WO2015079904A1 - Adhesive sheet for temporarily fixing electronic component, and method for using adhesive sheet for temporarily fixing electronic component - Google Patents

Abstract

Provided is an adhesive sheet for temporary fixing use, which cannot come off or cannot be detached even when an electronic material on a thin film is fixed temporarily onto a hard substrate using the adhesive tape and then the resultant product is subjected to an etching treatment or the like in an electronic component production process. An adhesive sheet for temporarily fixing an electronic component, which comprises a base material and an adhesive agent layer formed from a cured product of an adhesive agent composition and provided on both surfaces or one surface of the base material, said adhesive sheet being characterized in that the adhesive agent composition comprises at least a component (A) that is a silyl-terminal polymer, a component (B) that is a silane coupling agent and a component (C) that is a curing catalyst, the component (A), i.e., the silyl-terminal polymer, has a specific structure, and a component (D) that is an adhesiveness-imparting resin may be additionally contained or may not be contained in the adhesive agent composition wherein the amount of the component (D), i.e., the adhesiveness-imparting resin, is less than 10 parts by weight relative to 100 parts by weight of the component (A), i.e., the silyl-terminal polymer, when the component (D) is contained.

Description

Method of using adhesive sheet for temporarily fixing electronic parts and adhesive sheet for temporarily fixing electronic parts

The present invention relates to an adhesive sheet for temporarily fixing an electronic component and a method for using the adhesive sheet for temporarily fixing an electronic component. In particular, it is a pressure-sensitive adhesive sheet for temporarily fixing thin-film electronic components on glass, etc., and it floats even when exposed to high temperatures due to immersion or drying with a solvent in the etching process. TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive sheet for temporarily fixing electronic components and a method for using such a pressure-sensitive adhesive sheet for temporarily fixing electronic components.

Conventionally, when a pattern is formed on a thin film substrate such as a flexible printed circuit (FPC) or an organic thin film transistor, a double-sided adhesive tape is usually used to temporarily fix the electronic component of the thin film on a hard body such as glass. Has been.
Here, such double-sided adhesive tape is required to have a sufficient adhesive strength so that the electronic components of the thin film are not displaced by each processing process such as circuit formation, etching process, and drying process, as well as etching process and drying process. It is required that the double-sided pressure-sensitive adhesive tape does not float off due to the processing solvent or heat.

Furthermore, in the etching process etc., among the two pressure-sensitive adhesive layers through the base material in the double-sided pressure-sensitive adhesive tape, foaming and floating are particularly likely to occur from the pressure-sensitive adhesive layer on the side in contact with the hard body such as glass. Since there is a problem, the solvent resistance and heat resistance of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer on the surface are strongly required.

Thus, for example, an adhesive sheet for fixing a thin film substrate that can form a pattern without misalignment and can be fixed without air bubbles or distortion without pre-drying the double-sided tape has been proposed (for example, Patent Document 1).
That is, Patent Document 1 is an adhesive sheet for fixing a thin film substrate used for pattern formation on a thin film substrate, and has a porous substrate having a predetermined porosity and a predetermined pore diameter. An adhesive sheet for fixing is disclosed.

In addition, a double-sided pressure-sensitive adhesive sheet for fixing a flexible printed circuit board has been proposed (see, for example, Patent Document 2) having a characteristic that does not cause floating from an adherend during processing after sticking.
That is, Patent Document 2 discloses a double-sided pressure-sensitive adhesive sheet for fixing a flexible printed circuit board having a pressure-sensitive adhesive layer made of a predetermined acrylic polymer on both sides of a plastic film substrate having a predetermined thickness.

In addition, an adhesive tape has been proposed that, when peeled after being applied to an adherent, does not leave any adhesive residue on the adherent, maintains a good adhesive force even after peeling, and can be applied again (for example, a patent) Reference 3).
That is, Patent Document 3 discloses that 100 parts by mass of a terminal silyl group polymer having a urethane bond and / or a urea bond in the main chain or side chain and containing a hydrolyzable silyl group represented by the following general formula (A) at the terminal. And a pressure-sensitive adhesive precursor in which less than 10 parts by mass of a tackifying resin and 0.01 to 10 parts by mass of a curing catalyst for a terminal silyl group polymer are uniformly mixed are applied to the surface of a tape substrate or sheet substrate. A pressure-sensitive adhesive sheet is disclosed in which the pressure-sensitive adhesive precursor is used as a pressure-sensitive adhesive layer by curing the terminal silyl group polymer.

(In the general formula (A), X represents a hydroxy group or an alkoxy group, R represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.)

JP 2012-84324 A (Claims) JP 2010-68447 A (Claims) JP 2011-6630 A (Claims)

However, although the adhesive sheet for fixing a thin film substrate described in Patent Document 1 prevents air bubbles between the thin film substrate and the adhesive sheet, a special porous base material must be used. There was a problem of disadvantage.
Furthermore, with regard to heat resistance, although there is an effect that no floating is observed during heating, the pressure-sensitive adhesive layer is not defined at all, and no consideration is given to the resistance to the solvent used in the etching process. Therefore, there has been a problem that it is difficult to suppress the flaking off that occurs during the etching process.

Moreover, since the double-sided pressure-sensitive adhesive sheet for fixing a flexible printed circuit board described in Patent Document 2 defines the thickness of a base material and uses a predetermined acrylic pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, Although it was possible to prevent the float from being to some extent, there was still a problem that the solvent resistance and heat resistance were still insufficient in the etching process.

On the other hand, although the pressure-sensitive adhesive tape or sheet described in Patent Document 3 shows high removability, it does not take into account the resistance to the solvent used in the etching process or the heat resistance. There was a problem that it was difficult to suppress the flaking off that occurred.

Accordingly, the present inventors made extensive efforts in view of the circumstances as described above. As a result, the predetermined terminal silyl group polymer contains a predetermined silane coupling agent and a predetermined curing catalyst, and includes a tackifier resin. Even when the circuit formation of the thin film substrate and the etching process are performed by setting the amount to 0 or a small amount, the hard substrate such as glass and the thin film substrate are securely bonded to each other and the etching process is performed. The present invention has been completed by finding that it is possible to prevent floating-off due to foaming derived from the pressure-sensitive adhesive layer and to prevent positional displacement.
That is, an object of the present invention is to provide a temporary adhesive for an electronic component in which the pressure-sensitive adhesive layer has a predetermined adhesive strength and has excellent solvent resistance during etching and good heat resistance during drying. It is in providing the usage method of the adhesive sheet for fixing, and the adhesive sheet for temporary fixing of such an electronic component.

According to the present invention, there is provided a pressure-sensitive adhesive sheet for temporarily fixing an electronic component having a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on both sides or one side of a substrate, wherein the pressure-sensitive adhesive composition is at least (A ) A terminal silyl group polymer as a component, a silane coupling agent as a component (B), and a curing catalyst as a component (C). The chain has a polyoxyalkylene structure, a part of the main chain or a side chain has a urethane bond and / or a urea bond, and at both ends of the main chain, the following general formula (1) In the case of having a hydrolyzable silyl group represented by the formula (D) and including a tackifier resin as the component (D), the terminal silyl group polymer as the component (A) 10 parts per 100 parts by weight A value of less than parts, or be free of tackifying resin, for temporary fixing adhesive sheet of the electronic component, wherein is provided a, it is possible to solve the problems described above.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)

That is, in the case of the pressure-sensitive adhesive sheet for temporarily fixing an electronic component of the present invention, the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer contains a predetermined terminal silyl group polymer as a main agent, a predetermined silane coupling agent, and a predetermined curing. Since it contains a catalyst, it is possible to obtain resistance to solvents and heat resistance while exhibiting appropriate tackiness even when a small amount of tackifier resin is contained or not contained due to these interactions. .
Therefore, it has solvent resistance and heat resistance while properly bonding a hard body such as glass and a thin film substrate, etc., so that foaming and floating derived from the pressure-sensitive adhesive layer can be prevented during circuit formation and etching processing of the thin film substrate. It can be effectively prevented.
Moreover, since the terminal silyl group polymer as the component (A) has a polyoxyalkylene structure in the main chain, it is possible to impart appropriate flexibility to the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer to be obtained. .
Moreover, since it has the hydrolyzable silyl group represented by General formula (1) in the both ends of a principal chain, the crosslinking density of (A) components is adjusted to the suitable range, and in the adhesive composition after hardening The balance between adhesive force and cohesive force can be made favorable.

Further, in constituting the temporary fixing pressure-sensitive adhesive sheet of the present invention, the electronic component is a film made of at least one selected from polyethylene naphthalate, polyimide, polycarbonate, and polyethylene terephthalate, or a copper-clad polyimide laminate. It is preferable.
With such a configuration, even when the electronic component is fixed to a hard glass or the like and subjected to an etching process or the like, the electronic component can be fixed without causing positional displacement.

In constituting the temporary fixing pressure-sensitive adhesive sheet of the electronic component of the present invention, the weight average molecular weight of the terminal silyl group polymer as the component (A) is preferably set to a value within the range of 15,000 to 200,000. .
By comprising in this way, the crosslinking density of (A) component is adjusted to the suitable range, and the balance between the adhesive force and cohesion force in an adhesive composition can be adjusted to a more suitable range. it can.

Moreover, in constituting the temporary fixing pressure-sensitive adhesive sheet of the electronic component of the present invention, the blending amount of the silane coupling agent as the component (B) is 100 parts by weight of the terminal silyl group polymer as the component (A). A value within the range of 0.1 to 10 parts by weight is preferred.
By comprising in this way, hardening of an adhesive composition can be accelerated | stimulated effectively.

Moreover, in constituting the temporary fixing pressure-sensitive adhesive sheet of the electronic component of the present invention, the amount of the curing catalyst as the component (C) is set to 0. A value within the range of 001 to 10 parts by weight is preferred.
By comprising in this way, control of the crosslinking density of (A) component becomes easy, and adjustment of the balance between the adhesive force and cohesion force in the adhesive composition after hardening is made easier further. Can do.

Further, in constituting the temporary fixing pressure-sensitive adhesive sheet of the electronic component of the present invention, when the tackifier resin is included as the component (D), the tackifier resin is a rosin resin, a terpene phenol resin, and a rosin phenol resin. It is preferable that it is at least one of these.
Thus, by comprising, even if it is a case where a small amount of tackifying resin is contained, the foaming and the float which generate | occur | produce from an adhesive layer can be effectively prevented by an etching process etc.

Another aspect of the present invention is a method for using a pressure-sensitive adhesive sheet for temporarily fixing an electronic component provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on both sides or one side of a base material, which comprises the following steps: (1) to (6). A method of using a pressure-sensitive adhesive sheet for temporarily fixing an electronic component.
(1) The terminal silyl group polymer as the component (A), the silane coupling agent as the component (B), and the curing catalyst as the component (C), and the terminal as the component (A) The silyl group polymer has a polyoxyalkylene structure in the main chain, a urethane bond and / or a urea bond in a part of the main chain or a side chain, or one of them, and at both ends of the main chain, When having a hydrolyzable silyl group represented by the following general formula (1) and including a tackifier resin as the component (D), the blending amount of the tackifier resin is changed to the component (A). Step (2) of preparing a pressure-sensitive adhesive composition containing less than 10 parts by weight or 100% by weight of the terminal silyl group polymer, or including no tackifying resin. Or the process of laminating on one side 3) Step of curing the pressure-sensitive adhesive composition to obtain a pressure-sensitive adhesive sheet for temporarily fixing an electronic component provided with a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition (4) Adhesion of the pressure-sensitive adhesive sheet for temporarily fixing an electronic component The step of placing the electronic component on at least one surface of the adhesive layer (5) The step of performing an etching process on the electronic component (6) The electronic component subjected to the etching process is detached from the surface of the adhesive layer Process

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)

By using in this way, a hard body such as glass and an electronic component can be securely bonded, and foaming and floating derived from the pressure-sensitive adhesive layer can be effectively prevented even after the etching process. .
Therefore, high reliability can be obtained as an adhesive sheet for temporarily fixing electronic components.

In using the temporary fixing pressure-sensitive adhesive sheet of the electronic component of the present invention, between the step (3) and the step (4), (3 ′) the prepared temporary fixing pressure-sensitive adhesive sheet is made of a glass substrate, a metal substrate, Or it is preferable to further include the process of laminating | stacking on the hard board | substrate containing a polycarbonate board | substrate.
By using in this way, high reliability can be obtained for the production of various thin film substrates such as FPC.

FIGS. 1 (a) to 1 (b) are diagrams for explaining the terminal silyl group polymer. FIGS. 2A to 2B are views for explaining the usage mode of the temporary fixing pressure-sensitive adhesive sheet, respectively. 3 (a) to 3 (d) are diagrams provided for explaining a method of manufacturing and a method of using the temporary fixing pressure-sensitive adhesive sheet, respectively. 4 (a) to 4 (b) are diagrams provided for explaining a method of using the temporary fixing pressure-sensitive adhesive sheet, respectively.

[First Embodiment]
An embodiment of the present invention is a pressure-sensitive adhesive sheet for temporarily fixing an electronic component provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on both sides or one side of a substrate, and the pressure-sensitive adhesive composition is at least ( A) a terminal silyl group polymer as a component, a silane coupling agent as a component (B), and a curing catalyst as a component (C), and a terminal silyl group polymer as the component (A) The main chain has a polyoxyalkylene structure, a part of the main chain or a side chain has a urethane bond and / or a urea bond, and at both ends of the main chain, the following general formula (1 ) And a tackifying resin as the component (D), the blending amount of the tackifying resin is changed to the terminal silyl group as the component (A). 10 parts per 100 parts by weight of polymer A value less than the amount unit, or be free of tackifying resin is a temporary fixing pressure-sensitive adhesive sheet for electronic parts characterized by.
Hereinafter, the temporary fixing pressure-sensitive adhesive sheet according to the first embodiment of the present invention will be specifically described with reference to the drawings as appropriate.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)

1. Adhesive Layer The temporary fixing pressure-sensitive adhesive sheet of the present invention comprises a predetermined terminal silyl group polymer as component (A), a silane coupling agent as component (B), and a curing catalyst as component (C). It consists of the predetermined | prescribed adhesive composition containing.
Hereinafter, this adhesive composition is demonstrated for every component.

(1) Component (A): Terminal silyl group polymer (1) -1 type The terminal silyl group polymer as component (A) has a urethane bond and / or a urea bond in the main chain or side chain, It has the hydrolyzable silyl group represented by the general formula (1) described above at both ends of the main chain.

The reason for this is that the component (A) has a bifunctional hydrolyzable terminal silyl group represented by the general formula (1), and is therefore effective by hydrolytic dehydration condensation between the components (A). This is because a three-dimensional network structure can be formed.
Moreover, if it is such (A) component, since it has the bifunctional hydrolyzable terminal silyl group represented by General formula (1), in the adhesive composition after hardening, it is with respect to a to-be-adhered body. This is because sufficient adhesive strength can be exhibited.
Therefore, even if the amount of the tackifier is small, or even when it does not contain the tackifier, the pressure-sensitive adhesive layer is hardly deformed due to the high cohesive force of the pressure-sensitive adhesive composition. Swelling due to the generation of gas from the pressure-sensitive adhesive or adherend surface can be effectively prevented.
That is, by using a predetermined terminal silyl group polymer as the component (A), it is possible to obtain a pressure-sensitive adhesive composition excellent in adhesion between an electronic component and a hard body, and excellent in solvent resistance and heat resistance. it can.
In general formula (1), the number of carbon atoms of the alkyl group represented by R is more preferably 1 to 12 and even more preferably 1 to 3 from the viewpoint of hydrolytic dehydration condensation reactivity.
In the general formula (1), when X ¹ or X ² is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 12 from the viewpoint of hydrolytic dehydration condensation reactivity. 3 is more preferable.

(I) Basic Configuration Next, the basic configuration of the predetermined terminal silyl group polymer as the component (A) will be described.
That is, the terminal silyl group polymer is composed of a predetermined end portion and a predetermined skeleton portion.
In addition, the urethane prepolymer (diisocyanate compound) represented by the formula (1) and the halogenated silyl group represented by the formula (2) shown in FIG. A specific method for synthesizing the terminal silyl group polymer will be described in the second embodiment.

(Ii) Terminal part First, the specific structure of the terminal part in the terminal silyl group polymer represented by the formula (3) in FIG. 1A is represented by the following general formulas (2) to (8) (terminal part-A). To G).

(In the general formula (2), R ² and R ³ are alkyl groups having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and R, X ¹ and X ² are the same as those in the general formula (1) The same applies to the following general formulas (3) to (8).)

(In the general formula (8), X ³ represents an alkylene group, and X ⁴ represents an organic group having 1 to 20 carbon atoms.)

That is, when the terminal silyl group polymer has such a terminal portion, a cross-linking reaction by dehydration condensation as shown in FIG. 1B is caused and adhesion to the adherend is further strengthened. be able to.

(Iii) Skeletal portion The skeleton of the main chain or side chain (not shown) of the terminal silyl group polymer represented by the formula (3) in FIG. 1A is polyoxyalkylene. To do.
The reason for this is that if it is polyoxyalkylene, an appropriate flexibility can be imparted to the resulting pressure-sensitive adhesive composition, and adhesion to an adherend can be improved.
Specific examples of such polyoxyalkylene include polyoxypropylene and polyoxyethylene.

(Iv) Position of hydrolyzable silyl group The predetermined terminal silyl group polymer as component (A) is hydrolyzable represented by the general formula (1) in the side chain as shown in FIG. It is characterized by being a both-end silyl group polymer having no hydrolyzable silyl group represented by the general formula (1) only at both ends of the main chain, having no silyl group.
The reason for this is that with such a terminal silyl group polymer, the crosslink density between the components (A) is adjusted to a suitable range, and the balance between the adhesive force and the cohesive force in the adhesive composition after curing is adjusted. This is because it can be made easier.

Further, as the component (A ′), the polymer further contains a one-terminal silyl group polymer having a hydrolyzable silyl group represented by the general formula (1) only at one end of the main chain, The value is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.
The reason for this is that the cross-linking density between the components (A) is adjusted to a more suitable range by mixing the one-end silyl group polymer within a predetermined range with respect to the both-end silyl group polymer, and the pressure-sensitive adhesive after curing This is because it is possible to further easily adjust the balance between the adhesive force and the cohesive force in the composition.
That is, if the blending amount of the one-terminal silyl group polymer is less than 0.1 part by weight, the effect of addition may not be sufficiently obtained. On the other hand, when the blending amount of the one-terminal silyl group polymer exceeds 30 parts by weight, the crosslinking density between the components (A) may be excessively decreased, and it may be difficult to obtain a predetermined gel fraction. Because there is.
Therefore, the blending amount of the one-terminal silyl group polymer is more preferably within a range of 0.5 to 10 parts by weight with respect to 100 parts by weight of both terminal silyl group polymers. More preferably, the value is within the range.
However, since it has been confirmed that a pressure-sensitive adhesive composition having excellent adhesive force can be obtained even when only the both-end silyl group polymer is used, if not particularly required, a one-end silyl group polymer is used. It is also preferable to use only the terminal silyl group polymer without mixing from the viewpoint of simplification of the production process.

(1) -2 Weight average molecular weight The weight average molecular weight of the predetermined terminal silyl group polymer as the component (A) is preferably set to a value within the range of 15,000 to 200,000.
The reason for this is that when the weight average molecular weight is less than 15,000, the molecular structure becomes dense and sufficient adhesion cannot be obtained, the viscosity becomes too low, and the workability is poor when forming a sheet by solution coating. This is because there may be cases. On the other hand, when the weight average molecular weight exceeds 200,000, a decrease in processability due to an increase in viscosity or the like becomes remarkable, or a crosslinking density decreases excessively, and a balance between adhesive force and cohesive force. This is because it may be difficult to adjust the value.
Accordingly, it is more preferable that the weight average molecular weight of the predetermined terminal silyl group polymer as the component (A) is a value within the range of 20,000 to 150,000, and a value within the range of 30,000 to 100,000. More preferably.
In addition, the weight average molecular weight of the terminal silyl group polymer which is (A) component can be measured using well-known molecular weight measuring apparatuses, such as a gel permeation chromatography (GPC).
In addition, when mix | blending (A ') component mentioned above, it can be made to be the same as that of (A) component also about the weight average molecular weight of (A') component.

(1) -3 Blending amount The blending amount of the predetermined terminal silyl group polymer as component (A) should be 70% by weight or more with respect to 100% by weight of the total amount of the pressure-sensitive adhesive composition before curing. Is preferred.
The reason for this is that when the blending amount is less than 70% by weight, the absolute amount of the component (A) with respect to the entire pressure-sensitive adhesive composition becomes excessively small, and it may be difficult to obtain sufficient adhesive force. It is.
Therefore, the blending amount of the predetermined terminal silyl group polymer as the component (A) is more preferably 90% by weight or more with respect to 100% by weight of the total amount of the pressure-sensitive adhesive composition before curing, and 95% by weight. More preferably, the above is used.

(2) Component (B): Silane Coupling Agent (2) -1 Type The pressure-sensitive adhesive composition is characterized by containing a silane coupling agent as component (B).
And it is preferable that the said silane coupling agent is a silane coupling agent which has an amino group.
The reason for this is that by blending a silane coupling agent having an amino group in such a range, the effect of the predetermined terminal silyl group polymer as a crosslinking aid is exhibited, and the cohesive force of the pressure-sensitive adhesive composition is more suitable. This is because the range can be adjusted.

Examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like are preferably used.

(2) -2 Blending amount The blending amount of the silane coupling agent as the component (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). It is preferable to set the value within the range.
The reason for this is that by blending the silane coupling agent in such a range, the effect of the predetermined terminal silyl group polymer as a crosslinking aid is exhibited, and the cohesive force of the pressure-sensitive adhesive composition is adjusted to a more suitable range. Because it can.
Therefore, the blending amount of the silane coupling agent as the component (B) is set to a value within the range of 0.2 to 3 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). More preferred is a value in the range of 0.3 to 1 part by weight.

(3) Component (C): Curing Catalyst (3) -1 Type In addition, the pressure-sensitive adhesive composition, as component (C), cures for promoting the curing of the predetermined terminal silyl group polymer as component (A) In addition to containing a catalyst, the curing catalyst is preferably at least one selected from the group consisting of an aluminum-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, and a boron trifluoride-based catalyst.
The reason for this is that if these catalysts are used, the crosslinking density between the components (A) can be easily controlled, and the balance between the adhesive force and the cohesive force in the adhesive composition after curing is further facilitated. Because it can.

As the aluminum-based catalyst, aluminum alkoxide, aluminum chelate, and aluminum (III) chloride are preferable. As the titanium-based catalyst, titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferable. As the zirconium-based catalyst, Zirconium alkoxides, zirconium chelates, and zirconium (IV) chloride are preferable. As the boron trifluoride-based catalyst, an amine complex or an alcohol complex of boron trifluoride is particularly preferably used.

(3) -2 Blending amount The blending amount of the curing catalyst as the component (C) is in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). It is preferable to set the value within the range.
The reason for this is that when the amount is less than 0.001 part by weight, the catalytic action becomes insufficient and the cohesive force of the pressure-sensitive adhesive composition may be excessively reduced. On the other hand, when the blending amount exceeds 10 parts by weight, the catalytic action becomes excessive, and the pressure-sensitive adhesive composition may be cured before being applied to the substrate.
Therefore, the blending amount of the curing catalyst as the component (C) is set to a value within the range of 0.005 to 5 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). More preferably, the value is in the range of 0.01 to 1 part by weight.

(4) (D) component: Tackifying resin In constituting the temporary fixing pressure-sensitive adhesive sheet of the present invention, when the tackifying resin is included as the (D) component, the blending amount of the tackifying resin is the component (A). The value is less than 10 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer, or does not contain a tackifier resin.
The reason for this is that when the tackifying resin has a value of 10 parts by weight or more, the gas derived from the tackifying resin is likely to be generated from the pressure-sensitive adhesive layer. This is because swelling may occur.
Therefore, when the tackifier resin is included as the component (D), the amount of the tackifier resin is a value within the range of 0 to 1 part by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). (However, 0 is not included), more preferably 0 to 0.01 part by weight (however, 0 is not included).
In addition, even when it does not contain tackifying resin, it has been confirmed that it is possible to form a circuit without causing misalignment by adhering properly to electronic components, and the temporary fixing adhesive sheet is more swollen. This is a more preferable aspect in that it does not occur.
When a tackifier resin is included, the kind of the tackifier resin is preferably at least one of a rosin resin, a terpene phenol resin, and a rosin phenol resin.
This is because such a tackifier resin is unlikely to swell even when added in a small amount to the pressure-sensitive adhesive composition.

(5) Additive In addition, the pressure-sensitive adhesive composition used for the temporary fixing pressure-sensitive adhesive sheet of the present invention includes, for example, an anti-aging agent, a dehydrating agent such as a vinylsilane compound or calcium oxide, a filler, Difficulty such as conductive materials, heat conductive materials, plasticizers, thixotropic agents such as anhydrous silica and amide wax, diluents such as isoparaffin, aluminum hydroxide, halogen flame retardants, phosphorus flame retardants, silicone flame retardants A functional oligomer such as a flame retardant, a silicone alkoxy oligomer, and an acrylic oligomer, a pigment, a titanate coupling agent, an aluminum coupling agent, a drying oil, and the like may be added and mixed.
In addition, when these additives are added, although depending on the type of the additive, it is preferable to add the additives so as not to impair the effects of the present invention. A value within the range of 0.01 to 100 parts by weight is preferable with respect to 100 parts by weight of the silyl group polymer, and a value within a range of 0.01 to 70 parts by weight is preferable. A value within the range of 40 parts by weight is particularly preferred.

(6) Gel fraction In the pressure-sensitive adhesive composition used for the temporary fixing pressure-sensitive adhesive sheet of the present invention, the gel fraction of the pressure-sensitive adhesive layer is preferably set to a value in the range of 30 to 100%.
The reason for this is that by setting the gel fraction of the pressure-sensitive adhesive layer to a value within such a range, an excellent cohesive force can be exhibited, and even when an electronic component is subjected to etching treatment or the like, the pressure-sensitive adhesive This is because floating and peeling originating in the layer can be suppressed.
That is, when the gel fraction of the pressure-sensitive adhesive layer becomes a value of less than 30%, the cohesive force becomes excessively small, and it may be difficult to suppress the peeling from the pressure-sensitive adhesive layer.
Accordingly, the gel fraction of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive composition is more preferably set to a value within the range of 35 to 100%, and further preferably set to a value within the range of 40 to 99%.
The “gel fraction of the pressure-sensitive adhesive layer” means that after the pressure-sensitive adhesive composition is applied to the base material or the release material, seasoning is performed for 14 days in a 23 ° C., 50% RH environment, and then after the seasoning. This means the gel fraction measured by the dipping method using the pressure-sensitive adhesive composition (pressure-sensitive adhesive layer) as a measurement sample.
Moreover, about the specific measuring method of a gel fraction, it describes in an Example.

(7) Thickness The thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is usually preferably a value in the range of 1 to 100 μm, more preferably a value in the range of 5 to 50 μm. preferable.
The reason for this is that when the thickness of the pressure-sensitive adhesive layer is less than 1 μm, sufficient pressure-sensitive adhesive properties may not be obtained, and conversely, when the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the residual solvent increases. This is because the adhesive properties and the like are likely to change.

(8) Aspect Also, as shown in FIG. 2A, it is preferable to laminate adhesive layers 40 and 40 ′ made of a cured product of the above-described predetermined adhesive composition on both surfaces of the substrate 2.
Moreover, as shown in FIG.2 (b), it is also a preferable aspect that the adhesive layer 40 which consists of the hardened | cured material of the above-mentioned predetermined adhesive composition is laminated | stacked only on the single side | surface of the base material 2. FIG.
Here, as shown in FIG. 2B, when the pressure-sensitive adhesive layer 40 made of a cured product of the above-mentioned predetermined pressure-sensitive adhesive composition is laminated only on one side of the base material 2, it is laminated on the other side of the base material. The pressure-sensitive adhesive layer 50 is not particularly limited, but is preferably a silicone-based pressure-sensitive adhesive, a UV curable pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, or the like.
The reason for this is that the adhesive layer, which is a problem when etching a thin film substrate such as an FPC, is lifted and peeled out of the two pressure-sensitive adhesive layers of the temporary fixing pressure-sensitive adhesive sheet, in particular, with a hard body such as glass. This is because it is known to occur from the side of the pressure-sensitive adhesive layer in contact.
Therefore, if at least the pressure-sensitive adhesive layer side is provided with a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition containing the terminal silyl group polymer of the present invention, it is possible to effectively prevent floating.

2. Base Material Further, the temporary fixing pressure-sensitive adhesive sheet of the present invention preferably has pressure-sensitive adhesive layers 40, 40 'on one side or both sides of the base material 2, as shown in FIGS.
Examples of such a substrate include polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polyetherketone, polyetheretherketone, polycarbonate, polymethylmethacrylate, triacetylcellulose, polynorbornene. A resin film made of a resin such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinyl chloride, polyurethane acrylate, polyether sulfone, polyphenyl ether sulfone is preferable. Can be mentioned.
In particular, when the temporary fixing pressure-sensitive adhesive sheet of the present invention is used for circuit formation of an organic transistor or a flexible printed board, the base material is more preferably polyethylene naphthalate or polyimide.

Further, the thickness of the substrate is not particularly limited, but it is usually preferably a value in the range of 1 to 1,000 μm, more preferably a value in the range of 10 to 100 μm. .

3. Release substrate (release film)
Moreover, it is also preferable that the adhesive sheet for temporary fixing of this invention is an aspect by which the peeling base material (peeling film) is bonded with respect to both surfaces of an adhesive layer.
Such an embodiment is required when only the pressure-sensitive adhesive layer has to be transported, for example, because the production of the pressure-sensitive adhesive layer and the use of the pressure-sensitive adhesive layer are performed in different places.
In addition, as such a release substrate, for example, a release agent such as a silicone resin is applied to a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene, and a release layer. Are provided.
In addition, the thickness of the release substrate can usually be a value within the range of 20 to 150 μm.
In addition, by providing a predetermined difference in the peeling force from the pressure-sensitive adhesive layer in the two peeling substrates, the pressure-sensitive adhesive layer partially follows when the peeling substrate having the lower peeling force is peeled off. This can be prevented.

[Second Embodiment]
2nd Embodiment is a usage method of the adhesive sheet for temporary fixing of the electronic component provided with the adhesive layer which consists of a hardened | cured material of an adhesive composition on both surfaces or one side of a base material, Comprising: The following process (1) A method for using a pressure-sensitive adhesive sheet for temporarily fixing electronic parts, comprising: (6) to (6).
(1) The terminal silyl group polymer as the component (A), the silane coupling agent as the component (B), and the curing catalyst as the component (C), and the terminal as the component (A) The silyl group polymer has a polyoxyalkylene structure in the main chain, a urethane bond and / or a urea bond in a part of the main chain or a side chain, or one of them, and at both ends of the main chain, When having a hydrolyzable silyl group represented by the following general formula (1) and including a tackifier resin as the component (D), the blending amount of the tackifier resin is changed to the component (A). Step (2) of preparing a pressure-sensitive adhesive composition containing less than 10 parts by weight or 100% by weight of the terminal silyl group polymer, or including no tackifying resin. Or the process of laminating on one side 3) Step of curing the pressure-sensitive adhesive composition to obtain a pressure-sensitive adhesive sheet for temporarily fixing an electronic component provided with a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition (4) Adhesion of the pressure-sensitive adhesive sheet for temporarily fixing an electronic component The step of placing the electronic component on at least one surface of the adhesive layer (5) The step of performing an etching process on the electronic component (6) The electronic component subjected to the etching process is detached from the surface of the adhesive layer Process

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)

Hereinafter, with reference to the drawings, a method for using the pressure-sensitive adhesive sheet for temporary fixing will be specifically described with reference to the drawings, with a focus on differences from the contents described in the first embodiment.

1. Step (1) (Preparation step of pressure-sensitive adhesive composition)
Step (1) is a step of preparing a predetermined pressure-sensitive adhesive composition containing the components (A) to (C).
Here, with reference to Fig.1 (a), the synthesis example of the terminal silyl group polymer which is (A) component is shown.
First, in FIG. 1A, an isocyanate compound having an isocyanate group at the end of the main chain or side chain of the molecule, represented by the formula (1), is prepared.
Next, in FIG. 1 (a), an active hydrogen group capable of reacting with an isocyanate group is present at one end of the molecule represented by formula (2), and the other end of the molecule is represented by general formula (1). A silylating agent having a hydrolyzable silyl group is prepared.
Next, after the isocyanate compound represented by the formula (1) and the silylating agent represented by the formula (2) are uniformly mixed, for example, the reaction is performed by heating under a nitrogen atmosphere at 80 ° C. for 1 hour. The terminal silyl group polymer represented by (3) can be obtained.
As shown in FIG. 1B, the terminal silyl group polymer represented by the formula (3) passes through hydrolysis of the hydrolyzable silyl group represented by the general formula (1), and is further crosslinked by dehydration condensation. As the reaction proceeds, a three-dimensional network structure can be formed.

In synthesizing the terminal silyl group polymer represented by the formula (3), the silylating agent has an isocyanate group and a predetermined polymer skeleton, contrary to the case of FIG. The compound which has may have an active hydrogen group.
In addition, the active hydrogen in the urethane bond or urea bond introduced into the main chain or side chain of the predetermined terminal silyl group polymer may be substituted with an organic group as described in the first embodiment.
Therefore, allophanate bonds are also included in the category of urethane bonds, and burette bonds are also included in the category of urea bonds.

Next, it is preferable to dilute the obtained component (A) with a diluent solvent as desired, and add the components (B) and (C) with stirring to obtain a uniform mixed solution.
Subsequently, after adding the component (D) or other additives to the obtained mixed liquid, further adding a diluting solvent as necessary so as to obtain a desired viscosity while stirring until uniform. Thus, it is preferable to obtain a solution of the pressure-sensitive adhesive composition.
In addition, since the detail of each component, the compounding quantity, etc. are as having already described, it abbreviate | omits.

2. Process (2) (Lamination process of an adhesive composition)
Step (2) is a step of forming the coating layers 4 and 4 ′ by applying the pressure-sensitive adhesive composition to the substrate 2 as shown in FIG.
Moreover, as a method of apply | coating an adhesive composition on the base material 2, a solvent is added using the bar coat method, the knife coat method, the roll coat method, the blade coat method, the die coat method, the gravure coat method etc., for example. It is preferable to dry after applying the adhesive composition to form the coating layer 4 (coating film).
At this time, the thickness of the coating layer 4 is preferably set to a value in the range of 1 to 100 μm, and more preferably set to a value in the range of 5 to 50 μm.
This is because if the thickness of the coating layer 4 is too thin, sufficient adhesive properties and the like may not be obtained, and conversely, if it is too thick, the residual solvent may become a problem.
The drying conditions are usually 50 to 150 ° C. and preferably 10 seconds to 10 minutes.
The details of the base material are the same as described above, and will be omitted.

3. Step (3) (Coating layer curing step)
Step (3) is a step in which the coating layers 4 and 4 ′ of the pressure-sensitive adhesive composition are cured to form the coating layers 4 and 4 ′ as pressure-sensitive adhesive layers 40 and 40 ′.
That is, as shown in FIGS. 3B to 3C, in a state where the release substrates 8 and 8 ′ are laminated on the surfaces of the coating layers 4 and 4 ′ that are dried on the substrate 2. It is preferable to make it harden | cure and it is set as the adhesive layers 40 and 40 '.
Alternatively, the application layers 4 and 4 'of the pressure-sensitive adhesive composition applied on the substrate 2 are first cured to form the pressure-sensitive adhesive layers 40 and 40', and then laminated on the release substrates 8 and 8 '. May be.
Or it is not necessary to laminate | stack the peeling base material 8 to the last.

In addition, hardening in the application layer 4 of an adhesive composition is performed through the drying process mentioned above and a seasoning process.
Conditions for the seasoning step include a temperature of 20 to 50 from the viewpoint of uniformly curing the coating layer 4 of the pressure-sensitive adhesive composition without damaging the coating layer 4 or the base material 2 of the pressure-sensitive adhesive composition. Preferably, the temperature is 23 ° C to 30 ° C.
The humidity is preferably 30 to 75% RH, more preferably 45 to 65% RH.

4). Process (3) '(Lamination process on hard substrate)
Step (3) ′ is a step of laminating the obtained electronic component temporary fixing pressure-sensitive adhesive sheet 100 on a hard substrate 200 including a glass substrate, a metal substrate, or a polycarbonate substrate.
More specifically, as a method of bonding the finally obtained temporary fixing pressure-sensitive adhesive sheet 100 to the hard substrate 200, first, as shown in FIGS. It is preferable that the release film 8 laminated on the substrate is peeled off, and then the surface of the pressure-sensitive adhesive layer 40 that appears is adhered to the hard substrate 200 to be bonded.
In the case where the pressure-sensitive adhesive layer 40 containing the terminal silyl group polymer of the present invention is laminated only on one side of the substrate and the other pressure-sensitive adhesive layer 50 is laminated on the other side of the substrate, FIG. As shown in (b), it is preferable that the side of the pressure-sensitive adhesive layer 40 containing the terminal silyl group polymer of the present invention is adhered to the hard substrate 200 so as to adhere to each other.

5. Process (4) (Electronic component placement process)
Step (4) is a step of placing the electronic component on at least one surface of the pressure-sensitive adhesive layer of the temporary fixing pressure-sensitive adhesive sheet for the electronic component.
That is, as shown in FIG. 3 (d), the release substrate 8 ′ laminated on the other surface of the temporary fixing pressure-sensitive adhesive sheet bonded to the hard substrate 200 is peeled, and then the pressure-sensitive adhesive layer 40 appears. It is preferable that the electronic component 300 is adhered to the surface of ′ by sticking together.
As a method for placing the electronic component, after the electronic component in step (4) is bonded to the temporary fixing adhesive sheet, the temporary fixing adhesive sheet on which the electronic component in step (3) ′ is mounted is hard. Bonding to the substrate 200 is also a preferred method of use.

6). Process (5) (Electronic component processing process)
Step (5) is a step of performing at least an etching process on the electronic component.
That is, as shown in FIG. 3D, after the electronic component 300 is brought into close contact with the hard substrate 200 with the temporary fixing pressure-sensitive adhesive sheet 100, the electronic component is preferably subjected to processing such as etching.

7). Step (6) (Electronic component removal step)
Step (6) is a step of detaching the etched electronic component from the surface of the pressure-sensitive adhesive layer.
That is, as shown in FIGS. 4A to 4B, the processed electronic component 300 is preferably detached from the hard substrate 200.
The method for detaching the electronic component is not particularly limited, but as shown in FIG. 4 (a), a pressure-sensitive adhesive comprising a cured product of the pressure-sensitive adhesive composition containing the terminal silyl group polymer of the present invention. If the adhesive sheet for temporary fixing using the layers on both sides of the base material, first, the electronic component and the adhesive sheet for temporary fixing are both peeled from between the hard substrate 200 and the adhesive layer 40, and then the electronic component is removed. It is preferable to peel from the temporary fixing pressure-sensitive adhesive sheet.
As shown in FIG. 4B, for example, when a UV curable resin is used for the pressure-sensitive adhesive layer 50, the adhesive force of the pressure-sensitive adhesive layer 50 is reduced by ultraviolet irradiation, and temporarily fixed to the electronic component. It is preferable to peel only the electronic component from between the adhesive sheet for use.

8). Hard substrate Further, the type of the hard substrate targeted by the temporary fixing pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it can hold an electronic component, but is not limited to a glass substrate, a metal substrate, a polycarbonate substrate, An acrylic board etc. are mentioned.

9. Electronic component The type of electronic component targeted by the temporary fixing pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it is a material having heat resistance, dimensional stability, gas barrier properties, and surface smoothness. For example, it is preferable to use a film made of polyethylene naphthalate, polyimide, polycarbonate, polyethylene terephthalate, or the like. It is also preferable to use a thin film laminate such as a copper-clad polyimide laminate. When using these films and laminates, those having a gas barrier layer or the like on the surface may be used.

Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.

[Example 1]
1. Preparation of pressure-sensitive adhesive composition (1) Preparation of silylating agent In a reaction vessel equipped with a stirrer, 206 parts by weight of N-aminoethyl-γ-aminopropylmethyldimethoxysilane and 172 parts by weight of methyl acrylate were charged. The mixture was heated and reacted at 80 ° C. for 10 hours with stirring in a nitrogen atmosphere to obtain a silane compound serving as a silylating agent.

(2) Preparation of urethane prepolymer In a reaction vessel with a stirrer, polyoxypropylene diol (Asahi Glass Co., Ltd., PML S4015, weight average molecular weight 15,000) 1000 parts by weight and isophorone diisocyanate 24.6 parts by weight (NCO / OH ratio = 1.7) and 0.05 parts by weight of dibutyltin dilaurate were added and reacted under heating in a nitrogen atmosphere at 85 ° C. for 7 hours to obtain a urethane prepolymer (isocyanate). Compound) was obtained.

(3) Synthesis of terminal silyl group polymer In a reaction vessel equipped with a stirrer, 1000 parts by weight of the obtained urethane prepolymer and 42.1 parts by weight of the obtained silylating agent were accommodated, under a nitrogen atmosphere, While stirring, heat treatment was performed at 80 ° C. for 1 hour to obtain a terminal silyl group polymer.
At this time, the disappearance of isocyanate group absorption (2265 cm ⁻¹ ) was observed using a Fourier transform infrared spectrophotometer (FT-IR), thereby confirming the progress of the reaction.
The obtained terminal silyl group polymer is a both-end silyl group polymer having a terminal moiety represented by the following formula (9) at both ends of polyoxypropylene as a main chain and having a weight average molecular weight of 40,000. there were.
In addition, by using N-aminoethyl-γ-aminopropylmethyldimethoxysilane as a raw material for the silylating agent, a bifunctional terminal silyl group was introduced into the terminal silyl group polymer obtained.

(4) Preparation of pressure-sensitive adhesive composition Next, 100 parts by weight of ethyl acetate as a solvent and 0.12 parts by weight of boron trifluoride monoethylamine complex as a catalyst with respect to 100 parts by weight of the obtained terminal silyl group polymer, Add 0.4 parts by weight of 3-aminopropyltrimethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and stir until uniform to obtain a solution-state pressure-sensitive adhesive composition before curing. Obtained.

2. Preparation of pressure-sensitive adhesive sheet Next, the thickness of the pressure-sensitive adhesive layer after drying the obtained pressure-sensitive adhesive composition on one side of a 100 μm-thick polyester film (Teonex Q65FA, manufactured by Teijin DuPont) using a knife coater method After applying so that it might become 25 micrometers, it heat-processed on 100 degreeC and the conditions for 1 minute, and was set as the adhesive sheet provided with the adhesive layer.

3. Seasoning of the pressure-sensitive adhesive sheet Next, the pressure-sensitive adhesive sheet composed of the obtained pre-curing pressure-sensitive adhesive composition and the base material (polyester film) was left for 14 days in an environment of 23 ° C. and 50% RH ( The pressure-sensitive adhesive composition was sufficiently cured to obtain a temporary fixing pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 25 μm, which was subjected to various evaluations.

4). Evaluation (1) Solvent immersion evaluation On a glass plate used for a solvent resistance test for acetone, isopropyl alcohol (IPA), and an etchant, an oil-based magic (manufactured by Zebra Co., Ltd., trade name “Mackey Extra Fine”) is 40 mm long × 20 mm wide. In the frame, 40 grids are written every 5 mm and 4 mm in width, and the adhesive layer for temporarily fixing the adhesive sheet prepared in the examples and comparative examples is covered so that all the writing parts of the oily magic are covered. Was pasted on a glass plate to prepare a solvent resistance test plate.
Also, on a glass plate used for a solvent resistance test against distilled water, a medicine wrapping paper (manufactured by Hakuaisha Co., Ltd., trade name “Parapin”) cut to 40 mm in length and 20 mm in width is placed, and the release film is peeled off from it Paste the adhesive layer to the glass plate so that the entire surface of the medicine-wrapped paper is covered with the adhesive sheet for temporary fixing produced in the examples and comparative examples in which the adhesive layer is exposed to produce a solvent resistance test plate did.
Then, the above-mentioned solvent resistance test plate is immersed in each solvent of acetone, IPA, etchant (trade name “SEA-1” manufactured by Kanto Chemical Co., Ltd.) and distilled water for 1 hour, The bleeding of the writing part or the wetness of the medicine wrapping paper was visually observed, and the solvent resistance of the temporary fixing adhesive sheet when immersed in each solvent was evaluated according to the following criteria.
A: Solvent intrusion was not confirmed.
○: Some solvent intrusion was confirmed, but no lifting or peeling was observed.
(Triangle | delta): The floating peeling by solvent penetration was confirmed a little.
X: The floating peeling by solvent penetration | invasion was confirmed notably.

(2) Evaluation of heat resistance The heat resistance of the obtained adhesive sheet for temporary fixing was evaluated.
That is, the pressure-sensitive adhesive layer of the temporary fixing pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples was attached to a glass plate using a 2 kg rubber roller to prepare a heat resistance test plate.
Subsequently, after heating this heat resistance test board at 150 degreeC for 1 hour, the external appearance of the test board was observed visually and the heat resistance of the temporary fixing adhesive sheet was evaluated by the following references | standards.
○: No swelling was observed.
×: Swelled

(3) Evaluation of gel fraction The gel fraction of the pressure-sensitive adhesive in the obtained temporary fixing pressure-sensitive adhesive sheet, that is, the pressure-sensitive adhesive composition after curing through the seasoning step was measured.
That is, only the pressure-sensitive adhesive layer in the temporary fixing pressure-sensitive adhesive sheet was immersed in ethyl acetate for 120 hours in an environment of 23 ° C. and 50% RH, and then dried at 100 ° C. for 30 minutes, and the weight before and after immersion was measured. The gel fraction was calculated by substituting these weights into the following formula (10). The obtained results are shown in Table 1.
Gel fraction (%) = (weight after immersion / weight before immersion) × 100 (10)

[Example 2]
In Example 2, a temporary fixing adhesive was used in the same manner as in Example 1 except that 5 parts by weight of terpene phenol resin (manufactured by Yashara Chemical Co., TH130) was added as a tackifying resin to the adhesive composition before curing. Sheets were manufactured and evaluated. The obtained results are shown in Table 1.

[Comparative Example 1]
In Comparative Example 1, in a nitrogen atmosphere, 30 parts by weight of n-butyl acrylate, 70 parts by weight of 2-ethylhexyl acrylate, 7 parts by weight of methyl methacrylate, 3 parts by weight of acrylic acid, 2-hydroxyhexyl acrylate 0 Acrylate copolymer having a weight average molecular weight of 500,000 by reacting .9 parts by weight with 0.25 parts by weight of azobisisobutyronitrile (polymerization initiator) in ethyl acetate at 60 ° C. for 24 hours. A solution (solid concentration 45% by weight) was obtained.
Next, 3 parts by weight of a crosslinking agent made of a polyisocyanate compound (manufactured by Nippon Polyurethane, Coronate L, solid content concentration: 75% by weight) is dissolved in 100 parts by weight of the resulting acrylate copolymer solution. The adhesive sheet for temporary fixing was manufactured and evaluated in the same manner as in Example 1 except that the adhesive composition before curing was obtained. The obtained results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 2, 90 parts by weight of n-butyl acrylate, 10 parts by weight of acrylic acid, and 0.25 parts by weight of azobisisobutyronitrile (polymerization initiator) were added in ethyl acetate under a nitrogen atmosphere. The mixture was reacted at 24 ° C. for 24 hours to obtain an acrylate copolymer solution having a weight average molecular weight of 500,000 (solid content concentration: 30% by weight).
Next, with respect to 100 parts by weight of the resulting acrylate copolymer solution, 0.5 part by weight of a crosslinking agent comprising a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate L, solid content concentration: 75% by weight), The adhesive sheet for temporary fixing was manufactured and evaluated in the same manner as in Example 1 except that the PSA composition was dissolved to obtain a PSA composition before curing. The obtained results are shown in Table 1.

[Comparative Example 3]
In Comparative Example 3, in a nitrogen atmosphere, 61 parts by weight of n-butyl acrylate, 18 parts by weight of methyl methacrylate, 3.5 parts by weight of styrene, 12 parts by weight of methyl acrylate, 5 parts by weight of 2-hydroxyethyl methacrylate, acrylic acid Acrylic ester copolymer having a weight average molecular weight of 450,000 by reacting 0.15 part by weight with 0.1 part by weight of azobisisobutyronitrile (polymerization initiator) in toluene at 60 ° C. for 24 hours. A solution (solid content concentration 40% by weight) was obtained.
Next, with respect to 100 parts by weight of the resulting acrylate copolymer solution, 4 parts by weight of a crosslinking agent composed of a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate L, solid content concentration: 75% by weight) Example 1 except that 3 parts by weight of an isocyanate compound (D-110N (solid content: 75% by weight), manufactured by Takeda Pharmaceutical Co., Ltd.) was dissolved to obtain a pressure-sensitive adhesive composition before curing. Similarly, a temporary fixing pressure-sensitive adhesive sheet was produced and evaluated. The obtained results are shown in Table 1.

In the temporary fixing pressure-sensitive adhesive sheets of Examples 1 and 2 of the present invention, no floating peeling was confirmed with respect to each solvent used in the etching process, and in the heat resistance evaluation, the temporary fixing pressure-sensitive adhesive sheet was swollen. It was never done.
On the other hand, in Comparative Examples 1 and 2 using a predetermined acrylic ester copolymer as a pressure-sensitive adhesive composition, some peeling occurred depending on the type of the solvent, and in the heat resistance evaluation, both were swollen. confirmed. Moreover, although the comparative example 3 which used the other acrylic ester copolymer as an adhesive composition obtained the favorable result about heat resistance, all floated with respect to the solvent used by etching process. Peeling was confirmed.

As described above in detail, according to the present invention, a pressure-sensitive adhesive sheet for temporary fixing provided with a pressure-sensitive adhesive layer comprising a cured product of a pressure-sensitive adhesive composition containing a predetermined terminal silyl group polymer on both sides or one side of a substrate. Then, even if an electronic component is temporarily fixed on a hard substrate and subjected to etching treatment, cleaning treatment, heat treatment, etc., it is possible to suppress floating and foaming, that is, temporarily fixed electronic It is now possible to process parts without causing positional shift.
Therefore, the pressure-sensitive adhesive sheet for temporarily fixing an electronic component of the present invention is used as a pressure-sensitive adhesive sheet for temporarily fixing the component during circuit formation or various processing of a thin film substrate such as a flexible printed circuit board or an organic transistor component. It is expected.

2: base material, 4, 4 ′: coating layer, 8, 8 ′: release base material, 40, 40 ′: pressure-sensitive adhesive layer, 50: other pressure-sensitive adhesive layer, 100: pressure-sensitive adhesive sheet for temporary fixing, 100 ′: Adhesive sheet for temporary fixing with release substrate, 200: hard substrate, 300: electronic component

Claims (8)

A pressure-sensitive adhesive sheet for temporarily fixing an electronic component provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on both sides or one side of a substrate,
The pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as the component (A), a silane coupling agent as the component (B), and a curing catalyst as the component (C).
The terminal silyl group polymer as the component (A) has a polyoxyalkylene structure in the main chain, a urethane bond and / or a urea bond in a part of the main chain or a side chain, or one of these, And having hydrolyzable silyl groups represented by the following general formula (1) at both ends of the main chain,
And when (D) component contains tackifying resin, the compounding quantity of the said tackifying resin is a value less than 10 weight part with respect to 100 weight part of terminal silyl group polymers which are said (A) component. Or no tackifying resin,
A pressure-sensitive adhesive sheet for temporarily fixing electronic components.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.) 2. The electronic component according to claim 1, wherein the electronic component is a film made of at least one selected from polyethylene naphthalate, polyimide, polycarbonate, and polyethylene terephthalate, or a copper-clad polyimide laminate. Adhesive sheet. 2. The pressure-sensitive adhesive sheet for temporarily fixing an electronic component according to claim 1, wherein the weight average molecular weight of the terminal silyl group polymer as the component (A) is set to a value in the range of 15,000 to 200,000. The blending amount of the silane coupling agent as the component (B) is set to a value within the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). The pressure-sensitive adhesive sheet for temporarily fixing an electronic component according to claim 1. The blending amount of the curing catalyst as the component (C) is set to a value within the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). The pressure-sensitive adhesive sheet for temporarily fixing an electronic component according to claim 1. When the tackifier resin is included as the component (D), the tackifier resin is at least one of a rosin resin, a terpene phenol resin, and a rosin phenol resin. Adhesive sheet for temporarily fixing electronic components. It is a method of using a pressure-sensitive adhesive sheet for temporarily fixing an electronic component provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on both sides or one side of a substrate,
A method of using an adhesive sheet for temporarily fixing an electronic component, comprising the following steps (1) to (6):
(1) The terminal silyl group polymer as the component (A), the silane coupling agent as the component (B), and the curing catalyst as the component (C) are the component (A). The terminal silyl group polymer has a polyoxyalkylene structure in the main chain, has a urethane bond and / or a urea bond in a part or a side chain of the main chain, and further has both ends of the main chain. In the case where it has a hydrolyzable silyl group represented by the following general formula (1) and a tackifying resin is included as the component (D), the blending amount of the tackifying resin is set to (A ) A step of preparing a pressure-sensitive adhesive composition having a value of less than 10 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as a component or not including a tackifying resin.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)
(2) Step of laminating the pressure-sensitive adhesive composition on both sides or one side of the substrate (3) A pressure-sensitive adhesive layer comprising a cured product of the pressure-sensitive adhesive composition by curing the pressure-sensitive adhesive composition (4) The step of placing the electronic component on at least one surface of the pressure-sensitive adhesive layer of the temporary fixing pressure-sensitive adhesive sheet of the electronic component (5) The electronic component On the other hand, at least an etching process (6) a process of removing the etched electronic component from the surface of the pressure-sensitive adhesive layer Between the step (3) and the step (4), (3 ′) a step of laminating the prepared temporary fixing pressure-sensitive adhesive sheet on a hard substrate including a glass substrate, a metal substrate, or a polycarbonate substrate The usage method of the adhesive sheet for temporary fixing of Claim 7 characterized by the above-mentioned.

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