JP6835558B2 - Method for producing styrene-based elastomer resin composition, photocrosslinked product of styrene-based elastomer resin composition, heat-resistant adhesive film, surface protective film, and heat-resistant adhesive film - Google Patents

Description

The present invention has a high adhesive strength (initial adhesive strength), but the adhesive strength does not easily increase over time or even at high temperatures, and a styrene-based elastomer that does not leave low molecular weight components or solvents on the surface of the adherend when peeled off. The present invention relates to a resin composition, a photocrosslinked product of the styrene-based elastomer resin composition, a heat-resistant adhesive film, a surface protective film made of the heat-resistant adhesive film, and a method for producing the heat-resistant adhesive film.

Adhesive films are used in various industrial fields because they can be easily bonded. In the construction field, temporary fixing of curing sheets, bonding of interior materials, etc., in the automobile field, fixing of interior parts such as seats and sensors, fixing of exterior parts such as side moldings and side visors, etc., in the electrical and electronic field, module assembly, Adhesive films are used for bonding modules to housings. More specifically, for example, an adhesive film is widely used as a surface protective film for protecting the surface of a member such as an optical device, a metal plate, a painted metal plate, a resin plate, or a glass plate (for example, a patent). Documents 1 to 3). In particular, in recent years, surface protective films have been used to protect the surface of optical members for liquid crystal displays. Some optical members have a concavo-convex shape on one or both sides, such as a prism sheet and a diffusion film, and in order not to damage the concavo-convex shape, the surface is surfaced prior to the use of the optical member. It is protected by a protective film.
The adhesive film is required to have high adhesive strength depending on the application. For example, when the film is attached to an adherend having an uneven shape on the surface, a large contact area cannot be obtained and peeling tends to occur at the interface between the adherend and the adhesive film. In such applications, the adhesive film is required to have particularly high adhesive strength.

It has been studied to use a styrene-based elastomer as the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, but the pressure-sensitive adhesive layer using the styrene-based elastomer is used as a surface protective film or the like to be attached to an adherend having an uneven shape on the surface. Had a problem of insufficient adhesive strength. In general, it is effective to increase the amount of the tackifier in the pressure-sensitive adhesive layer in order to improve the adhesive strength. However, the adhesive film has an increased adhesive strength due to an increase in the contact area between the adherend and the pressure-sensitive adhesive layer over time or at a high temperature, especially when the adherend has an uneven shape on the surface. It is known that the problem of stickiness occurs.

As a method for preventing stickiness, it is common to add a low molecular weight component such as a bleeding agent (for example, ethylenebis-stearic acid amide) or a solvent to the pressure-sensitive adhesive layer. However, when the adhesive film containing a low molecular weight component such as a bleeding agent or a solvent is peeled off from the adherend, the low molecular weight component or the solvent may remain on the surface of the adherend and contaminate it. There was a problem. For example, a surface protective film that protects an optical member in recent years is required not to contaminate the surface of the optical member after being peeled from the optical member. When the surface of the optical member is contaminated and the surface tension decreases, minute coating unevenness occurs when an adhesive or hard coating agent is applied to the surface of the optical member after the surface protective film is peeled off, resulting in a product. When assembled in the above, poor brightness and color unevenness occur.

Japanese Unexamined Patent Publication No. 1-129085 Japanese Unexamined Patent Publication No. 6-1958 Japanese Unexamined Patent Publication No. 8-12952

In view of the above situation, the present invention has high adhesive strength (initial adhesive strength), but it is difficult for the adhesive strength to increase even with time or at high temperature, and when peeled off, a low molecular weight component or a solvent is applied to the surface of the adherend. An object of the present invention is to provide a styrene-based elastomer resin composition that does not remain, a photocrosslinked product of the styrene-based elastomer resin composition, a heat-resistant adhesive film, a surface protective film made of the heat-resistant adhesive film, and a method for producing the heat-resistant adhesive film.

The present invention is a styrene-based elastomer resin composition containing a hydrogenated styrene-based elastomer, a hydrogen-extracting photoinitiator, and a monomer or oligomer having a radically polymerizable double bond.
The present invention will be described in detail below.

As a result of diligent studies, the present inventors have found that a styrene-based elastomer resin composition containing a hydrogenated styrene-based elastomer, a hydrogen-withdrawing photoinitiator, and a monomer or oligomer having a radically polymerizable double bond has been obtained. It was found that while it does not react even at high temperatures and can be easily extruded, it can be crosslinked by irradiating it with light. The hydrogen abstraction type photoinitiator is highly stable even at high temperatures and is not activated at the normal extrusion molding temperature (about 100 to 220 ° C.) of the hydrogenated styrene elastomer. However, when the hydrogen abstraction type photoinitiator is irradiated with light, it is activated to generate radicals, and the radicals abstract hydrogen of CH in the hydrogenated additive of the styrene elastomer, and a monomer having a radically polymerizable double bond or It is considered that the cross-linking reaction occurs via the oligomer.
Furthermore, by using the photocrosslinked product of the styrene-based elastomer resin composition as the pressure-sensitive adhesive layer, the present inventors suppress the adhesion of the pressure-sensitive adhesive layer without adding a low molecular weight component such as a bleeding agent or a solvent. We have found that a heat-resistant adhesive film that can be used is obtained, and have completed the present invention.

The styrene-based elastomer resin composition of the present invention contains a hydrogenated styrene-based elastomer and a hydrogen-extracting photoinitiator.
The hydrogenated additive of the styrene-based elastomer is not particularly limited as long as it has rubber elasticity at room temperature, but includes a polystyrene layer called a hard segment, ethylene-butylene, ethylene-propylene, ethylene-butadiene, and the like. A styrene-based elastomer hydrogenated additive having a diblock or triblock structure with the soft segment is suitable.

Specific examples of the styrene-based elastomer include styrene-butadiene-styrene (SBS) block copolymer, styrene-butadiene-butylene-styrene (SBBS) block copolymer, and styrene-isoprene-styrene (SIS) block. Examples include block polymers.
Specific examples of the hydrogenated additive of the styrene-based elastomer include styrene-ethylene-butylene-styrene (SEBS) block copolymer, hydrogenated styrene-butylene rubber (HSBR), and styrene-ethylene-propylene-styrene (SEPS). Examples include block copolymers and styrene-isobutylene-styrene (SIBS) block copolymers.
These styrene-based elastomers or their hydrogenated additives may be used alone or in combination of two or more. Of these, styrene-ethylene-butylene-styrene (SEBS) block copolymers or styrene-ethylene-propylene-styrene (SEPS) block copolymers are preferred because they are relatively stable to heat and light.

The hydrogenated product of the styrene-based elastomer may be a partially hydrogenated product or a completely hydrogenated product. Among them, since more excellent heat resistance and weather resistance can be obtained, the double bond (unsaturated bond) of the conjugated diene compound unit is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more. Is preferably converted to a saturated bond by hydrogenation.
The hydrogenation ratio (hydrogenation rate) means the hydrogenation rate calculated from ^{the 1} H-NMR spectrum at 270 MHz using carbon tetrachloride as a solvent.

The hydrogen abstraction type photoinitiator is activated by irradiation with light to generate active radicals.
The hydrogen abstraction type photoinitiator is not particularly limited, and examples thereof include benzophenone, thioxanthone, and Michler's ketone. These hydrogen abstraction type photoinitiators may be used alone or in combination of two or more. Among them, benzophenone is preferable because it is excellent in activity at the time of light irradiation, is particularly excellent in stability at high temperature, and is hardly activated at the extrusion temperature of the hydrogenated product of the styrene-based elastomer.

The content of the hydrogen abstraction type photoinitiator is not particularly limited, but the preferable lower limit is 0.1 parts by weight and the preferable upper limit is 5.0 parts by weight with respect to 100 parts by weight of the hydrogenated product of the styrene-based elastomer. If the content of the hydrogen-extracting photoinitiator is less than 0.1 parts by weight, the desired effect may not be exhibited without sufficient cross-linking even when irradiated with light, and 5.0 parts by weight. If it exceeds, the weather resistance may deteriorate and yellowing may occur. A more preferable lower limit of the content of the hydrogen abstraction type photoinitiator is 0.3 parts by weight, a more preferable upper limit is 3.0 parts by weight, a further preferable lower limit is 0.4 parts by weight, and a further preferable upper limit is 1.5 parts by weight. By weight, a particularly preferred lower limit is 0.5 parts by weight and a particularly preferred upper limit is 1.0 parts by weight.

The styrene-based elastomer resin composition of the present invention contains a monomer or oligomer having a radically polymerizable double bond.
The monomer or oligomer having a radically polymerizable double bond acts as a bridge that bridges between styrene-based elastomers when irradiated with light. When a particularly high crosslink density is required, a polyfunctional monomer or oligomer having two or more radically polymerizable double bonds in the molecule is suitable.

The polyfunctional monomer or oligomer includes, for example, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, and ethoxytrimethylolpropane. Examples thereof include triacrylate, dimethylolpropane triacrylate, and the same methacrylates as described above. Other examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polypropylene glycol # 700 diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and the same methacrylates as described above. These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

The monomer or oligomer having a radically polymerizable double bond preferably has a molecular weight of 10,000 or less. If a monomer or oligomer having a radically polymerizable double bond having a molecular weight of 10,000 or less is used, three-dimensional network formation can be efficiently performed by irradiation with light. The molecular weight of the monomer or oligomer having a radically polymerizable double bond is more preferably 5000 or less.

The content of the monomer or oligomer having a radically polymerizable double bond is not particularly limited, but the preferable lower limit with respect to 100 parts by weight of the hydrogenated product of the styrene-based elastomer is 0.1 part by weight, and the preferable upper limit is 40 parts by weight. .. When the content of the monomer or oligomer having a radically polymerizable double bond is within this range, cross-linking can be reliably performed, but granular local cross-linking does not occur due to heating during extrusion molding. A more preferable lower limit of the content of the monomer or oligomer having a radically polymerizable double bond is 0.5 parts by weight, a more preferable upper limit is 25 parts by weight, a further preferable lower limit is 1 part by weight, and a further preferable upper limit is 15 parts by weight. The upper limit is 8 parts by weight.

The styrene-based elastomer resin composition of the present invention further comprises an adhesive strength modifier, a tackifier resin, a plasticizer, an emulsifier, a softener, fine particles, a filler, a pigment, a dye, a silane coupling agent, and an antioxidant, if necessary. It may contain known additives such as agents, surfactants and waxes.

The styrene-based elastomer resin composition of the present invention can be crosslinked by irradiating with light.
The method of irradiating the light is not particularly limited, and examples thereof include a method of irradiating the styrene-based elastomer resin composition after molding with an ultraviolet irradiation device such as an ultra-high pressure mercury lamp.
The wavelength and illuminance of the light at the time of light irradiation may be appropriately set depending on the type of the hydrogen abstraction type photoinitiator and the like. For example, when benzophenone is used as the hydrogen abstraction type photoinitiator, ^{it is preferable to irradiate light having a wavelength of 250 to 400 nm at an illuminance of 10 mW / cm 2} for 10 seconds to 30 minutes.
A photocrosslinked product obtained by irradiating a styrene-based elastomer resin composition containing a hydrogenated styrene-based elastomer, a hydrogen-extracting photoinitiator, and a monomer or oligomer having a radically polymerizable double bond with light to crosslink the composition. The photocrosslinked product of the styrene-based elastomer resin composition is also one of the present inventions.

When the styrene-based elastomer resin composition of the present invention is used, the adhesive strength (initial adhesive strength) is high, but the adhesive strength does not easily increase over time or at high temperatures, and low molecules are formed on the surface of the adherend when peeled off. A heat-resistant adhesive film that does not leave components or solvents can be obtained.
A heat-resistant adhesive film having a base material layer and an adhesive layer, wherein the adhesive layer is a monomer having a hydrogen additive of a styrene-based elastomer, a hydrogen-extracting photoinitiator, and a radically polymerizable double bond. A heat-resistant adhesive film containing a photocrosslinked product of a styrene-based elastomer resin composition containing an oligomer is also one of the present inventions.

The excellent effect of the present invention is to light a styrene elastomer resin composition containing a hydrogenated styrene elastomer, a hydrogen abstraction type photoinitiator, and a monomer or oligomer having a radically polymerizable double bond. It can be exhibited only by cross-linking. However, although the photocrosslinked product after cross-linking can be indirectly represented by the storage elastic modulus or the like, it is extremely difficult to directly specify the cross-linked state between the styrene-based elastomers. "Photocrosslinking in which a styrene elastomer resin composition containing a hydrogenated styrene elastomer, a hydrogen abstraction type photoinitiator, and a monomer or oligomer having a radically polymerizable double bond is crosslinked by irradiating light. It must be said that it is impossible or almost impractical to directly identify a "thing" by its structure or properties. Therefore, in the present invention, "a styrene elastomer resin composition containing a hydrogen additive of a styrene elastomer, a hydrogen abstraction type photoinitiator, and a monomer or oligomer having a radically polymerizable double bond is irradiated with light. It should be permissible to describe it as "a photocrosslinked product that has been crosslinked."

The heat-resistant adhesive film of the present invention has a base material layer and an adhesive layer.
The base material layer is not particularly limited, but preferably contains a polyolefin resin.
The polyolefin resin is not particularly limited, and conventionally known polyolefin resins can be used, and examples thereof include polypropylene (PP) resin and polyethylene (PE) resin.
Examples of the polypropylene resin include homopolypropylene, random polypropylene, block polypropylene and the like. Examples of the polyethylene resin include high-pressure low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. Among them, polypropylene resin is preferable from the viewpoint of transparency, rigidity and heat resistance, and homopolypropylene or a copolymer of propylene and at least one α-olefin is more preferable.

The base material layer is an additive such as an antistatic agent, a mold release agent, an antioxidant, a weather resistant agent, a crystal nucleating agent, and a resin such as polyolefin, polyester, polyamide, and elastomer, as long as the effects of the present invention are not impaired. It may contain a modifier.

The thickness of the base material layer is not particularly limited, but a preferable lower limit is 25 μm and a preferable upper limit is 200 μm. If the thickness of the base material layer is less than 25 μm, the heat-resistant adhesive film may be easily broken during handling. If the thickness of the base material layer exceeds 200 μm, curls may remain in the base material layer. The more preferable lower limit of the thickness of the base material layer is 50 μm, and the more preferable upper limit is 188 μm.

The pressure-sensitive adhesive layer contains a photocrosslinked product of the styrene-based elastomer resin composition of the present invention. By containing such a photocrosslinked product, the pressure-sensitive adhesive film can be obtained because the pressure-sensitive adhesive layer can suppress the adhesion of the pressure-sensitive adhesive layer without blending a low-molecular component such as a bleeding agent or a solvent. ..

The pressure-sensitive adhesive layer may further contain a pressure-sensitive adhesive.
The tackifier is not particularly limited, but the softening point is preferably 80 ° C. or higher, and more preferably 90 to 140 ° C. Examples of the tackifier include petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic aromatic copolymers, and alicyclic copolymers, kumaron-indene resins, and terpene resins. Examples thereof include terpene phenol-based resins, rosin-based resins such as copolymerized rosins, (alkyl) phenol-based resins, xylene-based resins, and hydrogenated products thereof. Further, a commercially available tackifier may be used as a mixture with the polyolefin resin. These tackifiers may be used alone or in combination of two or more. In order to improve the peelability, weather resistance, etc. of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive is preferably a hydrogenated additive.

The content of the tackifier is not particularly limited, but the preferable lower limit with respect to 100 parts by weight of the styrene-based elastomer in the styrene-based elastomer resin composition is 3 parts by weight, and the preferable upper limit is 50 parts by weight. When the content of the pressure-sensitive adhesive is within this range, the pressure-sensitive adhesive remains on the surface of the adherend when the heat-resistant adhesive film is peeled off from the surface of the adherend while exhibiting particularly high initial adhesive strength ( It is possible to prevent the adhesive residue). The more preferable lower limit of the content of the tackifier is 5 parts by weight, and the more preferable upper limit is 40 parts by weight.

The pressure-sensitive adhesive layer may contain additives such as a softening agent, an antioxidant, and an anti-adhesive agent, if necessary, for the purpose of controlling the adhesive strength and the like.
Since the pressure-sensitive adhesive layer may contaminate the adherend, it is preferable that the pressure-sensitive adhesive layer does not contain a low molecular weight component such as a bleeding agent or a solvent.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but the preferable lower limit is 3 μm and the preferable upper limit is 30 μm. If the thickness of the pressure-sensitive adhesive layer is less than 3 μm, the adhesive strength of the pressure-sensitive adhesive layer may decrease. If the thickness of the pressure-sensitive adhesive layer exceeds 30 μm, it may be difficult to peel off the heat-resistant adhesive film when peeling the heat-resistant adhesive film from the surface of the adherend. The more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 5 μm, and the more preferable upper limit is 20 μm.

The method for producing the heat-resistant adhesive film of the present invention is not particularly limited. For example, a laminate having the base material layer and the uncrosslinked pressure-sensitive adhesive layer containing the styrene-based elastomer resin composition is prepared in advance, and the laminate is prepared. A method of irradiating the uncrosslinked pressure-sensitive adhesive layer of the body with light can be mentioned.
A base material layer and an uncrosslinked pressure-sensitive adhesive layer containing a styrene-based elastomer resin composition containing a hydrogen additive of a styrene-based elastomer, a hydrogen-extracting photoinitiator, and a monomer or oligomer having a radically polymerizable double bond. A method for producing a heat-resistant adhesive film, which comprises a step of preparing a laminate to have and a step of irradiating the uncrosslinked pressure-sensitive adhesive layer of the laminate with light, is also one of the present inventions.
The irradiation conditions of the light are not particularly limited, but when benzophenone is used as the hydrogen abstraction type photoinitiator, light having a wavelength of 250 to 400 nm is irradiated with ^{an illuminance of 10 mW / cm 2} for 10 seconds to 30 minutes. Is preferable.

The laminate is an uncrosslinked adhesive containing the styrene-based elastomer resin composition on a substrate layer previously obtained by T-die molding or inflation molding by a known lamination method such as extrusion lamination or extrusion coating. A method of laminating the agent layer, a method of laminating the base material layer and the uncrosslinked pressure-sensitive adhesive layer containing the styrene-based elastomer resin composition as independent films, and then laminating each of the obtained films by dry lamination. The resin constituting the material layer and the styrene-based elastomer resin composition can be produced by a method such as coextrusion molding by the T-die method.

The heat-resistant adhesive film of the present invention has high adhesive strength (initial adhesive strength), but the adhesive strength does not easily increase over time or even at high temperatures, and low molecular weight components and solvents remain on the surface of the adherend when peeled off. I won't let you.
The heat-resistant adhesive film of the present invention may be used as a surface protective film for protecting the surface of an adherend having a smooth surface, but is a surface for protecting the surface of an adherend having an uneven surface. It is particularly effective when used as a protective film.
A surface protective film made of the heat-resistant adhesive film of the present invention is also one of the present inventions.

The surface protective film of the present invention is suitably used for protecting the surface of members such as optical devices, metal plates, painted metal plates, resin plates, and glass plates. Among them, it is particularly suitable for protecting an optical member having an uneven shape on one side or both side surfaces such as a prism sheet and a diffusion film.

According to the present invention, while the adhesive strength (initial adhesive strength) is high, the adhesive strength does not easily increase over time or at high temperature, and styrene that does not leave low molecular weight components or solvents on the surface of the adherend when peeled off. A method for producing a surface protective film and a heat-resistant adhesive film comprising a based elastomer resin composition, a photocrosslinked product of the styrene-based elastomer resin composition, a heat-resistant adhesive film, and a heat-resistant adhesive film can be provided.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1)
A monomer having a radically polymerizable double bond and 1 part by weight of benzophenone as a hydrogen abstraction type photoinitiator with respect to 100 parts by weight of SEBS block copolymer (Dinaron "1321P" manufactured by JSR) as a hydrogen additive of a styrene elastomer. A styrene-based elastomer resin composition was obtained by blending 4 parts by weight of trimesterol propanetriacrylate as a mixture and stirring and mixing using a laboplastomill twin-screw extruder.

A polyolefin resin (trade name "J715M", manufactured by Prime Polymer Co., Ltd.) was prepared as a raw material for the base material layer.
The obtained styrene-based elastomer resin composition and polyolefin resin were coextruded by the T-die method to obtain a laminate having a base material layer of 35 μm and an uncrosslinked pressure-sensitive adhesive layer of 5 μm.
A heat-resistant adhesive film was obtained from the uncrosslinked pressure-sensitive adhesive layer side of the obtained laminate by ^{irradiating light having a wavelength of 365 nm with an illuminance of 10 mW / cm 2 for 1200 seconds using an ultra-high pressure mercury lamp.}

(Examples 2 to 12, Comparative Examples 1 to 4)
Except as shown in Tables 1 and 2 for the types or amounts of hydrogenated styrene elastomers, hydrogen-extracted photoinitiators, monomers or oligomers with radically polymerizable double bonds, and the presence or absence of ultraviolet irradiation. A heat-resistant adhesive film was obtained in the same manner as in Example 1.
The hydrogenated styrene elastomer shown below was used.
-SEBS block copolymer (Tough Tech "H1041" manufactured by Asahi Kasei Corporation)
-SEPS block copolymer (Kuraray Septon "2063")

<Evaluation>
The heat-resistant adhesive films obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1 and 2.

(1) Evaluation of Initial Adhesive Strength The heat-resistant adhesive film was cut into a width of 25 mm. The cut heat-resistant adhesive film was attached to an acrylic plate at a room temperature of 23 ° C. and a relative humidity of 50% at a speed of 300 mm / min using a 2 kg pressure-bonded rubber roller. After standing for 30 minutes, the heat-resistant adhesive film was peeled off at a speed of 300 mm / min according to JIS Z0237, and the peeling strength was measured at 180 degrees. This was used as the initial adhesive strength and evaluated according to the following criteria.
◯: Initial adhesive strength is 0.05 N / 25 mm or more and less than 0.45 N / 25 mm ×: Initial adhesive strength is less than 0.05 N / 25 mm or 0.45 N / 25 mm or more

(2) Evaluation of Adhesive Promotion Rate The heat-resistant adhesive film was cut into a width of 25 mm. The cut heat-resistant adhesive film was attached to an acrylic plate at a room temperature of 23 ° C. and a relative humidity of 50% at a speed of 300 mm / min using a 2 kg pressure-bonded rubber roller. Next, an acrylic plate to which a heat-resistant adhesive film was attached was sandwiched between two 2 mm-thick polycarbonate plates, ^{a pressure of 6.0 × 10 -3} MPa was applied, and the mixture was left in that state at 60 ° C. for 168 hours. After being taken out to room temperature and left for 60 minutes, the heat-resistant adhesive film was peeled off at a speed of 300 mm / min according to JIS Z0237, and the peeling strength was measured at 180 degrees. This was defined as the adhesive strength over time.
The rate of change in adhesive strength over time (adhesive advancement rate) was calculated from the initial adhesive strength by the following formula and evaluated according to the following criteria.
Adhesive rate = (adhesive strength over time / initial adhesive strength) x 100
⊚: Adhesive advancement rate is 350% or less ○: Adhesive advancement rate exceeds 350%, 400% or less ×: Adhesive advancement rate exceeds 400%

(3) Evaluation of surface tension on the surface of the adherend after peeling A heat-resistant adhesive film is applied to a corona-treated polyethylene terephthalate (PET) film at room temperature of 23 ° C. and relative humidity of 50% using a 2 kg pressure-bonded rubber roller to 300 mm. It was pasted at a speed of / min. In that state, it was left in an oven at 40 ° C. for 24 hours. After taking out at room temperature and leaving it for 60 minutes, the heat-resistant adhesive film was peeled off.
The surface tension of the surface of the PET film before and after the application was measured, the surface tension reduction rate was calculated by the following formula, and the evaluation was made according to the following criteria.
Surface tension reduction rate = (1- (surface tension after peeling / surface tension before pasting)) x 100
◯: Surface tension reduction rate is 35% or less ×: Surface tension reduction rate exceeds 35%

According to the present invention, while the adhesive strength (initial adhesive strength) is high, the adhesive strength does not easily increase over time or at high temperature, and styrene that does not leave low molecular weight components or solvents on the surface of the adherend when peeled off. A method for producing a surface protective film and a heat-resistant adhesive film comprising a based elastomer resin composition, a photocrosslinked product of the styrene-based elastomer resin composition, a heat-resistant adhesive film, and a heat-resistant adhesive film can be provided.

Claims (9)

It contains a hydrogenated additive of a styrene-based elastomer, a hydrogen-withdrawing photoinitiator, and a monomer or oligomer having a radically polymerizable double bond .
The monomer or oligomer having a radically polymerizable double bond is a polyfunctional acrylate or polyfunctional methacrylate having two or more radically polymerizable double bonds in the molecule.
The content of the monomer or oligomer having a radically polymerizable double bond is 0.1 to 50 parts by weight with respect to 100 parts by weight of the hydrogenated product of the styrene-based elastomer. Elastomer resin composition. The styrene-based elastomer resin according to claim 1, wherein the hydrogenated additive of the styrene-based elastomer is a styrene-ethylene-butylene-styrene (SEBS) block copolymer or a styrene-ethylene-propylene-styrene (SEPS) block copolymer. Composition. The styrene-based elastomer resin composition according to claim 1 or 2, wherein the hydrogen-extracting photoinitiator is a benzophenone. The styrene-based elastomer resin according to claim 1, 2 or 3, wherein the content of the hydrogen-drawing type photoinitiator is 0.1 to 5 parts by weight with respect to 100 parts by weight of the hydrogenated additive of the styrene-based elastomer. Composition. A photocrosslinked product obtained by irradiating a styrene-based elastomer resin composition containing a hydrogenated styrene-based elastomer, a hydrogen-extracting photoinitiator, and a monomer or oligomer having a radically polymerizable double bond with light to crosslink the composition. I der,
The monomer or oligomer having a radically polymerizable double bond is a polyfunctional acrylate or polyfunctional methacrylate having two or more radically polymerizable double bonds in the molecule.
The content of the monomer or oligomer having a radically polymerizable double bond is 0.1 to 50 parts by weight with respect to 100 parts by weight of the hydrogenated product of the styrene-based elastomer. Photocrosslinked product of based elastomer resin composition. A heat-resistant adhesive film having a base material layer and an adhesive layer.
The pressure-sensitive adhesive layer contains a photocrosslinked product of a styrene-based elastomer resin composition containing a hydrogenated styrene-based elastomer, a hydrogen-extracting photoinitiator, and a monomer or oligomer having a radically polymerizable double bond. And
The monomer or oligomer having a radically polymerizable double bond is a polyfunctional acrylate or polyfunctional methacrylate having two or more radically polymerizable double bonds in the molecule.
The content of the monomer or oligomer having a radically polymerizable double bond is 0.1 to 50 parts by weight with respect to 100 parts by weight of the hydrogenated product of the styrene-based elastomer. Adhesive film. The heat-resistant adhesive film according to claim 6, wherein the pressure-sensitive adhesive layer further contains a pressure-sensitive adhesive. A surface protective film comprising the heat-resistant adhesive film according to claim 6 or 7. A base material layer and an uncrosslinked pressure-sensitive adhesive layer containing a styrene-based elastomer resin composition containing a styrene-based elastomer hydrogen additive, a hydrogen-extracting photoinitiator, and a monomer or oligomer having a radically polymerizable double bond. The process of preparing the laminate to have and
A method of manufacturing a heat-proof adhesive film that have a irradiating light to the uncrosslinked pressure-sensitive adhesive layer of the laminate,
The monomer or oligomer having a radically polymerizable double bond is a polyfunctional acrylate or polyfunctional methacrylate having two or more radically polymerizable double bonds in the molecule.
The content of the monomer or oligomer having a radically polymerizable double bond is 0.1 to 50 parts by weight with respect to 100 parts by weight of the hydrogenated product of the styrene-based elastomer.
A method for producing a heat-resistant adhesive film .