JP2003073629A - Adhesive composition and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition and an adhesive sheet loosing adhesive power by curing with ultraviolet-light irradiation, wherein an adherend can be easily peeled after curing with an ultraviolet-light irradiation, and the adherend has no residue thereon after the peeling. SOLUTION: The adhesive composition comprises (a) a (meth)acrylic adhesion polymer having a functional group with an active hydrogen, (b) a photopolymerizable (meth)acrylic oligomer or a (meth)acrylic monomer, (c) a photopolymerization initiator, (d) a crosslinking agent having reactivity with the active hydrogen, and (e) a silicone graft copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive composition and an adhesive sheet which can be cured by ionizing radiation such as ultraviolet rays.
Furthermore, the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet suitable for use in a flexible printed circuit board manufacturing process.

[0002]

2. Description of the Related Art Conventionally, as an ultraviolet curable adhesive composition,
Those containing an acrylic compound have been proposed.
However, many of these are not easy to peel off after being attached to an adherend and irradiated with ultraviolet rays, and therefore the adherend is likely to be deformed (curl or the like), and it is easy for adhesive residue to remain. There's a problem. In addition, the pressure-sensitive adhesive sheet provided with this pressure-sensitive adhesive is applied to an adherend and used in a method of peeling after being irradiated with ultraviolet rays (for example, in a flexible printed circuit board manufacturing step, other board dicing step, and various masking steps. The surface of the adherend may have unevenness, and when applied to the adherend, there is unevenness in the adhesive part and unevenness in the cured part when exposed to ultraviolet light, making it easy to peel from the adherend. There is a problem such as not being adhered or remaining on the adherend when peeled off. Furthermore, when a gap is formed between the adherend and the pressure-sensitive adhesive sheet when they are bonded together, in addition to the above-mentioned problem, this bonded product is heated and heated in a liquid (for example, in a printed circuit board manufacturing process, When used in a state of being immersed in an etching solution or a plating solution, etc., the problem that some or all of the sheet may peel off, or the liquid from the part where the sheet is peeled off between the sheet and the adherend There is also the problem of being absorbed into.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a pressure-sensitive adhesive composition whose pressure-sensitive adhesive strength is reduced by curing with ultraviolet irradiation and a pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition, which is adhered to an adherend and then irradiated with ultraviolet rays. It is an object of the present invention to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet that can be easily peeled off and do not remain on the adherend when peeled off. Further, it is an object to provide an adhesive sheet suitable for use in a flexible printed circuit board manufacturing process.

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, the following pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet are provided. (1) (a) (meth) acrylic adhesive polymer having a functional group having active hydrogen, (b) photopolymerizable (meth) acrylic oligomer or (meth) acrylic monomer,
A pressure-sensitive adhesive composition comprising (c) a photopolymerization initiator, (d) a cross-linking agent having reactivity with the active hydrogen, and (e) a silicone-based graft copolymer. (2) The pressure-sensitive adhesive composition according to (1), wherein the silicone-based graft copolymer contains a functional group having active hydrogen. (3) The photopolymerizable (meth) acrylic oligomer or (meth) acrylic monomer is composed of a bisphenol A type epoxy acrylate oligomer and ditrimethylolpropane tetraacrylate, as described in (1) or (2) above. Adhesive composition. (4) A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive composition provided on a substrate in a layered form, wherein the pressure-sensitive adhesive composition according to any one of (1) to (3) is used as the pressure-sensitive adhesive composition. . (5) A pressure-sensitive adhesive sheet for producing a flexible printed circuit board, comprising the pressure-sensitive adhesive sheet according to (4) above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention contains (a) a (meth) acrylic adhesive polymer having a functional group having active hydrogen as an adhesive component. This polymer can be obtained by homopolymerizing a (meth) acrylic monomer having a functional group having active hydrogen or by copolymerizing with another (meth) acrylic monomer, and is at room temperature (23 ° C). ) Is an adhesive polymer. The polymerization method in this case is a radical polymerization method, and includes an emulsion polymerization method, a solution polymerization method, a soul-like polymerization method, a photopolymerization method and the like. The functional group having active hydrogen includes a hydroxyl group, an amino group, a mercapto group, a carboxyl group and the like.
The (meth) acrylic type means an acrylic type and /
Or, it means a methacrylic type.

The (meth) acrylic monomer having a functional group having active hydrogen can be represented by the following general formula (1).

[Chemical 1] In the above formula, R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, an alkyleneoxy group or a polyalkyleneoxy group, and X represents an active hydrogen-containing functional group. t represents the number of 0 or 1.

In the above alkylene group, oxyalkylene group or polyalkyleneoxy group R ² , the number of atoms (carbon or carbon and oxygen) contained in its main chain is 1 to 1.
8, preferably 2 to 12, more preferably 2 to 8.
These include methylene, ethylene, propylene, butylene, hexylene, octylene, dodecylene,
It includes ethyleneoxy, diethyleneoxy, triethyleneoxy, propyleneoxy, dipropyleneoxy, butyleneoxy, dibutyleneoxy and the like.

As the active hydrogen-containing functional group X, --COO
H, -CONH _2, in -COO-R ³ -Y (wherein, R ³ is 1 to 12 carbon atoms, preferably 2 to 8 alkylene group, Y represents a hydroxyl group, a carboxyl group, a mercapto group, active such as an amino group Indicates a hydrogen-containing functional group). In the general formula (1), when t is 0, it means that the functional group X is directly bonded to the carbon atom of the vinyl group without interposing R ² .
When t is 1, it indicates that the functional group X is bonded to the carbon atom of the vinyl group via R ² .

Specific examples of the (meth) acrylic monomer having a functional group having active hydrogen include (meth) acrylic acid, (meth) acrylic acid amide, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include 2-hydroxypropyl acrylate and glycidyl hydroxypropyl (meth) acrylate.

Examples of the (meth) acrylic monomer containing no active hydrogen, which is copolymerized with the (meth) acrylic monomer having a functional group having active hydrogen, include acrylic acid esters such as methyl acrylate and ethyl acrylate. Butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, isononyl acrylate, decyl acrylate, benzyl acrylate, and the like, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate,
2-ethylhexyl methacrylate and the like can be mentioned.

The preferred (meth) acrylic adhesive polymer used in the present invention is a copolymer of 2-ethylhexyl acrylate, acrylic acid and methacrylic acid.

The (meth) acrylic adhesive polymer used in the present invention has a weight average molecular weight of 50,000.
It is in the range of 0 to 1,500,000. When the weight average molecular weight is smaller than this, the cohesion of the polymer becomes weak and the adhesive strength becomes weak. On the other hand, if it is larger than this, the compatibility of the pressure-sensitive adhesive composition becomes poor. A more preferable weight average molecular weight range is 50,000 to 1,000,000.

The composition of the present invention contains (b) a photopolymerizable (meth) acrylic oligomer or (meth) acrylic monomer. The photopolymerizable oligomer includes various conventionally known ones, for example, urethane (meth) acrylate-based oligomer and epoxy (meth) acrylate-based oligomer, and the epoxy (meth) acrylate-based oligomer includes, for example, bisphenol A type, Various types such as bisphenol F type, novolak type, cresol novolak type and the like can be mentioned.

As the photopolymerizable (meth) acrylic monomer, various conventionally known ones such as bisphenol A di (meth) acrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (methacryloxyethyl) are used. Hydroxyethyl isocyanurate,
Tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, bisphenol F di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris Various modified products of (methacryloxyethyl) isocyanurate, various modified products of bisphenol A di (meth) acrylate, bisphenol F di (meth) Various modified forms of acrylate, various modified products of trimethylolpropane tri (meth) acrylate, various types of modified products such as dipentaerythritol hexa (meth) acrylate is used. These may be used alone or in combination of two or more. Among these, the combination of epoxy acrylate-based oligomer and ditrimethylolpropane tetraacrylate is
It is preferable in terms of heat resistance and adhesive strength before and after irradiation with ultraviolet rays. A particularly preferred epoxy acrylate-based oligomer is represented by the following general formula (2).

[Chemical 2] In the formula, n represents a number of 1 to 5, n is preferably 1 or 2, and n is preferably about 1.2. The blending ratio with the oligomer or the monomer can be appropriately selected according to the heat resistance of the pressure-sensitive adhesive to be obtained and the pressure-sensitive adhesive force before and after irradiation with ultraviolet rays. Here, the description of (meth) acrylate means acrylate, methacrylate, or a mixture thereof.

The composition of the present invention contains (c) a photopolymerization initiator. Examples of the photopolymerization initiator include various conventionally known ones. Such things include, for example:
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2 -Monofolinopropane-1, diethoxyacetophenone, 4- (2-hydroxyethoxy)
Phenyl (2-hydroxy-2propyl) ketone, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
Acetophenone-based ones such as ON, benzophenone-based ones such as benzophenone and hydroxybenzophenone,
Thioxanthone, 2-methylthioxanthone, 2,4-
Thioxanthones such as diethylthioxanthone, chlorothioxanthone, dimethylthioxanthone, dodecylthioxanthone, diethylthioxanthone, benzyl, anthraquinone, 2-ethylanthraquinone, 2-ter
Examples thereof include t-butyl anthraquinone. Among these, benzoin-based compounds such as benzoin isobutyl ether and benzyl dimethyl ketal are particularly preferable in terms of reactivity of radical polymerization of photopolymerizable oligomer or monomer by ultraviolet rays and heat resistance of the pressure-sensitive adhesive. These may be used alone or in combination of two or more.

The composition of the present invention contains (d) a crosslinking agent reactive with active hydrogen. As such a cross-linking agent, various conventionally known ones can be used. Such materials include epoxy crosslinking agents and isocyanate crosslinking agents.

The epoxy-based cross-linking agent usually contains two or more epoxy groups in the molecule, and various known compounds such as sorbitol polyglycidyl ether,
Examples thereof include polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl ether and the like.

The isocyanate cross-linking agent usually contains two or more isocyanate groups in the molecule, and various conventionally known ones such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylolpropanone tolylene diisocyanate. 3 additions,
Examples thereof include polyisocyanate.

The composition of the present invention contains (e) a releasability-imparting agent, a silicone-based graft copolymer. The releasing property-providing agent is for preventing cohesive failure of the pressure-sensitive adhesive composition and facilitating peeling from the adherend after irradiation with ultraviolet rays. The silicone-based graft copolymer (polymer) has a silicone chain as a side chain of the polymer. As the silicone chain in this case, for example, one represented by the following general formula (3) can be used.

[Chemical 3] In the above formula, R ¹ and R ² represent a hydrocarbon group, a halogen-containing (fluorine, chlorine, etc.) hydrocarbon group or a hydrocarbon oxy group,
R ³ represents hydrogen, halogen, a hydrocarbon group, a halogen-containing hydrocarbon group or a hydrocarbon oxy group. n represents a number of 0 to 500, preferably 10 to 300.

The hydrocarbon group, the halogen-containing hydrocarbon group and the hydrocarbon oxy group have 1 to 12 carbon atoms, preferably 1 carbon atom.
~ 8. The hydrocarbon group includes a chain or cyclic alkyl group, an aryl group, an arylalkyl group and the like. The halogen-containing hydrocarbon group includes a chain-like or cyclic halogen-containing alkyl group, a halogen-containing aryl group, a halogen-containing arylalkyl group and the like. The hydrocarbon oxy group includes a chain or cyclic alkyloxy group, an aryloxy group, an arylalkyloxy group and the like. Specific examples of the hydrocarbon group include methyl, ethyl, propyl, cyclohexyl, dodecyl, phenyl and benzyl.

The silicone-based graft copolymer can be obtained by radically polymerizing a macrovinyl monomer having a silicone chain and a non-silicone-based vinyl monomer. As the non-silicone vinyl monomer in this case, the above various acrylic vinyl monomers can be used, and the type thereof is not particularly limited.

As the macro vinyl monomer having a silicone chain, those represented by the following general formulas (4) and (5) are generally used.

[Chemical 4] In the above formula, R ¹ represents hydrogen or a methyl group, R ² and Y represent a linking group, and R ³ represents a silicone chain. m, t, and q show the number of 0 or 1. For m, t and q, m,
When t and q are 0, the R ² oxygen atoms O and Y are
Means that there is no. Examples of the linking groups R ² and Y include divalent aliphatic groups such as alkylene groups and polyalkyleneoxy groups. The carbon number is 1 to 12, preferably 2 to 6. The silicone chain R ³ is mainly composed of a siloxane chain or a polysiloxane chain, and is, for example, a conventionally known siloxane chain or polysiloxane chain represented by the general formula (3). Further, a silicon atom to which a hydrocarbon group such as a methyl group or a phenyl group is bonded, for example,
SiR ₃ (R: methyl or phenyl) and the like.

[0023]

[Chemical 5] In the above formula, R ¹ represents hydrogen or a methyl group. Ar represents a divalent aromatic group (phenylene, xylylene, phenylenemethylene, etc.). R ³ represents a silicone chain. In the present invention, the silicone graft copolymer preferably contains a functional group having active hydrogen. Such functional groups include active hydrogen-containing groups such as hydroxyl group, carboxyl group, amino group and mercapto group. A preferred functional group is a hydroxyl group. The introduction into the copolymer can be easily carried out by using a copolymerized vinyl monomer component having such an active hydrogen-containing functional group. The content of the functional group (active hydrogen-containing group) in the copolymer is 0.1 to 50% by weight in terms of the weight% of the functional group-containing monomer component with respect to the total amount of the monomer components constituting the copolymer. It is preferably 1 to 30% by weight.

The number average molecular weight of the macrovinyl monomer having a silicone chain is about 1,000 to 20,000. By containing this copolymer, it is possible to obtain an adhesive composition which is attached to an adherend and is easily peeled off after irradiation with ultraviolet rays, and when peeled, does not remain on the adherend. .

The proportion of each compounding component in the composition of the present invention is shown as follows: Component (b) (photopolymerizable (meth) acrylic) per 100 parts by weight of component (a) ((meth) acrylic adhesive polymer). The ratio of the (system oligomer or (meth) acrylic monomer) is 5 to 200 parts by weight, preferably 10 to
It is a ratio of 100 parts by weight. The ratio of the component (c) (photopolymerization initiator) is 0.1 to 30 with respect to the component (b).
%, Preferably 0.5 to 20% by weight. (D)
The ratio of the component (crosslinking agent) is 0.0 per 1 equivalent of the total active hydrogen including active hydrogen contained in the component (a) and active hydrogen contained in the component (e) described later.
The ratio is 5 to 1.2 equivalents, preferably 0.1 to 1.0 equivalents. Component (e) (silicone-based graft copolymer)
The ratio is 0.1-10 per 100 parts by weight of the component (a).
The proportion is 0 parts by weight, preferably 0.5 to 60 parts by weight.

The pressure-sensitive adhesive composition of the present invention includes the above (a) to
In addition to the component (e), for example, a lubricant, a stabilizer, a colorant,
Antioxidants, preservatives, leveling agents (for example, acrylic leveling agents, silicone leveling agents, fluorine leveling agents), reaction modifiers, and other known additives can be added, and especially leveling agents and reaction modifiers can be included. Is preferably contained.

The composition of the present invention can be applied to a base material to give an adhesive sheet. In this case, the base material of the pressure-sensitive adhesive sheet is not particularly limited and may be appropriately selected depending on the application of the pressure-sensitive adhesive sheet. For example, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, triacetyl cellulose, cellophane, celluloid, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polysulfone, polyether sulfone, aromatic polyamide and the like synthetic resin film,
Examples thereof include a glass plate, which may be transparent, opaque, colored containing pigments or dyes, or matt transparent or opaque surface. Surface treatment such as discharge treatment or easy adhesion treatment may be applied. In addition, general paper, synthetic paper, cloth, wood, metal plate, ceramics and the like can be used.

The adhesive sheet of the present invention is attached to an adherend,
It is suitable for use after peeling off after being irradiated with ultraviolet rays, and particularly suitable for being used by being attached to the side opposite to the circuit forming surface of the circuit board in the process for producing a flexible printed circuit board. When the pressure-sensitive adhesive sheet of the present invention is used by adhering it to the substrate during the process for producing a flexible printed circuit board, it may be immersed in a heated liquid (for example, a liquid at 60 ° C. to 100 ° C.). The base material is preferably a synthetic resin film having heat resistance, solvent resistance, and UV transparency.
When the ultraviolet rays are radiated from the base material surface side of the pressure-sensitive adhesive sheet after pasting, it is necessary to use a base material that transmits the ultraviolet rays (300 nm to 380 nm), and the thickness is usually 25 to 200 μm.
m polyethylene terephthalate film is used. When ultraviolet rays are irradiated from the surface of the adherend after sticking, the base material may or may not transmit the ultraviolet rays.

The pressure-sensitive adhesive sheet of the present invention has a structure in which a layer made of the pressure-sensitive adhesive composition is laminated on the base material, and the one obtained by dissolving or dispersing the pressure-sensitive adhesive composition in a solvent is formed on the base material. It can be obtained, for example, by applying with a usual applying means such as a roll coater method and then heating and drying. Examples of the solvent used at this time include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and cellosolve. Further, the thickness of the adhesive layer after heating and drying is preferably 3 to 100 μm, and if it is thinner than this, sufficient initial adhesive force cannot be obtained, and if it is thicker than this, the adhesive force is less likely to decrease after ultraviolet irradiation. The thickness of the adhesive layer after heating and drying is more preferably 5 to 80 μm from the viewpoint of the initial adhesive strength and the decrease in adhesive strength after irradiation with ultraviolet rays.

The pressure-sensitive adhesive sheet of the present invention is preferably provided with a protective layer on the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive layer. This protective layer is to be peeled off when the pressure-sensitive adhesive sheet is used, and examples thereof include synthetic resin films, sheets of paper, plastics, rubbers, etc., or sheets of surface-treated synthetic resin films, papers, plastics, rubbers, etc.

[0031]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a pressure-sensitive adhesive composition which does not undergo cohesive failure, although the pressure-sensitive adhesive force is reduced by ultraviolet irradiation. The pressure-sensitive adhesive layer formed from this composition contains a silicone-based graft copolymer, so that the contact angle between the surface of the pressure-sensitive adhesive layer and water becomes large. In the case of the present invention, the adhesive layer has a smooth surface of 2 after irradiation with ultraviolet rays.
The contact angle with water at 23 ° C at 3 ° C and 65RH% is 10
It is preferably 0 degrees or more, and such an adhesive layer can effectively prevent the occurrence of residual glue. Also,
It is possible to provide a pressure-sensitive adhesive sheet having no adhesive residue, which is easily peeled off by irradiating with ultraviolet rays after application. Furthermore, it is possible to provide an adhesive sheet suitable for use in a process for producing a flexible printed circuit board, which does not come off even in a heated liquid after sticking and does not soak into the liquid.

[0032]

EXAMPLES Next, examples of the present invention will be described in more detail. The specific contents of the evaluation method shown below are as follows.

(Initial Adhesive Strength) A pressure-sensitive adhesive sheet that has not been subjected to heat treatment or ultraviolet ray irradiation treatment after production is treated at 23 ° C. and 65% R
Under H condition, 2k of a 25 μm-thick polyimide film (manufactured by Toray DuPont Co., Ltd., trade name “Kapton 100H”) is cut on a test piece cut into a width of 25 mm and a length of 250 mm.
g A rubber roller was used to make one reciprocating movement at a speed of 300 mm / min for pressure bonding, and a test piece that had been left for 30 minutes under the conditions of 23 ° C and 65% RH was subjected to a tensile tester at 23 ° C and 65% RH. Using, pulling speed 300 mm / min
The force (N) at the time of peeling off the test piece crimped by the method in the direction of 180 degrees was measured and used as the initial adhesive force. ○: 2N or more ×: less than 2N

(Adhesive force after ultraviolet irradiation) In the initial adhesive force measuring method, after pressure bonding, 3 ° C. under a condition of 23 ° C. and 65% RH.
An ultraviolet irradiation device (HITEC
UV Co., Ltd., UV-5600-3H) is used to irradiate an ultraviolet ray amount of 600 mJ / cm ² from the base material surface side of the pressure-sensitive adhesive sheet to cure the pressure-sensitive adhesive layer, and then at 23 ° C. and 65% RH conditions. The peeling force (N) was measured in the same manner as the initial adhesive force except that the test piece was allowed to stand for 30 minutes, and this was taken as the adhesive force after ultraviolet irradiation.

(Adhesive force after heating and UV irradiation) In the initial adhesive force measuring method, the pressure-bonded test piece was heated to 100 ° C.
After heating for 1 hour in an ultraviolet irradiation device (HI
UV-5600-3H manufactured by TECH Corp.) is used to irradiate the base material surface of the pressure-sensitive adhesive sheet with an ultraviolet ray amount of 600 mJ / cm ² to cure the pressure-sensitive adhesive layer, and then under conditions of 23 ° C. and 65% RH. The force (N) at the time of peeling was measured in the same manner as the initial adhesive force except that the test piece was left for 30 minutes, and this was taken as the adhesive force after heating and UV irradiation.

(Glue remaining) 25 μm thick polyimide film (manufactured by Toray DuPont Co., Ltd., trade name “Kapton 1”)
00H ") with a 230 μm-thick reinforcing polyester film attached to a part thereof as an adherend. After making, after sticking the pressure-sensitive adhesive sheet that has not been subjected to heat treatment or ultraviolet irradiation treatment to the adherend under the conditions of 23 ° C. and 65% RH,
Fully pressure bonded using a 2 kg rubber roller, 100 ° C
UV irradiation device (HITEC
UV Co., Ltd., UV-5600-3H) is used to irradiate an ultraviolet ray amount of 600 mJ / cm ² from the base material side of the adhesive sheet to cure the adhesive layer, and the adhesive layer is cured at 23 ° C. and 65% RH under conditions of 30%.
The adhesive sheet was peeled off after being left for more than a minute, and the presence or absence of adhesive residue on the polyimide film was evaluated using a 50 × optical microscope.

After making the (contact angle), the UV irradiation device (manufactured by HITECH, UV-5600-3) was applied to the base material surface of the pressure-sensitive adhesive sheet which was not subjected to heat treatment or UV irradiation treatment.
H) is used to cure the adhesive layer by irradiating it with an ultraviolet ray amount of 600 mJ / cm ² , and then at 23 ° C. and 65% RH,
The contact angle between the surface of the adhesive layer and water at 23 ° C. was measured by a droplet method using a contact angle measuring device (G-1 / 2MG type, manufactured by Elma Co., Ltd.).

Example 1 100% by mass of SK Dyne SW-2B (trade name, manufactured by Soken Chemical Industry Co., Ltd., an acrylic adhesive polymer solution having an active hydrogen-containing group-carboxyl group, solid content concentration: 35%), Viscoat # 540 (Brand name: Osaka Organic Chemical Industry Co., Ltd., bisphenol A type epoxy acrylate oligomer)
7.4% by mass, NK ester AD-TMP (trade name of Shin-Nakamura Chemical Co., Ltd., ditrimethylolpropane tetraacrylate) 12% by mass, Irgacure 651 (trade name of Ciba Specialty Chemicals Co., Ltd.), Benzyl dimethyl ketal) 1.8% by mass, Cymac U
S-270 (trade name of Toagosei Co., Ltd., hydroxyl group-containing graft silicone copolymer liquid, solid content concentration 30%)
2% by mass, Coronate L (Japan Polyurethane Industry Co., Ltd.)
Product name, trimethylolpropane tolylene diisocyanate 3 adduct liquid, solid content concentration 75%, NCO content 13%) 4.8% by mass, methyl ethyl ketone 45% by mass are uniformly mixed and dissolved to obtain an adhesive composition. The liquid was adjusted. This solution was applied on a surface of a transparent polyethylene terephthalate film having a thickness of 75 μm, which was easily adhered on one surface, to an easily adhered surface by a baker type applicator, and then this was applied at 130 ° C.
Was dried for 3 minutes to form an adhesive layer having a thickness of 12 μm to prepare an adhesive sheet.

Example 2 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that Cymac US-270 was changed to 1%.

Example 3 An adhesive sheet was produced in the same manner as in Example 1 except that Cymac US-270 was changed to 20%.

Example 4 An adhesive sheet was produced in the same manner as in Example 1 except that Cymac US-270 was changed to 60%.

Comparative Example 1 An adhesive sheet was produced in the same manner as in Example 1 except that Cymac US-270 was not added.

Comparative Example 2 AS-409 (acrylic acid ester copolymer, trade name manufactured by Yushisha Kogyo Co., Ltd., solid content concentration 42%) 100% by mass, product name D-170N {hexamethylene diisocyanate trimer Body, (3OCN (CH ₂ ) ₆ NCO, trade name of Takeda Pharmaceutical Co., Ltd., NCO 20.7%} 1.
35% by mass, Cymac US-270 (graft silicone acrylic copolymer having hydroxyl group, Toagosei Co., Ltd.)
Product name, solid content concentration 30%) 4.2% by mass, toluene 34% by mass, and methyl isobutyl ketone 34% by mass were uniformly mixed and dissolved to prepare an adhesive composition liquid. This solution was applied to a surface of a transparent polyethylene terephthalate film having a thickness of 75 μm, which had been easily adhered on one surface, with an easy-adhesion treated surface using a baker type applicator, and this was then applied at 130 ° C. for 3 hours.
It was dried for a minute to form an adhesive layer having a thickness of 12 μm to prepare an adhesive sheet.

Comparative Example 3 SK Dyne SW-22 (trade name of Soken Chemical Industry Co., Ltd., acrylic adhesive, solid content concentration 43%) 100% by mass, EX
-0205 (trade name of Kyoei Chemical Co., Ltd., epoxy acrylate-based oligomer, solid content concentration 70%) 9.3 mass%, Viscoat # 540 (trade name of Osaka Organic Chemical Industry Co., Ltd.) 6.5 mass %, Coronate L-45 (trade name of Soken Kagaku Co., Ltd., trimethylolpropane tolylene diisocyanate 3 adduct liquid, solid content concentration 45%, NCO
2.5% by mass of content 8%), 0.8% by mass of Irgacure 651 (manufactured by Ciba-Geigy) and 11.4% by mass of toluene were uniformly mixed and dissolved to prepare an adhesive composition liquid.
This liquid was applied to a surface of a transparent polyethylene terephthalate film having a thickness of 75 μm, which was easily adhered on one surface, with an easily adhered surface by a Baker type applicator, and then applied to
It was dried at 3 ° C. for 3 minutes to form an adhesive layer having a thickness of 12 μm to prepare an adhesive sheet.

Table 1 shows the evaluation results of the pressure-sensitive adhesive sheet.

[0046]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Satoshi Asai             Somer, 4-11-2 Ginza, Chuo-ku, Tokyo             Le Co., Ltd. F-term (reference) 2H025 AA14 AA15 AA16 AB15 AC01                       AD01 BC13 BC42 BC74 BH02                       CA00 CB32 CB51 CC17 EA08                 4J004 AA02 AA10 AA11 AA17 AB07                       CA04 CA06 CA07 CB02 CC02                       CD08 DB02 FA05 FA08                 4J040 DF021 DF061 DF101 DL122                       EF291 FA131 GA11 GA20                       HB14 JA09 JB08 JB09 KA13                       KA16 NA20 PA23 PA42

Claims (5)

[Claims] 1. A (meth) acrylic adhesive polymer having a functional group having active hydrogen, (b) a photopolymerizable (meth) acrylic oligomer or (meth) acrylic monomer, and (c) a light. A pressure-sensitive adhesive composition comprising a polymerization initiator, (d) a crosslinking agent having reactivity with the active hydrogen, and (e) a silicone-based graft copolymer. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the silicone-based graft copolymer contains a functional group having active hydrogen. 3. The photopolymerizable (meth) acrylic oligomer or (meth) acrylic monomer is composed of a bisphenol A type epoxy acrylate oligomer and ditrimethylolpropane tetraacrylate.
Or the adhesive composition according to 2. 4. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition provided on a substrate in a layered form, wherein the pressure-sensitive adhesive composition according to claim 1 is used as the pressure-sensitive adhesive composition. 5. A pressure-sensitive adhesive sheet for producing a flexible printed circuit board, which comprises the pressure-sensitive adhesive sheet according to claim 4.