JP2018070737A - Adhesive sheet for heat resistant process and manufacturing method of adhesive sheet for heat resistant process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet for heat resistant process or the like having no generation of swellings and maintaining good easy detachability even when a high temperature treatment at 150°C or higher is conducted, for example.SOLUTION: There are provided an adhesive sheet for heat resistant process having a first substrate having glass transition temperature of 120°C or higher, a first adhesive layer derived from an energy ray curable adhesive composition, a second substrate having glass transition temperature of 80°C or higher and a second adhesive layer derived from a silylated urethane adhesive composition in this order and a manufacturing method therefor, the silylated urethane adhesive composition contains a prescribed terminal silyl group polymer as (A) component and moisture vapor transmission rate of the second adhesive layer is a value of 100 g/m/Hrs or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a pressure-sensitive adhesive sheet for a heat-resistant process and a method for producing a pressure-sensitive adhesive sheet for a heat-resistant process.
That is, the present invention provides a pressure-sensitive adhesive sheet for a heat-resistant process that does not swell even when it is subjected to a high-temperature treatment of a predetermined temperature or more and maintains good easy peelability, and such a heat-resistant process. The present invention relates to an efficient method for producing a pressure-sensitive adhesive sheet.

Conventionally, in an electronic component manufacturing process, it is necessary to temporarily fix an electronic material or the like on a heat-resistant process pressure-sensitive adhesive sheet and perform various processing steps. It was necessary to have peelability.
For example, in order to perform an etching process, it is necessary to immerse the electronic material etc. on the adhesive sheet for heat-resistant processes in solvents, such as an organic solvent and water.
Moreover, in order to perform a washing process, it is necessary to apply an ultrasonic wave in the state which immersed the electronic material etc. on the adhesive sheet for heat-resistant processes in the solvent.
Furthermore, in order to dry the electronic material etc. on the heat-resistant process pressure-sensitive adhesive sheet, it is necessary to perform a heat treatment at a predetermined temperature.
Therefore, the pressure-sensitive adhesive sheet for a heat-resistant process used in such a treatment process is required to have solvent resistance and heat resistance, while the pressure-sensitive adhesive sheet for a heat-resistant process damages electronic components and the like after the completion of the treatment process. There is also a need for the ability to peel from them.

Thus, a temporary fixing pressure-sensitive adhesive sheet having excellent heat resistance, which uses a pressure-sensitive adhesive composition containing a predetermined terminal silyl group polymer and a tackifier resin, is disclosed (for example, Patent Document 1). ).
More specifically, 100 parts by weight 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 predetermined hydrolyzable silyl group at the molecular end, and a tackifying resin Uniformly 10 to 150 parts by weight and 0.001 to 10 parts by weight of a fluorine compound selected from the group consisting of boron trifluoride and / or a complex thereof, a fluorinating agent and an alkali metal salt of a fluorine inorganic acid The pressure-sensitive adhesive precursor obtained by mixing the above-mentioned pressure-sensitive adhesive precursor is applied to the surface of the tape base material or sheet base material, and then the terminal silyl group polymer is cured to form the pressure-sensitive adhesive precursor as a pressure-sensitive adhesive layer. A temporary fixing pressure-sensitive adhesive sheet is disclosed.

On the other hand, the applicant has proposed an adhesive sheet for temporary fixing having excellent heat resistance, using an adhesive composition containing a predetermined terminal silyl group polymer and a tackifier resin (for example, Patent Document 2).
More specifically, a predetermined terminal silyl group polymer includes a predetermined silane coupling agent and a predetermined curing catalyst, and the blending amount of the tackifying resin is set to 0 or a small amount, thereby forming a circuit of a thin film substrate. Even when the etching process is performed, the hard substrate such as glass and the thin film substrate are securely bonded, and during the etching process, the floating due to the foam derived from the adhesive layer is prevented, It is a pressure-sensitive adhesive sheet for temporary fixing that can prevent displacement.

Japanese Patent No. 5284362 (Claims etc.) WO2015 / 079904 (Claims etc.)

  However, in the case of the temporary fixing pressure-sensitive adhesive sheet disclosed in Patent Document 1, since a predetermined terminal silyl group polymer and a tackifying resin are used as the main components of the pressure-sensitive adhesive layer on both surfaces of the support, There was a problem that the fixing pressure-sensitive adhesive sheet could not be easily peeled off from the temporarily fixing member.

Moreover, in the case of the adhesive sheet for temporary fixing disclosed by patent document 2, the heat resistance of a base material, the water vapor transmission rate of the adhesive layer derived from the silylated urethane adhesive composition, etc. were not considered.
Therefore, when used as a pressure-sensitive adhesive sheet for a heat-resistant process and subjected to a predetermined treatment (solder reflow treatment or the like) under a high temperature condition of 150 ° C. or more, there has been a problem that blister resistance is not sufficient and swelling tends to occur.

Then, in view of the circumstances as described above, the present inventors diligently made efforts to find a predetermined first base material, a first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, By sequentially providing the second base material and the second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition, and adjusting the moisture permeability of the second pressure-sensitive adhesive layer to a predetermined range, For example, even when a high temperature treatment of 150 ° C. or higher is carried out, it is found that a pressure-sensitive adhesive sheet for a heat-resistant process that does not swell and maintains easy peelability and the like can be obtained, and the present invention has been completed. It is a thing.
That is, the object of the present invention is a pressure-sensitive adhesive sheet for a heat-resistant process that does not swell and maintains easy peelability even when a high-temperature treatment at a predetermined temperature or higher is performed, and for such a heat-resistant process. It is providing the efficient manufacturing method of an adhesive sheet.

According to the present invention, the first substrate having a glass transition temperature of 120 ° C. or higher, the first pressure-sensitive adhesive layer derived from the energy ray curable pressure-sensitive adhesive composition, and the glass transition temperature of 80 ° C. or higher. A pressure-sensitive adhesive sheet for a heat-resistant process, comprising a second base material and a second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition in order, wherein the silylated urethane pressure-sensitive adhesive composition is at least ( A) a terminal silyl group polymer as a component, and the component (A) has a polyoxyalkylene structure in the main chain, and a urethane bond and a urea bond in a part or side chain of the main chain, or Any one, having hydrolyzable silyl groups represented by the following (1) at both ends of the main chain, and the moisture permeability of the second pressure-sensitive adhesive layer is 100 g / m ² / Adhesive sheet for heat-resistant process, characterized by having a value equal to or higher than Hrs Is provided, it is possible to solve the problems described above.

(In 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, a first base material having predetermined heat resistance, a first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, a second base material having predetermined heat resistance, and silylated urethane A second pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition in order, and by adjusting the configuration and the water vapor transmission rate of the second pressure-sensitive adhesive layer to a predetermined range, for example, a high-temperature treatment at 150 ° C. or higher Even when a solder reflow process or an organic transistor manufacturing process is performed, it is possible to obtain a pressure-sensitive adhesive sheet for a heat-resistant process that does not swell and can maintain easy peelability from a glass substrate or the like.
Moreover, not only the type and thickness of the second pressure-sensitive adhesive layer, but also the type and thickness of the first base material, the type and thickness of the first pressure-sensitive adhesive layer, the type of the second base material, The versatility as the pressure-sensitive adhesive sheet for the heat-resistant process can be improved by appropriately adjusting the thickness and the like.

Moreover, in constituting the heat-resistant process pressure-sensitive adhesive sheet of the present invention, the silylated urethane pressure-sensitive adhesive composition is a tackifier (may be referred to as a tackifier resin as component (B). The same applies hereinafter). The amount of the tackifier is preferably less than 50 parts by weight with respect to 100 parts by weight of component (A).
Thus, the reaction rate and reaction rate of the alkoxysilyl group in silylated urethane resin can be made more favorable by restrict | limiting the compounding quantity of the tackifier which is (B) component.
Moreover, even if it is a case where a solder reflow process etc. are implemented at predetermined temperature, the adhesive sheet for heat-resistant processes which can maintain the easy peelability with respect to a glass substrate etc. can be obtained even if it does not generate | occur | produce.

Further, in constituting the heat-resistant process pressure-sensitive adhesive sheet of the present invention, the silylated urethane pressure-sensitive adhesive composition contains a curing catalyst for curing the component (A) as the component (C), and the curing catalyst is an aluminum-based material. It is preferably at least one selected from the group consisting of a catalyst, a titanium-based catalyst, a zirconium-based catalyst, a bismuth-based catalyst, and a boron trifluoride-based catalyst.
Thus, by restricting the type of component (C) and configuring, the adhesiveness to various adherends and the curability of component (A) can be controlled.

Moreover, when comprising the adhesive sheet for heat-resistant processes of this invention, it is preferable that a 1st base material is a polyethylene naphthalate film or a polyimide film.
By configuring in this way, for example, the heat shrinkage rate at 150 ° C. can be controlled to a value of 0.5% or less, and as a result, heat resistance excellent in flatness and heat resistance in the manufacturing process of organic transistors and the like. It can be suitably used as a process pressure-sensitive adhesive sheet.

Moreover, when comprising the adhesive sheet for heat-resistant processes of this invention, it is preferable that a 2nd base material is a polyethylene terephthalate film or a polyphenylene sulfide film.
By comprising in this way, in the adhesive sheet for heat-resistant processes, not only predetermined heat resistance and flexibility can be obtained, but also transparency is excellent, so that the transmission loss of energy rays can be kept low.

Moreover, in constituting the heat-resistant process pressure-sensitive adhesive sheet of the present invention, the main component of the energy ray-curable pressure-sensitive adhesive composition is referred to as an acrylic polymer ((meth) acrylic acid ester polymer or (meth) acrylic acid ester copolymer). In the following, the same applies to the above), and an energy ray curable resin obtained by adding a (meth) acryloyl group is preferable.
By comprising in this way, the ultraviolet ray hardening of an energy-beam curable adhesive composition becomes easy, and the adhesive sheet for heat resistant processes which is economically advantageous can be provided.

Another embodiment of the present invention is the first base material having a glass transition temperature of 120 ° C. or higher, the first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, and the glass transition temperature of 80. It is a manufacturing method of the pressure-sensitive adhesive sheet for a heat-resistant process, which is sequentially provided with a second base material having a temperature equal to or higher than ° C. and a second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition.
The silylated urethane pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as the component (A), the component (A) has a polyoxyalkylene structure in the main chain, It has a urethane bond and / or a urea bond in part or in the side chain, and has a hydrolyzable silyl group represented by the following (1) at both ends of the main chain. It is a manufacturing method of the adhesive sheet for heat-resistant processes whose moisture permeability of an agent layer is a value of 100 g / m < ² > / Hrs or more.
In addition, a method for producing a pressure-sensitive adhesive sheet for a heat-resistant process, comprising the following steps (1) to (4).
(1) Step of forming a second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition on one side of the second base material (2) Energy ray on the other side of the second base material Step of applying curable pressure-sensitive adhesive composition (3) Step of laminating the first substrate on the surface of energy-ray-curable pressure-sensitive adhesive composition (4) Energy for energy-ray-curable pressure-sensitive adhesive composition Irradiating a line to form a first pressure-sensitive adhesive layer

(In 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, according to the manufacturing method of the pressure-sensitive adhesive sheet for heat-resistant process of the present invention, the predetermined first base material, the first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, and the predetermined second By forming the base material and the second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition, and adjusting the configuration and moisture permeability of the second pressure-sensitive adhesive layer to a predetermined range, for example, Even when a high-temperature treatment at 150 ° C. or higher is performed, it is possible to provide an efficient method for producing a pressure-sensitive adhesive sheet for a heat-resistant process that does not swell and can maintain easy peelability from a glass substrate or the like. .
However, the above-described steps (1) to (4) are preferably performed sequentially, but are not necessarily performed in this order, and can be appropriately changed.
Therefore, after carrying out steps (2) to (4), finally, step (1) may be carried out to produce a heat-resistant pressure-sensitive adhesive sheet.

Moreover, when implementing the manufacturing method of the adhesive sheet for heat-resistant processes of this invention, it is preferable that a 1st base material is a polyethylene naphthalate film or a polyimide film.
By implementing in this way, the adhesive sheet for heat resistant processes excellent in flatness and heat resistance suitable for manufacturing processes, such as an organic transistor, can be obtained.

Drawing 1 (a)-(b) is a figure offered in order to explain the structure and use mode of an adhesive sheet for heat-resistant processes. FIGS. 2A to 2C are diagrams provided for explaining an example of an organic transistor manufacturing process. FIGS. 3A to 3D are diagrams provided to explain the swelling phenomenon (Example 1, Comparative Examples 1 to 3) in the evaluation of blister resistance.

[First Embodiment]
As illustrated in FIGS. 1A to 1B, the first embodiment of the present invention includes a first substrate 12 having a glass transition temperature of 120 ° C. or higher, and an energy ray-curable pressure-sensitive adhesive composition. A first pressure-sensitive adhesive layer 14 derived from a product, a second substrate 16 having a glass transition temperature of 80 ° C. or higher, and a second pressure-sensitive adhesive layer 18 derived from a silylated urethane pressure-sensitive adhesive composition. It is the adhesive sheet 10 for heat-resistant processes provided in order.
The silylated urethane pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as the component (A), the component (A) has a polyoxyalkylene structure in the main chain, It has a urethane bond and / or a urea bond in part or in the side chain, or has a hydrolyzable silyl group represented by the following (1) at both ends of the main chain, and The pressure-sensitive adhesive layer for the heat-resistant process is characterized in that the moisture permeability of the pressure-sensitive adhesive layer 18 is 100 g / m ² / Hrs or more.

(In 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, the heat-resistant process pressure-sensitive adhesive sheet according to the first embodiment will be specifically described with reference to the drawings as appropriate.

1. 1st adhesive layer As FIG.1 (a)-(b) illustrates, as 1st adhesive layer 14, the energy ray-curable polymer as a main component, and the energy containing a photoinitiator A pressure-sensitive adhesive layer derived from the wire curable pressure-sensitive adhesive composition can be mentioned.

(1) Main component The energy beam curable polymer which is the main component of the energy beam curable pressure-sensitive adhesive composition has a predetermined polymer component as a molecular chain, and has an energy beam curable functional group in the molecular chain. It is a polymer that causes a polymerization reaction with a photoinitiator (hereinafter sometimes referred to as a photopolymerization initiator).
Therefore, it is usually preferable to set the weight average molecular weight of the energy beam curable polymer to a value within the range of 300 to 2,000,000, preferably within the range of 500 to 1,500,000, More preferably, the value is within the range.
However, in the case of a polymer component having a weight average molecular weight exceeding 2 million, its content is 15% by weight of the total amount of the energy beam curable polymer in order to stably generate a uniform polymerization reaction with a photoinitiator. The following value is preferable, and a value of 10% by weight or less is more preferable.

In addition, typical examples of energy beam curable polymers are acrylic polymers ((meth) acrylic acid ester polymers and (meth) acrylic acid) derived from repeating units such as one or more (meth) acrylic acid ester monomers. Ester copolymer) has an energy ray-curable functional group introduced therein.
That is, in such an acrylic polymer, by containing a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a monomer unit constituting the acrylic polymer, preferable tackiness can be expressed. it can.
Examples of the (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid n-. Butyl, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, (meth) acrylic acid Examples include n-dodecyl, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
Among these, from the viewpoint of further improving the adhesiveness, (meth) acrylic acid esters having 1 to 8 carbon atoms in the alkyl group are preferable, and more specifically, methyl (meth) acrylate, ethyl (meth) acrylate, And n-butyl (meth) acrylate is particularly preferred.
In addition, these may be used independently and may be used in combination of 2 or more type.

On the other hand, examples of the compound that introduces an energy ray-curable functional group into the energy ray-curable polymer include, for example, methacryloyloxyethyl isocyanate; meta-isopropenyl-α, α-dimethylbenzyl isocyanate; methacryloyl isocyanate; allyl isocyanate; Acrylyl monoisocyanate compound obtained by reaction of compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth) acrylate Less acryloyl monoisocyanate compound; glycidyl (meth) acrylate; 2- (1-aziridinyl) ethyl (meth) acrylate There is one.
In addition, vinyl compounds such as vinyl acetate, styrene, α-methylstyrene, acrylamide, and (meth) acrylic acid may be copolymerized in the energy ray curable polymer in addition to the above-described acrylic monomer component.

In particular, if the energy ray curable polymer is an energy ray curable resin obtained by adding a (meth) acryloyl group to an acrylic polymer, a predetermined amount of a photoinitiator must be blended. It is possible to cure quickly by simply irradiating a predetermined amount of ultraviolet rays using an ultraviolet irradiation device.
That is, with such an energy beam curable resin, an economically advantageous pressure-sensitive adhesive sheet for a heat-resistant process can be provided.

(2) Photoinitiator In addition, when the energy ray curable pressure-sensitive adhesive composition is UV-cured, it is preferable to blend a predetermined photoinitiator with respect to the main component.
Such photoinitiators include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl- [4- (methylthio) phenyl] -2 Acetophenone compounds such as morpholino-1-propanone and 2,2-dimethoxy-2-phenylacetophenone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone compounds such as benzoylone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone; thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone; 4,4′-dimethylamino Anthraquinone compounds such as thioxanthone, 4,4′-diethylaminobenzophenone, α-acyloxime ester, methylbenzoylformate, 2-ethylanthraquinone; Acylphosphine oxide compounds such as 1,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) ) Single or a combination of two or more such as benzophenone and acrylated benzophenone.

Further, the blending amount of the photoinitiator is not particularly limited, but is preferably a value within a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the main component.
The reason for this is that when the amount of the photoinitiator is less than 0.01 parts by weight, poor curing may occur.
On the other hand, when the blending amount of the photoinitiator exceeds 10 parts by weight, the photoinitiator may be precipitated or the outgas derived from the photoinitiator may increase.
Therefore, the blending amount of the photoinitiator is more preferably set to a value within the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the main component, and a value within the range of 0.1 to 1 part by weight More preferably.

(3) Thickness Moreover, it is preferable to make the thickness of a 1st adhesive layer into the value within the range of 1-100 micrometers.
The reason for this is that if the thickness of the first pressure-sensitive adhesive layer becomes excessively thin, sufficient adhesion may not be exhibited for various adherends. This is because the residual solvent or the like when producing one adhesive layer may be extremely large.
Therefore, the thickness of the first pressure-sensitive adhesive layer is more preferably set to a value within the range of 2 to 50 μm, and further preferably set to a value within the range of 3 to 30 μm.

2. Second pressure-sensitive adhesive layer (1) (A) component: terminal silyl group polymer (1) -1 structure Silylated urethane constituting the second pressure-sensitive adhesive layer 18 shown in FIGS. The terminal silyl group polymer as the component (A) of the pressure-sensitive adhesive composition has a urethane bond and a urea bond in the main chain or side chain, or one of them, and the general formula (1) described above at both ends of the main chain. It has the hydrolyzable silyl group represented by these.
The reason for this is that the component (A) having such a structure has a bifunctional hydrolyzable silyl group represented by the general formula (1) at the terminal, so that hydrolysis dehydration between the components (A) is performed. This is because a three-dimensional network structure can be effectively formed by condensation.
Therefore, the compatibility with the predetermined tackifier can be adjusted to a suitable range, and the gel fraction and the constant load property can be easily adjusted. As a result, the high-temperature treatment is performed on the heat-sensitive adhesive sheet. Even in this case, the occurrence of swelling and floating can be effectively prevented.
In addition, as shown to Fig.1 (a), the peeling film 19 can be provided in this 2nd adhesive layer 18 as needed.
That is, when using the heat-resistant process pressure-sensitive adhesive sheet 10, the release film 19 is peeled off, and then, for example, attached to the glass substrate 20 via the second pressure-sensitive adhesive layer 18 as shown in FIG. can do.

Moreover, regarding the hydrolyzable silyl group represented by the general formula (1), the number of carbon atoms of the alkyl group represented by R is preferably 1 to 12 from the viewpoint of hydrolytic dehydration condensation reactivity, and 1 to 3 More preferably.
Furthermore, regarding the hydrolyzable silyl group represented by the general formula (1), when X ¹ or X ² is an alkoxy group, the number of carbons in the alkoxy group is 1 to 1 from the viewpoint of hydrolytic dehydration condensation reactivity. It is preferably 12, and more preferably 1 to 3.

Moreover, the specific structure in the terminal part of a predetermined terminal silyl group polymer is shown to the following general formula (2)-(8) (terminal part: AG).
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 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. Yes.
That is, when the terminal silyl group polymer has such terminal portions A to G, adhesion to the adherend can be further strengthened.

Further, the skeleton of the main chain of the terminal silyl group polymer as the component (A) is polyoxyalkylene.
The reason for this is that if it is polyoxyalkylene, it is possible to impart appropriate flexibility to the resulting pressure-sensitive adhesive layer, and to further improve the adhesive force to the adherend.
Accordingly, the skeleton of the side chain of the terminal silyl group polymer as the component (A) is preferably polyoxyalkylene.
Specific examples of such polyoxyalkylene include polyoxypropylene and polyoxyethylene.

Furthermore, the predetermined terminal silyl group polymer as the component (A) does not have the hydrolyzable silyl group represented by the general formula (1) in the side chain, and the general formula (1) only at both ends of the main chain. It is preferable that it is a both terminal silyl group polymer which has a hydrolyzable silyl group represented by this.
The reason for this is that the cross-linking density between the components (A) is adjusted to a suitable range for such a terminal silyl group polymer, and the compatibility of the predetermined tackifier with the predetermined terminal silyl group polymer is more suitable. This is because the range can be adjusted.

  In addition, about the manufacturing method of the predetermined | prescribed terminal silyl group polymer which is (A) component, although a conventionally well-known manufacturing method can be used, for example, a silylating agent and a urethane prepolymer are prepared beforehand, It can be accommodated in a container equipped with a stirrer and heated and stirred (as an example at 80 ° C. for 1 hour) under a predetermined condition in a nitrogen atmosphere to obtain a predetermined silyl group polymer.

(1) -2 Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight (Mw) of the predetermined | prescribed terminal silyl group polymer which is (A) component into the value within the range of 5,000-150,000.
The reason for this is that when the weight average molecular weight is less than 5,000, the molecular structure becomes dense, sufficient tackiness cannot be obtained, the viscosity becomes too low, and the processability when forming a sheet by solution coating is low. This is because it may worsen.
On the other hand, when the weight average molecular weight exceeds 150,000, the processability may be significantly reduced due to an increase in viscosity or the like.
Therefore, the weight average molecular weight of the component (A) is more preferably set to a value within the range of 10,000 to 130,000, and further preferably set to a value within the range of 20,000 to 100,000.
In addition, the weight average molecular weight of the terminal silyl group polymer as the component (A) can be measured using a known molecular weight measuring apparatus such as gel permeation chromatography (GPC). This will be described in detail in 1.

(1) -3 Blending amount The blending amount of the predetermined terminal silyl group polymer as the component (A) is 50 to 99.5 wt% with respect to 100 wt% of the total amount of the second pressure-sensitive adhesive layer. A value within the range is preferable.
The reason for this is that when the blending amount is less than 50% by weight, the absolute amount of the component (A) with respect to the entire pressure-sensitive adhesive layer becomes excessively small, and it may be difficult to obtain sufficient tackiness. Because.
On the other hand, when the blending amount exceeds 99.5% by weight, the water vapor permeability may be lowered.
Therefore, the blending amount of the predetermined terminal silyl group polymer as the component (A) is more preferably set to a value in the range of 70 to 99% by weight with respect to 100% by weight of the total amount of the pressure-sensitive adhesive layer. More preferably, the value is in the range of -99% by weight.

(2) (B) Component: Tackifier (2) -1 Type (B) of silylated urethane pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer 18 shown in FIGS. ) As a component, a tackifier (sometimes referred to as a tackifier resin) can be blended.
That is, by blending a tackifier, the compatibility with a predetermined terminal silyl group polymer can be adjusted to a good range, and thus excellent adhesion to an adherend having a low polarity surface. It is estimated that it can exert its power.
Therefore, the types of tackifiers include rosin resins such as polymerized rosin, polymerized rosin ester, rosin derivatives, terpene resins such as polyterpene resins and aromatic modified terpene resins and hydrogenated products thereof (partially hydrogenated and fully hydrogenated). ), Terpene phenolic resins and their hydrogenated products (including partially and fully hydrogenated), coumarone-indene resins, aliphatic petroleum resins, aromatic petroleum resins, aliphatic / aromatic Petroleum resins such as copolymer petroleum resins and hydrogenated products thereof (including partially hydrogenated and fully hydrogenated) From low molecular weight styrene or substituted styrene, hydroabiethyl alcohol, esters derived from hydroabiethyl alcohol, etc. It is preferable to use at least one selected from the group consisting of
This is because these tackifiers can impart excellent adhesive strength to the adhesive composition by a combination with the predetermined terminal silyl group polymer as the component (A). .

And as a suitable tackifier, the terpene phenol resin which is a copolymer resin of a terpene resin and a phenol, or the partial hydrogenation product of this terpene phenol resin, or a complete hydrogenation product is mentioned.
The reason for this is that if it is such a terpene phenolic resin, when mixed with the component (A), it is easy to obtain a relatively high adhesive force on an adherend having a low polarity surface, and also has a good constant load property. This is because a phase structure that can also be obtained can be formed.
On the other hand, a partially hydrogenated product or a completely hydrogenated product of a terpene phenol resin, particularly a fully hydrogenated product of a terpene phenol resin, improves the balance between the adhesive force and the cohesive force in the pressure-sensitive adhesive composition. This is because a constant load peeling characteristic can be obtained.

(2) -2 Blending amount Moreover, the blending amount of the tackifier as the component (B) may be a value less than 50 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). preferable.
This is because when the blending amount of the component (B) reaches a value of 50 parts by weight or more, the water vapor permeability may be lowered.
Therefore, the blending amount of the component (B) is more preferably set to a value within the range of 10 to 40 parts by weight with respect to 100 parts by weight of the component (A), and a value within the range of 20 to 30 parts by weight. More preferably.

(3) (C) component: catalyst (3) -1 type In addition, (C) of silylated urethane pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer 18 shown in FIGS. And a catalyst for accelerating the curing of the predetermined terminal silyl group polymer as the component (A), the catalyst being an aluminum-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, and a boron trifluoride-based catalyst. It is preferably at least one selected from the group consisting of
The reason for this is that these catalysts make it easy to control the crosslinking density of the components (A), and the compatibility of the predetermined tackifier with the predetermined terminal silyl group polymer can be adjusted to a more suitable range. Because.

  As the aluminum catalyst, aluminum alkoxide, aluminum chelate, and aluminum (III) chloride are preferable. As the titanium catalyst, titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferable, and as the zirconium catalyst, Zirconium alkoxides, zirconium chelates, and zirconium chloride (IV) are preferred. Boron trifluoride catalysts include boron trifluoride amine complexes (such as boron trifluoride monoethylamine and boron trifluoride monomethylamine) and alcohol complexes. Is particularly preferably used.

(3) -2 Blending amount The blending amount of the catalyst as the component (C) is within 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 of.
The reason for this is that when the amount of the component (C) is less than 0.001 part by weight, the pressure-sensitive adhesive layer may be insufficiently cured.
On the other hand, when the blending amount of the component (C) exceeds 10 parts by weight, the catalytic action becomes excessive, and a silylated urethane pressure-sensitive adhesive composition that forms the second pressure-sensitive adhesive layer during production ( This is because the pot life of the coating liquid may be significantly shortened.
Therefore, the blending amount of the component (C) is more preferably 0.01 to 8 parts by weight with respect to 100 parts by weight of the component (A), and the range of 0.05 to 5 parts by weight. More preferably, the value is within the range.

(4) (D) component: amino group-containing alkoxysilane (D) component of silylated urethane pressure-sensitive adhesive composition constituting second pressure-sensitive adhesive layer 18 shown in FIGS. As an amino group-containing alkoxysilane (including a silane coupling agent having an amino group in the molecule), it is preferable to contain 0.01 part by weight or more with respect to 100 parts by weight of the component (A).
The reason for this is that by blending the component (D) in such a range, the effect as a crosslinking aid is exhibited, and the gel fraction and cohesive force of the silylated urethane pressure-sensitive adhesive composition are adjusted to a more suitable range. Because it can.
In addition, by including a predetermined amount of amino group-containing alkoxysilane as component (D), gelation of the silylated urethane pressure-sensitive adhesive composition in a solution state can be prevented, and the pot life can be significantly increased.

However, when there is too much compounding quantity of this (D) component, there exists a possibility that an adhesive may yellow.
That is, for example, the YI value as a measure of yellowing after a pressure-sensitive adhesive derived from the silylated urethane pressure-sensitive adhesive composition is left to stand in an oven at 120 ° C. for 7 days may change greatly.
Therefore, from the viewpoint of preventing yellowing, the blending amount of the component (D) is more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the component (A). More preferably, the value is in the range of 1 to 0.5 parts by weight.

  As the amino group-containing alkoxysilane as component (D), 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N At least one of 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like is preferable. Used for.

(5) Additive In addition, in the pressure-sensitive adhesive layer in the present invention, as components other than those described above, for example, silane coupling agents other than the component (D), anti-aging agents, dehydrating agents such as vinyl silane compounds and calcium oxide, Filler, conductive material, heat conductive material, plasticizer, anhydrous silica, thixotropic agent such as amide wax, diluent such as isoparaffin, aluminum hydroxide, halogen flame retardant, phosphorus flame retardant, silicone flame retardant Or a functional oligomer such as a silicone alkoxy oligomer or an acrylic oligomer, a pigment, a titanate coupling agent, an aluminum coupling agent, or a drying oil 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. The value is preferably in the range of 0.01 to 100 parts by weight, more preferably in the range of 0.01 to 70 parts by weight, with respect to 100 parts by weight of the silyl group polymer. A value in the range of ˜40 parts by weight is particularly preferable.

(6) Thickness In addition, the thickness of the second pressure-sensitive adhesive layer is usually preferably set to a value within the range of 1 to 100 μm.
The reason is that if the thickness of the pressure-sensitive adhesive layer is excessively thin, sufficient adhesion may not be exerted on various adherends. This is because there may be an extremely large amount of solvent remaining when the pressure-sensitive adhesive layer is produced.
Therefore, the thickness of the second pressure-sensitive adhesive layer is more preferably set to a value within the range of 2 to 50 μm, and further preferably set to a value within the range of 3 to 30 μm.

(7) Moisture permeability The moisture permeability of the second pressure-sensitive adhesive layer is set to a value of 100 g / m ² / Hrs or more.
The reason for this is that when the moisture permeability of the second pressure-sensitive adhesive layer is less than 100 g / m ² / Hrs, a predetermined heat-resistant pressure-sensitive adhesive sheet is formed and solder reflow is applied to a glass substrate or the like. This is because the blister resistance is lowered and the so-called swelling may occur when the treatment is performed.
Therefore, it is preferable that a value within the range of the second moisture permeability of 150~500g / m ² / Hrs pressure-sensitive adhesive layer, more preferably to a value within the range of 200 to 400 g / m ² / Hrs .
A method for measuring the moisture permeability of the second pressure-sensitive adhesive layer will be described in detail in Example 1.

3. 1st base material The adhesive sheet 10 for heat-resistant processes is equipped with the 1st base material 12 whose glass transition temperature is 120 degreeC or more, It is characterized by the above-mentioned.
This is because, when the glass transition temperature of the first base material becomes a value of less than 120 ° C., a predetermined heat-resistant process pressure-sensitive adhesive sheet is formed and attached to a glass substrate or the like, and a high-temperature treatment such as solder reflow treatment is performed. This is because the blister resistance decreases, so-called swelling occurs, and the easy peelability to the glass substrate may not be maintained.
However, if the glass transition temperature of the first substrate is excessively high, flexibility may be reduced, or the types of constituent materials that can be used may be excessively limited.
Therefore, the glass transition temperature of the first substrate is preferably set to a value within the range of 140 to 200 ° C, and more preferably set to a value within the range of 150 to 180 ° C.
The glass transition temperature of the first substrate can be measured in a film state using DSC (Differential Scanning Calorimeter), DTA (Differential Thermal Analysis), or the like.
More specifically, in accordance with JIS K 7121, DSC Q2000 (manufactured by TA Instruments Japan Co., Ltd.), which is a differential scanning calorimeter, is used to determine the rate of temperature increase / decrease in temperature. Measurement was performed at 20 ° C./min under a nitrogen atmosphere.

  Examples of the first base material having a glass transition temperature of 120 ° C. or higher include, for example, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polyetherketone, polyetheretherketone, polycarbonate, and polymethyl. Preferable examples include resin films composed of methacrylate, triacetyl cellulose, polynorbornene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinyl chloride, polyurethane acrylate, polyether sulfone and the like.

In particular, if the first base material is a polyethylene naphthalate film or a polyimide film, the heat shrinkage rate at 150 ° C. can be controlled to a value of 0.5% or less. As a result, an organic transistor (organic EL element) Etc.) can be suitably used as a pressure-sensitive adhesive sheet for a heat-resistant process excellent in flatness and heat resistance.
Moreover, if it is a polyethylene naphthalate film, it is excellent in not only the heat resistance mentioned above but transparency and a low dielectric constant (about 2.9), and it is comparatively cheap also in terms of cost. .
Furthermore, if it is a polyimide film, it is because it is excellent not only in the heat resistance mentioned above but also in mechanical strength and flame retardancy (UL standard: V-0).

Further, the thickness of the first base material is not particularly limited, but it is usually preferable to set the thickness within a range of 1 to 1,000 μm.
The reason for this is that when the thickness of the first base material is less than 1 μm, the smoothness, heat resistance, or handleability of the adhesive sheet for a predetermined heat-resistant process is significantly reduced. Because there is.
In addition, when solder reflow treatment or the like is performed in a state of being attached to a glass substrate or the like, blister resistance may be reduced, and so-called swelling may occur.
On the other hand, when the thickness of the first base material exceeds 1000 μm, when a predetermined heat-resistant process pressure-sensitive adhesive sheet is formed, the smoothness, handleability and the like are remarkably lowered, or the cost is increased. This is because it may be economically disadvantageous.
Therefore, the thickness of the first base material is more preferably set to a value within the range of 10 to 100 μm, and further preferably set to a value within the range of 20 to 50 μm.

4). 2nd base material Moreover, the adhesive sheet 10 for heat-resistant processes is equipped with the 2nd base material 16 whose glass transition temperature is 80 degreeC or more so that it may be illustrated by FIG. Features.
The reason for this is that when the glass transition temperature of the second base material is less than 80 ° C., a predetermined heat-resistant process pressure-sensitive adhesive sheet is formed and solder reflow treatment or the like is applied to the glass substrate or the like. In some cases, the blister resistance is lowered, so-called swelling may occur, or easy peelability to a glass substrate or the like may not be maintained.
However, if the glass transition temperature of the second substrate is excessively high, flexibility and mechanical strength may be reduced, and the types of usable constituent materials may be excessively limited.
Therefore, the glass transition temperature of the second substrate is preferably set to a value within the range of 90 to 140 ° C, and more preferably set to a value within the range of 100 to 120 ° C.
The glass transition temperature of the second substrate is the same as that of the first substrate, but it should be measured in a film state using DSC (Differential Scanning Calorimeter) or DTA (Differential Thermal Analysis). Can do.

  Further, the kind of the second base material may be the same as the kind of the first base material described above. For example, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl Resins such as methacrylate, triacetyl cellulose, polynorbornene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinyl chloride, polyurethane acrylate, polyether sulfone, polyphenylene sulfide, polyphenyl ether sulfone A resin film made of is preferably mentioned.

In particular, if the second substrate is a polyethylene terephthalate film or a polyphenylene sulfide film, in the pressure-sensitive adhesive sheet for the heat-resistant process, not only the predetermined heat resistance and flexibility can be obtained, but also excellent in transparency. A preferred resin film.
Moreover, since it is excellent also in adhesiveness with the silylated urethane adhesive composition which comprises a 2nd adhesive layer if it is these 2nd base materials, in manufacturing processes, such as an organic transistor, for example This is because the easy releasability from the glass substrate or the like can be effectively maintained.

Also, the thickness of the second base material is not particularly limited, but it is usually preferable to set the thickness within a range of 1 to 1,000 μm.
The reason for this is that when the thickness of the second base material is less than 1 μm, the smoothness, heat resistance, or handleability of the adhesive sheet for a predetermined heat resistance process is significantly reduced. Because there is. In addition, when high temperature processing such as solder reflow processing is performed in a state of being attached to a glass substrate or the like, blister resistance may be reduced, and so-called swelling may occur.
On the other hand, when the thickness of the second base material exceeds 1000 μm, when a predetermined heat-resistant process pressure-sensitive adhesive sheet is constructed, flexibility, handling properties and the like are remarkably lowered, or cost is increased. This is because it may be economically disadvantageous.
Therefore, the thickness of the second base material is more preferably set to a value within the range of 10 to 100 μm, and further preferably set to a value within the range of 20 to 50 μm.

5. Applications Applications of the heat-resistant process pressure-sensitive adhesive sheet 10 according to the first embodiment include application to the manufacturing process of the organic transistor 50 as shown in FIGS.
That is, as shown in FIG. 2A, for example, the heat-resistant process pressure-sensitive adhesive sheet 10 is stuck on the glass substrate 20.
At that time, the pressure-sensitive adhesive sheet 10 for the heat-resistant process is stuck on the glass substrate 20 through the second pressure-sensitive adhesive layer 18.
Next, as shown in FIG. 2B, after the planarization layer 22 is provided on the first base 12 of the heat-resistant process pressure-sensitive adhesive sheet 10, an aluminum vapor deposition method and a photolithography method are used in combination. A gate electrode 24, a gate insulating film 26, a source 28 and a drain 30 are formed on the planarizing layer 22.

Further, after forming the organic semiconductor separation layer 32 using a photolithography method or the like, the organic semiconductor vapor deposition layer 34 is formed using pentacene or the like as an organic semiconductor material.
Finally, as shown in FIG. 2 (c), peeling is performed between the first base 12 and the first pressure-sensitive adhesive layer 14.
Therefore, the organic transistor 50 formed on the first base material 12 can be peeled from the glass substrate 20 and taken out as a semiconductor product.
That is, if it is the heat-resistant process pressure-sensitive adhesive sheet 10 according to the first embodiment, no swelling occurs between the glass substrate and the like even when a high-temperature treatment at 150 ° C. or higher is performed, and Easy peelability can be maintained.
In addition, the manufacturing time of the organic transistor 50 can be shortened, and the manufacturing yield can be extremely increased.
In addition, if the 1st base material 12 and the organic transistor 50 are peeled in a post process if desired, the obtained organic transistor 50 can be applied to various uses as a semiconductor product.

[Second Embodiment]
In the second embodiment of the present invention, the first base material having a glass transition temperature of 120 ° C. or higher, the first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, and the glass transition temperature of 80. It is a manufacturing method of the adhesive sheet for heat-resistant processes which comprises sequentially the 2nd substrate which is ° C or more, and the 2nd adhesive layer derived from silylated urethane adhesive composition.
The silylated urethane pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as the component (A), the component (A) has a polyoxyalkylene structure in the main chain, It has a urethane bond and / or a urea bond in part or in the side chain, and has a hydrolyzable silyl group represented by the following (1) at both ends of the main chain. The moisture permeability of the agent layer is set to a value of 100 / Hrs or more.
And it is a manufacturing method of the adhesive sheet for heat-resistant processes characterized by including the following process (1)-(4) sequentially.
(1) Step of forming a second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition on one side of the second base material (2) Energy ray on the other side of the second base material Step of applying curable pressure-sensitive adhesive composition (3) Step of laminating the first substrate on the surface of energy-ray-curable pressure-sensitive adhesive composition (4) Energy for energy-ray-curable pressure-sensitive adhesive composition Step of forming a first pressure-sensitive adhesive layer by irradiating a line Note that the order of performing step (3) and step (4) described above may be reversed.
Therefore, in such a case, the pressure-sensitive adhesive sheet for a heat-resistant process is produced in the order of step (1), step (2), step (4), and step (3). More specifically, in the step (3), the first base material is laminated on the surface of the first pressure-sensitive adhesive layer formed by the energy ray irradiation in the step (4).

(In 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. Step (1) (second adhesive layer forming step)
In the step (1), a silylated urethane pressure-sensitive adhesive composition that is a second pressure-sensitive adhesive composition is prepared, and is laminated on one surface of a second base material having a predetermined glass transition temperature (80 ° C. or higher). And a step of forming a second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition.
More specifically, for example, the terminal silyl group polymer as the component (A) is diluted with a diluent solvent as desired, and a tackifier as the component (B) is added with stirring to obtain a uniform mixed solution. It is preferable to do.
Next, after adding the component (C) and other additives to the obtained mixture, further diluting solvent is added as necessary to achieve the desired viscosity while stirring until uniform. Thus, it is preferable to obtain a solution of the silylated urethane pressure-sensitive adhesive composition.
In addition, since it is as having already described in 1st Embodiment about the detail and the compounding quantity of each component, and also the 2nd base material etc., description for the second time is abbreviate | omitted.

And as a method of apply | coating this silylated urethane adhesive composition to the one surface of a 2nd base material, a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method, for example It is preferable to once heat-dry after forming a coating layer (coating film).
At this time, it is usually preferable to set the silylated urethane pressure-sensitive adhesive composition to a value within the range of 50 to 150 ° C. and 10 seconds to 10 minutes.

Moreover, it is preferable that hardening of this silylated urethane adhesive composition is performed through the drying process mentioned above and a seasoning process.
Here, as a condition of the seasoning step, the curing temperature is 20 to 50 ° C. from the viewpoint of uniform curing without damaging the coating layer of the silylated urethane pressure-sensitive adhesive composition and the second substrate. It is preferable to set it as the value within the range, and it is more preferable to set it as the value within the range of 23-30 degreeC.
Moreover, as humidity of a seasoning process, it is preferable to set it as the value within the range of 30-75% RH, and it is more preferable to set it as the value within the range of 45-65% RH.

2. Process (2) (application process of energy ray-curable adhesive composition)
Step (2) may be referred to as the surface (the B surface side) opposite to the side (which may be referred to as the A surface side) on which the silylated urethane pressure-sensitive adhesive composition is applied in the second substrate. ) Is a step of applying an energy ray-curable pressure-sensitive adhesive composition.
Moreover, as a method of apply | coating this energy-beam curable adhesive composition to the predetermined surface (A surface side) of a 2nd base material, a bar coat method, a knife coat method, a roll coat method, a blade coat method, for example A die coating method, a gravure coating method, or the like can be used, and it is preferable that a coating layer is once formed and then dried.
At this time, it is preferable to appropriately adjust the thickness of the coating layer so as to be a predetermined thickness of the pressure-sensitive adhesive layer obtained after drying.
Moreover, as drying conditions, it is usually preferable to set it within a range of 10 to 10 minutes at 50 to 150 ° C.

3. Step (3) (first substrate lamination step)
Step (3) is a step of laminating a first base material having a predetermined glass transition temperature (120 ° C. or higher) on the surface of the energy ray curable pressure-sensitive adhesive composition applied on the second base material. is there.
Therefore, it is preferable to laminate a PEN film, for example, as the first base material on the surface of the energy ray-curable pressure-sensitive adhesive composition using a laminator or the like.
As described above, step (3) may be performed after step (4) described later. Therefore, in such a case, in the step (3), the first base material is laminated on the surface of the first pressure-sensitive adhesive layer formed in the step (4).

4). Process (4) (Formation process of a 1st adhesive layer)
Step (4) is a step of irradiating the energy ray-curable pressure-sensitive adhesive composition, which is the first pressure-sensitive adhesive composition, with energy rays to form a first pressure-sensitive adhesive layer.
That is, for the energy ray-curable adhesive composition, upon irradiation with energy ray, as an example, using an ultraviolet irradiation device, illuminance 100~400mW / cm ^2, that the condition of light intensity 100 to 500 mJ / cm ² Is preferred.
And it is preferable to irradiate an ultraviolet-ray with respect to the ultraviolet curable line adhesive composition which is one of the energy-beam curable adhesive compositions, and to form a 1st adhesive layer.
The irradiation of energy rays such as ultraviolet rays may be performed through the first base material, or may be performed through the second base material and the second pressure-sensitive adhesive layer.

5. Other steps (seasoning treatment of the second adhesive layer)
Before the step (4) described above, it is preferable to perform a seasoning treatment of the second pressure-sensitive adhesive layer as another step.
That is, in the above-mentioned step (4), before irradiating the energy ray-curable pressure-sensitive adhesive composition with energy rays, the silylated urethane pressure-sensitive adhesive composition formed by laminating on one side of the second substrate. A seasoning treatment is preferably performed on the coating layer.
Therefore, as an example, the reaction of the silylated urethane pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer is allowed to stand (seasoning) for 1 to 20 days in an environment of 20 to 40 ° C. and 30 to 50% RH. It is preferable to proceed sufficiently.

Hereinafter, with reference to an Example, the adhesive sheet for heat-resistant processes of this invention is demonstrated more concretely.
However, it goes without saying that the scope of the present invention is not limited by the description of these examples and the like without any particular reason.

[Example 1]
1. Preparation of first pressure-sensitive adhesive composition (energy-ray curable pressure-sensitive adhesive) In a nitrogen atmosphere, a stirrer, a condenser, a thermometer, and a nitrogen introduction tube were attached, and the reactor was purged with nitrogen. Part, 100 parts by weight of a monomer component consisting of 30 parts by weight of methyl methacrylate and 20 parts by weight of 2-hydroxyethyl acrylate, a predetermined amount of ethyl acetate as a solvent, and azobisisobutyronitrile (polymerization initiator) ) 0.25 part by weight was mixed and stirred until uniform.
Next, in the reaction apparatus, the monomer component is subjected to a solution polymerization reaction under a condition of 60 ° C. for 24 hours while refluxing the solvent, and an acrylic polymer solution containing an acrylic polymer having a weight average molecular weight of 400,000 (solid (Min. Concentration: 40% by weight).
Next, a predetermined amount of methyl ethyl ketone was further added to the obtained acrylic polymer solution for dilution, and the solid content concentration was adjusted to 35% by weight.
Next, 12 parts by weight of methacryloyloxyethyl isocyanate and 0.13 parts by weight of dibutyltin dilaurate are added to the reactor, and the reaction is carried out under the conditions of 50 ° C. and 12 hours to obtain an acrylate copolymer having a methacryloyl group added thereto. A polymer solution containing was obtained.
Thereafter, 0.25 parts by weight of a polyisocyanate-based crosslinking agent (manufactured by Tosoh Corp., Coronate L, solid content: 75% by weight) and a photopolymerization initiator (manufactured by BASF, Irgacure) were obtained. 184) was added in an amount of 3.5 parts by weight to obtain a solution state energy ray-curable pressure-sensitive adhesive composition A (sometimes referred to as UV pressure-sensitive adhesive A).

2. Preparation of second pressure-sensitive adhesive composition (silylated urethane pressure-sensitive adhesive) (1) Preparation of silylating agent
In a reaction vessel equipped with a stirrer, 100 parts by weight of N-aminoethyl-γ-aminopropylmethyldimethoxysilane and 83.5 parts by weight of methyl acrylate were charged and stirred at 80 ° C. for 10 hours in a nitrogen atmosphere. The reaction was carried out under heating conditions to obtain a silylating agent.

(2) Preparation of urethane prepolymer In another reaction vessel equipped with a stirrer, polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., PML S4015, weight average molecular weight: 15,000) 100 parts by weight, isophorone diisocyanate 2.46 Part by weight (NCO / OH ratio = 1.7) and 0.005 part by weight of dibutyltin dilaurate were charged and heated under a nitrogen atmosphere with stirring at 85 ° C. for 7 hours to obtain a predetermined urethane prepolymer. It was.

(3) Synthesis of terminal silyl group polymer (silylated urethane polymer) Next, 4.21 parts by weight of a silane compound as a silylating agent was added to 100 parts by weight of the obtained urethane prepolymer, and a nitrogen atmosphere was added. Under stirring, the mixture was reacted at 80 ° C. for 1 hour to obtain a terminal silyl group polymer (silylated urethane polymer) as component (A).
At this time, the disappearance of the isocyanate group absorption peak (2265 cm ⁻¹ ) was measured by an infrared spectrophotometer (FT-IR), thereby confirming the degree of progress of the reaction.
In addition, since the raw material of the silylating agent was N-aminoethyl-γ-aminopropylmethyldimethoxysilane, a bifunctional terminal silyl group was introduced into the obtained terminal silyl group polymer.

Furthermore, the obtained terminal silyl group polymer as the component (A) has both ends of a weight average molecular weight of 40,000 having terminal portions represented by the following formula (9) at both ends of polyoxypropylene as a main chain. It was a silyl group polymer.
That is, the weight average molecular weight of the component (A) was measured under the following conditions using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name: HLC-8020), and measured in terms of standard polystyrene. Values were used.
(Measurement condition)
Column: “TSK guard column HXL-H”, “TSK gel GMHXL (× 2)”, “TSK gel G2000HXL” (both manufactured by Tosoh Corporation), column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min

(4) Preparation of silylated urethane pressure-sensitive adhesive composition Next, 100 parts by weight of ethyl acetate as a solvent and 100 parts by weight of a catalyst as component (C) with respect to 100 parts by weight of the terminal silyl group polymer as component (A). 0.12 part by weight of boron trifluoride monoethylamine complex as a component, and 0.4 of 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking aid as component (D) By weight, each was added and stirred until it became more uniform to obtain silylated urethane pressure-sensitive adhesive composition A (referred to as silylated urethane A) as the second pressure-sensitive adhesive composition.

3. Application of the first pressure-sensitive adhesive composition and the second pressure-sensitive adhesive composition Next, the obtained second pressure-sensitive adhesive composition (silylated urethane A) was used as a second substrate, and a polyester film having a thickness of 50 μm. (Toray Industries, Ltd., Lumirror T60, glass transition temperature 110 ° C.) Using a knife coater method, the coating is dried to a thickness of 25 μm, and then heated at 100 ° C. for 1 minute. It processed and it was set as the laminated body provided with the 2nd adhesive layer.
Next, the obtained first pressure-sensitive adhesive composition (UV pressure-sensitive adhesive A) was coated with the second pressure-sensitive adhesive composition in the laminate (A surface side) and the opposite side (B surface side) polyester. It applied to the surface of a film so that the thickness after drying might be set to 25 micrometers using the knife coater method.
Then, it heat-processed on 100 degreeC and the conditions for 1 minute, and was set as the double-sided adhesive sheet provided with the 1st adhesive layer.

4). Seasoning Step Next, a polyester release sheet having a thickness of 50 μm was attached to both sides of the obtained double-sided PSA sheet.
In this state, it was allowed to stand (seasoning) in an environment of 23 ° C. and 50% RH for 14 days to sufficiently promote the reaction of the silylated urethane pressure-sensitive adhesive composition constituting the second pressure-sensitive adhesive layer.

5. Process (4) (Formation process of a 1st adhesive layer)
Then, after peeling off the polyester release sheet attached to the first pressure-sensitive adhesive composition (UV pressure-sensitive adhesive A) side, as a first substrate for the coating layer of the first pressure-sensitive adhesive composition, A polyethylene 2,6-naphthalate film (PEN film, manufactured by Teijin Ltd., Teonex, thickness: 25 μm, glass transition temperature: 120 ° C.) was laminated.
Next, after peeling off the polyester release sheet attached to the second pressure-sensitive adhesive composition (silylated urethane A) side, it was attached to the glass plate via the second pressure-sensitive adhesive layer, and then from the PEN film side. , UV irradiation (Lintec Co., Ltd., using the device name Adwill RAD-2000m / 8, illuminance of 310 mW / cm ² , light amount of 300 mJ / cm ² ), and UV-curing the coating layer of the first pressure-sensitive adhesive composition The pressure-sensitive adhesive sheet for heat-resistant process of Example 1 was obtained.

6). Evaluation (1) Measurement of moisture permeability Separately, a single film of the second pressure-sensitive adhesive layer (silylated urethane A) was prepared.
Next, an evaluation sample in which the single film of the second pressure-sensitive adhesive layer was sandwiched between two polyester meshes (NBC Meshtec, EX-screen 79-055 / 200 PW) was prepared.
The moisture permeability of this evaluation sample was measured in accordance with the cup method (JIS Z0208) and used as the moisture permeability of the second pressure-sensitive adhesive layer.

(2) Evaluation of blister resistance The pressure-sensitive adhesive sheet for a heat-resistant process adhered to a glass plate is left in an oven at 150 ° C. for 1 hour, and its appearance change is visually observed. A sex assessment was performed. FIG. 3 (a) shows the appearance (photograph) of the heat-sensitive adhesive sheet for heat resistance process used for the evaluation of blister resistance.
○: No swelling is observed.
Δ: Slight swelling is observed.
X: Remarkable swelling is observed.

(3) Evaluation of chemical resistance An ultrasonic device (frequency: 40 Hz) is immersed in 100 g of isopropyl alcohol (IPA) housed in a glass beaker container, with the pressure-sensitive adhesive sheet for heat-resistant process attached to a glass plate. Used and irradiated with ultrasound for 10 minutes.
Then, the external appearance change of the adhesive sheet for heat-resistant processes was observed visually, and chemical-resistant evaluation was implemented according to the following reference | standard.
○: No floating is observed at all.
Δ: Some floats are observed, and some IPA intrusion is observed.
X: Remarkable floating is observed, and intrusion of IPA is clearly observed.

(4) Evaluation of peelability The pressure-sensitive adhesive sheet for a heat-resistant process stuck on a glass plate was placed in an oven at 150 ° C for 1 hour.
Next, the pressure-sensitive adhesive sheet for heat-resistant process was taken out of the oven, and after waiting for the temperature to reach room temperature, the PEN film was peeled off, and peelability was evaluated according to the following criteria.
○: Can be easily peeled off when triggered.
X: Even if a trigger is created, it cannot be easily peeled off, and it cannot be peeled unless the PEN film is bent.

[Example 2]
In Example 2, a pressure-sensitive adhesive sheet for a heat-resistant process was produced in the same manner as in Example 1 except that UV adhesive B was prepared and used instead of UV adhesive A constituting the first adhesive composition. And evaluated.
That is, in a nitrogen atmosphere, a monomer component comprising 95 parts by weight of n-butyl acrylate and 5 parts by weight of 2-hydroxyethyl acrylate is installed in a reactor substituted with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube. 100 parts by weight and a predetermined amount of a mixed solution composed of ethyl acetate / toluene (mixing ratio: 50/50) as a solvent are accommodated, and further 0.1 parts by weight of azobisisobutyronitrile (polymerization initiator) Were mixed and stirred until uniform.
Next, in the reactor, the monomer component is subjected to solution polymerization under conditions of 65 ° C. and 17 hours while refluxing the solvent, and an acrylic polymer solution (solid) containing an acrylic polymer having a weight average molecular weight of 680,000 is obtained. Minor concentration: 30% by weight).
Next, 6.7 parts by weight of methacryloyloxyethyl isocyanate and 0.004 parts by weight of dibutyltin dilaurate were added to the acrylic polymer solution in the reactor, and the mixture was stirred at room temperature for 6 hours.
Then, it was made to react with stirring on conditions of 40 degreeC and 18 hours, and it was set as the acryl-type polymer which added the methacryloyl group.
Finally, with respect to 100 parts by weight of the acrylic polymer to which the methacryloyl group was added, an energy ray-curable urethane acrylate oligomer having a carbonate ester structure (manufactured by Nippon Synthetic Chemical Co., Ltd., purple light UV-3210EA, weight average molecular weight 10, 000) 15 parts by weight, 1.5 parts by weight of a photopolymerization initiator (BASF, Irgacure 184), and 0.5 parts by weight of an XDI polyisocyanate compound (manufactured by Soken Chemical Co., Ltd., TD-75) as a crosslinking agent. Were added to obtain energy ray-curable pressure-sensitive adhesive composition B (UV pressure-sensitive adhesive B).
As a result, as shown in Table 1, since the pressure-sensitive adhesive sheet for heat-resistant process of Example 2 satisfies the predetermined configuration, good results were obtained in the evaluation of blister resistance, chemical resistance, and peelability, respectively. It was.

[Comparative Example 1]
In Comparative Example 1, a heat-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive A was used instead of the silylated urethane A constituting the second pressure-sensitive adhesive layer.
That is, in a nitrogen atmosphere, a stirrer, a condenser, a thermometer, and a nitrogen introduction tube were attached, and in a reactor purged with nitrogen, 100 parts by weight of a monomer component consisting of 90 parts by weight of n-butyl acrylate and 10 parts by weight of acrylic acid, And a predetermined amount of ethyl acetate as a solvent.
Next, 0.25 parts by weight of azobisisobutyronitrile (polymerization initiator) was placed in the reactor and stirred until uniform.
Next, an acrylic polymer solution (solid content concentration: 40) containing an acrylic polymer having a weight average molecular weight of 400,000 is subjected to a solution polymerization reaction in ethyl acetate in a reaction apparatus under conditions of 60 ° C. and 24 hours. % By weight).
Next, 1.2 parts by weight of a polyisocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate L, solid content: 75% by weight) is added to the resulting acrylic polymer solution, and acrylic adhesive A is added. And used it.
As a result, as shown in Table 1, the heat-resistant process pressure-sensitive adhesive sheet of Comparative Example 1 has a second pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive A having a moisture permeability of less than a predetermined value. It became clear that there was a problem with blister resistance.
In addition, in FIG.3 (b), the external appearance (photograph) of the adhesive sheet for heat-resistant processes used for blister-proof evaluation is shown.

[Comparative Example 2]
In Comparative Example 2, a heat-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive B was used instead of the silylated urethane A constituting the second pressure-sensitive adhesive layer.
That is, the acrylic adhesive B was replaced with 1.2 parts by weight of a polyisocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate L, solid content 75% by weight), an aluminum chelate-based crosslinking agent (manufactured by Soken Chemical Co., Ltd., M-5A, 5 wt% solid content) Except for using 4 parts by weight, it was prepared in the same manner as the acrylic pressure-sensitive adhesive A, and the acrylic pressure-sensitive adhesive B was used.
As a result, as shown in Table 1, in the heat-resistant process pressure-sensitive adhesive sheet of Comparative Example 2, the second pressure-sensitive adhesive layer is composed of an acrylic pressure-sensitive adhesive B having a moisture permeability of less than a predetermined value. It became clear that there was a problem with blister resistance.
In addition, in FIG.3 (c), the external appearance (photograph) of the adhesive sheet for heat-resistant processes used for blister-proof evaluation is shown.

[Comparative Example 3]
In Comparative Example 3, instead of silylated urethane A constituting the second pressure-sensitive adhesive layer, it was changed to silylated urethane B having a moisture permeability of less than a predetermined value, as in Example 1, for the heat-resistant process. An adhesive sheet was manufactured and evaluated.
That is, 100 parts by weight of a terpene phenol tackifying resin (manufactured by Yashara Chemical Co., TH130) is added to the second pressure-sensitive adhesive composition described above, and the silylation having a moisture permeability of 18 (g / m ² / Hrs) is added. It was prepared and used in the same manner as silylated urethane A except that modified urethane B was prepared.
As a result, as shown in Table 1, in the heat-resistant process pressure-sensitive adhesive sheet of Comparative Example 3, the second pressure-sensitive adhesive layer is composed of silylated urethane B having a moisture permeability of less than a predetermined value. It became clear that there was a problem with blister resistance.
In addition, in FIG.3 (d), the external appearance (photograph) of the adhesive sheet for heat resistance processes used for blister-proof evaluation is shown.

[Comparative Example 4]
In Comparative Example 4, a pressure-sensitive adhesive sheet for a heat-resistant process was produced and evaluated in the same manner as in Example 1 except that instead of the UV pressure-sensitive adhesive A constituting the first pressure-sensitive adhesive layer, the acrylic pressure-sensitive adhesive A described above was used. did.
As a result, as shown in Table 1, the pressure-sensitive adhesive sheet for heat-resistant process of Comparative Example 4 has blister resistance and peelability due to the reason that the first pressure-sensitive adhesive layer is composed of the acrylic pressure-sensitive adhesive A. , Each revealed a problem.

[Comparative Example 5]
In Comparative Example 5, a pressure-sensitive adhesive sheet for heat-resistant process was produced and evaluated in the same manner as in Example 1, except that the above-described silylated urethane A was used instead of the UV adhesive A constituting the first adhesive layer. did.
As a result, as shown in Table 1, the heat-resistant process pressure-sensitive adhesive sheet of Comparative Example 5 has a problem in peelability due to the reason that the first pressure-sensitive adhesive layer is composed of silylated urethane A. It became clear.

As described above in detail, according to the present invention, the predetermined first base material, the first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, and the predetermined second base material And a second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition in order, and by adjusting the structure and moisture permeability of the second pressure-sensitive adhesive layer to a predetermined range, Even when solder reflow treatment, organic transistor production, or the like is carried out, a pressure-sensitive adhesive sheet for a heat-resistant process that does not swell and maintains good easy peelability can be obtained.
Therefore, for example, even when a high temperature treatment at 150 ° C. or higher is performed, the pressure-sensitive adhesive sheet for a heat-resistant process that does not swell and maintains good easy peelability, and such a pressure-sensitive adhesive for heat-resistant process An efficient method for producing a sheet can be provided.
That is, according to the pressure-sensitive adhesive sheet for a heat-resistant process of the present invention, it contributes to the improvement of heat resistance in the pressure-sensitive adhesive sheet for a heat-resistant process, and particularly to the yield improvement of a predetermined product in a solder reflow process or an organic transistor manufacturing process. It is expected.

10: Adhesive sheet 12 for heat-resistant process, 12 ': 1st base material 14: 1st adhesive layer 16: 2nd base material 18, 18': 2nd adhesive layer 19: Release film 20: Glass Substrate 50: Organic transistor

Claims (8)

A first substrate having a glass transition temperature of 120 ° C. or higher, a first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, and a second substrate having a glass transition temperature of 80 ° C. or higher; A second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet for a heat-resistant process,
The silylated urethane pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as a component (A),
The component (A) has a polyoxyalkylene structure in the main chain, and has a urethane bond and a urea bond, or one of the main chain and a side chain,
It has hydrolyzable silyl groups represented by the following (1) at both ends of the main chain,
And the moisture permeability of the said 2nd adhesive layer shall be a value 100 g / m < ² > / Hrs or more, The adhesive sheet for heat-resistant processes characterized by the above-mentioned.
(In 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.)   The silylated urethane pressure-sensitive adhesive composition contains a tackifier as the component (B), and the blending amount of the tackifier is less than 50 parts by weight with respect to 100 parts by weight of the component (A). It is set as a value, The adhesive sheet for heat-resistant processes of Claim 1 characterized by the above-mentioned.   The silylated urethane pressure-sensitive adhesive composition contains, as the component (C), a curing catalyst that cures the component (A), and the curing catalyst includes an aluminum catalyst, a titanium catalyst, a zirconium catalyst, a bismuth catalyst, and It is at least 1 type selected from the group which consists of a boron trifluoride type catalyst, The adhesive sheet for heat-resistant processes of Claim 1 or 2 characterized by the above-mentioned.   The pressure-sensitive adhesive sheet for a heat-resistant process according to any one of claims 1 to 3, wherein the first substrate is a polyethylene naphthalate film or a polyimide film.   The pressure-sensitive adhesive sheet for a heat-resistant process according to any one of claims 1 to 4, wherein the second substrate is a polyethylene terephthalate film or a polyphenylene sulfide film.   6. The energy ray curable resin, wherein the main component of the energy ray curable pressure-sensitive adhesive composition is an energy ray curable resin formed by adding a (meth) acryloyl group to an acrylic polymer. The pressure-sensitive adhesive sheet for a heat-resistant process according to claim 1. A first substrate having a glass transition temperature of 120 ° C. or higher, a first pressure-sensitive adhesive layer derived from the energy ray-curable pressure-sensitive adhesive composition, and a second substrate having a glass transition temperature of 80 ° C. or higher; A second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition, and a method for producing a pressure-sensitive adhesive sheet for a heat-resistant process, comprising:
The silylated urethane pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as a component (A),
The component (A) has a polyoxyalkylene structure in the main chain, and has a urethane bond and a urea bond, or one of the main chain and a side chain,
It has hydrolyzable silyl groups represented by the following (1) at both ends of the main chain,
The moisture permeability of the second pressure-sensitive adhesive layer is set to a value of 100 g / m ² / Hrs or more,
And the manufacturing method of the adhesive sheet for heat-resistant processes characterized by including the following process (1)-(4).
(1) Step of forming the second pressure-sensitive adhesive layer derived from the silylated urethane pressure-sensitive adhesive composition on one side of the second base material (2) The other side of the second base material (3) The step of laminating the first substrate on the surface of the energy beam curable pressure-sensitive adhesive composition (4) The energy beam curable pressure-sensitive adhesive The process of irradiating the agent composition with energy rays to form the first pressure-sensitive adhesive layer
(In 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.)   The method for producing a pressure-sensitive adhesive sheet for a heat-resistant process according to claim 7, wherein the first substrate is a polyethylene naphthalate film or a polyimide film.