JP6347945B2 - Method for producing acrylic resin for heat-resistant adhesive film - Google Patents

Description

The present invention relates to a method of manufacturing a heat-proof adhesive film for acrylic resin, in particular, heat-resistant adhesive film for acrylic residual amount of the polymerization initiator to allow the production of a reduced heat adhesive film for acrylic resins The present invention relates to a method for producing a resin.

  Flexible printed wiring (FPC) substrates are used in information terminal electronic devices such as mobile phones. In recent years, thinning of laminates including FPC substrates has become possible due to higher circuit performance and smaller and lighter electronic devices. Miniaturization is progressing. As a result, since the strength of the laminated plate is reduced and easily damaged, it is necessary to protect the laminated plate with a protective film during the manufacturing process in order to prevent the damage. However, since it is exposed to a high temperature during the production process, the adhesive layer of the protective film is fixed to the laminated board, and the laminated board may be damaged when the protective film is peeled off, or contamination due to adhesive residue may occur. Moreover, since adhesive force may fall and a float may be produced under high temperature, there also exists a problem which cannot exhibit sufficient protective ability as a protective film. In order to solve these problems, the following pressure-sensitive adhesive / adhesive compositions have been proposed.

  For example, a pressure-sensitive adhesive composition containing a (meth) acrylic polymer having an alkenyl group in the side chain and a crosslinking agent having a siloxane bond and at least two hydrosilyl groups in the molecule is disclosed (patent) Reference 1).

  The pressure-sensitive adhesive composition further comprises a pressure-sensitive adhesive polymer having a hydroxyl group, and a crosslinking accelerator that is a metal organic compound containing at least one metal selected from tin, zinc, lead, and bismuth, and further contains a volatile acid. And the releasable adhesive tape using this adhesive composition is disclosed (refer patent document 2).

JP 2010-235845 A JP 2002-241732 A

  However, in the technique disclosed in Patent Document 1, a pressure-sensitive adhesive containing a (meth) acrylic polymer having an alkenyl group in the side chain and a crosslinking agent having a siloxane bond and at least two hydrosilyl groups in the molecule. For example, after adding 0.24 parts by weight of azobisisobutyronitrile (polymerization initiator), the reaction has only been carried out at 60 ° C. for 24 hours. Since much calculation may remain, adherend contamination may occur after the heat-resistant process. Moreover, it is inferior to heat resistance of higher temperature, and an adhesive residue may arise.

  The technique disclosed in Patent Document 2 includes a pressure-sensitive adhesive containing a pressure-sensitive adhesive polymer having a hydroxyl group and a crosslinking accelerator that is a metal organic compound containing at least one metal selected from tin, zinc, lead, and bismuth. Although it is a releasable pressure-sensitive adhesive tape obtained by crosslinking the composition with an isocyanate cross-linking agent, for example, in the production of the pressure-sensitive adhesive, a benzoyl peroxide-based initiator (Nyper BMT-K40, manufactured by NOF Corporation) 0.36 Since the reaction has only been carried out at 86 ° C. for 4 hours after the addition of parts by weight and a large amount of residual polymerization initiator may remain in the calculation, adherend contamination may occur after the heat-resistant step. . Moreover, there is a possibility that the added crosslinking accelerator and volatile acid may cause adherend contamination.

  Thus, in any of the pressure-sensitive adhesive / adhesive compositions, as described later, bonds in the pressure-sensitive adhesive layer are caused by radicals generated by decomposition of the residual polymerization initiator in the pressure-sensitive adhesive layer, particularly in a high temperature environment. It is difficult to prevent the above-mentioned problems only by the method of improving the degree of crosslinking (for example, improving the degree of crosslinking with a crosslinking accelerator or crosslinking using a hydrosilyl group). is there.

The present invention may also view of the above circumstances, the remaining amount of the polymerization initiator and an object thereof is to provide a reduced process for producing heat-resistant adhesive film for an acrylic resin which allows for manufacturing acrylic resins heat-resistant adhesive film It is.

  As a result of examining the problem that the adherend as described above is contaminated particularly in a high temperature environment, the present inventors did not cut the chemical bond or the physical bond of the pressure-sensitive adhesive only by heat in the high-temperature heat-resistant process. , The polymerization initiator remaining in the adhesive, oxygen in the resin and nitrogen oxides in the air generate radicals, and the radicals attack chemical bonds in the adhesive to break chemical bonds and physical bonds. I have found out what causes it.

  And the present inventors diligently investigated in order to solve the said problem, and paid their attention to the polymerization initiator which remain | survives in an adhesive. As a result, even after the polymerization reaction is almost completed and the consumption of the polymerization initiator is completed, the remaining polymerization initiator is decomposed by heating (decomposition to a state that does not function as a polymerization initiator) by continuing to heat. ) To reduce the amount of the polymerization initiator remaining in the acrylic resin that is the finally obtained polymer.

  Therefore, as a result of further investigations from the above viewpoint, the present inventors used an acrylic resin adjusted to a content that is much smaller than the content in which the polymerization initiator usually remains in a high temperature environment. Even when the adherend is not contaminated, the adhesive performance is sufficiently high, the aging period for producing the adhesive film is short, and the present invention has been found to be economically efficient.

  Furthermore, when the content of the polymerization initiator in the polymerization reaction liquid of the acrylic resin is not more than a certain value, when heated at a temperature higher than the 10-hour half-life temperature of the polymerization initiator for 2 hours or more, it is obtained. The present invention has been found that a pressure-sensitive adhesive composition suitable for heat-resistant pressure-sensitive adhesive film application can be obtained by effectively reducing the residual amount of the polymerization initiator in the acrylic resin to be used without causing a problem as a pressure-sensitive adhesive. did.

<< Summary of the Invention >>
That is , the present invention is a method for producing an acrylic resin in which a polymerization component [I] containing a (meth) acrylic acid alkyl ester monomer as a main component is polymerized in the presence of an azo polymerization initiator, A method for producing an acrylic resin for a heat-resistant adhesive film, wherein the polymerization initiator is heated for 2 hours or more at a temperature higher than the 10-hour half-life temperature of the azo polymerization initiator in a state where the content of the polymerization initiator is 300 ppm or less in the calculated value the the gist of it.

  The “heat-resistant adhesive film” in the present invention conceptually includes a heat-resistant adhesive sheet, a heat-resistant adhesive film, and a heat-resistant adhesive tape.

As described above, when the acrylic resin is produced by polymerizing the polymerization component [I] containing the (meth) acrylic acid alkyl ester monomer as a main component in the presence of an azo polymerization initiator, Acrylic resin for heat-resistant adhesive film produced by heating for 2 hours or more at a temperature higher than the 10-hour half-life temperature of the azo polymerization initiator in a state where the concentration of the polymerization initiator in the reaction solution is 300 ppm or less. According to the method of manufacturing, the polymerization initiator-containing concentrations Ru can be obtained a heat-adhesive film for acrylic resin is less than 80 ppm. The heat-resistant adhesive film using an adhesive made of this acrylic resin does not cause contamination of the adherend even when used in a high-temperature environment, and has sufficiently high adhesive performance. The period is short and economically efficient. Therefore, the acrylic resin for heat-resistant adhesive film obtained by the production method of the present invention (hereinafter sometimes referred to as “acrylic resin for heat-resistant adhesive film of the present invention” or “acrylic resin of the present invention”) is, for example, Used for heat-resistant processes such as flexible printed circuit board applications. Specifically, it is useful for a masking application in a heat-resistant process or a fixing application in a heat-resistant process .

  And in the said manufacture, when it superposes | polymerizes in presence of antioxidant in addition to a polymerization initiator, the heat resistance of an adhesive will improve further.

The description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and is not limited to these contents.
Hereinafter, the present invention will be described in detail.
In the present specification, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate. As described above, the “film” conceptually includes a sheet, a film, and a tape.

Resistant adhesive film for acrylic resins of the present invention, (meth) using a polymerization component containing as a main component acrylic acid alkyl ester monomer [I], which can be polymerized in the presence of an azo-based polymerization initiator Is obtained.

<Polymerization component [I]>
In the present invention, the polymerization component [I] is obtained by polymerizing the polymerization component [I] (monomer component) containing the (meth) acrylic acid alkyl ester monomer (a1) as a main component. As other monomer components other than (a1) contained in component [I], functional group-containing monomer (a2) other than nitrogen atom-containing monomer (a3), nitrogen atom-containing monomer (a3), and other polymerizability A monomer appropriately selected from the monomers (a4) is contained. The “main component” that contains the (meth) acrylic acid alkyl ester monomer (a1) as a main component specifically refers to the (meth) acrylic acid alkyl ester monomer (a1) being a polymerization component. [I] (Monomer component) It means that the content is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more. The upper limit is usually 100% by weight.

[(Meth) acrylic acid alkyl ester monomer (a1)]
Examples of the (meth) acrylic acid alkyl ester monomer (a1) include, 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 (meth) acrylate, iso-stearyl (meth) acrylate and other (meth) acrylic acid alkyl esters; cyclohexyl (meth) acrylate, isobornyl (meth) a Alicyclic such relations (meth) acrylic acid ester. And in the case of (meth) acrylic acid alkyl ester, it is preferable that carbon number of an alkyl group is 1-20 normally, Especially 1-12, Furthermore, 1-8, Especially 4-8. These may be used alone or in combination of two or more.

[Functional group-containing monomer (a2) (other than nitrogen atom-containing monomer (a3))]
The functional group-containing monomer (a2) is a functional group-containing monomer other than the nitrogen atom-containing monomer (a3) described later, and includes a hydroxyl group-containing monomer, an acetoacetyl group-containing monomer, an isocyanate group-containing monomer, a glycidyl group-containing monomer, and the like. These may be used alone or in combination of two or more. Among these, a hydroxyl group-containing monomer is preferably used in terms of efficient crosslinking reaction.

In order to improve the heat resistance of the pressure-sensitive adhesive, it is necessary that the pressure-sensitive adhesive film is sufficiently cross-linked. For this purpose, there is a functional group to be cross-linked in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film. If it is not crosslinked, sufficient heat resistance will not be exhibited. Therefore, the adhesive of the heat-resistant adhesive film containing an acrylic resin of the present invention is preferably that there is a functional group in the acrylic resin, that functional group is most preferably a hydroxyl group, a hydroxyl group-containing as above Monomers are preferably used. Therefore, an adhesive having no functional group serving as a reaction point is not preferable because the heat resistance is insufficient and the adherend is contaminated.

  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 ( (Meth) acrylic acid hydroxyalkyl esters such as (meth) acrylate; caprolactone-modified caprolactone-modified monomers such as 2-hydroxyethyl (meth) acrylate; oxyalkylene-modified monomers such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate; other Primary hydroxyl group-containing monomers such as 2-acryloyloxyethyl 2-hydroxyethylphthalic acid; 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Can be mentioned 2,2-dimethyl 2-hydroxyethyl (meth) tertiary hydroxyl group-containing monomers such as acrylate; meth) acrylate, secondary hydroxyl group-containing monomers such as 3-chloro-2-hydroxypropyl (meth) acrylate. Among these, (meth) acrylic acid hydroxyalkyl ester is preferable from the viewpoint of copolymerizability and polarity. In particular, it is easy to react with a crosslinking agent and has few impurities such as di (meth) acrylic acid ester and is easy to polymerize. From the viewpoint, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 4-hydroxybutyl acrylate are preferably used. In addition, it is preferable to use two or more kinds of hydroxyl group-containing monomers in view of increasing the cross-linking structure and improving the heat resistance. From this point, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly preferable. It is to use together.

  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.

  The content of the functional group-containing monomer (a2) is preferably 1 to 30% by weight, particularly preferably 3 to 20% by weight, more preferably 5 to 15%, based on the entire polymerization component (monomer component) [I]. % By weight, most preferably 7-13% by weight. If the content ratio of the functional group-containing monomer (a2) is too large, the adhesive strength tends to decrease, and if it is too small, the crosslinking density tends to decrease and the adherend contamination resistance tends to decrease.

[Nitrogen atom-containing monomer (a3)]
As said nitrogen atom containing monomer (a3), what is necessary is just a monomer containing a nitrogen atom, for example, an amino group containing monomer, an amide group containing monomer, a nitrogen-type heterocyclic containing monomer, a cyano group containing Monomers, imide group-containing monomers, betaine monomers, and the like. Among them, a highly basic monomer exhibiting a catalytic activity is preferable, for example, a monomer selected from a substituted amino group-containing monomer, a substituted amide group-containing monomer, and a nitrogen-based heterocyclic ring-containing monomer is preferable. A substituted amino group-containing monomer is preferred. These monomers are preferably (meth) acrylic monomers. These nitrogen atom-containing monomers (a3) can be used alone or in combination of two or more.

The amino group-containing monomer may be any polymerizable monomer having an ethylenically unsaturated double bond and an amino group (unsubstituted or substituted amino group), such as aminomethyl (meth) acrylate, N such as aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminoalkyl (meth) acrylate such as aminoisopropyl (meth) acrylate and N- (t-butyl) aminoethyl (meth) acrylate -Monosubstituted amino group-containing (meth) acrylic acid esters such as (meth) acrylic acid esters of alkylaminoalkyl;
N, N-dialkylaminoalkyl (meth) such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate Disubstituted amino group-containing (meth) acrylic acid esters such as acrylic acid esters;
Dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamide, quaternized salts of these amino group-containing monomers, and the like;
amino group-containing styrenes such as p-aminostyrene;
Styrenes having a dialkylamino group such as 3- (dimethylamino) styrene and dimethylaminomethylstyrene; dialkylaminoalkyl vinyl ethers such as N, N-dimethylaminoethyl vinyl ether and N, N-diethylaminoethyl vinyl ether;
Allylamine, 4-diisopropylamino-1-butene, trans-2-butene-1,4-diamine, 2-vinyl-4,6-diamino-1,3,5-triazine and the like are used.

The amide group-containing monomer may be any polymerizable monomer having an ethylenically unsaturated double bond and an amide group (group having an amide bond). For example, (meth) acrylamide: N-methyl ( (Meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Ns- Butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, diacetone (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N- (1,1-dimethyl) N-alkyl (meth) acryl such as (3-oxobutyl) (meth) acrylamide Luamide:
N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di (n-butyl) (Meth) acrylamide, N, N-diisobutyl (meth) acrylamide, N, N-di (s-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide, N, N-dipentyl (Meth) acrylamide, N, N-dihexyl (meth) acrylamide, N, N-diheptyl (meth) acrylamide, N, N-dioctyl (meth) acrylamide, N, N-diallyl (meth) acrylamide, N, N-ethyl N, N-dialkyl (meth) acrylamides such as methylacrylamide:
Dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamide:
Substituted amide group-containing monomers such as N-vinylacetamide, N-vinylformamide, (meth) acrylamide ethylethyleneurea, (meth) acrylamide-t-butylsulfonic acid;
Hydroxyl group-containing (meth) acrylamides such as N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide;
Alkoxy group-containing (meth) acrylamides such as N-methoxymethyl (meth) acrylamide and N- (n-butoxymethyl) (meth) acrylamide;
Examples thereof include quaternized salts of these amide group-containing monomers.

The nitrogen-based heterocyclic ring-containing monomer may be any polymerizable monomer having an ethylenically unsaturated double bond and a nitrogen-based heterocyclic ring (a heterocyclic ring having a nitrogen atom as a ring constituent element). N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, 1-vinylimidazole, 4-vinylpyridine, 2-vinylpyridine, 2-vinylpyrazine, N-vinyl-2-pyrrolidone, N-vinylcarbazole, N-vinylphthalimide, 2- N-vinyl monomers such as vinyl-2H-indazole;
N-allylic monomers such as N-allylmorpholine;
N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylaziridine, N- (meth) acryloylaziridine, aziridini N- (meth) acryloyl monomers such as ruethyl (meth) acrylate;
A quaternized salt of a nitrogen-based heterocycle-containing monomer obtained by allowing a known quaternizing agent such as alkyl halide, benzyl halide, alkyl or arylsulfonic acid or dialkyl sulfate to act on the above monomer; 4 -Methyl-5-vinylthiazole and the like.

  The cyano group-containing monomer may be any polymerizable monomer having an ethylenically unsaturated double bond and a cyano group, and examples thereof include acrylonitrile and methacrylonitrile.

The imide group-containing monomer may be any polymerizable monomer having an ethylenically unsaturated double bond and an imino group, such as maleimide, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide. Maleimide monomers such as N-phenylmaleimide and isopropylmaleimide;
Itacimide imides such as N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl leuconacimide, N-lauryl itaconimide, itacon imide, etc. Mer;
Examples thereof include succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyoctamethylene succinimide.

  Examples of the betaine-containing monomer include N- (3-sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N-methacryloylamidopropyl- N, N-dimethylammonium betaine, N- (3-carboxymethyl) -N-methacryloylamidopropyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N-methacryloyloxyethyl-N, N- Examples thereof include dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

  Among these nitrogen atom-containing monomers (a3), amino group-containing monomers and amide group-containing monomers are preferred from the viewpoints of copolymerizability with other monomers and crosslinking promotion effects. Particularly preferred are (meth) acrylic acid N, N-dimethylaminoethyl (dimethylaminoethyl (meth) acrylate) and (meth) acrylic acid N, N-diethylaminoethyl (diethylaminoethyl methacrylate), which contain the above amide group As the monomer, N, N-dimethylaminopropyl (meth) acrylamide [dimethylaminopropyl (meth) acrylamide] and N, N-dimethyl (meth) acrylamide [dimethyl (meth) acrylamide] are particularly preferable.

  More preferably, dimethylaminoethyl (meth) acrylate, dimethylaminopropylacrylamide, dimethylacrylamide, and diethylaminoethyl methacrylate are preferred in view of copolymerization with other monomers and the effect of promoting crosslinking, as well as availability as raw materials. is there.

  The content ratio of the nitrogen atom-containing monomer (a3) is preferably 0.001 to 30% by weight, particularly preferably 0.005 to 5% by weight, and still more preferably based on the entire polymerization component (monomer component) [I]. Is from 0.01 to 2% by weight, most preferably from 0.05 to 1% by weight. When the content ratio of the nitrogen atom-containing monomer (a3) is too large, the molecular weight tends to decrease during polymerization or the pressure-sensitive adhesive tends to be colored, and when it is too small, the catalytic effect tends to be hardly obtained.

[Other polymerizable monomer (a4)]
The other polymerizable monomer (a4) is a monomer other than the monomers (a1), (a2), and (a3), and examples thereof include phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (meta). ) Monomers containing one aromatic ring such as acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, α-methylstyrene; 2-methoxyethyl (meth) acrylate, 2 -Ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytri Tylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycol-mono (meth) acrylate, lauroxypolyethyleneglycolmono Monomers containing alkoxy groups or oxyalkylene groups such as (meth) acrylate and stearoxypolyethylene glycol mono (meth) acrylate; acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, Alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate Examples thereof include esters, dialkyl esters of fumaric acid, allyl alcohol, acrylic chloride, methyl vinyl ketone, allyl trimethyl ammonium chloride, dimethyl allyl vinyl ketone and the like. Preferably, it is a monomer having a glass transition temperature (Tg) of the homopolymer of 0 ° C. or higher. These other polymerizable monomers (a4) may be used alone or in combination of two or more.

  The content of the other polymerizable monomer (a4) is preferably 0 to 80% by weight, particularly preferably 0 to 50% by weight, and more preferably 0 to 0% by weight with respect to the entire polymerization component (monomer component) [I]. 30% by weight. When there is too much content rate of the said other polymerizable monomer (a4), there exists a tendency for heat resistance to fall or for adhesive force to fall.

[Hard monomer (X)]
Among the monomer components (a1) to (a4), specific examples of the hard monomer (X) having a glass transition temperature of −30 ° C. or higher include, for example, a (meth) acrylic acid ester monomer (a1). Among them, iso-butyl acrylate, tert-butyl acrylate, ethyl acrylate, methyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, methacryl Iso-butyl acid, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl (meth) acrylate, and the like.
Examples of the nitrogen atom-containing monomer (a3) include acryloylmorpholine, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropylacrylamide, and the like.
Examples of the other polymerizable monomer (a4) include phenoxyethyl acrylate and styrene.

Among these hard monomers (X), methyl (meth) acrylate, ethyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, butyl methacrylate and propyl methacrylate are preferred. Particularly preferred is methyl (meth) acrylate .

[Polymerization initiator]
Examples of the azo polymerization initiator used for radical polymerization in the acrylic resin production method of the present invention include 2,2′-azobis (2-methylbutyronitrile) (67 ° C.) and 2,2′-azo. Bisisobutyronitrile (65 ° C.), (1-phenylethyl) azodiphenylmethane (58 ° C.), 2,2′-azobis (2,4-dimethylvaleronitrile) (52 ° C.), 2,2′-azobis ( Specific examples include azo polymerization initiators such as 2-cyclopropylpropionitrile) (49.6 ° C.) and 2,2′-azobis (4-methoxy2,4-dimethylvaleronitrile) (30 ° C.). . As polymerization initiators other than the azo polymerization initiator, benzoyl peroxide (73.6 ° C.), lauroyl peroxide (61.6 ° C.), t-butyl peroxypivalate (54.6 ° C.), t-hexyl peroxy Peroxides such as pivalate (53.2 ° C), t-hexylperoxyneodecanoate (44.5 ° C), diisopropylperoxycarbonate (40.5 ° C), diisobutyryl peroxide (32.7 ° C) Specific examples include polymerization initiators. In addition, the numerical value in () described following each compound name is the 10-hour half-life temperature of each compound.

  In the present invention, the preferable 10-hour half-life temperature of the azo polymerization initiator is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, further preferably 80 ° C. or lower, and most preferably 70 ° C. or lower.

  In the method for producing an acrylic resin of the present invention, the amount of the azo polymerization initiator used in the entire polymerization reaction is usually 0.001 to 10 parts by weight, preferably 0, per 100 parts by weight of the polymerization component [I]. 0.005 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight, and more preferably 0.05 to 0.5 part by weight. If the amount of the azo polymerization initiator used is too small, it is difficult to obtain the effect of the addition, and even if the amount used is too large, it becomes uneconomical.

  In the method for producing an acrylic resin of the present invention, in the polymerization reaction, other additives such as an antioxidant can be appropriately used as necessary together with the polymerization component [I] and the azo polymerization initiator. .

[Antioxidant]
Examples of the antioxidant include phenolic antioxidants, amine-based antioxidants, amino ether-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl-4-methylphenol. 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl- 4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL-α-tocopherol, Monocyclic phenolic compounds such as ril-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4 ′ -Butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6 -Di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis [3- (3-t-butyl-4- Droxy-5-methylphenyl) propionate], triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl); ) Isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate , Tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 A tricyclic phenol compound such as -hydroxybenzyl) benzene; a tetracyclic phenol compound such as tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane; bis (3,5- And phosphorous-containing phenol compounds such as di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium and bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) nickel; .

  Examples of the amine-based antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 , 6,6-tetramethylpiperidineethanol polycondensate, N, N ′, N ″, N ′ ″-tetrakis- [4,6-bis- {butyl- (N-methyl-2,2,6) , 6-Tetramethylpiperidin-4-yl) amino} -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis Polycondensate of (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3- Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6 -Tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6 -Tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-pepyridyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n- Butyl malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5- Tetramethylpiperazinone), ( Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4- Piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3 , 9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6 Pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2, 3,4-butanetetracarboxylate N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro- 1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino ] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1 , 2-dibromoethane, N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl and the like.

  Examples of the amino ether antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 -Propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2) , 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 Heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-nonyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-dodecyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phos. Phyto, cyclic neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetra Irtris (dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite, tri (2,4-di-t-butylphenyl) phosphite and the like.

Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, ditridecyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), 4,4-thiobis. (2-tert-butyl-5-methylphenol) bis-3- (dodecylthio) propionate, dimyristyl-3,3′-thiodipropionate, lauryl-stearyl-3,3′-thiodipropionate, neopentanetetra Iltetrakis (3-lauryl thiopropionate) and the like.
Each of these antioxidants may be used alone or in combination of two or more.

  Among them, it is preferable to use a phenolic antioxidant, and particularly preferably a hindered phenolic antioxidant. As the hindered phenol-based antioxidant, pentaerythritol ester of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid (BASF Japan, Irganox 1010) is preferable. More preferably, a phenolic antioxidant and at least one of a phosphorus antioxidant and a sulfur antioxidant are used in combination. When the above combination is used, the combined ratio (weight ratio) is usually 10 to 2000 parts by weight, preferably at least one of a phosphorus antioxidant and a sulfur antioxidant with respect to 100 parts by weight of the phenolic antioxidant. Is 50 to 500 parts by weight.

  The amount of the antioxidant is preferably 0.01 to 20 parts by weight, particularly preferably 0.03 to 10 parts by weight, with respect to 100 parts by weight of the acrylic resin obtained using the polymerization component [I]. More preferably, it is 0.05-5 weight part, Most preferably, it is 0.08-3 weight part, Most preferably, it is 0.1-2 weight part. In addition, the said antioxidant may be added at the time of superposition | polymerization, and may be added separately after superposition | polymerization.

[Manufacture of acrylic resin]
In the acrylic resin of the present invention, the actually measured residual polymerization initiator amount (polymerization initiator-containing concentration) is 80 ppm or less in the acrylic resin. The amount of residual polymerization initiator is preferably small, but the lower limit is usually 0.1 ppm.
This measured value is based on a value measured using LC-MS / MS [LC apparatus: manufactured by Shimadzu Corporation, LC-10A; MS apparatus: Applied Biosystems API 3000].

  In the present invention, such an acrylic resin can be produced by appropriately selecting and polymerizing the polymerization component [I] containing the (meth) acrylic acid alkyl ester monomer (a1). In the case of the above polymerization, there are conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization and a method of polymerizing after coating by adding a monomer or a polymerization initiator after partial polymerization using these methods. The method can be used. For example, a polymerization component [I] containing an (meth) acrylic acid alkyl ester monomer (a1) and an azo polymerization initiator are mixed or dropped in an organic solvent and polymerized under predetermined polymerization conditions. Among these polymerization methods, a solution radical polymerization, bulk polymerization, a method of polymerizing after partial polymerization after addition of a monomer or a polymerization initiator is preferred, and a method of polymerizing after solution radical polymerization or partial polymerization is more preferred. This is a method in which a polymerization initiator is added and polymerized after coating, and solution radical polymerization is most preferred.

  Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, n-propyl alcohol, and isopropyl alcohol. Examples thereof include aliphatic alcohols, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these solvents, ethyl acetate, acetone, methyl ethyl ketone, butyl acetate, toluene, and methyl isobutyl ketone are preferred from the viewpoint of ease of polymerization reaction, chain transfer effect, ease of drying during adhesive coating, and safety. More preferably, ethyl acetate, acetone, and methyl ethyl ketone are preferable.

  When the polymerization component [I] is charged, any charging method may be used, such as batch charging, multi-stage split charging, or the like. In the case of multi-stage divided preparation, it is usually sufficient to prepare in 2 to 4 stages, and preferably 3 stages. In the case of charging in three stages, 90 to 99.5% by weight of the total amount of the polymerization component [I] is charged in the first stage, and the remaining 10 to 0.1% by weight is charged in the second and subsequent stages. . Specifically, it is preferable to charge 0.01 to 5% by weight of the total amount of the functional group monomer (a2) in the polymerization component [I] in the second and subsequent stages.

  The charging method of the azo polymerization initiator may be batch charging, multi-stage split charging, or any charging method as in the case of the polymerization component [I]. In the case of division by multiple stages, it is usually sufficient to charge in 2 to 4 stages, preferably 3 stages. In the case of charging in three steps, 10 to 80% by weight of the total amount of the azo polymerization initiator may be charged in the first step and 20 to 90% by weight in the second and subsequent steps. Thus, when charging by multistage division, it is preferable to use those having a 10-hour half-life temperature of 100 ° C. or less as the azo polymerization initiators in the second and subsequent stages.

  As the method for adding the azo polymerization initiator, for example, the first stage polymerization initiator may be added before the addition of the polymerization component [I], or the polymerization component [I] It may be added after completion of the addition, or, at the same time as the dropping of the polymerization component [I], it is dissolved in the polymerization component [I], or a polymerization initiator is separately dissolved in a solvent and added simultaneously with the polymerization component [I]. May be.

  The polymerization temperature in the polymerization reaction is usually 50 to 95 ° C, preferably 65 to 90 ° C. In addition, the polymerization time in the polymerization reaction (that is, the time until the start of driving after-mentioned heating) is not particularly limited, but is 2 hours or more, preferably 3 hours or more from the last addition of the azo polymerization initiator, more preferably 4 hours or more, particularly preferably 5 hours or more.

  In the method for producing an acrylic resin of the present invention, the heating operation after the polymerization initiator-containing concentration in the reaction solution is 300 ppm or less (at a temperature higher than the 10-hour half-life temperature of the polymerization initiator). (Heating operation) is defined as “forced heating” for thermally decomposing the polymerization initiator.

The start-up heating as the heating operation is specifically performed in a state where the concentration of the initiator in the reaction solution is 300 ppm or less as a calculated value, and the reaction rate of the polymerization component [I] is 80. It is preferable to perform driving-up heating in a state of at least%. The reaction rate of the polymerization component [I] is particularly preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more. The upper limit of the reaction rate is usually 100%. In addition, the reaction rate of superposition | polymerization component [I] can be measured and confirmed as follows, for example.
The reaction rate of the polymerization component [I], that is, the reaction rate (%) of the acrylic resin was precisely weighed on a 1 g sample of the resin whose reaction rate is to be confirmed on an aluminum foil, and a ket (infrared dryer, The solid content during the reaction was calculated from the remaining amount after heating for 45 minutes at 185 W, height 5 cm), and the reaction rate was calculated from the monomer content (solid content assuming that all the monomers had reacted) by the following formula. Can be calculated.
Reaction rate (%) = [(solid content during reaction) / (monomer content)] × 100

  And, as described above, the driving-in heating temperature must be higher than the 10-hour half-life temperature of the azo polymerization initiator. For example, a temperature that is 10 ° C. or more higher than the 10-hour half-life temperature of the azo polymerization initiator is particularly preferred, and a temperature that is 15 ° C. or more is more preferred. The higher the heating temperature, the higher the temperature. However, since it cannot be heated above the boiling point of the reaction solution at normal pressure, it is usually at most about 100 ° C. Therefore, specifically, the driving-in heating temperature is usually 50 to 95 ° C, preferably 65 to 90 ° C, and particularly preferably 70 to 90 ° C. That is, it is preferable to set so that the final residual polymerization initiator amount (concentration) calculated from the reaction temperature, reaction time, and blended polymerization initiator amount is smaller.

  The time required for the follow-up heating (that is, the time from when the polymerization initiator concentration in the reaction solution becomes 300 ppm or less as a calculated value to the end of the reaction) needs to be 2 hours or more. Preferably it is 3 hours or more, particularly preferably 4 hours or more, more preferably 5 hours or more, and there is usually no upper limit, but economically it is within 48 hours. That is, it is preferable to set so that the final residual polymerization initiator amount (concentration) calculated from the reaction temperature, reaction time, and blended polymerization initiator amount is smaller.

  In the acrylic resin obtained by the production method of the present invention using the polymerization component [I], a glass transition of the acrylic resin is particularly preferable in order to obtain a pressure-sensitive adhesive having a high adhesive strength and preferable for use in fixing applications. The temperature (Tg) is preferably −40 ° C. or higher. The upper limit is particularly preferably −35 ° C. or more, and the upper limit is preferably 40 ° C. or less, particularly preferably 10 ° C. or less, more preferably 0 ° C. or less, and particularly preferably −10 ° C. or less. If the glass transition temperature (Tg) is too low, the adhesive strength tends to decrease, and if it is too high, the pressure-sensitive adhesive sheet tends not to fit the adherend and tends to float. Therefore, in order to set to the glass transition temperature (Tg), it is preferable to use the above-mentioned combination of the polymerization components [I] [hard monomer (X)].

  On the other hand, in the acrylic resin obtained by using the polymerization component [I], in order to obtain a pressure-sensitive adhesive having a particularly low adhesive strength and a small increase in the adhesive strength after heat resistance and preferable for use in surface protection, an acrylic resin is used. The glass transition temperature (Tg) of the resin is preferably −30 ° C. or lower. Particularly preferred is −35 ° C. or lower, more preferred is −40 ° C. or lower, particularly preferred is −45 ° C., particularly preferred is −50 ° C. or lower. The lower limit is usually −100 ° C. If the glass transition temperature (Tg) is too high, the adhesive strength becomes too high and the adherend is damaged, and the increase in the adhesive strength after the heat-resistant treatment also increases, which increases the risk of damage to the adherend. There is.

Ｔg ：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）
Ｔgb：モノマーＢのホモポリマーのガラス転移温度（Ｋ）
Ｔgn：モノマーＮ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
Ｗb ：モノマーＢの重量分率
Ｗn ：モノマーＮの重量分率
（ただし、Ｗa＋Ｗb＋・・・＋Ｗn＝１である。） The glass transition temperature (Tg) of the acrylic resin is calculated from the following Fox equation.

Tg: Glass transition temperature of polymer (K)
Tga: Glass transition temperature (K) of homopolymer of monomer A
Tgb: Glass transition temperature of monomer B homopolymer (K)
Tgn: Glass transition temperature of monomer N homopolymer (K)
Wa: weight fraction of monomer A Wb: weight fraction of monomer B Wn: weight fraction of monomer N (Wa + Wb +... + Wn = 1)

  The weight average molecular weight of the acrylic resin is preferably 100,000 to 2,500,000, particularly preferably 200,000 to 2,000,000, and more preferably 300,000 to 1,000,000. If the weight average molecular weight is too small, the heat resistance tends to decrease and the adherend contamination resistance tends to decrease. If it is too large, a large amount of diluent solvent is required, which tends to be undesirable in terms of coating properties and cost. .

  The degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin is preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, and particularly preferably 7 or less. When the degree of dispersion is too high, the heat resistance of the pressure-sensitive adhesive layer is lowered, and foaming or the like tends to occur. The lower limit of the dispersity is usually 1.1 for manufacturing reasons.

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 polymer, filler particles The number average molecular weight is also measured by the same method. The degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.

  The viscosity (mPa · s (25 ° C.)) of the acrylic resin is preferably 10 to 500,000 mPa · s (25 ° C.), particularly preferably 100 to 100,000 mPa · s (25 ° C.) at 25 ° C. is there. If the viscosity is too low, the pressure-sensitive adhesive composition tends to sag or repel from the substrate during coating, making coating difficult.If the viscosity is too high, the viscosity increases when blending with the crosslinking agent. Work tends to be difficult. In addition, when the coating becomes difficult due to the thickening of the pressure-sensitive adhesive composition, it may be diluted as necessary to reduce the solid content concentration. The viscosity can be measured according to the 4.5.3 rotational viscometer method of JIS K5400 (1990).

<Adhesive composition>
Pressure-sensitive adhesive composition containing an acrylic resin of the present invention as an essential component (hereinafter sometimes referred to as "pressure-sensitive adhesive composition of the present invention"), by cross-linking the this, for example, pressure-sensitive adhesive for heat-adhesive film Become an agent. In cross-linking the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition further contains a cross-linking agent.

  Examples of the crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, melamine crosslinking agents, aldehyde crosslinking agents, and amine crosslinking agents. Among these, an isocyanate-based crosslinking agent is preferably used in terms of improving the adhesion of the heat-resistant adhesive film to the base material and the reactivity with the base polymer.

  Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and hexamethylene. Diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and polyisocyanate compounds thereof And adducts of polyol compounds such as trimethylolpropane, and burettes and isocyanurates of these polyisocyanate compounds. Among these, in terms of heat resistance, isocyanurate of hexamethylene diisocyanate, buret of hexamethylene diisocyanate, 2,4-tolylene diisocyanate and / or adduct of 2,6-tolylene diisocyanate and trimethylolpropane, 2 , 4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate isocyanurate, tetramethylxylylene diisocyanate and trimethylol propane adduct, most preferably hexamethylene diisocyanate isocyanurate and burette Is preferred.

  Examples of the epoxy crosslinking agent 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) cyclohexane, N , N, N ′, N′-tetraglycidyl-m-xylenediamine and the like.

  Examples of the aziridine-based crosslinking agent include tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N, N′-diphenylmethane-4,4. Examples include '-bis (1-aziridinecarboxamide), N, N'-hexamethylene-1,6-bis (1-aziridinecarboxyamide), and the like.

  Examples of the oxazoline-based crosslinking agent include 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, and 1,4-bis (2-oxazoline-2-). Yl) butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) Bisoxazoline compounds containing aliphatic or aromatic such as benzene, 1,3-bis (2-oxazolin-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl- - one or more polymers such as addition polymerizable oxazoline oxazoline and the like.

  Examples of the melamine crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, melamine resin and the like. .

  Examples of the aldehyde-based crosslinking agent include glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.

  Examples of the amine-based crosslinking agent include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, polyamide, and the like.

  The above crosslinking agents may be used alone or in combination of two or more.

  The content of the crosslinking agent is usually preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 2 to 20 parts by weight with respect to 100 parts by weight of the acrylic resin. Particularly preferred is 5 to 15 parts by weight. If the amount of the cross-linking agent is too small, the cohesive force of the pressure-sensitive adhesive tends to decrease and cause adhesive residue. If the amount is too large, the pressure-sensitive adhesive is excessively cross-linked and the pressure-sensitive adhesive strength decreases. There is a tendency to float between the surface.

  In addition, the crosslinking reaction of an adhesive composition can also be performed by irradiating an active energy ray. As the active energy rays, for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price. In this case, it is preferable to blend a polyfunctional (meth) acrylate. Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate and ethylene oxide-modified trimethylolpropane tri (meth) acrylate. Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, and the like. In addition, it is preferable to use together the bridge | crosslinking by active energy ray irradiation with the bridge | crosslinking by a crosslinking agent.

  The pressure-sensitive adhesive composition of the present invention further includes an antioxidant, a plasticizer, a filler, an antistatic agent, 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, other additives 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. In addition to these 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.

  As said antioxidant, the antioxidant similar to the above-mentioned suitably used in the said polymerization reaction is used. Moreover, the compounding quantity of antioxidant is also set similarly to the above-mentioned.

  The pressure-sensitive adhesive composition of the present invention is mainly composed of an acrylic resin. Here, “main component” means that the acrylic resin is usually contained in an amount of 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more based on the total amount of the pressure-sensitive adhesive composition. means. The upper limit is usually 99.9% by weight.

  Moreover, it is preferable that the adhesive composition of this invention does not contain an acid substantially, and can reduce corrosion of adherends, such as a metal, by this. Here, “substantially free of acid” specifically means that the acid value is preferably 5 mgKOH / g or less, particularly preferably 1 mgKOH / g or less, more preferably 0.1 mgKOH / g or less. means.

  The gel fraction of the pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition of the present invention is usually 40 to 100%, preferably 60 to 100%, particularly preferably 80 to 100%, more preferably 90 to 100%, Particularly preferred is 97 to 100%, and most preferred is 98 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.

  In addition, in adjusting the gel fraction of an adhesive to the said range, it is achieved by adjusting the kind and quantity of a crosslinking agent, adjusting the composition ratio of the hydroxyl group in a composition, etc., for example. Moreover, since the gel fraction changes with each interaction, the ratio between the crosslinking agent and the functional group amount needs to be balanced.

  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 calculated by subtracting.

  The adhesive strength of the pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition of the present invention is preferably 0.01 N / 25 mm or more, particularly preferably 0.05 N when the adhesive strength is particularly high and preferable for use in fixing applications. / 25 mm or more, more preferably 0.5 N / 25 mm or more, and particularly preferably 0.8 N / 25 mm or more. Particularly, the adhesive strength is low, the increase in adhesive strength after heat resistance is small, and the adhesive strength of the pressure-sensitive adhesive preferable for use in surface protection is preferably 5.0 N / 25 mm or less, particularly preferably 1.00 N / 25 mm or less, More preferably, it is 0.50 N / 25 mm or less, Most preferably, it is 0.20 N / 25 mm or less. Furthermore, the adhesive strength after heat resistance is preferably 20.0 N / 25 mm or less, particularly preferably 10.00 N / 25 mm or less, more preferably 5.00 N / 25 mm or less, and particularly preferably 2.00 N / 25 mm or less. In addition, the said adhesive force is 180 degree peel strength (N / 25mm) obtained according to the test method of [Adhesive strength] in the below-mentioned Example.

In the present invention, by laminating forming an adhesive layer in which the adhesive composition is cross-linked on the film as the substrate, it is possible to obtain the anti-heat adhesive film.
Examples of the base material on which the pressure-sensitive adhesive layer is laminated include, but are not limited to, single layer or laminated film made of metal, polyester resin, polyfluorinated ethylene resin, polyimide and derivatives thereof, and epoxy resin. From the viewpoint of convenience in actual use, a polyimide film and a polyester film are more preferable. Specific examples include aromatic polyimide films such as DuPont's trade name “Kapton” and polyethylene naphthalate films such as “Teonex”. The heat-resistant adhesive film is preferably provided with a release film on the surface of the pressure-sensitive adhesive layer opposite to the base material. When the 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.

  In producing the heat-resistant adhesive film, the method for crosslinking the pressure-sensitive adhesive composition of the present invention is as follows: [1] A pressure-sensitive adhesive composition for heat-resistant adhesive film is applied on a substrate, dried, and then a release film is used. A method of pasting and performing an aging treatment, [2] A method of applying a pressure-sensitive adhesive composition for a heat-resistant pressure-sensitive adhesive film on a release film, drying, 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 a pressure-sensitive adhesive film usually imparted with heat resistance usually requires aging at a high temperature for a long time, but in the present invention, the use of a nitrogen atom-containing monomer makes it possible to achieve a lower temperature and a shorter temperature. The aging process can be completed in 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 less than 30 days, preferably less than 14 days, particularly preferably less than 7 days. Specifically, it can be carried out, for example, at 23 ° C. for 3 to 10 days, at 40 ° C. for 1 to 7 days, etc. .

  In applying the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition is preferably diluted with a solvent and applied, and the dilution concentration is preferably 5 to 60% by weight, particularly preferably 10 to 30% by weight. %. In addition, the solvent is not particularly limited as long as it dissolves the pressure-sensitive adhesive composition for heat-resistant adhesive film, for example, ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, ethyl acetoacetate, A ketone solvent such as acetone, methyl ethyl ketone and 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 heat-resistant adhesive film is preferably 3 to 300 μm, more preferably 5 to 100 μm, particularly preferably 7 to 50 μm, and further 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 heat-resistant adhesive film tends to be too thick and the usability tends to deteriorate.

The heat-resistant adhesive film obtained by using the pressure-sensitive adhesive composition of the present invention (hereinafter sometimes referred to as “heat-resistant adhesive film of the present invention”) is, for example, a temporary surface of a circuit board such as a semiconductor or an FPC board, or an electronic component. As a heat-resistant adhesive film for temporary surface protection (masking) to protect, or as a heat-resistant adhesive film for temporary fixation or a heat-resistant adhesive film for laminating to temporarily fix or reinforce products during the manufacturing process Can be used. Furthermore, it can be used as a heat-resistant adhesive film for temporary surface protection (masking), a heat-resistant adhesive film for temporary fixing, or a film for laminating even for surface protection or temporary fixing in the production process of optical products. Moreover, it is used for the use used at the process which heats another adhesive sheet and a to-be-adhered body.

  Examples of the adherend to which the heat-resistant adhesive film of the present invention is attached include base materials made of the following materials.

Metal plates or metal foils such as aluminum, copper, iron, stainless steel, magnesium, nickel, titanium;
Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, ester acrylate;
Polyethylene, chlorinated polyethylene, chlorosulfonated polyethylene, ethylene propylene rubber, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid Polyolefin resins such as acid copolymers, ionomers, polypropylene, polyallomer polybutylene, polymethylpentene;
Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer;
Polystyrene, polyalphamethyl styrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylate copolymer;
Acrylics such as polyalkyl (meth) acrylates such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate, methyl methacrylate-styrene copolymers, and methyl methacrylate-α-methylstyrene copolymers resin;
Polyvinyl chloride, plasticized polyvinyl chloride, ABS-modified polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinyl chloride-acrylic resin alloy, vinyl chloride-propylene copolymer, vinyl chloride-vinyl acetate copolymer, polychlorinated Polyvinyl chloride polymers such as vinylidene and derivatives thereof;
Polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, polyvinyl acetate such as vinylon, and derivatives thereof;
Polyvinyl methyl ether, polyvinyl methyl ketone;
Polyethers such as polyformaldehyde, acetal copolymer, polyethylene oxide, polypropylene oxide, chlorinated polyether, phenoxy resin, polyphenylene oxide;
Fluorinated resins such as polyterolafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, chlorotrifluoroethylene-vinylidene fluoride copolymer;
Polycarbonate, polycarbonate ABS alloy;
Nylons (polyamides) such as nylon, nylon-6, nylon-6,6, nylon-6 / 6,6 copolymer, nylon-6,10, nylon-6,12, nylon-11, nylon-12;
Butadiene-styrene copolymer, butadiene plastic;
Polyimide and its derivatives, polysulfone, polyphenylene sulfide, high acrylonitrile copolymer;
Silicon resins, semi-inorganic and inorganic polymers;
Phenolic resins such as phenolic resins, phenol-furfural resins, modified phenolic resins and their derivatives;
Formalin resins such as furan resin, xylene resin, aniline resin, acetone formaldehyde resin;
Unsaturated polyester and alkyd resin;
Epoxy resins such as bisphenol type epoxy resin, epoxy resin composite material, alicyclic epoxy resin, epoxy novolac, biphenyl type epoxy resin, epoxy acrylate;
Polyurethanes such as polyurethane, urethane foam, urethane acrylate;
Allyl resins such as diallyl phthalate resin, triallyl cyanurate resin, polyallyl sulfone, allyl diglycol carbonate, polyallyl ether, polyarylate;
Cellulosic resins such as cellulose plastic, cellulose acetate, cellulose propionate, cellulose acetate butyrate, ethyl cellulose, nitrocellulose and celluloid.

  In particular, heat-resistant materials include aluminum, copper, iron, stainless steel, magnesium, nickel, titanium and other metal plates or metal foils; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer Polyester resins such as ester acrylates; polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymers; polyimides and derivatives thereof; bisphenol-type epoxy resins, Examples thereof include epoxy resin composite materials, alicyclic epoxy resins, epoxy novolacs, biphenyl type epoxy resins, and epoxy resins such as epoxy acrylate.

  Applications of the heat-resistant adhesive film obtained by using the adhesive composition of the present invention include a carrier film for a process such as a printed circuit board, particularly a flexible printed circuit board; for curling, wrinkling and contamination of a film or foil having a heating process. Protective film for printed circuit boards; protective film for solder plating of printed circuit boards; insulating and heat protective film for heat-resistant transformers; masking film during solder reflow process for electronic circuit boards; various temporary fixing and protective films for parts; It can be used widely for masking applications requiring heat resistance and temporary fixing applications in general.

The usage method of the heat-resistant adhesive film for masking among the heat-resistant adhesive films of this invention is demonstrated. First, paste resistant adhesive film for Masking on the surface of the adherend. Examples of the attaching means include a rubber roller. Next, the adherend to which the heat-resistant adhesive film is attached is subjected to a heating step of 170 ° C. or higher, preferably 175 ° C. or higher, particularly preferably 180 ° C. or higher. After the heating step is completed, the heat-resistant masking pressure-sensitive adhesive film is peeled off from the adherend surface.

  When the heat-resistant adhesive film of the present invention is used for masking, it is difficult to cause contamination when peeled off from an adherend after use at a high temperature, and the adhesive performance is sufficiently high. It is effective for protection.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “parts” and “%” mean weight standards.

[Example 1]
<Manufacture of acrylic resin (A-1)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 80 parts of ethyl acetate was charged, the temperature was increased while stirring, and when the temperature reached 78 ° C., butyl acrylate (BA: a1) 91 .85 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 7 parts, dimethylaminoethyl acrylate (DMAEA: a3) 0.15 parts and 2,2-azobisisobutyronitrile (AIBN) 0.06 parts The dripping of the mixture in which the mixture was dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 6.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.06 part of AIBN in 6.0 parts of ethyl acetate was added. Further, a solution in which 0.1 part of pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was dissolved in 10.0 parts of ethyl acetate 7 hours after the start of the reaction was added. The reaction was continued for another 3 hours.

  After 10 hours from the start of the reaction, the mixture was diluted with ethyl acetate so that the solid content became 40% to obtain a 40% solution of acrylic resin (A-1). The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 81 ° C. Further, the time required for the driving-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 98.4%.

[Example 2]
<Manufacture of acrylic resin (A-2)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 80 parts of ethyl acetate was charged, the temperature was increased while stirring, and when the temperature reached 78 ° C., butyl acrylate (BA: a1) 91 .85 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 7 parts, dimethylaminoethyl acrylate (DMAEA: a3) 0.15 parts and 2,2-azobisisobutyronitrile (AIBN) 0.06 parts The dripping of the mixture in which the mixture was dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 6.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.06 part of AIBN in 6.0 parts of ethyl acetate was added.

  Furthermore, 10 hours after the start of the reaction, the mixture was diluted with ethyl acetate so that the solid content became 40%, and a 40% solution of acrylic resin (A-2) was obtained. The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 81 ° C. Further, the time required for the driving-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 98.4%.

[Example 3]
<Manufacture of acrylic resin (A-3)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 100 parts of ethyl acetate was charged, the temperature was increased while stirring, and when the temperature reached 78 ° C, butyl acrylate (BA: a1) 41 .85 parts, methyl acrylate (MA: a1) 50 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 7 parts, dimethylaminoethyl acrylate (DMAEA: a3) 0.15 parts and 2,2-azobisiso The dropping of a mixture in which 0.06 part of butyronitrile (AIBN) was mixed and dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 6.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.06 part of AIBN in 6.0 parts of ethyl acetate was added.

  Further, 10 hours after the start of the reaction, the mixture was diluted with ethyl acetate so that the solid content was 40%, to obtain a 40% solution of acrylic resin (A-3). The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 80 ° C. The time required for the drive-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 99.3%.

[Example 4]
<Manufacture of acrylic resin (A-4)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 60 parts of ethyl acetate was charged, and the temperature was raised while stirring. When the temperature reached 78 ° C., butyl acrylate (BA: a1) 35 Parts, methyl acrylate (MA: a1) 54.50 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 9 parts, dimethylaminoethyl acrylate (DMAEA: a3) 0.5 parts and 2,2-azobisiso The dropping of a mixture in which 0.3 part of butyronitrile (AIBN) was mixed and dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 8.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.04 part of AIBN in 8.0 parts of ethyl acetate was added. Further, a solution in which 0.1 part of pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was dissolved in 10.0 parts of ethyl acetate 7 hours after the start of the reaction was added. The reaction was continued for another 2 hours.

  Furthermore, 10 hours after the start of the reaction, the mixture was diluted with ethyl acetate so that the solid content became 40%, and a 40% solution of acrylic resin (A-4) was obtained. The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 82 ° C. The time required for the drive-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 99.6%.

[Example 5]
<Manufacture of acrylic resin (A-5)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 80 parts of ethyl acetate was charged, the temperature was increased while stirring, and when the temperature reached 78 ° C, butyl acrylate (BA: a1) 87 85 parts, 11 parts 2-hydroxyethyl acrylate (2-HEA: a2), 0.15 parts dimethylaminopropylacrylamide (DMAPAA: a3) and 0.06 parts 2,2-azobisisobutyronitrile (AIBN) The dripping of the mixture in which the mixture was dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 6.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.06 part of AIBN in 6.0 parts of ethyl acetate was added. Further, a solution in which 0.1 part of pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was dissolved in 10.0 parts of ethyl acetate 7 hours after the start of the reaction was added. The reaction was continued for another 3 hours.

  Furthermore, it diluted so that solid content might become 40% with ethyl acetate 10 hours after the reaction start, and the 40% solution of acrylic resin (A-5) was obtained. The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 80 ° C. Further, the time required for the driving-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 98.6%.

[Example 6]
<Manufacture of acrylic resin (A-6)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 80 parts of ethyl acetate was charged, the temperature was increased while stirring, and when the temperature reached 78 ° C., butyl acrylate (BA: a1) 91 .85 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 7 parts, dimethylaminopropylacrylamide (DMAPAA: a3) 0.15 parts and 2,2-azobisisobutyronitrile (AIBN) 0.06 parts The dripping of the mixture in which the mixture was dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 6.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.06 part of AIBN in 6.0 parts of ethyl acetate was added. Further, a solution in which 0.1 part of pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was dissolved in 10.0 parts of ethyl acetate 7 hours after the start of the reaction was added. The reaction was continued for another 3 hours.

  Further, 10 hours after the start of the reaction, the mixture was diluted with ethyl acetate so that the solid content became 40%, to obtain a 40% solution of acrylic resin (A-6). The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 81 ° C. Further, the time required for the driving-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 98.7%.

[Example 7]
<Manufacture of acrylic resin (A-7)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 70 parts of ethyl acetate was charged, and the temperature was raised while stirring. When the temperature reached 78 ° C., butyl acrylate (BA: a1) Parts, methyl acrylate (MA: a1) 54.80 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 9 parts, dimethylaminoethyl acrylate (DMAEA: a3) 0.2 parts and 2,2-azobisiso The dropping of a mixture in which 0.3 part of butyronitrile (AIBN) was mixed and dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 8.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.04 part of AIBN in 8.0 parts of ethyl acetate was added. Further, a solution in which 0.1 part of pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was dissolved in 10.0 parts of ethyl acetate 7 hours after the start of the reaction was added. The reaction was continued for another 2 hours.

  Further, 10 hours after the start of the reaction, the mixture was diluted with ethyl acetate so that the solid content became 40%, and a 40% solution of acrylic resin (A-7) was obtained. The time from the last addition of the polymerization initiator to the end of the reaction was 5 hours, and the reaction temperature was 80 ° C. The time required for the drive-in heating was 3 hours. And the reaction rate of the polymerization component at the time of start-up heating was 99.6%.

[Comparative Example 1]
<Manufacture of acrylic resin (A'-1)>
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 80 parts of ethyl acetate was charged, the temperature was increased while stirring, and when the temperature reached 78 ° C., butyl acrylate (BA: a1) 91 .85 parts, 2-hydroxyethyl acrylate (2-HEA: a2) 7 parts, dimethylaminoethyl acrylate (DMAEA: a3) 0.15 parts and 2,2-azobisisobutyronitrile (AIBN) 0.06 parts The dripping of the mixture in which the mixture was dissolved was started. This dripping start is taken as the reaction start time. This mixture was added dropwise over 2 hours. Three hours after the start of the reaction, a solution prepared by dissolving 0.8 part of 4-hydroxybutyl acrylate (4HBA: a2) and 0.05 part of AIBN in 6.0 parts of ethyl acetate was added. A solution prepared by dissolving 0.2 part of butyl acrylate (4HBA: a2) and 0.06 part of AIBN in 6.0 parts of ethyl acetate was added.

  Furthermore, it diluted so that solid content might become 40% with ethyl acetate 7 hours after the reaction start, and the 40% solution of acrylic resin (A'-1) was obtained. The time from the last addition of the polymerization initiator to the end of the reaction was 2 hours, and the reaction temperature was 81 ° C.

  Composition (polymerization component) of acrylic resin (A-1 to 7, A′-1) obtained in Examples 1 to 7 and Comparative Example 1, and acrylic resin content after heating (heating residue) Table 1 below shows the viscosity of the resulting acrylic resin, the total reaction time, the time required for the follow-up reaction, and the polymerization initiator used during the follow-up reaction. Further, the weight average molecular weight (Mw), dispersity (Mw / Mn), and glass transition temperature of the obtained acrylic resins (A-1 to 7, A′-1) were measured and calculated according to the above-described methods, The results are shown in Table 2 below.

  Production conditions of acrylic resin using polymerization component [I] in Examples 1 to 7 and Comparative Example 1 [Remaining amounts of polymerization initiators at each time, each temperature, after 5 hours, after 7 hours and at the end of reaction time] (Concentration) and follow-up heating time] are also shown in Table 3 below.

  As shown in Table 3 above, in Examples 1 to 7, at 7 hours from the start of the reaction, the amount (concentration) of the residual polymerization initiator was calculated to be 300 ppm or less, and an additional 3 hours were taken from that point. Then, a heating reaction was performed. For this reason, the amount of residual polymerization initiator at the end of the reaction of the acrylic resin was calculated to be 7 to 22 ppm.

  On the other hand, in Comparative Example 1, no rush heating was performed, and an acrylic resin was produced by a normal polymerization reaction, and the final amount of residual polymerization initiator at the end (calculated value) was as high as 150 ppm. It was.

The amount of residual polymerization initiator at the end (calculated value) (ppm) described in Table 3 above is the amount of residual polymerization initiator (parts by weight) calculated based on the following formulas (1) to (3) ) And according to the following calculation formula (4).

  The A value, B value, and D value in the calculation formulas (1) to (3) are shown in Table 4 below.

The calculation method of the A value, B value, and D value is shown below. That is, as shown below, the coefficient of the power approximation equation is calculated from the logarithm of the temperature of the polymerization initiator and the half-life temperature using the least square method. The relationship between temperature (H) and half-life time (T) when AIBN is used as the polymerization initiator is shown in Table 5 below.
Since the half-life time T = A × 10 ^B × (reaction temperature H) ^D , log (T) = log (A × 10 ^B ) + Dlog (H)

The amount of the polymerization initiator can be measured not only according to the above calculated value but also actually according to the following.
-Sample preparation The acrylic resin solution was dissolved in acetone and then reprecipitated with acetonitrile, and the supernatant was used for measurement by LC-MS / MS.
LC-MS / MS measurement conditions LC device: manufactured by Shimadzu Corporation, LC-10A
MS device: Applied Biosystems API 3000
Column: Inertsil ODS-3 (GL Science, 2.1 × 100 mm, 3 μm)
40 ℃
Eluent: 5 mM ammonium formate aqueous solution / acetonitrile = 60/40 (0 min) → 0/100 (5 min) → 0/100 (6 min), 0.2 mL / min
Injection volume: 3 μL
Detection: ESI (+), MRM m / z 182 (M + NH4) / 86, Dwell = 0.5 seconds DP, CE, CAD = 15, 8, 3

  In the present invention, the residual amount of the polymerization initiator is measured using LC-MS / MS, which is a kind of LC-MS. This is because the radical polymerization initiator is an unstable substance and is heated. This is because GC-MS or the like is detected with a value smaller than the actual residual amount of the polymerization initiator and cannot be measured accurately. Therefore, it is necessary to measure by LC-MS in order to evaluate the actual amount of polymerization initiator remaining. Furthermore, it is more preferable to measure by LC-MS / MS with particularly good measurement sensitivity.

  When the residual amount of polymerization initiator (end initiator amount at the end) of Example 2 and Comparative Example 1 in Table 3 is measured, it is found that there is a correlation with the theoretical value (calculated value). In other words, it can be seen that the calculation based on this half-life is effective and well represents the actual remaining amount of the polymerization initiator.

[Examples 8 to 20, Comparative Examples 2 to 3]
<Production of heat-resistant adhesive film>
In each acrylic resin solution obtained as described above, a crosslinking agent (isocyanurate of hexamethylene diisocyanate: Nippon Polyurethane, Coronate HX, hexamethylene diisocyanate burette in the amount shown in Table 6 below. : Asahi Kasei Chemicals, Duranate 24A-100) and antioxidant pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF Japan, Irganox) 1010) (Examples 10, 12, 16 and Comparative Example 2), and further diluted with ethyl acetate to a solid content concentration of 33.3% so that the thickness after drying is about 25 μm. And polyimide film as a base material (manufactured by Toray DuPont, Kapton: thickness 25 μm) It was applied and dried at 100 ° C. for 2 minutes. Thereafter, a polyethylene terephthalate (PET) film that had been subjected to a release treatment was adhered to the coated surface for protection, and the film was cured under an atmosphere at a temperature of 40 ° C. for 7 days to prepare a heat-resistant adhesive film.

  For gel fraction measurement, each acrylic resin solution was applied to a release-treated PET film (thickness: 38 μm) in the same manner as described above, and a heat-resistant adhesive layer without a substrate was applied in the same manner as described above. Got.

[Confirmation of cross-linking agent reaction]
About the crosslinking reaction of the obtained heat-resistant adhesive film, the peak of the residual isocyanate group was confirmed using infrared spectroscopy. As a measuring instrument, FT-IR Nicolet 380FT-IR manufactured by Thermo Electron was used, and the number of scans was 32 times by the ATR method. And it evaluated by the presence or absence of the peak of 2200-2300 cm < ^-1 > which is an absorption peak of an isocyanate group, and the magnitude | size of a peak. As a result, no peak was confirmed in all Examples and Comparative Examples.

[Adhesive force]
A heat-resistant adhesive film with a size of 25 mm x 100 mm is stuck on a stainless steel plate (SUS304BA plate) as an adherend under an atmosphere of 23 ° C x 50% relative humidity with two reciprocations of 2 kg rubber rollers, and 23 ° C x relative humidity. After leaving in a 50% atmosphere for 30 minutes, 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min.

[Adhesive strength after heat treatment]
A heat-resistant adhesive film having a size of 25 mm x 100 mm is pressure-applied to a stainless steel plate (SUS304BA plate) as an adherend in an atmosphere of 23 ° C x 50% relative humidity with two reciprocations of 2 kg rubber rollers. (180 ° C., 200 ° C.) for 5 hours. Then, after returning to 23 degreeC and leaving still for 3 hours, 180 degree peeling strength (N / 25mm) was measured with the peeling speed of 300 mm / min.

[Adhesive residue]
A test piece having a size of 25 mm × 100 mm was prepared (cut out) using the obtained heat-resistant adhesive film, and this test piece was pressure-bonded to the adherend (SUS304BA plate) by reciprocating a 2 kg roller twice. The mixture was allowed to stand at the temperature (180 ° C., 200 ° C.) and time (5 hours) described in Table 7 and returned to 23 ° C. Furthermore, after leaving for 2 hours in an atmosphere of 23 ° C. × 50% relative humidity, the appearance of the adherend surface after 180 ° peeling was visually observed at a peeling speed of 300 mm / min, and evaluated according to the following criteria.
○: No contamination was confirmed.
Δ: Slightly cloudy but no contamination was observed.
X: Contamination was confirmed.

[Gel fraction]
The gel fraction was computed about the obtained heat-resistant adhesive layer. That is, a heat-resistant pressure-sensitive adhesive layer to be a test piece is wrapped with a 200-mesh SUS wire mesh, immersed in toluene at 23 ° C. for 24 hours, and the weight percentage of the insoluble pressure-sensitive adhesive component remaining in the wire mesh is defined as the gel fraction. did.
These results are shown in Table 7 below.

  Furthermore, using the heat resistant adhesive films of Examples 12 to 16, 19, and 20, the adhesive strength and adhesive residue after heat resistance treatment at 250 ° C. were measured and evaluated according to the following methods. The results are shown in Table 8 below.

[Adhesive strength after heat treatment]
A stainless steel plate (SUS304BA plate) as an adherend was bonded with a heat-resistant adhesive film of size 25 mm x 100 mm in an atmosphere of 23 ° C x 50% relative humidity by two reciprocations of 2 kg rubber rollers, and 5 ° C at 250 ° C. Left for hours. Then, after returning to 23 degreeC and leaving still for 3 hours, 180 degree peeling strength (N / 25mm) was measured with the peeling speed of 300 mm / min.

[Adhesive residue]
A test piece having a size of 25 mm × 100 mm was prepared (cut out) using the obtained heat-resistant adhesive film, and this test piece was pressure-bonded to the adherend (SUS304BA plate) by reciprocating a 2 kg roller twice. After leaving at 5 ° C. for 5 hours, the temperature was returned to 23 ° C. Furthermore, after leaving for 2 hours in an atmosphere of 23 ° C. × 50% relative humidity, the appearance of the adherend surface after 180 ° peeling was visually observed at a peeling speed of 300 mm / min, and evaluated according to the following criteria.
○: No contamination was confirmed.
Δ: Slightly cloudy but no contamination was observed.
X: Contamination was confirmed.

  From the above results, Examples 8 to 20 using an acrylic resin with a small amount of remaining polymerization initiator were after heat treatment at 180 ° C. × 5 hours and 200 ° C. × 5 hours (in addition to Examples 12 to Nos. 16, 19 and 20 are clearly suitable for use in the heat-resistant process since there is no adhesive residue even after heat-resistant treatment at 250 ° C. for 5 hours. In contrast, Comparative Examples 2 to 3 using an acrylic resin having a large residual amount of the polymerization initiator are not suitable for use in the heat-resistant process because contamination due to adhesive residue was confirmed. . In addition, about Examples 12-14, 19, and 20, adhesive force is 0.8 N / 25mm or more even after 0.5 hours of sticking, and has high adhesive force, and it can be said that it is preferable for a fixing use. In addition, Examples 8 to 11 and 15 to 18 have a low adhesive force of less than 2.0 N / 25 mm even after heating at 200 ° C. for 5 hours, and can be said to be preferable because they are easily peeled off for surface protection.

  Further, in the above examples, AIBN was used as the azo polymerization initiator. However, instead of this, the above-described examples were carried out using azo polymerization initiators other than AIBN, which are other azo polymerization initiators described above. An acrylic resin was prepared in the same manner as described above to prepare a heat-resistant adhesive film. As a result of performing various evaluations in the same manner as described above, good results were obtained which were almost the same as those of AIBN.

  The acrylic resin obtained by the method for producing an acrylic resin of the present invention is used for various pressure-sensitive adhesive applications. Among them, a heat-resistant pressure-sensitive adhesive film widely used for general masking applications and temporary fixing applications requiring heat resistance, in particular, a heat-resistant pressure-sensitive adhesive film for masking. It can use suitably for an adhesive layer forming material.

Claims (4)

  A method for producing an acrylic resin in which a polymerization component [I] containing a (meth) acrylic acid alkyl ester monomer as a main component is polymerized in the presence of an azo polymerization initiator, comprising: A method for producing an acrylic resin for heat-resistant adhesive film, comprising heating at a temperature higher than the 10-hour half-life temperature of the azo polymerization initiator for 2 hours or more in a state where the content concentration is 300 ppm or less. When the content of the polymerization initiator in the reaction solution is 300 ppm or less and the reaction rate of the polymerization component [I] is 80% or more, the temperature is higher than the 10-hour half-life temperature of the azo polymerization initiator. method for producing a heat-resistant adhesive film for acrylic resin according to claim 1, wherein the heating or time. The method for producing an acrylic resin for a heat-resistant adhesive film according to claim 1 or 2, wherein the azo polymerization initiator has a 10-hour half-life temperature of 100 ° C or lower. The method of manufacturing heat-resistant adhesive film for acrylic resin according to any one of claims 1 to 3, characterized in that the polymerization in the presence of an antioxidant.