JP2001139901A - Curable pressure sensitive adhesive tape for adhering abs resin plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable pressure sensitive adhesive tape for adhering an ABS resin plate, having an excellent stickiness and initial adhesive power at normal temperature before hardening, excellent in workability and handleability because the adhesive is almost free from flash and leak out, curable by irradiation with a light before or after laminating to a substrate, and exhibiting an excellent adhesivity, heat resistance, impact resistance, or the like, after curing. SOLUTION: The curable pressure sensitive adhesive tape for adhering ABS resin plate comprises a curable pressure sensitive adhesive composition laminated on a side of a base material while the pressure sensitive adhesive comprises a thermoplastic resin, a compound capable of carrying out a cationic polymerization and a photo cationic polymerization initiator in the composition, where the ratio of the molar concentration of cations generated by the photo cationic polymerization initiator to that of an acrylonitrile component included in the ABS resin plate (a substrate) is 0.3-5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable adhesive tape for bonding an ABS resin plate.

[0002]

2. Description of the Related Art Curable pressure-sensitive adhesive tapes (including curable pressure-sensitive adhesive sheets) can be bonded at room temperature like ordinary pressure-sensitive adhesive tapes, and cured (post-cured) by any method after bonding. This is an adhesive material that can be converted into an adhesive to exhibit excellent adhesive performance. This curable adhesive sheet does not need to be applied to an adherend before bonding like a normal liquid adhesive, and has features such as easy positioning because it can be re-applied. Excellent workability and ease of use.

[0003] In recent years, a curable adhesive tape having such excellent advantages has been used as a novel adhesive material in place of a conventional adhesive, for example, for bonding electric / electronic parts, bonding automobile / vehicle parts, or structural bonding. Its use is expanding in the field.

[0004] As such a curable pressure-sensitive adhesive composition for a curable pressure-sensitive adhesive tape, for example, JP-T-10-5086
No. 36, "Cationically polymerizable monomer containing at least one free radical polymerizable polymer, at least one cationic polymerizable monomer, and at least one organometallic complex salt or at least one onium salt A curable pressure-sensitive adhesive containing a photoactive catalyst component used for, and, optionally, a monohydric alcohol or a polyhydric alcohol '' is disclosed,
Japanese Patent Application Laid-Open No. Hei 7-138550 discloses that "epoxy resin which is liquid at ordinary temperature, thermoplastic resin which is solid at ordinary temperature compatible with the epoxy resin, crosslinked rubber particles having an average particle diameter of 3 μm or less, and the potential for epoxy resin. Epoxy resin-based adhesive composition containing a curing agent as an essential component ”is disclosed.

On the other hand, ABS resins are widely used as general-purpose plastics because they have both toughness and flexibility, and are excellent in workability and mechanical strength. In particular, in recent years, attention has been paid to alternative resins to vinyl chloride resins. For example, molded articles such as fiber-reinforced ABS resin have been used as instrument panels for automobiles. Accordingly, it is required that the adhesive material for the ABS resin has high performance such as high adhesive strength.

However, the conventional liquid adhesive needs to be applied in advance to the ABS resin as an adherend, and the molded liquid generally has many curved surfaces and few horizontal surfaces, so that the applied liquid adhesive flows out. There are problems such as sticking out of the bonded portion and impairing the appearance.

Further, the so-called film adhesive which has been taped in advance has a problem that the molded article tends to be deformed due to the necessity of heating at the time of adhesion, although the above-mentioned flow-out or run-out is small, ), It is necessary to apply pressure during bonding, and there is a problem that a special jig is required especially in the case of bonding a molded body having many curved surfaces.

Further, the conventional adhesive tape has an adhesive property, so that it can be adhered by a simple method such as a finger pressure or the like, and is excellent in workability, but is insufficient in adhesive strength, durability, reliability and the like. There is a problem.

In the case of a curable pressure-sensitive adhesive tape using a curable pressure-sensitive adhesive disclosed in JP-T-10-508636, a curable pressure-sensitive adhesive tape mainly composed of an acrylic polymer and an epoxy resin is used. The adhesive has excellent tackiness at room temperature, but has a problem that the cohesive force after curing is not sufficiently increased because the acrylic polymer is flexible. Increasing the content of epoxy resin to increase cohesive strength after curing causes problems such as reduced adhesiveness at room temperature and excessively high elastic modulus after curing, resulting in reduced impact resistance and cold resistance. Occurs.

Further, in the case of a curable adhesive tape using the epoxy resin adhesive composition disclosed in Japanese Patent Application Laid-Open No. 7-138550, the epoxy resin adhesive Due to the high content of liquid epoxy resin, the shear adhesion after curing is excellent, but the cohesive force before curing is low. There is a problem that the adhesive composition exudes and the handleability deteriorates.

[0011]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to have excellent tackiness and initial tackiness at room temperature before curing, and hardly extrude or exude, so that workability and handling can be improved. ABS that is excellent in adhesiveness and is cured by irradiating light before or after laminating the adherend, and exhibits excellent adhesion, heat resistance, impact resistance, etc. after curing.
An object of the present invention is to provide a curable adhesive tape for bonding a resin plate.

[0012]

The curable pressure-sensitive adhesive tape for bonding an ABS resin plate according to the present invention comprises a thermoplastic resin, a cationically polymerizable compound and a cationic photopolymerization initiator. The ratio of the molar concentration of the cation generated by the photocationic polymerization initiator to the molar concentration of the acrylonitrile component contained in the adherend) is 0.
A curable pressure-sensitive adhesive composition having a content of 3 to 5% is laminated on at least one surface of a support.

Hereinafter, in the present specification, "curable adhesive composition" and "curable adhesive tape" are abbreviated simply as "adhesive composition" and "adhesive tape", respectively. .

As the thermoplastic resin used in the present invention, any thermoplastic resin may be used as long as it has good compatibility with the cationically polymerizable compound described later. Examples thereof include polyester resins and polyurethane resins. And polystyrene-based resins, poly (meth) acrylate-based resins, polyvinyl acetate-based resins, and the like. These may be a homopolymer or a copolymer.
In addition, these thermoplastic resins may be used alone, or two or more kinds may be used in combination.

The above-mentioned thermoplastic resin is taken into a network of cationic polymerization by a cationically polymerizable compound and a photo-cationic polymerization initiator, which will be described later, and forms a phase structure such as a so-called IPN structure, a cross-linked structure, and a pseudo-cross-linked structure. The cured adhesive tape exhibits excellent adhesive strength, heat resistance, durability, weather resistance, and the like.

Glass transition temperature (Tg) of thermoplastic resin
There is a range of choice depending on the bonding temperature and is not particularly limited, but is generally preferably 30 ° C. or less,
It is more preferably at most 10 ° C. Tg of thermoplastic resin
Exceeds 30 ° C., the cohesive strength of the thermoplastic resin becomes too high, and the adhesiveness and initial adhesive strength of the pressure-sensitive adhesive tape may decrease, or the impact resistance and cold resistance may be insufficient.

Therefore, in order to adjust the Tg of the thermoplastic resin, for example, a Tg adjusting component such as butadiene, alkyl (meth) acrylate, aromatic (meth) acrylate, or hydroxyalkyl (meth) acrylate is added to the thermoplastic resin. It may be copolymerized.

The number average molecular weight of the thermoplastic resin is not particularly limited, but is generally 300.
0 to 100,000 is preferred. If the number average molecular weight of the thermoplastic resin is less than 3,000, the cohesive strength may be insufficient, while if it exceeds 100,000, the compatibility with the cationically polymerizable compound may decrease.

Further, in order to impart a crosslinking property to the thermoplastic resin, for example, a hydroxyl group, a carboxyl group, an epoxy group,
A crosslinkable functional group such as an unsaturated double bond may be introduced into the thermoplastic resin. However, since a basic functional group such as an amino group may inhibit the cationic polymerization reaction, it is preferable not to introduce it or to introduce it as little as possible.

Among the above thermoplastic resins, polyester resins and polyurethane resins are preferably used. Polyester-based resins and polyurethane-based resins are not only highly polar and have excellent compatibility with cationically polymerizable compounds, but also have high cohesive strength. It is possible to obtain a self-adhesive adhesive tape, which is advantageous in that it can be easily formed into a tape and the adhesive time after light irradiation is long.

In particular, polyester resins have a high polarity because they have an ester group in the molecule and a hydroxyl group or a carboxyl group at the terminal of the molecule. For example, ABS, PET, PVC, P
It is particularly preferably used because it has excellent adhesion to high polar plastics such as EN and polycarbonate.

Specific examples of the polyester resin include, for example, “Byron” series and “Vylonal” series manufactured by Toyobo Co., Ltd., “Elitel” series manufactured by Unitika, and Dainippon Ink and Chemicals, Inc. “Takelac” series manufactured by Takeda Pharmaceutical Co., Ltd., and “Kuraboru” series manufactured by Kuraray Co., Ltd. These polyester resins may be used alone or in combination of two or more.

The cationically polymerizable compound used in the present invention is a polymer having a high molecular weight by cationic polymerization to cure the adhesive composition. After curing, the thermoplastic resin and the IPN structure, cross-linked structure, pseudo-cross-linked structure, etc. A compound capable of forming a phase structure and imparting high cohesive strength and adhesive strength, for example,
Compounds having a cationically polymerizable functional group such as an epoxy group, an alicyclic epoxy group, a vinyl ether group, a hydroxyl group, an ethyleneimine group, and an episulfide group in the molecule are exemplified.
The cationically polymerizable compounds may be used alone or in combination of two or more.

The molar equivalent of the cationically polymerizable functional group in the above cationically polymerizable compound is 1000 g · resin / mo.
It is preferably 1 or less. When the molar equivalent of the cationically polymerizable functional group exceeds 1000 g · resin / mol, the crosslink density decreases, and sufficient adhesive strength and heat resistance may not be obtained.

The cationically polymerizable compound is not particularly limited, but is preferably a liquid having a number average molecular weight of 5,000 or less at room temperature, more preferably 30 or less.
00 or less. When the number average molecular weight of the cationically polymerizable compound exceeds 5,000, the compatibility with the thermoplastic resin is reduced to cause phase separation, and the wettability to the surface of the adherend is reduced and the adhesion is not sufficiently performed, Adhesive strength may be insufficient.

Among the above-mentioned cationically polymerizable compounds, epoxy compounds having an epoxy group or an alicyclic epoxy group, or vinyl ether compounds having a vinyl ether group, which are excellent in cationic polymerizability, are preferably used. Epoxy compounds which can exhibit more excellent adhesive strength and heat resistance because of their high properties are particularly preferably used.

Specific examples of the above epoxy compound include:
For example, Yuka Shell Epoxy product name "Epicoat" series, Shell Chemical product name "Epon"
Asahi Denka Kogyo Co., Ltd. product name "ADEKARESIN" series and "ADEKA OPTOMER" series, Daicel Chemical Industries Co., Ltd. product name "CELOXIDE" series, "CYCLOMER" series, "EPO FRIEND" series and "EPOLIDE" A so-called epoxy resin such as a series may be used. Further, specific examples of the vinyl ether-based compound include, for example, a product name “Lapicure” series manufactured by ISP.

These cationically polymerizable compounds are cationically polymerized by a photo-cationic polymerization initiator described below, and the thermoplastic resin is contained in a polymer network of the cationically polymerizable compound to restrict movement, By a cross-linking reaction with hydroxyl groups and carboxyl groups of
Since a highly crosslinked structure is formed by forming a PN structure, the function of increasing the elastic modulus of the pressure-sensitive adhesive tape after curing and significantly improving the adhesive strength and heat resistance is exhibited. However, if the elastic modulus after curing of the pressure-sensitive adhesive tape becomes too high, impact resistance and cold resistance may decrease. Therefore, if necessary, a flexibility imparting agent such as rubber, You may adjust the elastic modulus after hardening by adding an imparting agent, a softener, a plasticizer, and the like.

The cationic photopolymerization initiator used in the present invention is activated by irradiating light to generate a photocationic polymerization initiator, and the above cationically polymerizable compound is photocationically polymerized at relatively low energy. As long as it can be performed, an ionic photoacid generating type cationic photopolymerization initiator may be used, or a nonionic photoacid generating type photocationic polymerization initiator may be used.

Examples of the ionic photoacid generating type cationic photopolymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts and aromatic sulfonium salts, iron-allene complexes, titanocene complexes, and arylsilanols. -Organometallic complexes such as aluminum complexes.

Specific examples of the ionic photoacid generating type cationic photopolymerization initiator include, for example, trade names “OPTMER SP-150” and “OPTMER SP-150” manufactured by Asahi Denka Kogyo Co., Ltd.
170 ", a product name" U "manufactured by General Electronics
VE-1014 ", product name" CD-1 "manufactured by Sartomer
012 "and the like.

Examples of the nonionic photoacid generating type cationic photopolymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidesulfonate and the like. No.

The above cationic photopolymerization initiator may be used alone or in combination of two or more. When two or more cationic photopolymerization initiators are used in combination, multistage curing may be performed using two or more different cationic photopolymerization initiators having different effective active wavelengths. Further, for example, one or more of other photopolymerization initiators such as a photoradical polymerization initiator and a photoanionic polymerization initiator may be used in combination. In this case, the wavelength of the light for activating the cationic photopolymerization initiator and the wavelength of the light for activating the other photopolymerization initiator need not always be equal. Further, one or more photosensitizers such as benzophenone and 9,10-anthraquinone may be used in combination.

The amount of the cationic photopolymerization initiator added is not particularly limited, but the amount of the cation generated by the cationic photopolymerization initiator relative to the molar concentration of the cationically polymerizable functional group in the cationically polymerizable compound is not limited. It is preferable that the molar concentration ratio (cation / functional group) is 0.001 to 10%, more preferably the molar ratio (cation / functional group) is 0.1 to 10%. If the above ratio (cation / functional group) is less than 0.001%, the cationic polymerization reaction may be slowed and require a long time for curing, and conversely, the ratio (cation / functional group) may exceed 10%. In such a case, it may not be possible to obtain a bondable time after light irradiation. Therefore, when light irradiation is performed after the adhesive tape of the present invention is adhered to an adherend, in other words, when the adhesive time after light irradiation is not required, the above ratio (cation / functional group) Does not necessarily need to be 10% or less.

The light for activating the photocationic polymerization initiator includes, for example, infrared rays, visible rays, ultraviolet rays,
X-rays, α-rays, β-rays, γ-rays, electron beams, and the like can be mentioned. Among them, light having a wavelength of ultraviolet light or more, which is highly safe and advantageous in cost, is preferably used, and particularly preferably used. Is a wavelength 2 that is easy to handle, simple and has a high energy content.
It is an ultraviolet ray of 00 to 400 nm. Examples of the light source that generates the ultraviolet light include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp,
Metal halide lamps, chemical lamps, xenon lamps, and the like.

The cationic photopolymerization initiator generates active cations upon irradiation with the above light, and cures the cationically polymerizable compound by a cationic polymerization reaction to increase the elastic modulus. In general, the cationic polymerization reaction has no polymerization inhibition due to oxygen as seen in a radical polymerization reaction, and once generated active cations continue the polymerization reaction in a chain even after light blocking, so by controlling the rate of the cationic polymerization reaction Alternatively, a semi-cured pressure-sensitive adhesive composition or pressure-sensitive adhesive sheet which can maintain a tacky state and maintain an adhesive state even after light irradiation can be used.

In this case, it is possible to bond the adhesive composition or the adhesive tape in a semi-cured state with time while the adhesiveness is maintained. The curing proceeds, and finally, a strong adhesive force such as an adhesive and heat resistance are developed. Therefore, it is possible to bond an opaque material that does not transmit light, and it is also possible to bond a material having low heat resistance because the polymerization reaction proceeds at room temperature without heating.

The adhesive composition constituting the adhesive tape of the present invention comprises, besides the above-mentioned thermoplastic resin, cationic polymerizable compound and the above-mentioned cationic photopolymerization initiator, contained as essential components. If necessary within the range not hindering the achievement of the task, a tackifier, a filler, a bulking agent, a thixotropic agent, a softener, a plasticizer, a stabilizer, an antioxidant, a crosslinking agent, a crosslinking auxiliary,
One or more of various additives such as a flame retardant, an antistatic agent, a colorant, and an organic solvent for dissolution or dilution may be added.

The organic solvent has good solubility and compatibility with a thermoplastic resin, a cationically polymerizable compound and a cationic photopolymerization initiator or other additives, and has a boiling point of 40.
~ 200 ° C is preferable, for example, acetone,
Examples include methyl ethyl ketone, methyl isobutyl ketone, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, toluene, p-xylene, n-hexane, cyclohexane, chloroform, carbon tetrachloride, and the like. Or two or more of them may be used in combination.

The method for producing the above-mentioned adhesive composition is not particularly limited, and may be performed at room temperature or by heating using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three-roll machine. In the following, predetermined amounts of each of the thermoplastic resin, the cationically polymerizable compound, and the photo-cationic polymerization initiator, and one or more predetermined amounts of one or more of the above various additives that are added as needed, are uniformly stirred and mixed. By doing so, a desired adhesive composition can be obtained.

Generally, the acrylonitrile component (AN) in the ABS resin is an inhibitor of the cationic polymerization reaction.
For example, when a pressure-sensitive adhesive tape is adhered to an ABS resin plate (substrate), the curing speed of the pressure-sensitive adhesive composition in contact with the interface of the adherend is higher in the bulk state where the composition is not in contact with the interface of the adherend. It is slower than the curing speed of the adhesive composition.

Accordingly, the adhesive composition in contact with the interface of the adherend is maintained at a low curing rate for a relatively long time, and can sufficiently wet the surface of the adherend, thereby increasing the effective adhesive area, High adhesive strength can be obtained. The delay of the cationic polymerization reaction due to the acrylonitrile component (AN) is considered to be reversible capture of cations generated by the photocationic polymerization initiator, and although the curing speed is slowed, the viscosity of the cation that is finally in contact with the adherend interface is reduced. The adhesive composition also cures to a level equivalent to that of the bulk adhesive composition not in contact with the adherend interface, so that heat resistance, durability, weather resistance, and the like are not impaired.

In the present invention, the cation generated by the cationic photopolymerization initiator contained in the adhesive composition with respect to the molar concentration of the acrylonitrile component (AN) contained in the ABS resin as the adherend. It is necessary that the molar concentration ratio (cation / AN) is 0.3 to 5%.

If the above ratio (cation / AN) is less than 0.3%, the cationic polymerization reaction is slowed down, and in particular, it takes too much time to cure the adhesive composition in contact with the interface of the adherend. Conversely, the above ratio (cation / AN)
Exceeds 5%, the retention time of the low curing rate of the adhesive composition in contact with the adherend interface becomes short, and the wetting on the adherend surface becomes insufficient, so that the effective adhesive area is sufficient. Does not increase,
It is difficult to obtain high adhesive strength.

The adhesive tape of the present invention comprises the above-mentioned adhesive composition laminated on at least one surface of a support.
In addition, the support referred to here is not only a support generally used as a base material of a normal adhesive tape such as cellophane or kraft paper, but also a release film usually used as a separator or Release paper and the like are also included.

The pressure-sensitive adhesive tape of the present invention may be a single-sided pressure-sensitive adhesive tape, a double-sided pressure-sensitive adhesive tape, or a support type pressure-sensitive adhesive tape. Alternatively, a non-support type adhesive tape may be used. If the adhesive composition is applied to the non-release surface of the support, it becomes a support type adhesive tape, and if the adhesive composition is applied to the release surface of the support, it becomes a non-support type. It becomes an adhesive tape.

The method for producing the above-mentioned adhesive tape is not particularly limited. For example, a roll-coating method, a gravure coating method, a casting coating method,
A direct coating method in which the adhesive composition is applied by various coating methods such as a calendar coating method and an extrusion coating method, and a drying step or a cooling step is performed to obtain an adhesive tape as required, or a release method. After applying a pressure-sensitive adhesive composition to the release surface of the film or release paper by the above-described various coating methods, passing through a drying step and a cooling step as necessary, laminating the pressure-sensitive adhesive tape on the support surface to form a pressure-sensitive adhesive tape. Depending on the transfer method obtained, a desired adhesive tape can be obtained.

Examples of the support include various materials in the form of a sheet, such as a plastic film such as a polyethylene terephthalate (PET) film, metal foil, paper, cloth, and non-woven fabric. Can be used for If necessary, these supports may be subjected to release treatment, surface oxidation treatment such as corona treatment, easy adhesion treatment such as primer coating, shaping treatment such as embossing or matting, friction processing, printing. By applying a surface treatment such as lamination treatment such as vapor deposition, lamination or the like, it becomes possible to obtain an adhesive tape having various characteristics.
For example, by protecting the surface of the adhesive composition with a plastic film that has been subjected to a release treatment with a silicone-based or non-silicone-based release agent, an adhesive tape excellent in shape processing such as cutting and punching. Can be obtained.

The thickness of the pressure-sensitive adhesive tape of the present invention is not particularly limited, but is generally preferably from 1 to 1000 μm, more preferably from 10 to 500 μm.
It is. When the thickness of the pressure-sensitive adhesive tape is less than 1 μm, the adhesive strength may be insufficient. On the other hand, when the thickness exceeds 1000 μm, it may take a long time to cure and the productivity may be reduced.

The bonding method using the adhesive tape of the present invention is performed by roll lamination, pressing, pressing by finger pressure or the like. The adhesive composition used in the present invention and the adhesive sheet of the present invention have excellent tackiness and initial adhesive strength at room temperature, and therefore can be easily bonded by the above-mentioned pressure bonding method.

[0051]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The following raw materials were used for the curable adhesive composition. 1. Thermoplastic resin (1) Polyester resin trade name “Byron 550” (Tg: -15 ° C, manufactured by Toyobo Co., Ltd.) (2) Urethane-modified polyester resin trade name “Byron UR3200” (Tg: -3 ° C, manufactured by Toyobo Co., Ltd.) ) 2. Cationic polymerizable compound (1) Bisphenol A type epoxy resin Trade name “Epicoat # 828” (epoxy equivalent: 19
0, manufactured by Yuka Shell Epoxy Co., Ltd.) (2) Alicyclic epoxy resin “CELLOXIDE 2081” (Epoxy equivalent: 15
0, manufactured by Daicel Chemical Industries, Ltd.) Photo-cationic polymerization initiator Aromatic sulfonium salt-type photo-cationic polymerization initiator Trade name “OPTMER SP-170” (molecular weight: 128
0, manufactured by Asahi Denka Kogyo Co., Ltd.) Organic solvent methyl ethyl ketone (MEK)

Example 1 Using a homodisper, a polyester resin “Vylon 550” was used as a thermoplastic resin.
70 parts by weight, 29 parts by weight of a bisphenol A type epoxy resin "Epicoat # 828" as a cationically polymerizable compound, and an aromatic sulfonium salt type photocationic polymerization initiator "Optomer SP-170" 1 as a photocationic polymerization initiator
Was dissolved in the same amount of MEK and uniformly stirred and mixed to prepare an adhesive composition having a solid content of 50% by weight.

Next, using a roll coater, the pressure-sensitive adhesive composition obtained above was applied to the release-treated surface of a 50 μm-thick PET film (separator) having been subjected to a release treatment on one side, and then dried. Coating was performed so that the working thickness was 50 μm, and the coating was dried to prepare an adhesive tape.

(Examples 2 to 4) and (Comparative Examples 1 and 2) The adhesive was prepared in the same manner as in Example 1 except that the adhesive composition was changed to the composition shown in Table 1. A composition and an adhesive tape were obtained.

Comparative Example 3 An ordinary moisture-curable adhesive (trade name “Super X”, manufactured by Cemedine Co., Ltd.) was used without preparing the adhesive composition and the adhesive tape.

The epoxy equivalents and the cation concentration (mol / 100 g) of the adhesive compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were calculated, and the cation to the epoxy group (functional group) concentration was calculated. The concentration ratio (cation / functional group) was calculated. Further, the concentration (mol / 10) of the acrylonitrile component (AN) contained in the ABS resin used as the adherend.
0g) was calculated to calculate the ratio of the cation concentration to the acrylonitrile component concentration (cation / AN). The results are shown in Table 1.

Next, the performance of the pressure-sensitive adhesive tape obtained in Examples 1 to 4 and Comparative Examples 1 and 2 and the moisture-curable adhesive “Super X” used in Comparative Example 3 (peeling adhesion to ABS resin plate) , Adhesive strength to rigid PVC board, presence or absence of protrusion)
Was evaluated by the following method. The results are shown in Table 1.
The above performance evaluation was performed at 23 ° C.-6 unless otherwise specified.
The test was performed under an atmosphere of 5% RH.

Peel adhesion to ABS resin plate: 100 μm thick with a corona treatment on one side using a laminator
An adhesive tape was laminated on the corona-treated surface of the PET film having a linear pressure of 20 N / cm and a laminating speed of 1 m / min. Next, the separator was peeled off, and the surface of the adhesive composition of the adhesive tape was irradiated with ultraviolet light having a central wavelength of 360 nm so as to have a light amount of ² J / cm ² using a high-pressure mercury lamp. K-6873 "AB
The ABS resin specified in the "S resin plate" was pressure-bonded to a test plate processed into a size of 50 mm in width, 100 mm in length, and 2 mm in thickness to produce an adhesion test piece. The obtained adhesive test piece was 6
After leaving for 1 day, 3 days, and 5 days in an atmosphere of 0 ° C.,
The sample was taken out, and the 180-degree square peeling adhesive force was measured at a peeling speed of 50 mm / min. However, the moisture-curable adhesive “Super X” used in Comparative Example 3 was applied to a corona-treated surface of a PET film and pressed on a test plate. In addition, the 180-degree square peel adhesion was measured only for the adhesion test piece left in an atmosphere of 60 ° C. for 5 days. The ABS resin used as the test plate (substrate) had an AN content of 25% by weight. If the molecular weight of AN was 53, the AN concentration was 0.1%.
It was 47 mol / 100 g · resin.

Peel adhesion to hard PVC plate: 50 mm wide, 100 mm long, 2 mm thick as test plate (substrate)
The 180-degree angle peel adhesion was measured in the same manner as in the case except that the hard PVC plate was used.

Presence or absence of protrusion: In the test, the presence or absence of protrusion of the pressure-sensitive adhesive composition or the moisture-curable adhesive due to the pressure at the time of pressure bonding with the test plate was visually observed.

[0062]

[Table 1]

[0063]

The adhesive composition constituting the adhesive tape of the present invention contains a thermoplastic resin, a cationically polymerizable compound and a photo-cationic polymerization initiator. Appropriately plasticized by the polymerizable compound, thus exhibiting excellent adhesiveness and initial adhesive strength, and also has good cohesive force even in an uncured state when formed into an adhesive tape, and when pressed Since there is almost no protrusion or bleeding due to the pressure described above, the workability and handleability are excellent.

Further, the cured adhesive composition which has been cationically polymerized by irradiation with light has a highly crosslinked structure by forming an IPN structure between the thermoplastic resin and the cationically polymerizable compound. It exhibits excellent adhesive strength, heat resistance, impact resistance, durability, weather resistance and the like.

Further, the above adhesive composition has a ratio of the molar concentration of the cation generated by the photocationic polymerization initiator to the molar concentration of the acrylonitrile component (AN) contained in the ABS resin as the adherend ( Cation / A
Since N) is specified to be in a specific range, A
By effectively reversing the cationic polymerization reaction inhibition by the acrylonitrile component (AN) in the BS resin, the curing rate of the adhesive composition in contact with the ABS resin (substrate) interface is relatively low for a relatively long time. It can be kept in a state. As a result, the adhesive composition can sufficiently wet the surface of the ABS resin (substrate), and the effective adhesive area increases, so that high adhesive strength is exhibited, and excellent heat resistance and impact resistance are achieved. Properties, durability and weather resistance are also maintained.

As described above, the curable pressure-sensitive adhesive tape according to the present invention is produced by using the above-mentioned curable pressure-sensitive adhesive composition, and therefore has the above-mentioned various excellent properties. And ABS resin plates.

Continued on the front page F-term (reference) 4J004 AA07 AA09 AA10 AA13 AA14 AA15 AA17 AB07 CA02 CA06 CA08 CB01 CB02 CC02 CC03 DB03 EA05 FA05 4J040 DB021 DE021 DF041 DF051 EC001 ED001 EF001 FA061 HB04 HD14 HD18 HC17 KA13 LA01 LA02 LA06 LA08 MA10 MB05

Claims (1)

[Claims] 1. A composition comprising a thermoplastic resin, a cationically polymerizable compound and a cationic photopolymerization initiator, and AB
A ratio of the molar concentration of the cation generated by the photocationic polymerization initiator to the molar concentration of the acrylonitrile component contained in the S resin (adherend) is 0.3 to 5%; A curable adhesive tape for bonding an ABS resin plate, comprising an adhesive composition laminated on at least one surface of a support.