The temporary fixation composite according to claim 1, wherein the thickness of the silicone-based adhesive layer is 1 μm to 100 μm.

21. A temporary fixation composite as claimed in claim 20, wherein the silicone-based adhesive layer has a thickness of 5 μm to 90 μm.

22. A temporary fixation composite as claimed in claim 21, wherein the silicone-based adhesive layer has a thickness of 8 to 80 μm.