JP2017071774A - Adhesive composition, adhesive formed by crosslinking the same, adhesive for masking film, heat resistant adhesive film for masking, and method for using heat resistant adhesive film for masking - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition capable of being used in an adhesive film for masking, which is excellent in quick curability, shows little increase in adhesive force after used in high temperature condition, can be peeled with a small force, hardly causes contamination when peeled from an adherend, and is used in high temperature environment.SOLUTION: There is provided an acrylic adhesive composition containing an acrylic resin (A) and a crosslinking agent (B), where the crosslinking agent (B) contains an epoxy-based crosslinking agent (B1) and a zirconium-based crosslinking agent (B2), and a content of the epoxy-based crosslinking agent (B1) is 2 to 30 pts.wt., a content of the zirconium-based crosslinking agent (B2) is 1 to 30 pts.wt. with respect to 100 pts.wt. of the acrylic resin (A), and a content ratio (X/B1) of the metal component (X) in the zirconium-based crosslinking agent (B2) to the epoxy-based crosslinking agent (B1) is 0.015 to 1.0.SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive obtained by crosslinking this, a pressure-sensitive adhesive for masking film, and a heat-resistant pressure-sensitive adhesive film for masking. It can form a smooth pressure-sensitive adhesive layer surface without transferring the uneven shape of the separator, and there is little increase in adhesive strength after use under high-temperature conditions, and it can be peeled off with a small force. Contamination hardly occurs when peeled, and can be used for a heat-resistant adhesive film for masking, an adhesive formed by crosslinking the adhesive composition, an adhesive for masking film comprising the adhesive, and the adhesive It is related with the heat-resistant adhesive film for masking which has an adhesive layer on a film.

  Conventionally, a re-peelable adhesive film has been used to temporarily fix and protect members when processing various members. In recent years, for example, circuit boards such as flexible printed wiring (FPC) boards and ITO It is used as a masking adhesive film for temporarily protecting the surface of a transparent electrode layer, and as a surface protecting adhesive film for flat panel displays, touch panels, and the like. Since the manufacturing process of the FPC board and the ITO transparent electrode layer includes a process exposed to high temperature, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is fixed to the laminated plate, and the FPC board and the ITO transparent electrode layer are peeled off when the pressure-sensitive adhesive film is peeled off. Laminate may be damaged or contamination due to adhesive residue may occur. For this reason, even after a high temperature process, it is required that the adhesive can be peeled off with a light force without any adhesive residue.

  As a pressure-sensitive adhesive composition used for a pressure-sensitive adhesive sheet satisfying such heat resistance, for example, in Patent Document 1, the sheet does not float even in a high-temperature environment, and the rate of change in adhesive force is small. As a pressure-sensitive adhesive composition suitably used for a heat-resistant pressure-sensitive adhesive sheet that hardly causes body contamination, a hydroxyl group-containing acrylic resin having a weight average molecular weight of 450,000 to 1,500,000 and an isocyanate-based cross-linking agent are used. In the range in which the amount of isocyanate groups in the isocyanate-based crosslinking agent is 0.6 to 1.6 times (molar ratio) relative to the amount of hydroxyl groups in the resin, and further 100 parts by weight of the hydroxyl group-containing acrylic resin , Non-reactive with hydroxyl group-containing acrylic resin and isocyanate crosslinking agent, and having a formula weight or number average molecular weight of 30 PSA composition containing 1500 the following ester compounds 3-20 parts by weight or more is disclosed.

  However, in the technique of Patent Document 1, in order to balance the adhesive physical properties of the adhesive, it is necessary to perform an aging treatment for a certain period after producing the adhesive sheet, and until the adhesive composition is crosslinked in the aging process. Moreover, the fine unevenness | corrugation etc. of a base film or a separator may be transcribe | transferred to an adhesive layer, and the adhesive film with a smooth adhesive layer surface may not be obtained. When the pressure-sensitive adhesive sheet is used for protecting the surface of an optical film such as a flat panel display or a touch panel, the fine irregularities of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet are transferred to the optical film as the adherend, and the visibility is reduced. Problems can arise.

  Therefore, there is a demand for a pressure-sensitive adhesive composition excellent in immediate curing property that can form a smooth pressure-sensitive adhesive layer surface without transferring the fine uneven shape of the base film or separator. For example, in Patent Document 2, as a pressure-sensitive adhesive composition that satisfies the required physical properties of a pressure-sensitive adhesive for a surface protective film and can shorten the curing time without shortening the pot life, An acrylic pressure-sensitive adhesive composition containing an acrylic copolymer (A) having a hydroxyl group, a dialkylacetylacetone tin complex catalyst (B), and an isocyanate compound (C) is disclosed.

JP 2007-327036 A JP 2008-13634 A

  However, in the technique of Patent Document 2, the curing time is short and the resin has immediate curing properties. However, although it has heat resistance at 70 ° C. in terms of heat resistance, it is inferior in heat resistance under higher temperature conditions. The rest can occur.

  Therefore, in the present invention, in such a background, it is excellent in immediate curing and has little increase in adhesive strength after use under high temperature conditions, and can be peeled off with a small force, and further when peeled off from the adherend. An object of the present invention is to provide a pressure-sensitive adhesive composition that can be used for a heat-resistant adhesive film for masking that is hardly contaminated and that is used in a high-temperature environment.

  However, as a result of intensive studies by the present inventors, in the pressure-sensitive adhesive composition containing an acrylic resin and a crosslinking agent, an epoxy crosslinking agent and a zirconium crosslinking agent are used as the crosslinking agent. It has been found that the above problems can be solved by adding more than usual, and the present invention has been completed.

  That is, the gist of the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic resin (A) and a crosslinking agent (B), and the crosslinking agent (B) is an epoxy-based crosslinking agent (B1) and a zirconium-based crosslinking agent. 2 to 30 parts by weight of the epoxy-based crosslinking agent (B1) with respect to 100 parts by weight of the acrylic resin (A), and 1 to 30 parts by weight of the zirconium-based crosslinking agent (B2). It is related with the adhesive composition characterized by these.

  The gist of the present invention is that the pressure-sensitive adhesive composition of the present invention is crosslinked, the pressure-sensitive adhesive for masking film characterized by comprising the pressure-sensitive adhesive of the present invention, and the pressure-sensitive adhesive of the present invention. The present invention also relates to a heat-resistant adhesive film for masking having a pressure-sensitive adhesive layer made of an agent on the film and a method for using the heat-resistant adhesive film for masking.

  The pressure-sensitive adhesive composition of the present invention uses an epoxy crosslinking agent that has not been used in a large amount as a crosslinking agent because of a decrease in pot life and poor coatability. By using a cross-linking agent in combination, the adhesive properties of the adhesive layer can be made close to the desired adhesive properties in a short time after coating, and the adhesive strength increases even when exposed to high temperature conditions. In addition, a pressure-sensitive adhesive composition having a very good balance between immediate curing property and heat resistance and having no problem of pot life and coating property, such as being less likely to cause adherend contamination, can be obtained.

  According to the pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive obtained by crosslinking the same, it has immediate curing properties, and is hardly contaminated when peeled off from an adherend after being used under high temperature conditions. A heat-resistant adhesive film for masking that can be peeled off with force can be produced.

The present invention will be described in detail below, but these show examples of desirable embodiments. In the present specification, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.
The “adhesive film” in the present invention conceptually includes an adhesive sheet, an adhesive film, and an adhesive tape.
Furthermore, the “heat-resistant adhesive film” in the present invention means an adhesive film that is exposed to a high temperature environment where heat resistance is required. Specifically, the adhesive layer surface of the adhesive film is Adhesive having an adhesive layer that does not cause problems such as adhesive residue and increased adhesive strength even when peeled off the adherend after being attached to the adherend and exposed to a high temperature environment of 130 ° C. or higher for 30 minutes or more. It means film.

  The acrylic resin (A) used in the present invention is obtained by polymerizing a polymerization component containing a (meth) acrylic acid ester monomer (a1) and a functional group-containing monomer (a2). Other polymerizable monomers (a3) may be contained as a polymerization component.

The (meth) acrylic acid ester monomer (a1) used in the present invention is a (meth) acrylate having an aliphatic or alicyclic alkyl ester. Carbon number of alkyl in the alkyl ester is usually 1-20, preferably 1-12, particularly preferably 1-8. When there are too many carbons, there exists a tendency for the adherend contamination after a heating process to increase.
Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate , N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl ( Aliphatic (meth) acrylic acid alkyl esters such as meth) acrylate and iso-stearyl (meth) acrylate; Alicyclic (meth) acrylic acid alkyl esters such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate Ester, and the like. These can be used alone or in combination of two or more.

  The (meth) acrylic acid ester monomer (a1) is preferably an aliphatic (meth) acrylic acid alkyl ester, particularly preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, They are iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The content of the (meth) acrylic acid ester monomer (a1) in the polymerization component is usually 40 to 99.99% by weight, preferably 45 to 99.9% by weight, particularly preferably 50 to 99% by weight. It is. When the content is too small, adherend contamination after the heating step tends to increase, and when too large, the adhesive strength after the heating step tends to be too high.
Moreover, content of the (meth) acrylic-acid alkylester type | system | group monomer (a1-1) which has a C1-C8 alkyl group in a (meth) acrylic-ester type | system | group monomer (a1) is 80 weight% or more. In view of excellent adherence contamination after the heating step, it is preferably 85% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

  The functional group-containing monomer (a2) is a monomer containing a functional group that can become a crosslinking point by reacting with the below-mentioned crosslinking agent (B). For example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer , Acetoacetyl group-containing monomers, isocyanate group-containing monomers, glycidyl group-containing monomers, and the like.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta ) Acrylic acid hydroxyalkyl esters such as acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other caprolactone-modified monomers, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate and other oxyalkylene-modified monomers, and other 2-acrylic Primary hydroxyl group-containing monomers such as leuoxyethyl-2-hydroxyethylphthalic acid;
Secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate;
There may be mentioned tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.
Among the hydroxyl group-containing monomers, it is particularly preferable to use 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate in terms of excellent reactivity with the crosslinking agent.

  In addition, as a hydroxyl-containing monomer used by this invention, it is also preferable to use a thing with the content rate of di (meth) acrylate which is an impurity 0.5% or less, Furthermore 0.2% or less, especially Is preferably 0.1% or less.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, and cinnamon. An acid etc. are mentioned, Especially, (meth) acrylic acid is used preferably.

  Examples of the amino group-containing monomer include t-butylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.

  Examples of the acetoacetyl group-containing monomer include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.

  Examples of the isocyanate group-containing monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

  Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, allyl glycidyl (meth) acrylate, and the like.

These functional group-containing monomers (a2) may be used alone or in combination of two or more.
Among these, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are preferably used because they can efficiently undergo a crosslinking reaction with the epoxy crosslinking agent (B1) and the zirconium-based crosslinking agent (B2), and further, immediate curing and heat resistance are used. From the viewpoint of coexistence, it is preferable to use a hydroxyl group-containing monomer and a carboxyl group-containing monomer in combination.

The content of the functional group-containing monomer (a2) in the polymerization component is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 15% by weight. If the content is too small, the degree of cross-linking decreases and adherend contamination increases or the adhesive strength immediately after application tends to be too high, and if it is too large, adherend contamination tends to increase.
When the hydroxyl group-containing monomer and the carboxyl group-containing monomer are used in combination as the functional group-containing monomer (a2) in the polymerization component, the hydroxyl group-containing monomer content is preferably 0.001 to 10% by weight, and more preferably 0. 0.01 to 8% by weight, particularly 0.1 to 5% by weight is preferable, the content of the carboxyl group-containing monomer is preferably 0.1 to 30% by weight, and more preferably 1 to 25% by weight. In particular, the content is preferably 2 to 20% by weight.

Examples of other copolymerizable monomer (a3) include ethoxymethyl (meth) acrylamide, n-butoxymethyl (meth) acrylamide, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth ) (Meth) acrylamide monomers such as acrylamide N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide;
Aminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate ;
One fragrance such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, α-methylstyrene, etc. A monomer containing a ring;
Biphenyloxy structure-containing (meth) acrylic acid ester monomers such as biphenyloxyethyl (meth) acrylate;
Alkoxy such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate A monomer containing a group or an oxyalkylene group;
Acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride Methyl vinyl ketone, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, and the like.
Of these copolymerizable monomers, (meth) acrylamide monomers are preferred in that adherend contamination after the heating step is reduced.
These can be used alone or in combination of two or more.

  The content of the other copolymerizable monomer (a3) in the polymerization component is usually 0 to 40% by weight, preferably 0.001 to 30% by weight, particularly preferably 0.01 to 25% by weight. . When there is too much content, there exists a tendency for an adhesive characteristic to fall easily.

  In the polymerization of the acrylic resin (A), for example, conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be employed. For example, a polymerization monomer containing the above (meth) acrylic acid ester monomer (a1), a functional group-containing monomer (a2), and, if necessary, another copolymerizable monomer (a3) in an organic solvent, a polymerization initiator Are mixed or dropped and polymerization is carried out at reflux or at 50 to 99 ° C. for 2 to 20 hours.

  The weight average molecular weight of the acrylic resin (A) is usually 100,000 to 2,500,000, preferably 200,000 to 2,200,000, particularly preferably 400,000 to 2,000,000. If the weight average molecular weight is too low, the heat resistance of the pressure-sensitive adhesive layer tends to decrease and the adherend contamination tends to increase. If it is too high, a large amount of dilution solvent is required, which is disadvantageous in terms of coating properties and cost. Tend to be.

  The degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is, for example, usually 20 or less, preferably 15 or less, particularly preferably 10 or less, and the lower limit is usually 1.1. is there. If the degree of dispersion is too high, the heat resistance of the pressure-sensitive adhesive layer tends to decrease, and foaming and the like tend to occur.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and it is a column in a high performance liquid chromatography (The Japan Waters company, "Waters 2695 (main body)" and "Waters 2414 (detector)"). : Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler The particle diameter is measured by using three series of 10 μm), and the same method can be used for the number average molecular weight. The degree of dispersion is determined from the weight average molecular weight and the number average molecular weight. In the measurement, the polymer may be derivatized or the type of the eluent may be appropriately changed.

  Furthermore, the glass transition temperature of acrylic resin (A) is -80 to 0 degreeC normally, Preferably it is -75 to -5 degreeC, Most preferably, it is -70 to -10 degreeC. If the glass transition temperature is too high, the adhesive strength after the heating step tends to be high, and if the glass transition temperature is too low, the heat resistance tends to decrease and adherend contamination tends to increase.

Ｔg：共重合体のガラス転移温度（Ｋ）
Ｔga：モノマーａのホモポリマーのガラス転移温度（Ｋ）
Ｗa：モノマーａの重量分率
Ｔgb：モノマーｂのホモポリマーのガラス転移温度（Ｋ）
Ｗb：モノマーｂの重量分率
Ｔgn：モノマーｎのホモポリマーのガラス転移温度（Ｋ）
Ｗn：モノマーｎの重量分率（Ｗa＋Ｗb＋・・・＋Ｗn＝１）
なお、上記においてアクリル系樹脂を構成する各モノマーのホモポリマーのガラス転移温度は、通常、示差走査熱量計（ＤＳＣ）で測定されるものである。 The glass transition temperature is calculated from the following Fox equation.

Tg: Glass transition temperature of copolymer (K)
Tga: Glass transition temperature (K) of homopolymer of monomer a
Wa: weight fraction of monomer a Tgb: glass transition temperature (K) of homopolymer of monomer b
Wb: weight fraction of monomer b Tgn: glass transition temperature (K) of homopolymer of monomer n
Wn: weight fraction of monomer n (Wa + Wb +... + Wn = 1)
In the above, the glass transition temperature of the homopolymer of each monomer constituting the acrylic resin is usually measured by a differential scanning calorimeter (DSC).

  The pressure-sensitive adhesive composition of the present invention preferably contains the acrylic resin (A) in an amount of 30 to 99% by weight, particularly preferably 40 to 97% by weight, and more preferably 50 to 95%, based on the total amount of the pressure-sensitive adhesive composition. % By weight.

  The pressure-sensitive adhesive composition of the present invention contains the epoxy-based crosslinking agent (B1) and the zirconium-based crosslinking agent (B2) as the crosslinking agent (B), and can achieve both heat resistance and quick curing. Is important.

Examples of the epoxy crosslinking agent (B1) include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol. Diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, 1,3'-bis (N, N-diglycidylaminomethyl) And cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like.
Among these, 1,3′-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetra is advantageous in that the increase in adhesive strength after heating is small and the other heat contamination is good. Glycidyl-m-xylenediamine is preferred.
In addition, these can be used 1 type or in combination of 2 or more types.

  In addition, as said epoxy type crosslinking agent (B1), what is necessary is just to use commercially available "Tetrad C" by Mitsubishi Gas Chemical Company, "Tetrad X" by Mitsubishi Gas Chemical Company, "S-610" by Synsia.

  The content (solid content equivalent amount) of the epoxy-based crosslinking agent (B1) is 2 to 30 parts by weight, preferably 3 to 20 parts by weight, particularly preferably 100 parts by weight of the acrylic resin (A). 4 to 15 parts by weight. If the content of the epoxy-based crosslinking agent (B1) is too small, the increase in adhesive strength after heating tends to decrease and the heat-resistant stain resistance tends to decrease. If too much, the heat-resistant stain resistance decreases and the pot life is reduced. The coatability tends to be shortened.

  Examples of the zirconium-based crosslinking agent (B2) include simple metals (zirconium simple substances), acetylacetone and acetoacetyl ester coordination compounds to zirconium, and the like.

Specific examples of the acetylacetone or acetoacetyl ester coordination compound to zirconium include zirconium acetate, zirconium acetyl acetate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetoacetate, zirconium acetylacetonate / ethyl. Zirconium-type chelate compounds, such as acetoacetate, etc. are mentioned.
Among these, it is preferable to use zirconium acetylacetonate or zirconium butoxyacetylacetonate from the viewpoint of quick curing.
In addition, these can be used 1 type or in combination of 2 or more types.

  The zirconium-based crosslinking agent (B2) is a commercially available product “ZC-700”, “ZC-580”, “ZC-150”, “ZC-540”, “ZC-200” manufactured by Matsumoto Fine Chemical Co., Ltd. "ZC-320", "ZC-126", "ZC-300", "ZA-45", "ZA-65", "Narsem Zirconium" manufactured by Nippon Chemical Industry Co., Ltd., King Industries, Inc. “K-KAT 4205”, “K-KAT 6212”, and the like manufactured by the manufacturer may be used.

  Content (solid content conversion amount) of the said zirconium type crosslinking agent (B2) is 1-30 weight part with respect to 100 weight part of acrylic resin (A), Preferably it is 2-20 weight part, Especially preferably, it is. 3 to 15 parts by weight. When there is too little content of a zirconium type crosslinking agent (B2), there exists a tendency for an immediate curing property to fall, and when too much, there exists a tendency for a pot life to become short and for coating property to fall.

  Moreover, the metal component (X in a zirconium type crosslinking agent (B2) with respect to an epoxy-type crosslinking agent (B1) (solid content conversion amount) from the point of quick-curing property, suppression of the adhesive force raise after a heating, and a heat-resistant stain | pollution property. ) Content ratio (weight ratio) (X / B1) is preferably 0.015 to 1.0, more preferably 0.03 to 0.5, and particularly preferably 0.06 to 0.3. . If the content of the metal component (X) in the zirconium-based cross-linking agent (B2) is too small relative to the content of the epoxy-based cross-linking agent (B1), the immediate curability tends to decrease. There is a tendency for the adhesive strength of the resin to increase greatly and the heat-resistant contamination property to decrease.

Moreover, in this invention, the other crosslinking agent normally used for an adhesive composition can also be used together in the range which does not impair the objective of this invention.
Examples of such a crosslinking agent include isocyanate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, melamine-based crosslinking agents, aldehyde-based crosslinking agents, and amine-based crosslinking agents. When other crosslinking agents are used in combination, it is preferable to use an isocyanate crosslinking agent in combination from the viewpoint of adjusting the adhesive properties.

  In this invention, content of a crosslinking agent (B) is 4-60 with respect to 100 weight part of acrylic resin (A) from the point of quick-curing property, suppression of the adhesive force raise after a heating, and a heat resistant stain | pollution property. The amount is preferably parts by weight, more preferably 6 to 40 parts by weight, and particularly preferably 8 to 30 parts by weight. If the content is too small, the cohesive force of the pressure-sensitive adhesive tends to decrease and cause adhesive residue.If the content is too large, the pressure-sensitive adhesive is excessively cross-linked, and the pressure-sensitive adhesive strength decreases. There is a tendency to float.

Moreover, it is preferable that the adhesive composition of this invention contains a crosslinking retarder (C) at the point which extends pot life and improves applicability | paintability.
The crosslinking retarder is contained to adjust the activity of the zirconium-based crosslinking agent (B2) and balance the pot life and curability of the pressure-sensitive adhesive composition. In the pressure-sensitive adhesive composition, the crosslinking retarder acts as a chelating agent for the zirconium-based cross-linking agent (B2) and blocks the zirconium-based cross-linking agent (B2). An increase in viscosity and gelation can be suppressed, and the pot life of the pressure-sensitive adhesive composition can be extended. Thereafter, when the cross-linking retarder volatilizes by applying the adhesive composition to a substrate or the like and drying it, the zirconium-based cross-linking agent (B2) blocked by the cross-linking retarder is activated, and the cross-linking promoting effect is obtained. Demonstrated and the cross-linking of the adhesive proceeds.

The crosslinking retarder (C) is a ketoenol tautomer, for example, β-ketoester such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, Examples include β-diketones such as acetylacetone, 2,4-hexanedione, and benzoylacetone.
Among these, it is preferable to use acetylacetone from the viewpoint of the balance between pot life and quick curing.
In addition, these can be used 1 type or in combination of 2 or more types.

  As the crosslinking retarder (C), commercially available “acetylacetone” manufactured by Daicel Corporation may be used.

  Since the crosslinking retarder (C) has an effect of suppressing crosslinking, contrary to the crosslinking promotion effect of the zirconium-based crosslinking agent (B2), the ratio of the crosslinking retarder (C) to the zirconium-based crosslinking agent (B2). Is preferably set appropriately.

In order to prolong the pot life of the pressure-sensitive adhesive composition and not impair the immediate curing, the content ratio (weight ratio) of the crosslinking retarder (C) and the zirconium-based crosslinking agent (B2) (solid content equivalent amount) is Crosslinking retarder (C): zirconium-based crosslinking agent (B2) = 1: 0.01 to 1:15 is preferable, and (C) :( B2) = 1: 0.1 is more preferable. ˜1: 13, particularly preferably (C) :( B2) = 1: 0.5 to 1:10.
When there is too little content of a crosslinking retarder (C), there exists a tendency for pot life to be short and for coating property to fall, and for too much, there exists a tendency for immediate curability to fall.

  The pressure-sensitive adhesive composition of the present invention further includes an antistatic agent, an antioxidant, a plasticizer, a filler, a pigment, a diluent, an anti-aging agent, an ultraviolet absorber, and an ultraviolet stabilizer as long as the effects of the present invention are not impaired. Further, an additive such as a tackifying resin may be further contained, and these additives may be used alone or in combination of two or more. In particular, the antioxidant is effective for maintaining the stability of the pressure-sensitive adhesive layer. The content when the antioxidant is blended is not particularly limited, but is preferably 0.01 to 5% by weight. In addition to the additives, a small amount of impurities contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained.

The gel fraction of the pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition of the present invention with the crosslinking agent (B) is usually 40 to 100%, preferably 60 to 100%, particularly preferably 80 to 100%, and still more preferably. Is 85 to 100%, particularly preferably 90 to 100%.
If the gel fraction is too low, the cohesive force of the pressure-sensitive adhesive is lowered, and adhesive residue is generated, which tends to cause adherend contamination.

  The gel fraction is a measure of the degree of crosslinking, and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive sheet (not provided with a separator) in which a pressure-sensitive adhesive layer is formed on a polymer sheet (for example, polyethylene terephthalate film or the like) as a base material is wrapped with a 200-mesh SUS wire mesh, and 23 in toluene. The weight percentage of the insoluble pressure-sensitive adhesive component immersed in the wire mesh at 24 ° C. for 24 hours is defined as the gel fraction. However, the weight of the substrate is subtracted.

  In the present invention, a heat-resistant adhesive film for masking can be obtained by preparing a pressure-sensitive adhesive for masking film from the above-mentioned pressure-sensitive adhesive composition and laminating and forming an adhesive layer on the base film. In addition, the adhesive which comprises an adhesive layer is the said adhesive composition bridge | crosslinked with the crosslinking agent (B).

  Examples of the base material on which the pressure-sensitive adhesive layer is laminated include a single layer or laminated film made of metal, polyester resin, polyfluorinated ethylene resin, polyimide and derivatives thereof, epoxy resin, and the like. In the heat-resistant adhesive film for masking, it is preferable to further provide a release film on the surface of the pressure-sensitive adhesive layer opposite to the base material. When the masking heat-resistant adhesive film is put to practical use, the release film is peeled off and used. As the release film, a silicon release film, an olefin release film, a fluorine release film, a long-chain alkyl release film, and an alkyd release film can be used.

  The method for producing the above adhesive film is as follows: [1] A method in which a pressure-sensitive adhesive composition is applied on a substrate and dried, and then a release film is bonded and an aging treatment is performed. [2] A release film Examples include a method of applying an adhesive composition on the top, drying the substrate, pasting a base material, and performing an aging treatment. Among these, the method [2] is preferable from the viewpoint of not damaging the substrate, workability and stable production.

  Here, the aging treatment of the pressure-sensitive adhesive film imparted with heat resistance usually requires aging at a high temperature for a long time. In the present invention, the epoxy-based crosslinking agent (B1) and the metal chelate-based crosslinking agent ( By using B2) together at a predetermined content, it becomes excellent in immediate curability, whereby the aging treatment can be completed at a low temperature and in a short time.

  The aging treatment is carried out to balance the physical properties of the adhesive. As the aging conditions, the temperature is usually 0 to 150 ° C., preferably 10 to 100 ° C., particularly preferably 20 to 80 ° C., and the time is Usually, it is 30 days or less, preferably 14 days or less, particularly preferably 7 days or less. Specifically, it can be carried out under conditions such as 3 to 10 days at 23 ° C., 1 to 7 days at 40 ° C. .

  In applying the pressure-sensitive adhesive composition, it is preferable to dilute and apply the pressure-sensitive adhesive composition to a solvent, and the dilution concentration is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. The solvent is not particularly limited as long as it dissolves the pressure-sensitive adhesive composition. For example, ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, and ethyl acetoacetate; acetone, methyl ethyl ketone, A ketone solvent such as methyl isobutyl ketone; an aromatic solvent such as toluene and xylene; and an alcohol solvent such as methanol, ethanol and propyl alcohol can be used. Among these, ethyl acetate, methyl ethyl ketone, and toluene are preferably used from the viewpoints of solubility, drying property, price, and the like.

  The pressure-sensitive adhesive composition can be applied by a conventional method such as roll coating, die coating, gravure coating, comma coating, or screen printing.

  The thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive film is usually 5 to 300 μm, preferably 5 to 50 μm, and particularly preferably 10 to 30 μm. If this pressure-sensitive adhesive layer is too thin, the physical properties of the adhesive tend to be difficult to stabilize, and if it is too thick, the entire pressure-sensitive adhesive film tends to be too thick and the usability tends to deteriorate.

  As the adherend of the adhesive film, it is preferable to use a base material of a material having heat resistance, such as a metal plate or metal foil of aluminum, copper, iron, stainless steel, magnesium, nickel, titanium, etc .; polyethylene terephthalate, Polyester resins such as polyethylene naphthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, ester acrylate; polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc. Polyfluorinated ethylene resin; polyimide and its derivatives; bisphenol type epoxy resin, epoxy resin composite material, alicyclic epoxy resin, epoxy novolac, biphenyl type epoxy resin, epoxy acrylate, etc. And the like.

  The adhesive strength of the adhesive layer of the adhesive film is adjusted as appropriate according to the material of the adherend. For example, when pasting on a SUS-BA plate, a hard-coated PET film, glass, a polyimide film, etc. The adhesive strength immediately after coating (before aging) is preferably 0.01 to 1.8 N / 25 mm, particularly preferably 0.05 to 1.5 N / 25 mm, more preferably 0.1 to 1. 0.0 N / 25 mm.

  Moreover, it is preferable that the adhesive force of the adhesive layer of the adhesive film after aging is 0.001-1.0N / 25mm, Especially preferably, it is 0.005-0.8N / 25mm, More preferably, it is 0.01. -0.5N / 25mm.

  Further, the adhesive strength of the adhesive layer of the adhesive film after heating is preferably 0.001 to 1.0 N / 25 mm, particularly preferably 0.005 to 0.8 N / 25 mm, and still more preferably 0.01 to 0.5 N / 25 mm.

The heat-resistant adhesive film for masking obtained using the pressure-sensitive adhesive composition of the present invention is hardly contaminated when peeled from the adherend even after being used under high temperature conditions, and can be peeled off with a small force. Because it can, for example, masking applications that require heat resistance, such as masking adhesive films for temporarily protecting the surface of circuit boards such as FPC boards and ITO transparent electrode layers, or temporarily holding and reinforcing products during the manufacturing process It can be used for general temporary fixing applications for fixing.
In addition, the pressure-sensitive adhesive composition of the present invention has an immediate curing property, and fine unevenness of the release film is difficult to be transferred to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer, so that it is used for protective films for displays such as flat panel displays and touch panels. Even when used as, it is possible to prevent a decrease in visibility due to unevenness.

  As a method of using the heat-resistant adhesive film for masking obtained by using the adhesive composition of the present invention, the masking adhesive film is usually attached to the surface of an adherend, usually 100 ° C. or higher, preferably 130 ° C. or higher, particularly preferably. Is preferably subjected to a heating step of 150 ° C. or higher, more preferably 170 ° C. or higher, and then the adhesive film for masking is peeled off from the surface of the adherend.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “%” and “parts” mean weight basis. The glass transition temperature was measured according to the method described above.
Each component is as follows.

<Manufacture of acrylic resin (A) solution>
[Production Example 1: Acrylic resin (A-1)]
A reactor equipped with a thermometer, stirrer, dropping funnel and reflux condenser was charged with 66.5 parts of ethyl acetate, 3.3 parts of toluene, and 0.07 part of azobisisobutyronitrile (AIBN) and stirred. While raising the temperature to 80 ° C., 46 parts of 2-ethylhexyl acrylate (2EHA), 45.9 parts of butyl acrylate (BA), 8 parts of acrylic acid (AAc), 0.1 part of hydroxyethyl methacrylate (HEMA) were added. The mixed solution was added dropwise over 2 hours. Further, during the polymerization, the polymerization catalyst solution in which 0.03 part of AIBN was dissolved in 8.37 parts of toluene was added successively and refluxed at the above temperature for 3.5 hours, and then diluted with ethyl acetate, A 37% solution of an acrylic resin (A-1) having an average molecular weight of 550,000 (dispersion degree 4.7, glass transition temperature -55.4 ° C.) was obtained.

<Crosslinking agent (B)>
[Epoxy crosslinking agent (B1)]
・ (B1-1)
1,3′-bis (N, N-diglycidylaminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd., “Tetrad-C”, solid content concentration 100%)
[Zirconium-based crosslinking agent (B2)]
・ (B2-1)
Zirconium tetraacetylacetonate (Matsumoto Fine Chemical Co., Ltd., “ZC-700”), solid content concentration 20%, metal component 18.5% in solid content
・ (B2-2)
Zirconium butoxybis (ethyl acetoacetate) (Matsumoto Fine Chemical Co., Ltd., “ZC-580”, solid content concentration 70%, metal component 18.4% in solid content)
[Other cross-linking agents]
Aluminum-based crosslinking agent Tris (2,4-pentanedionato) aluminum (III) (manufactured by Nippon Kagaku Sangyo Co., Ltd., “Narsem Aluminum”, solid content concentration 100%, metal component in solid content 8.3%)

<Crosslinking retarder (C)>
・ (C-1) Acetylacetone

<Example 1>
(Preparation of pressure-sensitive adhesive composition)
10 parts of epoxy crosslinking agent (B1-1) (solid content conversion amount) and zirconium crosslinking agent (B2-1) with respect to 100 parts of solid content of acrylic resin (A-1) obtained above. 3.4 parts (solid content conversion amount) and 1 part of acetylacetone (C-1) were blended to prepare an adhesive composition.

[Production of adhesive film]
The pressure-sensitive adhesive composition prepared above was applied to a base PET film (thickness 38 μm) so that the thickness of the pressure-sensitive adhesive layer after drying was 25 μm, and then dried at 100 ° C. for 2 minutes. Thereafter, a release-treated PET (release film) was adhered to the coated surface to protect the adhesive layer, and an adhesive film was produced.
The following evaluation was performed using the obtained adhesive film, and the results are shown in Table 1.

[Adhesive strength: 3 hours after preparation of adhesive film (immediate curing evaluation)]
A 25 mm × 100 mm test piece was prepared using the adhesive film after 3 hours from the preparation of the adhesive film, and the release film was peeled off. Then, a 25 μm-thick polyimide film (Toray Industries, Inc.)・ Pressurize the adhesive layer surface of the test piece on the polyimide film surface of the adherend to which DuPont “Kapton 100H”) is pasted in a reciprocating 2 kg rubber roller in an atmosphere of 23 ° C. and 50% relative humidity. After pasting and leaving for 30 minutes in the same atmosphere, 180 degree peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min, and evaluated according to the following criteria.
In addition, it shows that the pressure-sensitive adhesive layer is more cross-linked as the numerical value of the peel strength is smaller, and it can be seen that the cross-linking proceeds in a short time such as 3 hours from the production of the pressure-sensitive adhesive film. Therefore, it can be determined that the surface of the pressure-sensitive adhesive layer is smooth without transferring the fine uneven shape.
(Evaluation criteria)
◎ ・ ・ ・ less than 0.3N / 25mm ○ ・ ・ ・ 0.3N / 25mm or more, less than 1.0N / 25mm × ・ ・ ・ 1.0N / 25mm or more

[Adhesive strength: After aging]
After the adhesive film obtained above was aged at 40 ° C. for 7 days, a test piece of 25 mm × 100 mm was prepared and the release film was peeled off, and then a polyimide film having a thickness of 25 μm on a stainless steel plate (SUS304BA plate). The adhesive layer surface of the test piece is adhered to the surface of the adherend to which the adherend ("Kapton 100H" manufactured by Toray DuPont Co., Ltd.) is attached. After applying the pressure and leaving it in the same atmosphere for 30 minutes, the 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min, and evaluated according to the following criteria.
(Evaluation criteria)
◎ ・ ・ ・ less than 0.1N / 25mm ○ ・ ・ ・ 0.1N / 25mm or more, less than 0.5N / 25mm × ・ ・ ・ 0.5N / 25mm or more

[Adhesive strength: after heating]
After the adhesive film obtained above was aged at 40 ° C. for 7 days, a test piece of 25 mm × 100 mm was prepared and the release film was peeled off, and then a polyimide film having a thickness of 25 μm on a stainless steel plate (SUS304BA plate). Add the adhesive layer surface of the test piece to the polyimide surface of the adherend (Toray DuPont's “Kapton 100H”) attached in two reciprocations of a 2 kg rubber roller in an atmosphere of 23 ° C. and 50% relative humidity. The film was pressed and left in the same atmosphere for 30 minutes. Then, it exposed to 150 degreeC conditions for 1.5 hours, and returned to 23 degreeC after that. Further, after being left for 2 hours in an atmosphere of 23 ° C. and 50% relative humidity, 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min, and evaluated according to the following criteria.
(Evaluation criteria)
◎ ・ ・ ・ less than 0.3N / 25mm ○ ・ ・ ・ 0.3N / 25mm or more, less than 0.5N / 25mm × ・ ・ ・ 0.5N / 25mm or more

[Heat resistant contamination]
After the adhesive film obtained above was aged at 40 ° C. for 7 days, a test piece of 25 mm × 100 mm was prepared and the release film was peeled off, and then a polyimide film having a thickness of 25 μm on a stainless steel plate (SUS304BA plate). (Adhesive layer “Kapton 100H” manufactured by Toray DuPont Co., Ltd.) The pressure-sensitive adhesive layer surface of the test piece is pressure-applied by reciprocating 2 kg rubber rollers in an atmosphere of 23 ° C. and 50% relative humidity. , And left in the same atmosphere for 30 minutes. Then, it exposed to 150 degreeC conditions for 1.5 hours, and returned to 23 degreeC after that. Further, after being left for 2 hours in an atmosphere of 23 ° C. and 50% relative humidity, the appearance of the adherend surface after 180 ° peeling at a peeling speed of 300 mm / min was visually observed and evaluated according to the following criteria.
(Evaluation criteria)
○: No adhesive residue or sticking marks were observed.
X: Base material interface peeling was observed.

<Examples 2-5, Comparative Examples 1-6>
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the type and blending amount of the crosslinking agent (B) in the pressure-sensitive adhesive composition were blended in the proportions shown in Table 1, and a pressure-sensitive adhesive film was prepared. Evaluation similar to Example 1 was performed using the obtained adhesive film. The results are shown in Table 1.

  In the pressure-sensitive adhesive films of Examples 1 to 5 having a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing specific amounts of the epoxy-based cross-linking agent (B1) and the zirconium-based cross-linking agent (B2) as the cross-linking agent, The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film has low adhesive strength, that is, has excellent immediate curing properties, and the pressure-sensitive adhesive strength becomes excessive even after being exposed to a high temperature condition of 150 hours at 150 ° C. In other words, it can be peeled off from the adherend with a small force, and it can be seen that contamination hardly occurs when peeled off from the adherend.

On the other hand, in the pressure-sensitive adhesive films of Comparative Example 3 and Comparative Example 4 that do not contain the epoxy-based crosslinking agent (B1) or have a pressure-sensitive adhesive layer whose content does not satisfy a specific amount, Although it has, adhesive force becomes high after using on high temperature conditions, and it turns out that it is inferior to the peelability after a heating.
Further, in the pressure-sensitive adhesive films of Comparative Examples 1 and 2 having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition that does not contain the zirconium-based cross-linking agent (B2) or whose content does not satisfy the specific amount, 3 hours after the film production. It can be seen that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film has high adhesive strength and is inferior in immediate curing.
Furthermore, in Comparative Examples 5 and 6 having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition using an aluminum-based cross-linking agent that is also a metal cross-linking agent instead of the zirconium-based cross-linking agent (B2), the quick curing property is poor. In particular, in Comparative Example 6 in which the epoxy crosslinking agent (B1) is used in an amount usually used, it can be seen that in addition to quick curing, the peelability after heating and the heat-resistant stain resistance are also poor.

  The pressure-sensitive adhesive composition of the present invention includes a heat-resistant adhesive film for masking and a flat panel display for masking and fixing in a heating process included in a manufacturing process of touch panel-related members such as circuit boards such as FPC boards and ITO transparent electrodes. It can be suitably used for a surface protective adhesive film such as a touch panel.

Claims (8)

  An acrylic pressure-sensitive adhesive composition containing an acrylic resin (A) and a crosslinking agent (B), wherein the crosslinking agent (B) contains an epoxy-based crosslinking agent (B1) and a zirconium-based crosslinking agent (B2), The content of the epoxy crosslinking agent (B1) with respect to 100 parts by weight of the acrylic resin (A) is 2 to 30 parts by weight, and the content of the zirconium crosslinking agent (B2) is 1 to 30 parts by weight. Acrylic adhesive composition.   The content ratio (X / B1) of the metal component (X) in the zirconium-based crosslinking agent (B2) with respect to the epoxy-based crosslinking agent (B1) is 0.015 to 1.0. Adhesive composition.   The acrylic resin (A) is obtained by polymerizing a polymerization component containing a (meth) acrylic acid alkyl ester monomer (a1) and a functional group-containing monomer (a2). Adhesive composition.   The pressure-sensitive adhesive composition according to any one of claims 1 to 3, further comprising a crosslinking retarder (C).   A pressure-sensitive adhesive, wherein the pressure-sensitive adhesive composition according to claim 1 is crosslinked with a crosslinking agent (B).   A pressure-sensitive adhesive for masking film, comprising the pressure-sensitive adhesive according to claim 5.   A heat-resistant adhesive film for masking, comprising an adhesive layer comprising the adhesive for masking film according to claim 6 on the film. The heat-resistant adhesive film for masking according to claim 7 is attached to the surface of the adherend, and after being subjected to a heating step of 130 ° C. or higher, the heat-resistant adhesive film for masking is peeled off from the surface of the adherend. How to use heat-resistant adhesive film for masking.