JP5833498B2 - Blister-resistant adhesive sheet - Google Patents

Description

The present invention relates to an adhesive sheet for blister resistance.
In particular, the present invention relates to a blister-resistant pressure-sensitive adhesive sheet that can effectively suppress the generation of blisters even when the substrate in the pressure-sensitive adhesive sheet has gas barrier properties.

Conventionally, pressure-sensitive adhesive sheets coated with a pressure-sensitive adhesive (pressure-sensitive adhesive) on a substrate can be easily attached to an adherend by pressing, and thus are widely used in many fields.
In recent years, plastic molded products are frequently used due to demands for reducing the weight of products. Accordingly, the use of pressure-sensitive adhesive sheets using plastic molded products as adherends is increasing.

However, resins such as polycarbonate resin, polymethyl methacrylate resin, polystyrene resin, and ABS resin are used for such plastic molded products. However, the surface of these plastic molded products is a metal for reasons such as decoration. When an adhesive sheet using a base material formed by laminating a layer having gas barrier properties such as a vapor deposition layer was attached, there was a problem that blisters were generated.
That is, the gas generated from the plastic molded product forms bubbles between the pressure-sensitive adhesive sheet and the plastic molded product, so-called blisters such as swelling and floating, and the appearance of the molded product is impaired. It was seen.

Then, the blister-resistant adhesive composition for blister resistance which has blister resistance is disclosed (for example, patent documents 1-3).
That is, Patent Document 1 discloses that a (meth) acrylic acid ester is 65 to 96% by weight, a carboxyl group-containing compound that is copolymerizable with the (meth) acrylic acid ester is 3 to 15% by weight, and a tertiary amine having a vinyl group. An acrylic pressure-sensitive adhesive composition obtained by radical copolymerization of 1 to 20% by weight is disclosed.

  In Patent Document 2, an alkyl (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl group as a main component, a carboxyl group contained therein, and a copolymerizable unsaturated monomer of 0.5 to A resin composition (1) having a weight average molecular weight of 800,000 or more obtained by copolymerization of 10% by weight, a methacrylic acid alkyl ester or a methacrylic acid cycloalkyl ester having 1 to 20 carbon atoms in an alkyl group, and methacrylic acid Glass obtained by copolymerizing one or more monomers selected from benzyl or styrene as a main component, and containing 0.5 to 10% by weight of a copolymerizable unsaturated monomer containing an amino group. A resin composition (2) having a transition temperature (Tg) of 40 ° or more and a weight average molecular weight of 100,000 or less, and 100 parts by weight of the resin composition (1), the resin composition (2) 1-40 obtained by adding parts pressure-sensitive adhesive composition is disclosed.

Further, Patent Document 3 discloses that in acetone, (A) (meth) acrylic acid alkyl ester monomer 80 to 99% by weight, and (B) carboxyl group-containing α, β-ethylenically unsaturated monomer 1 A resin composition having a weight average molecular weight of 1.5 million or more and a weight average molecular weight / number average molecular weight of 4.0 or less, obtained by polymerizing ˜20% by weight, tolylene diisocyanate with respect to 100 parts of the resin composition 20 g / m ² of a composition to which 2 parts of trimethylolpropane adduct is added is coated on polyethylene terephthalate, laminated with a polycarbonate plate, and left to stand in an oven at 100 ° C. for 30 days. A resin composition is disclosed.

On the other hand, a pressure-sensitive adhesive sheet having excellent adhesive strength, characterized by using a pressure-sensitive adhesive composition containing a predetermined terminal silyl group polymer as a main ingredient, although not specifically aimed at improving blister resistance, is disclosed. (For example, Patent Document 4).
That is, Patent Document 4 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 (11) at the terminal. And 10 to 150 parts by mass of a tackifying resin, 0.001 to 10 mass of a fluorine-based compound selected from the group consisting of boron trifluoride and / or its complex, a fluorinating agent and an alkali metal salt of a fluorine-based inorganic acid The pressure-sensitive adhesive precursor is made into a pressure-sensitive adhesive layer by applying the pressure-sensitive adhesive precursor uniformly mixed to the surface of the tape base material or the sheet base material and then curing the terminal silyl group polymer. A pressure-sensitive adhesive sheet is disclosed.

(In general formula (11), 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-A-2-3481 (Claims) JP 10-310754 A (Claims) JP 2001-354745 A (Claims) WO2010 / 038715 (Claims)

However, when the blister-resistant pressure-sensitive adhesive composition described in Patent Documents 1 and 2 is used, it is difficult to achieve cohesion and adhesion at the interface, making it difficult to obtain sufficient blister resistance. The problem was seen.
Furthermore, when the pressure-sensitive adhesive composition for blister resistance described in Patent Document 3 is used, it is not only difficult to obtain sufficient blister resistance, because sufficient cohesive force cannot be obtained. There was a problem that the molecular weight was excessively large and it had to be diluted with a large amount of solvent.
On the other hand, in the case of the pressure-sensitive adhesive sheet of Patent Document 4, since the pressure-sensitive adhesive composition is excellent in adhesive force, the pressure-sensitive adhesive composition and the plastic molded product can be firmly adhered to each other to obtain a certain degree of blister resistance. Since the cohesive force of the product is not taken into account, there is a problem that the balance between the adhesive force and the cohesive force is poor and it is difficult to stably obtain sufficient blister resistance.

Therefore, the present inventors made extensive efforts in view of the above circumstances, and added a predetermined tackifying resin to a predetermined terminal silyl group polymer at a predetermined blending ratio, and a pressure-sensitive adhesive composition. It was found that by setting the gel fraction after crosslinking in a value within a predetermined range, the balance between the adhesive force and the cohesive force in the pressure-sensitive adhesive composition was improved, and excellent blister resistance was obtained. The invention has been completed.
That is, an object of the present invention is to provide a blister-resistant pressure-sensitive adhesive sheet that can effectively suppress the generation of blisters even when the substrate in the pressure-sensitive adhesive sheet has gas barrier properties.

  According to the present invention, it is a blister-resistant pressure-sensitive adhesive sheet having at least one pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer comprises a terminal silyl group polymer as the component (A) and a tackifier resin as the component (B). The terminal silyl group polymer as component (A) has a urethane bond and a urea bond in the main chain or side chain, or one of them, and the following general formula at both ends of the main chain: It is a terminal silyl group polymer having a hydrolyzable silyl group represented by (1), and the tackifier resin as component (B) is at least one of a styrene monomer, an α-methylstyrene monomer and an aliphatic monomer. At least one selected from the group consisting of a tackifying resin obtained by polymerization, a terpene phenol tackifying resin, and a rosin phenol tackifying resin. The amount of the tackifier resin as the component (B) is a value within the range of 10 to 140 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A), And the adhesive fraction for blisters characterized by making the gel fraction after the bridge | crosslinking in an adhesive composition into the value within the range of 30-100% is provided, and the problem mentioned above can be solved.

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

That is, if it is the blister-resistant pressure-sensitive adhesive sheet 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 and a predetermined tackifying resin as a tackifying resin. Therefore, an excellent adhesive force can be exhibited by these interactions.
Therefore, the pressure-sensitive adhesive composition and the plastic adherend can be firmly adhered to each other, and the generation of gas derived from the plastic adherend can be effectively contained.
Moreover, if it is the blister-resistant adhesive sheet of this invention, since the gel fraction after bridge | crosslinking in the adhesive composition which comprises an adhesive layer is made into the value within the predetermined range, it exhibits the outstanding cohesive force. be able to.
Therefore, the deformation due to the generation of gas derived from the plastic adherend, that is, the generation of blisters can be suppressed by the hardness of the pressure-sensitive adhesive composition itself.
Therefore, if it is a blister-resistant pressure-sensitive adhesive sheet of the present invention, it is excellent in the balance between the pressure-sensitive adhesive force and cohesive force in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer. The generation of blisters can be effectively suppressed.
The “pressure-sensitive adhesive composition” in the present invention is, for example, a pressure-sensitive adhesive composition having the above-described composition, whether it is an uncrosslinked pressure-sensitive adhesive composition or a pressure-sensitive adhesive composition after crosslinking. If there is, it is a broad meaning included.
However, in the following, the pressure-sensitive adhesive composition after crosslinking may be described as “pressure-sensitive adhesive” in particular.

In constituting the blister-resistant pressure-sensitive adhesive sheet of the present invention, the main chain or side chain skeleton in the terminal silyl group polymer as the component (A) is preferably polyoxyalkylene.
By comprising in this way, moderate softness | flexibility can be provided with respect to the adhesive composition which comprises the adhesive layer obtained.

In constituting the blister-resistant pressure-sensitive adhesive sheet of the present invention, the terminal silyl group polymer as the component (A) does not have a hydrolyzable silyl group represented by the general formula (1) in the side chain, It is preferable that it is a both-terminal silyl group polymer which has a hydrolyzable silyl group represented by General formula (1) only at both the terminal.
By comprising in this way, the crosslinking density of (A) component is adjusted to a suitable range, and the adjustment of the balance of the adhesive force and cohesion force in the adhesive composition after bridge | crosslinking can be made easier. .
Hereinafter, a terminal silyl group polymer having a predetermined hydrolyzable silyl group only at both ends of the main chain will be referred to as a “both terminal silyl group polymer”.

Further, in constituting the blister-resistant pressure-sensitive adhesive sheet of the present invention, as a component (A ′), a one-end silyl group polymer having a hydrolyzable silyl group represented by the general formula (1) only at one end of the main chain In addition, the blending amount is preferably set to a value in the range of 0.1 to 15 parts by weight with respect to 100 parts by weight of the both-end silyl group polymer.
By comprising in this way, the crosslinking density of (A) component is adjusted to a more suitable range, and the adjustment of the balance of the adhesive force and cohesion force in the adhesive composition after bridge | crosslinking can be made still easier. it can.
In the following, the terminal silyl group polymer having a predetermined hydrolyzable silyl group only at one end of the main chain will be referred to as “one-end silyl group polymer”.

Further, in constituting the blister-resistant pressure-sensitive adhesive sheet of the present invention, the component (C) includes a catalyst for promoting the crosslinking of the terminal silyl group polymer as the component (A), and the catalyst is an aluminum catalyst. It is preferably at least one selected from the group consisting of a titanium-based catalyst, a zirconium-based catalyst, and a boron trifluoride-based catalyst.
By comprising in this way, control of the crosslinking density of (A) component becomes easy, and adjustment of the balance of the adhesive force and cohesion force in the adhesive composition after bridge | crosslinking can be made still easier. .

Moreover, in constituting the blister-resistant pressure-sensitive adhesive sheet of the present invention, it is preferable to have a pressure-sensitive adhesive layer on one or both sides of the substrate, and it is particularly preferable that the substrate has a metal vapor-deposited layer.
By comprising in this way, since a metal vapor deposition layer has gas barrier property, it becomes easy to generate | occur | produce a blister, but if it is an adhesive sheet for blistering resistance of this invention, generation | occurrence | production of a blister can be suppressed effectively. it can.

FIGS. 1A to 1B are diagrams provided for explaining a predetermined terminal silyl group polymer. FIG. 2 is a diagram for explaining the relationship between the blending amount of a predetermined tackifying resin and the blister resistance. FIG. 3 is a diagram provided for explaining the relationship between the gel fraction and the blister resistance. 4 (a) to 4 (d) are diagrams provided for explaining the mode of the blister-resistant pressure-sensitive adhesive sheet. FIG. 5 is a diagram provided to show blister resistance in Example 1. FIG. 6 is a diagram provided to show the blister resistance in Example 2. FIG. 7 is a diagram provided to show blister resistance in Example 3. FIG. 8 is a diagram provided to show the blister resistance in Comparative Example 2. FIG. 9 is another diagram provided to show the blister resistance in Comparative Example 2. FIG. 10 is a diagram provided to show the blister resistance of Comparative Example 3. FIG. 11 is another diagram provided to show the blister resistance of Comparative Example 3. FIG. 12 is another diagram provided to show the blister resistance of Comparative Example 4.

An embodiment of the present invention is a blister-resistant pressure-sensitive adhesive sheet having at least one pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer comprising a terminal silyl group polymer as the component (A) and a tackifying resin as the component (B) The terminal silyl group polymer as component (A) has a urethane bond and / or a urea bond in the main chain or side chain, or a general formula at both ends of the main chain. It is a terminal silyl group polymer having a hydrolyzable silyl group represented by (1), and the tackifier resin as component (B) is at least one of a styrene monomer, an α-methylstyrene monomer and an aliphatic monomer. At least one selected from the group consisting of a tackifying resin obtained by polymerization, a terpene phenol tackifying resin, and a rosin phenol tackifying resin. The amount of the tackifier resin as the component (B) is a value within the range of 10 to 140 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A), And it is the adhesive sheet for blister resistance characterized by making the gel fraction after bridge | crosslinking in an adhesive composition into the value within the range of 30-100%.
Hereinafter, a first embodiment of the present invention will be specifically described with reference to the drawings as appropriate.

1. The pressure-sensitive adhesive layer The blister-resistant pressure-sensitive adhesive sheet of the present invention comprises a predetermined pressure-sensitive adhesive composition containing a predetermined terminal silyl group polymer as the component (A) and a predetermined tackifying resin as the component (B). It is characterized by.
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 the component (A) has a urethane bond and a urea bond in the main chain or side chain, or one of them, It has a hydrolyzable silyl group represented by the following general formula (1) at both ends of the main chain.

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

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.
Therefore, by combining with a predetermined tackifying resin, excellent adhesive force can be exhibited, and the pressure-sensitive adhesive composition and the plastic adherend are firmly adhered to each other, derived from the plastic adherend. It is possible to effectively contain the generated gas.
Moreover, if it is such (A) component, since it has the bifunctional hydrolyzable terminal silyl group represented by General formula (1), the gel fraction in the adhesive composition after bridge | crosslinking is a predetermined range. This is because an excellent cohesive force can be exhibited by adjusting to.
Therefore, the deformation due to the generation of gas derived from the plastic adherend, that is, the generation of blisters can be suppressed by the hardness of the pressure-sensitive adhesive composition itself.
Therefore, by using a predetermined terminal silyl group polymer as the component (A), it is possible to obtain a pressure-sensitive adhesive composition that is excellent in the balance between adhesive force and cohesive force, and thus excellent in blister resistance.
In general formula (1), the number of carbon atoms of the alkyl group represented by R ¹ is more preferably 1 to 12, more preferably 1 to 3, from the viewpoint of hydrolytic dehydration condensation reactivity. .
Moreover, when X < ¹ > or X < ² > is an alkoxy group in General formula (1), it is preferable that the carbon number in the said alkoxy group is 1-12 from a hydrolytic dehydration condensation reactivity viewpoint, 3 is more preferable.

(I) Basic Configuration Next, the basic configuration of a predetermined terminal silyl group polymer as the component (A) will be described with reference to FIG.
That is, FIG. 1A shows a synthesis example of a predetermined terminal silyl group polymer 30.
First, a polymer skeleton 10 having an isocyanate group 14 (14a, 14b) at the end of the main chain 12 or side chain (not shown) of the molecule is prepared.
Next, a silyl having an active hydrogen group 22 capable of reacting with an isocyanate group 14 (14a, 14b) at one end of the molecule and a hydrolyzable silyl group 24 represented by the general formula (1) at another end of the molecule. An agent 20 is prepared.
Next, after the polymer skeleton 10 and the silylating agent 20 are mixed, the predetermined terminal silyl group polymer 30 can be obtained, for example, by reacting at 80 ° C. for 1 hour in a nitrogen atmosphere.
In addition, as shown in FIG. 1B, the predetermined terminal silyl group polymer 30 is cured by a crosslinking reaction via hydrolysis (30 ′) of the hydrolyzable silyl group represented by the general formula (1). In other words, it is a so-called moisture curable polymer having a three-dimensional network structure (30 ″).

In FIG. 1 (a), a description has been given by taking as an example a both-end silyl group polymer having a predetermined silyl group only at both ends of the main chain, but the terminal silyl group polymer of the present invention has a side chain. A terminal silyl group polymer having a hydrolyzable silyl group at the terminal is also included.
When synthesizing the terminal silyl group polymer, the silylating agent 20 has the isocyanate group 14 and the polymer skeleton 10 has the active hydrogen group 22, contrary to the case of FIG. Also good.
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 shown below.
Therefore, allophanate bonds are also included in the category of urethane bonds, and burette bonds are also included in the category of urea bonds.

(Ii) Terminal part Moreover, the specific structure of the terminal part 32 (32a, 32b) of the predetermined | prescribed terminal silyl group polymer 30 shown to Fig.1 (a) is represented by following General formula (2)-(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 ¹ , X ¹ and X ² are those in the general formula (1). The same applies to the following general formulas (3) to (8).)

(In General Formula (8), A represents an alkylene group, and B represents an organic group having 1 to 20 carbon atoms.)

(Iii) Skeletal portion The skeleton of the main chain 12 or side chain (not shown) of the predetermined terminal silyl group polymer shown in FIG. 1 (a) is not particularly limited, but is polyoxyalkylene. Preferably there is.
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) Arrangement of hydrolyzable silyl group In addition, as shown in FIG. 1 (a), the predetermined terminal silyl group polymer as the component (A) is hydrolyzable represented by the general formula (1) in the side chain. It is preferable that it is a both-ends silyl group polymer which does not have a silyl group and has a hydrolyzable silyl group represented by the general formula (1) only at both ends of the main chain.
The reason for this is that the cross-linking density between the components (A) is adjusted to a suitable range with such a silyl group polymer at both terminals, and it is easy to adjust the balance between the adhesive force and cohesive force in the adhesive composition after crosslinking. It is because it can be made.

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, A value within the range of 0.1 to 15 parts by weight is preferable with respect to 100 parts by weight of the polymer.
The reason for this is that the crosslink density between the components (A) is adjusted to a more suitable range by mixing the one-end silyl group polymer in a predetermined range with respect to the both-end silyl group polymer, and the pressure-sensitive adhesive after crosslinking This is because the balance between the adhesive force and the cohesive force in the composition can be further easily adjusted.
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 15 parts by weight, the crosslinking density between the components (A) may be excessively lowered, making it difficult to obtain a predetermined gel fraction. Because there is.
Therefore, the blending amount of the one-terminal silyl group polymer is more preferably set to a value within the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of both terminal silyl group polymers, and the range of 1 to 5 parts by weight. More preferably, the value is within the range.
However, since it has been confirmed that a pressure-sensitive adhesive composition having excellent blister resistance can be obtained even when only both-end silyl group polymers are used, if not particularly required, one-end silyl group It is also preferable from the viewpoint of simplification of the manufacturing process to use only the both-end silyl group polymer without mixing the base polymer.

(1) -2 Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of the predetermined | prescribed terminal silyl group polymer which is (A) component into the value within the range of 1000-200,000.
The reason for this is that when the weight average molecular weight is less than 1000, the molecular structure becomes dense and sufficient adhesive strength cannot be obtained, and the viscosity becomes too low, resulting in poor workability when forming a sheet by solution coating. Because there is. On the other hand, when the weight average molecular weight is a value exceeding 200,000, the processability due to an increase in viscosity becomes remarkable, or the crosslinking density is excessively lowered, making it difficult to obtain sufficient blister resistance. This is because there is a case where it becomes.
Therefore, the weight average molecular weight of the predetermined terminal silyl group polymer as the component (A) is more preferably set to a value within the range of 1000 to 150,000, and further preferably set to a value within the range of 10,000 to 100,000. preferable.
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 the component (A) is in the range of 20 to 90 wt% with respect to 100 wt% of the total amount of the pressure-sensitive adhesive composition before crosslinking. It is preferable to set the value within the range.
The reason for this is that when the blending amount is less than 20% 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 cohesive force. Because there is. On the other hand, when the blending amount exceeds 90% by weight, the absolute amount of the component (A) with respect to the entire pressure-sensitive adhesive composition is excessively increased, and it may be difficult to obtain sufficient adhesive strength. Because.
Therefore, the blending amount of the predetermined terminal silyl group polymer as the component (A) is set to a value within the range of 25 to 85% by weight with respect to 100% by weight of the total amount of the pressure-sensitive adhesive composition before crosslinking. More preferably, the value is more preferably in the range of 30 to 80% by weight.

(2) Component (B): Tackifying resin (2) -1 type Tackifying resin as component (B) is polymerized with at least one of styrene monomer, α-methylstyrene monomer and aliphatic monomer. At least one selected from the group consisting of a tackifying resin, a terpene phenol tackifying resin, and a rosin phenol tackifying resin.
The reason for this is that if these tackifying resins are used, it is possible to impart excellent adhesive strength to the pressure-sensitive adhesive composition in combination with the predetermined terminal silyl group polymer as the component (A). .

Here, in the present invention, the terpene phenol-based tackifying resin means a copolymer resin of terpene resin and phenol.
The rosin phenol-based tackifying resin means a copolymer resin of rosin resin and phenol.
Therefore, in the present invention, rosin-based tackifying resins such as gum rosin, wood rosin, tall oil rosin, and the like mainly composed of resin acids such as abietic acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, dehydroabietic acid, And rosin ester type tackifying resin which is ester of these and various alcohol is not contained in rosin phenol type tackifying resin.

(2) -2 Blending amount The blending amount of the predetermined tackifying resin as the component (B) is 10 to 140 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). The value is within the range.
The reason for this is that a pressure-sensitive adhesive composition having an excellent balance between adhesive force and cohesive force can be obtained by setting the blending amount of the component (B) within the range.
That is, when the blending amount is less than 10 parts by weight, the adhesive strength in the pressure-sensitive adhesive composition is excessively lowered, making it difficult to effectively contain the generation of gas derived from the plastic adherend. This is because there may be cases. On the other hand, when the blending amount exceeds 140 parts by weight, the cohesive force in the pressure-sensitive adhesive composition is excessively reduced, and deformation due to generation of gas derived from the plastic adherend, that is, generation of blisters. This is because it may be difficult to suppress.
Therefore, the blending amount of the predetermined tackifying resin as the component (B) is set to a value within the range of 20 to 130 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). Preferably, the value is within the range of 30 to 120 parts by weight.

Then, the relationship between the compounding quantity of predetermined tackifying resin and blister resistance is demonstrated using FIG.
That is, in FIG. 2, the horizontal axis represents the blending amount (parts by weight) of a terpene phenol-based tackifier resin (YShara Chemical Co., Ltd., YS Polystar TH-130) with respect to 100 parts by weight of a predetermined terminal silyl group polymer. On the vertical axis, characteristic curves A and B are shown in which the blister resistance value (relative evaluation) of the blister-resistant pressure-sensitive adhesive sheet having the obtained pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer is taken.
The characteristic curve A is a characteristic curve when the adherend of the blister-resistant adhesive sheet is a polycarbonate resin plate, and the characteristic curve B is the adherend of the blister-resistant adhesive sheet to a polymethyl methacrylate resin plate. Is a characteristic curve.
The blister resistance value is an evaluation point (relative value) determined according to the following criteria.
Evaluation point 4: Blister is not confirmed on the whole substrate Evaluation point 3: A slight blister is confirmed on the outer peripheral portion of the substrate 2: Evaluation point 1: A slight blister is confirmed on the entire surface of the substrate Blisters are remarkably confirmed on the entire surface of the material. The specific composition of the pressure-sensitive adhesive composition and the method for evaluating blister resistance are the same as in Example 1.

First, looking at the characteristic curve A in which the adherend is a polycarbonate resin plate, the blister resistance is insufficient when the blending amount of the predetermined tackifying resin is less than 10 parts by weight, while 10 to 100. It is understood that excellent blister resistance can be obtained in the range of parts by weight.
On the other hand, it is understood that when the blending amount of the predetermined tackifying resin exceeds 100 parts by weight, the blister resistance starts to decrease, and when it is 160 parts by weight, the blister generation is reduced to a level at which the occurrence of blisters cannot be completely suppressed. Is done.
Next, looking at the characteristic curve B where the adherend is a polymethyl methacrylate resin plate, when the blending amount of the predetermined tackifying resin is less than 10 parts by weight, sufficient blister resistance cannot be obtained. In the range of 10 parts by weight to 120 parts by weight, it is understood that relatively excellent blister resistance can be obtained although the adherend is at a lower level than that of the polycarbonate resin plate.
On the other hand, when the amount of the predetermined tackifying resin exceeds 120 parts by weight, the blister resistance starts to decrease, and when it is 160 parts by weight, the blister generation may be reduced to a level that cannot be completely suppressed. Understood.
Therefore, from the characteristic curves A and B, in order to stably obtain the blister resistance, whether the adherend is a polycarbonate resin plate or a polymethyl methacrylate resin plate. It is understood that the blending amount of the predetermined tackifying resin should be a value within the range of 10 to 140 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer.

(3) Component (C): Catalyst (3) -1 Type Further, in constituting the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer in the blister-resistant pressure-sensitive adhesive sheet of the present invention, as component (C), component (A) And a catalyst for promoting the crosslinking of the predetermined terminal silyl group polymer, and the catalyst is at least selected from the group consisting of an aluminum-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, and a boron trifluoride-based catalyst. One type is preferred.
The reason for this is that these catalysts make it easy to control the crosslink density between the components (A) and further facilitate the balance between the adhesive force and the cohesive force in the adhesive composition after crosslinking. This is 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 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 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 catalyst as the component (C) is more preferably set to a value within the range of 0.01 to 8 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). Preferably, the value is in the range of 0.05 to 5 parts by weight.

Moreover, it is preferable to contain 1 mol or more of amino group containing alkoxysilane with respect to 1 mol of (C) component as (D) component.
The reason for this is that by blending the amino group-containing alkoxysilane in such a range, the effect as a crosslinking assistant for the predetermined terminal silyl group polymer is exhibited, and the cohesive force of the pressure-sensitive adhesive composition is adjusted to a more suitable range. This is because it can be done.
Therefore, the blending amount of the amino group-containing alkoxysilane as component (D) is more preferably set to a value within the range of 1 to 30 mol relative to 1 mol of component (C), and within the range of 2 to 10 mol. More preferably, the value of
Examples of the amino group-containing alkoxysilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl). ) -3-Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like are preferably used.

(4) Additive In addition, the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet for blister according to the present invention includes, for example, a silane coupling agent, an anti-aging agent, a vinyl silane compound and an oxidation component other than those described above. Dehydrating agents such as calcium, fillers, 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, etc. 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.
Moreover, when adding these additives, although it depends on the kind of additive, the compounding quantity is 0.01-30 with respect to 100 weight part of predetermined | prescribed terminal silyl group polymers which are (A) components. A value within the range of parts by weight is preferred.

(5) Gel fraction The pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer in the blister-resistant pressure-sensitive adhesive sheet of the present invention is characterized in that the gel fraction after cross-linking is set to a value within the range of 30 to 100%. .
The reason for this is that by setting the gel fraction after cross-linking to a value within such a range, excellent cohesive force can be exhibited, and as a result, deformation due to the generation of gas derived from the plastic adherend, that is, blister It is because generation | occurrence | production of can be suppressed.
That is, when the gel fraction after cross-linking becomes a value of less than 30%, the cohesive force becomes excessively small, and it is possible to suppress the deformation due to the generation of gas derived from the plastic adherend, that is, the generation of blisters. This is because it may be difficult.
On the other hand, if the gel fraction after crosslinking becomes excessively high, sufficient adhesive strength cannot be obtained.
Therefore, the gel fraction after crosslinking in the pressure-sensitive adhesive composition is more preferably set to a value within the range of 32 to 90%, and further preferably set to a value within the range of 35 to 80%.
The “gel fraction after cross-linking” means that after the adhesive composition is applied to a substrate, seasoned for 14 days in an environment of 23 ° C. and 50% RH, It means the gel fraction measured by a dipping method as a measurement sample.
Moreover, about the specific measuring method of a gel fraction, it describes in an Example.

Next, the relationship between the gel fraction after crosslinking in the pressure-sensitive adhesive composition and the blister resistance will be described with reference to FIG.
That is, in FIG. 3, the horizontal axis represents the gel fraction (%) after crosslinking in the pressure-sensitive adhesive composition, and the vertical axis represents the blister resistance in the blister-resistant pressure-sensitive adhesive sheet having the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer. Characteristic curves A and B taking the sex value (relative evaluation) are shown.
The characteristic curve A is a characteristic curve when the adherend of the blister-resistant adhesive sheet is a polycarbonate resin plate, and the characteristic curve B is the adherend of the blister-resistant adhesive sheet to a polymethyl methacrylate resin plate. Is a characteristic curve.
Moreover, the value of blister resistance is a relative value determined along the same criteria as in the case of the characteristic curve in FIG.
In addition, the specific composition of an adhesive composition and the evaluation method of blister resistance are according to Example 1.

First, looking at the characteristic curve A in which the adherend is a polycarbonate resin plate, the blister resistance is improved as the gel fraction value increases, and the gel fraction value is in the range of 30% or more. If so, it is understood that a predetermined or higher blister resistance can be stably obtained.
Next, also in the case of the characteristic curve B in which the adherend is a polymethyl methacrylate resin plate, the blister resistance is improved as the gel fraction value increases, and the gel fraction value is 30. It is understood that when the amount is in the range of% or more, the blister resistance of a predetermined level or more can be stably obtained although the adherend is at a lower level than that of the polycarbonate resin plate.
Therefore, from the characteristic curves A and B, in order to stably obtain the blister resistance, whether the adherend is a polycarbonate resin plate or a polymethyl methacrylate resin plate. It is understood that the gel fraction after crosslinking in the pressure-sensitive adhesive composition should be a value in the range of 30 to 100%.

(6) Thickness Further, the thickness of the pressure-sensitive adhesive layer is preferably set to a value within the range of 1 to 100 μm, and more preferably set to a value within the range of 5 to 50 μm.
This is because if the thickness of the pressure-sensitive adhesive layer is too thin, sufficient adhesive properties and the like may not be obtained, and conversely, if it is too thick, the residual solvent may cause a problem.

2. Base material Moreover, it is preferable that the adhesive sheet for blister resistance of this invention has an adhesive layer on the single side | surface or both surfaces of a base material.
Examples of such a substrate include polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polyether ketone, polyether ether ketone, polycarbonate, polymethyl methacrylate, triacetyl cellulose, poly Preferred examples include resin films made of resins such as norbornene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, vinyl chloride, polyurethane acrylate.

Moreover, as shown to Fig.4 (a), it is preferable that the base material 2 has the metal vapor deposition layer 6. FIG.
The reason for this is that when the substrate has a metal vapor-deposited layer, the metal vapor-deposited layer has gas barrier properties, so that blisters are likely to occur. It is because it can suppress effectively.
Moreover, as a metal which comprises a metal vapor deposition layer, aluminum, silver, copper, tin etc. are mentioned, for example.
In addition, although the metal vapor deposition layer was mentioned as a representative of what has gas barrier property, if it has gas barrier property, it will not restrict to this, For example, the gas barrier film obtained by performing plasma ion implantation with respect to the thin layer of a silicon compound, for example In the present invention, the same blistering resistance effect can be obtained even if these are laminated on a substrate.
Moreover, the thickness of the layer having gas barrier properties such as a metal vapor deposition layer is not particularly limited, but it is usually preferably a value within the range of 0.01 to 10 μm, and preferably 0.02 to 5 μm. A value within the range is more preferable.
In addition, as a specific use of the adhesive sheet | seat for blisters which a base material has a metal vapor deposition layer, the nameplate label attached | subjected to household appliances etc. can be mentioned preferably, for example.

  In addition, the thickness of the base material 2 is not particularly limited, but it is usually preferably a value within the range of 1 to 1,000 μm, and more preferably within the range of 10 to 100 μm. preferable.

Moreover, it is also preferable that the peeling film is bonded to the both surfaces of an adhesive layer as for the adhesive sheet for blister resistance of this invention.
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 film, for example, a release layer 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 is formed. What was provided is mentioned.
Moreover, the thickness of this peeling film can be normally taken as the value within the range of 20-150 micrometers.
In addition, by providing a predetermined difference in the peeling force between the two peeling films, it is possible to prevent the pressure-sensitive adhesive layer from partially following when the peeling film having the lower peeling force is peeled off. .

3. Manufacturing Method The blister-resistant pressure-sensitive adhesive sheet of the present invention can be constituted through the following steps (1) to (3).
(1) Step of preparing a predetermined pressure-sensitive adhesive composition containing the components (A) to (B) (2) Step of applying the pressure-sensitive adhesive composition to a substrate to form a coating layer (3) Step of cross-linking the pressure-sensitive adhesive composition to make the coating layer a pressure-sensitive adhesive layer Hereinafter, the steps of constituting the pressure-sensitive adhesive sheet will be specifically described with reference to the drawings as appropriate.

(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 (B).
More specifically, for example, it is preferable to dilute the component (A) with a diluent solvent as desired, and add the component (B) with stirring to obtain a uniform mixed solution.
Subsequently, after the component (C) and other additives are added to the obtained mixed liquid, a diluent solvent is further added 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) Step (2) (Applying step of pressure-sensitive adhesive composition)
Step (2) is a step of forming the coating layer 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, on the basis of drying.
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.
Moreover, as drying conditions, it is usually preferable to set it within a range of 10 to 10 minutes at 50 to 150 ° C.
The details of the base material are the same as described above, and will be omitted.

(3) Step (3) (Coating layer crosslinking step)
Step (3) is a step in which the coating layer 4 of the pressure-sensitive adhesive composition is crosslinked to make the coating layer 4 a pressure-sensitive adhesive layer 40.
That is, as shown in FIGS. 4 (b) to 4 (c), the surface of the coating layer 4 dried on the substrate 2 is cross-linked in a state where the release film 8 is laminated, and the pressure-sensitive adhesive layer 40 is preferable.
Alternatively, the pressure-sensitive adhesive composition coating layer 4 coated on the substrate 2 may be cross-linked first to form the pressure-sensitive adhesive layer 40 and then laminated to the release film 8.
Or it is not necessary to laminate the peeling film 8 to the last.

In addition, the crosslinking in the coating 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 crosslinking the pressure-sensitive adhesive composition coating layer 4 without damaging the pressure-sensitive adhesive composition coating layer 4 and the base material 2. It is preferable to set it as ° C, and it is more preferable to set it as 23-30 ° C.
The humidity is preferably 30 to 75% RH, and more preferably 45 to 65% RH.
In addition, as a method of bonding the finally obtained pressure-sensitive adhesive sheet 100 to the adherend 200, first, as shown in FIGS. It is preferable that the film 8 is peeled off and then bonded by bringing the surface of the pressure-sensitive adhesive layer 40 that is exposed into close contact with the adherend 200.

(4) Adhered body The type of adherend to which the blister-resistant pressure-sensitive adhesive sheet of the present invention is intended is not particularly limited, but its blister resistance compared to other pressure-sensitive adhesive sheets. From the standpoint of prominent appearance, it is preferable to use a resin such as a polycarbonate resin, a polymethyl methacrylate resin, a polystyrene resin, or an ABS resin, which is known to be particularly susceptible to blistering, as the adherend.

[Example 1]
1. Preparation of pressure-sensitive adhesive composition (1) Preparation of silylating agent A reaction vessel was charged with 100 parts by weight of N-aminoethyl-γ-aminopropylmethyldimethoxysilane and 83.5 parts by weight of methyl acrylate under a nitrogen atmosphere. The mixture was stirred at 80 ° C. for 10 hours to obtain a silane compound to be a silylating agent.

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

(3) Synthesis of terminal silyl group 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 the mixture was heated at 80 ° C. in a nitrogen atmosphere. It was made to react for 1 hour and the terminal silyl group polymer was obtained.
At this time, the progress of the reaction was confirmed by the disappearance of the isocyanate group absorption (2265 cm ⁻¹ ) by IR.
The obtained terminal silyl group polymer was a both-end silyl group polymer having 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.
Further, by using N-aminoethyl-γ-aminopropylmethyldimethoxysilane as a raw material for the silylating agent, a bifunctional terminal silyl group was introduced into the obtained terminal silyl group polymer.

(4) Mixing Next, 100 parts by weight of ethyl acetate as a solvent and terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar TH-130) 100 as a tackifying resin with respect to 100 parts by weight of the obtained terminal silyl group polymer. Part by weight was added and stirred until homogeneous to obtain a mixture.
Next, 0.1 part by weight of boron trifluoride monoethylamine complex as a catalyst and 0.1 part by weight of 3-aminopropyltrimethoxysilane as a crosslinking aid with respect to 100 parts by weight of the terminal silyl group polymer contained in the obtained mixture. 6 parts by weight was added and stirred until uniform to obtain a pressure-sensitive adhesive composition before crosslinking.
In the following, the above-described tackifier resin may be abbreviated as “YS Polystar TH-130”.

2. Application of pressure-sensitive adhesive composition Next, the obtained pressure-sensitive adhesive composition before crosslinking was applied to a polyester film having a thickness of 50 μm (manufactured by Toray Industries, Inc., Lumirror T60) by a knife coater method, and then at 100 ° C. It was dried for 1 minute to form a coating layer having a thickness of 23 μm.

  Similarly, the obtained adhesive composition before cross-linking is applied to the vapor-deposited surface of a vapor-deposited polyethylene terephthalate film (made by Toray Film Processing Co., Ltd., Metal Me # 50) having a thickness of 50 μm and aluminum-deposited on one side. After coating by the knife coater method, it was dried at 100 ° C. for 1 minute to form a coating layer having a thickness of 23 μm.

3. Seasoning of the pressure-sensitive adhesive composition Next, a laminate comprising the obtained coating layer of the pressure-sensitive adhesive composition before crosslinking and a base material (polyester film and vapor-deposited polyethylene terephthalate film) was placed in an environment of 23 ° C. and 50% RH. It was allowed to stand (seasoning) for 14 days to sufficiently crosslink the pressure-sensitive adhesive composition before crosslinking, and the coating layer was used as a pressure-sensitive adhesive layer to obtain two types of blister-resistant pressure-sensitive adhesive sheets of Example 1.

4). Evaluation (1) Evaluation of Gel Fraction The gel fraction of the pressure-sensitive adhesive in the obtained pressure-sensitive adhesive sheet, that is, the pressure-sensitive adhesive composition after cross-linking after the seasoning process was measured.
That is, the pressure-sensitive adhesive was immersed in ethyl acetate for 3 days in an environment of 23 ° C. and 50% RH, and the weight before and after immersion was substituted into the following formula (1) to calculate the gel fraction. The obtained results are shown in Table 1.
Gel fraction (%) = (weight after immersion / weight before immersion) × 100 (1)

(2) Evaluation of adhesive strength (2) -1 Polycarbonate resin plate The adhesive strength of the obtained blister-resistant adhesive sheet (the base material was a polyester film) was measured.
That is, a 25 mm × 250 mm test piece was cut out from the obtained blister-resistant pressure-sensitive adhesive sheet, and the cut-out blister-resistant pressure-sensitive adhesive sheet was made from a polycarbonate resin plate (Mitsubishi Chemical Corporation, Iupilon sheet NF-) using a 2 kg rubber roller. 200 UV) and left in a standard environment of 23 ° C. and 59% RH for 24 hours immediately after the bonding.
Next, using a tensile tester (Orientec Co., Ltd., Tensilon), the blister-resistant pressure-sensitive adhesive sheet after being left is peeled from the polycarbonate resin plate at a peeling speed of 300 mm / min and a peeling angle of 180 °. The peel load measured at this time was taken as the adhesive strength (N / 25 mm). The obtained results are shown in Table 1.

(2) -2 Polymethyl methacrylate resin plate In addition to the polycarbonate resin plate, a polymethyl methacrylate resin plate (manufactured by Mitsubishi Rayon Co., Ltd., Acrylite L001) is used, as in the case of the polycarbonate resin plate. The adhesive strength was measured. The obtained results are shown in Table 1.

(3) Evaluation of blister resistance (3) -1 Polycarbonate resin plate The blister resistance of the obtained blister-resistant pressure-sensitive adhesive sheet (the base material was a vapor-deposited polyethylene terephthalate film) was evaluated.
That is, a 40 mm × 50 mm test piece was cut out from a blister-resistant adhesive sheet based on an aluminum-deposited polyethylene terephthalate film, and the cut-out adhesive sheet for blister was removed from a polycarbonate resin plate (Mitsubishi Chemical Corporation) using a 2 kg rubber roller. ), Iupilon sheet NF-200UV).
Then, after 30 minutes have passed from the pasting, the polycarbonate resin plate in which the blister-resistant adhesive sheet has been pasted is allowed to stand in a 90 ° C. environment for 5 hours, and the base material in the blister-resistant adhesive sheet at that time The external appearance was confirmed and evaluated according to the following criteria. The obtained results are shown in Table 1.
Moreover, the photograph which image | photographed the external appearance by the side of the base material in the adhesive sheet for blisters at this time is shown in FIG.
A: Blisters are not confirmed on the entire base material B: A slight blister is confirmed on the outer peripheral portion of the base material C: A slight blister is confirmed on the entire surface of the base material D: A blister is marked on the entire surface of the base material It is confirmed

(3) -2 Polymethyl methacrylate resin plate In addition to the polycarbonate resin plate, a polymethyl methacrylate resin plate (manufactured by Mitsubishi Rayon Co., Ltd., Acrylite L001) is used, as in the case of the polycarbonate resin plate. Blister resistance was evaluated. The obtained results are shown in Table 1.

[Example 2]
In Example 2, when preparing the pressure-sensitive adhesive composition, Example 1 except that the terpene phenol resin as the tackifier resin was changed to another terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T130). In the same manner as above, a blister-resistant adhesive sheet was produced and evaluated. The obtained results are shown in Table 1.
Moreover, the photograph which shows the blister resistance at the time of using a polycarbonate resin board as a to-be-adhered body is shown in FIG.
In the following, the above-described tackifier resin may be abbreviated as “YS polystar T130”.

[Example 3]
In Example 3, when preparing the pressure-sensitive adhesive composition, Example 1 except that the terpene phenol resin as the tackifier resin was changed to another terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T160). In the same manner as above, a blister-resistant adhesive sheet was produced and evaluated. The obtained results are shown in Table 1.
Moreover, the photograph which shows the blister resistance at the time of setting a polymethyl methacrylate resin board as a to-be-adhered body is shown in FIG.
Hereinafter, the above-described tackifier resin may be abbreviated as “YS polystar T160”.

[Example 4]
In Example 4, when preparing the pressure-sensitive adhesive composition, the terpene phenol resin as the tackifier resin was changed to another terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar G150). In the same manner as above, a blister-resistant adhesive sheet was produced and evaluated. The obtained results are shown in Table 1.
In the following, the above-described tackifier resin may be abbreviated as “YS polystar G150” in some cases.

[Example 5]
In Example 5, when preparing the pressure-sensitive adhesive composition, the tackifier resin was changed to styrene, α-methylstyrene, and an aliphatic monomer copolymer resin (FTR7100, manufactured by Mitsui Chemicals). In the same manner as in Example 1, a blister-resistant adhesive sheet was produced and evaluated. The obtained results are shown in Table 1.
Hereinafter, the above-described tackifier resin may be abbreviated as “FTR7100”.

[Example 6]
In Example 6, when preparing the pressure-sensitive adhesive composition, the tackifier resin was changed to α-methylstyrene-based resin (Eastman Chemical Co., Ltd., Crystallex 3100), and was the same as Example 1. An adhesive sheet for blister resistance was manufactured and evaluated. The obtained results are shown in Table 1.
In the following description, the above-described tackifier resin may be abbreviated as “Crystalx 3100”.

[Example 7]
In Example 7, when preparing the pressure-sensitive adhesive composition, the blister resistance was the same as in Example 1, except that the tackifying resin was changed to a rosin phenol-based resin (Tamanor 803L, manufactured by Arakawa Chemical Industries, Ltd.). A pressure-sensitive adhesive sheet was manufactured and evaluated. The obtained results are shown in Table 1.
In the following, the above-described tackifier resin may be abbreviated as “Tamanol 803L”.

[Example 8]
In Example 8, when preparing the pressure-sensitive adhesive composition, the blister resistance was the same as in Example 1, except that the tackifying resin was changed to a rosin phenolic resin (Tamanor 901, manufactured by Arakawa Chemical Industries, Ltd.). A pressure-sensitive adhesive sheet was manufactured and evaluated. The obtained results are shown in Table 1.
In the following, the above-described tackifier resin may be abbreviated as “Tamanol 901”.

[Example 9]
In Example 9, when preparing the pressure-sensitive adhesive composition, a blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the compounding amount of the tackifying resin was changed to 20 parts by weight. The obtained results are shown in Table 1.

[Example 10]
In Example 10, when preparing the pressure-sensitive adhesive composition, a blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the compounding amount of the tackifying resin was changed to 80 parts by weight. The obtained results are shown in Table 1.

[Example 11]
In Example 11, when preparing the pressure-sensitive adhesive composition, a blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the compounding amount of the tackifying resin was changed to 120 parts by weight. The obtained results are shown in Table 1.

[Example 12]
In Example 12, when preparing the pressure-sensitive adhesive composition, instead of 100 parts by weight of both terminal silyl group polymers, 90 parts by weight of both terminal silyl group polymers and 10 parts by weight of one-terminal silyl group polymer as terminal silyl group polymers. A blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the polymer mixture was used. The obtained results are shown in Table 1.
The single-terminal silyl group polymer had the same configuration as the double-terminal silyl group polymer except that only one terminal of the polymer molecule had a hydrolyzable silyl group.

[Comparative Example 1]
In Comparative Example 1, a blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that no tackifying resin was added when preparing the pressure-sensitive adhesive composition. The obtained results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 2, instead of adding 100 parts by weight of N-aminoethyl-γ-aminopropylmethyldimethoxysilane when preparing the silylating agent, N-aminoethyl-γ-aminopropyltrimethoxysilane 107.8 was added. A blister-resistant adhesive sheet was produced and evaluated in the same manner as in Example 1 except that parts by weight were added. The obtained results are shown in Table 1.
Further, FIG. 8 shows a photograph showing blister resistance when a polycarbonate resin plate is used as an adherend, and FIG. 9 shows a photograph showing blister resistance when a polymethyl methacrylate resin plate is used as an adherend. Show.
Moreover, the obtained terminal silyl group polymer was a both-ends silyl group polymer which has the terminal part represented by following formula (10) in the both ends of the polyoxypropylene which is a principal chain.
In addition, by using N-aminoethyl-γ-aminopropyltrimethoxysilane as a raw material for the silylating agent, a trifunctional terminal silyl group was introduced into the obtained terminal silyl group polymer.
In Comparative Example 2, since the terminal silyl group of the terminal silyl group polymer was trifunctional, gas permeability in the pressure-sensitive adhesive layer was lowered, and as a result, it was estimated that sufficient blister resistance was not obtained. Is done.

[Comparative Example 3]
In Comparative Example 3, blister resistant as in Example 1 except that the tackifier resin was changed to a rosin resin (Arakawa Chemical Industries, Ltd., KE-604) when preparing the adhesive composition. A pressure-sensitive adhesive sheet was manufactured and evaluated. The obtained results are shown in Table 1.
Further, a photograph showing blister resistance when a polycarbonate resin plate is used as an adherend is shown in FIG. 10, and a photograph showing blister resistance when a polymethyl methacrylate resin plate is used as an adherend is shown in FIG. Show.

[Comparative Example 4]
In Comparative Example 4, when preparing the pressure-sensitive adhesive composition, instead of 100 parts by weight of both terminal silyl group polymers, 70 parts by weight of both terminal silyl group polymers and 30 parts by weight of one terminal silyl group polymer as terminal silyl group polymers A blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the polymer mixture was used. The obtained results are shown in Table 1.
Moreover, the photograph which shows the blister resistance at the time of using a polycarbonate resin board as a to-be-adhered body is shown in FIG.
The one-terminal silyl group polymer had the same configuration as the both-terminal silyl group polymer except that it had a hydrolyzable silyl group only at one end of the polymer molecule.

[Comparative Example 5]
In Comparative Example 5, when preparing the pressure-sensitive adhesive composition, instead of 100 parts by weight of both terminal silyl group polymers, 50 parts by weight of both terminal silyl group polymers and 50 parts by weight of one terminal silyl group polymer were used as terminal silyl group polymers. A blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the above mixed polymer was used. The obtained results are shown in Table 1.
The one-terminal silyl group polymer had the same configuration as the both-terminal silyl group polymer except that it had a hydrolyzable silyl group only at one end of the polymer molecule.

[Comparative Example 6]
In Comparative Example 6, a blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the pressure-sensitive adhesive composition was prepared as follows. The obtained results are shown in Table 1.
That is, 100 parts by weight of n-butyl acrylate, 11.1 parts by weight of acrylic acid, and 0.33 parts by weight of azobisisobutyronitrile were charged in a reaction vessel, and the mixture was stirred at 60 ° C. in ethyl acetate under a nitrogen atmosphere. The reaction was carried out for a time to obtain an acrylic ester copolymer solution (solid content concentration 35%) having a weight average molecular weight of 600,000.
Next, 2.0 parts by weight of a tolylene diisocyanate-based crosslinking agent (manufactured by Toyo Ink Co., Ltd., BHS8515) is added to and mixed with 100 parts by weight of the resulting acrylate copolymer solution, and the adhesive before crosslinking. An agent composition was obtained.

[Comparative Example 7]
In Comparative Example 7, when preparing the pressure-sensitive adhesive composition, a blister-resistant pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 1 except that the compounding amount of the tackifying resin was changed to 160 parts by weight. The obtained results are shown in Table 1.
In Comparative Example 7, since the compounding amount of the tackifying resin was excessive, the adhesive strength was excessively increased and the gas permeability was decreased. As a result, sufficient blister resistance was not obtained. It is estimated to be.

* “Z” indicates that zipping (vibration phenomenon seen in the measurement chart of adhesive force within a certain range) occurred.
* “AT” indicates that interface fracture occurred.

As described above in detail, according to the present invention, a predetermined tackifying resin is added to a predetermined terminal silyl group polymer at a predetermined blending ratio, and the gel fraction after crosslinking in the pressure-sensitive adhesive composition By setting the value within the predetermined range, the balance between the adhesive force and the cohesive force in the pressure-sensitive adhesive composition is improved, and excellent blister resistance can be obtained.
As a result, even if the base material in the pressure-sensitive adhesive sheet has gas barrier properties, the generation of blisters can be effectively suppressed.
Therefore, the blister-resistant pressure-sensitive adhesive sheet of the present invention is, for example, the quality of a decorative sheet for a plastic molded article having a metal vapor-deposited layer or the like on a base material, such as used for a nameplate label attached to home appliances. It is expected to contribute significantly to improvement.

2: base material, 4: coating layer, 6: metal deposition layer, 10: polymer skeleton, 12: main chain of molecule, 14: isocyanate group, 20: silylating agent, 22: active hydrogen group, 30: terminal silyl group Polymer: 40: pressure-sensitive adhesive layer, 100: pressure-sensitive adhesive sheet for blister resistance, 200: adherend

Claims (7)

A blister-resistant pressure-sensitive adhesive sheet having a base material provided with a gas barrier metal deposition layer having a thickness of 0.01 to 10 μm, and at least one pressure-sensitive adhesive layer ,
The pressure-sensitive adhesive layer is composed of pressure-sensitive adhesive composition comprising a terminal silyl group polymer as component (A), and a tackifying resin as component (B),
The terminal silyl group polymer as the component (A) has a urethane bond and / or a urea bond in the main chain or side chain, or one of them, and hydrolysis represented by the following general formula (1) at both ends of the main chain A terminal silyl group polymer having a functional silyl group,
The tackifying resin as the component (B) is a tackifying resin obtained by polymerizing at least one of a styrene monomer, an α-methylstyrene monomer and an aliphatic monomer, a terpene phenol tackifying resin, and rosin phenol. A system tackifying resin, and at least one tackifying resin selected from the group consisting of:
The terminal silyl group polymer as the component (A) does not have a hydrolyzable silyl group represented by the general formula (1) in the side chain, and the hydrolysis represented by the general formula (1) at both ends of the main chain. A silyl group polymer having both terminal silyl groups,
Furthermore, as the component (A ′), a single-end silyl group polymer having a hydrolyzable silyl group represented by the general formula (1) is included only at one end of the main chain, A value within the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer,
The blending amount of the tackifying resin as the component (B) is set to a value within the range of 10 to 140 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A).
And,
The blister-resistant pressure-sensitive adhesive sheet, wherein the gel fraction after crosslinking in the pressure-sensitive adhesive composition has a value within a range of 30 to 100%.

(In General Formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R ¹ is an alkyl group having 1 to 20 carbon atoms.)   The blister-resistant pressure-sensitive adhesive sheet according to claim 1, wherein the backbone of the terminal silyl group polymer as the component (A) is a polyoxyalkylene skeleton. The component (C) includes a catalyst for promoting the crosslinking of the terminal silyl group polymer as the component (A), and the catalyst is an aluminum catalyst, a titanium catalyst, a zirconium catalyst, or a boron trifluoride catalyst. The blister-resistant pressure-sensitive adhesive sheet according to claim 1 or 2 , which is at least one selected from the group consisting of:   The pressure-sensitive adhesive sheet for blister resistance according to claim 3, wherein the component (D) contains 1 mol or more of an amino group-containing alkoxysilane per 1 mol of the component (C).   The blister-resistant pressure-sensitive adhesive sheet according to claim 4, wherein the amino group-containing alkoxysilane is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane. The pressure-sensitive adhesive sheet for blister resistance according to any one of claims 1 to 5 , wherein the pressure-sensitive adhesive layer is provided on one side or both sides of a substrate.   A method for producing a blister-resistant pressure-sensitive adhesive sheet comprising a base material provided with a gas barrier metal deposition layer having a thickness of 0.01 to 10 μm, and at least one pressure-sensitive adhesive layer,
  The manufacturing method of the adhesive sheet for blister resistance characterized by including the following process (1)-(3).
(1) As a component (A), the main chain or the side chain has a urethane bond and / or a urea bond, and a hydrolyzable silyl group represented by the following general formula (1) at both ends of the main chain Having a terminal silyl group polymer;
  As the component (A ′), a single-end silyl group polymer having a hydrolyzable silyl group represented by the following general formula (1) only at one end of the main chain;
  (B) As a component, a tackifying resin formed by polymerizing at least one of a styrene monomer, an α-methylstyrene monomer and an aliphatic monomer, a terpene phenol tackifying resin, and a rosin phenol tackifying resin, And at least one selected from the group consisting of:
  The blending amount of the component (A ′) is set to a value within the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of both terminal silyl group polymers,
  The process of preparing the adhesive composition which contains the compounding quantity of the said (B) component with the value within the range of 10-140 weight part with respect to 100 weight part of said both terminal silyl group polymers.
(2) The process of apply | coating the said adhesive composition with respect to the said base material, and forming an application layer.
(3) Step of forming the pressure-sensitive adhesive layer by crosslinking the pressure-sensitive adhesive composition and setting the gel fraction after crosslinking in the pressure-sensitive adhesive composition as a value within a range of 30 to 100%.
(In the general formula (1), X ¹ And X ² Are independently a hydroxy group or an alkoxy group, R ¹ Is an alkyl group having 1 to 20 carbon atoms. )