JPH0645782B2 - Method for producing adhesive tape, sheet, label or foil - Google Patents

Description

The present invention relates to a method for producing an adhesive tape, sheet, label or foil. More specifically, it relates to a method for producing an adhesive tape, sheet, label or foil having particularly good silicone releasability.

[Prior Art] Conventionally, as a pressure-sensitive adhesive having good heat resistance, a silicone pressure-sensitive adhesive containing a silicone resin based on dimethylpolysiloxane gum has been known.

However, as is generally known, this silicone adhesive has strong adhesiveness to non-polar substances such as polytetrafluoroethylene, and silicone release paper coated with a so-called silicone release agent. Since they are both containing polysiloxane and have a good compatibility with each other, they have drawbacks such as difficulty in peeling and good release properties.

On the other hand, as a pressure-sensitive adhesive having good release properties, a rubber-based pressure-sensitive adhesive prepared by blending a tackifying resin with natural rubber or synthetic rubber, or an acrylic-based pressure-sensitive adhesive obtained by copolymerizing an acrylic ester, Some are composed of components that have only an organic skeleton, but it is difficult to expect heat resistance because the former is a non-crosslinking type, and the latter also has heat resistance of the crosslinked product itself even though crosslinking has been introduced by an isocyanate crosslinking agent. However, the heat resistance of the pressure-sensitive adhesive is not sufficient.

In recent years, a hydrolyzable silicon-containing group is introduced into a polymer having an organic skeleton, a thermally stable siloxane crosslink is formed by a condensation reaction of the hydrolyzable silicon-containing group, and a pressure-sensitive adhesive having good heat resistance is obtained. It is proposed that

An example of this is the pressure-sensitive adhesive composition found in JP-A-59-71377, but this siloxane-crosslinking pressure-sensitive adhesive has a polymer main chain that is essentially an organic skeleton. As with the above-mentioned silicone adhesive, there is a problem that the releasability from the silicone release paper is poor. That is, when it is attached to a release paper or release film coated with a silicone release agent, or when it is applied to a substrate coated with a silicone release agent as a backside treatment and wound up, As a result, the peeling resistance between the adhesive and the release paper or the release film is increased, and in the worst case, the release paper may be broken to make the release impossible.

As is generally known, in adhesive tapes, silicone release paper is often used as a constituent material of products, but the so-called silicone adhesive as described above has insufficient releasability from silicone release paper. Is. Further, development of a release paper coated with a non-silicone (for example, fluorine-based) release agent has been studied, but its application to this application has been hindered because of its difficulty in release.

[Problems to be Solved by the Invention] In view of the fact that the present invention does not have a pressure-sensitive adhesive composition that has excellent heat resistance and has good releasability from a release paper coated with a silicone-based release agent. It was made.

[Means for Solving Problems] The present invention provides (A) 100 parts (part by weight, the same applies hereinafter) of an organic polymer having at least one hydrolyzable silicon-containing group in the molecule, (B) a tackifying resin. 10 to 140 parts, general formula of (C) curing catalyst: (In the formula, n is 0, 1, 2, 3 or 4, l is 0, 1,
2, or 3, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Y is a hydrocarbon group having 1 to 18 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, A group selected from the group consisting of a cyanoalkoxy group and an amino group, which may be the same or different), and a composition comprising 0.01 to 20 parts of organozirconium or organoaluminum represented by Adhesive tapes, sheets, characterized by being applied to and being cured by exposure to moisture or water.
Regarding the method for producing a label or foil, by using a specific organozirconium or organoaluminum as a curing catalyst in combination with the organic polymer (A), it has excellent heat resistance, and from a release paper coated with a silicone-based release agent, etc. It was found that an adhesive tape, sheet, label or foil having good releasability can be obtained, and the present invention has been completed.

[Examples] The organic polymer (A) having at least one hydrolyzable silicon-containing group in the molecule used in the present invention means at least one hydrolyzable silicon-containing group at the end or side chain in the molecule per molecule. An organic polymer having one, and the main chain of the organic polymer includes, for example, an alkylene oxide polymer, an ether / ester block copolymer, a vinyl-based polymer, a vinyl-based copolymer, a gen-based polymer, and the like. It is exemplified by one.

Organic polymers having an alkylene oxide polymer or an ether / ester block copolymer as a main chain of the organic polymer are described in, for example, JP-B-45-36319 and 46-12154.
No. 49-32673, JP-A No. 50-156599, 51-73561
No. 54, No. 54-6096, No. 55-13768, No. 55-82123, No. 55-
123620, 55-125121, 55-131021, 55-13102
No. 2, No. 55-135135, No. 55-137129 and the like. Further, an organic polymer having a vinyl polymer or a vinyl copolymer as a main chain is disclosed in, for example, JP-B-51-28301 and JP-A-57-1.
It can be obtained by the method proposed in Japanese Patent Publication No. 79210. Further, an organic polymer having a gen-based polymer as a main chain is disclosed in, for example, JP-B-45-17553 and JP-A-
It can be obtained by the method proposed in Japanese Patent No. 47-1389.

The hydrolyzable silicon-containing group, for example, in the presence of moisture or a cross-linking agent, such as a silicon-containing group or a silanol group having a hydrolyzable group bonded to a silicon atom, by using a catalyst or the like as necessary. A group that causes a condensation reaction, typically represented by the general formula (1) (In the formula, R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a general formula: (R ′) ₃ SiO— (In the formula, R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. And may be the same or different), a triorganosiloxy group, X is a hydroxyl group or a hydrolyzable group, and when two or more are bonded,
May be the same or different, a is 0,1,2
Or 3, b is 0, 1 or 2, m is 0 or an integer of 1 to 18).

R ² in the general formula (1) is a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different when two or more are bonded to the general formula (1). Specific examples thereof include an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. Further, R ² may be a triorganosiloxy group represented by the general formula: (R ′) ₃ SiO—. Of the above-mentioned R ^2, a methyl group or a phenyl group is preferable from the viewpoint of easy availability of raw materials.

X in the general formula (1) is a hydrolyzable group in addition to the hydroxyl group, such as a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group. , Alkenyloxy groups and the like can be exemplified. Of these, an alkoxy group is preferable because it is easy to handle.

When an alkylene oxide-based polymer is used as the organic polymer (A) in the present invention, the main chain of the alkylene oxide-based polymer has essentially the following general formula: —R ¹ —O— (wherein R ¹ Is a divalent hydrocarbon group having 1 to 8 carbon atoms, most preferably most of which is a hydrocarbon group having 1 to 4 carbon atoms). Specific examples of R ¹ , which is a divalent hydrocarbon group having 1 to 8 carbon atoms, include —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ — and so on. The main chain of the alkylene oxide polymer may consist repeating units of only one kind may be made from two or more repeating units, but especially as R ¹ Is preferred. The alkylene oxide polymer preferably has a molecular weight of 500 to 30,000, more preferably 3,000 to 15,000, and particularly has a hydrolyzable silicon-containing group at the terminal of the molecule and has a molecular weight of 3,000 to 15,000. preferable.

The alkylene oxide-based polymer having a hydrolyzable silicon-containing group in the molecule has, for example, the general formula (2): (Wherein R ² , X, a, b and m are the same as above), a silicon hydride compound represented by the general formula (3): (In the formula, R ³ is a hydrogen atom, a halogen atom or a carbon number 1
~ 10 substituted or unsubstituted monovalent aliphatic hydrocarbon groups,
Z is a divalent organic group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms,
c represents an integer of 0 or 1) and an alkylene oxide polymer having an unsaturated group represented by the formula (1) can be produced by adding a platinum compound such as chloroplatinic acid as a catalyst by a hydrosilylation reaction. It is not limited to such a method.

Specific examples of the silicon hydride compound represented by the general formula (2) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, methyldimethoxy. Silane,
Alkoxysilanes such as phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; Bis (dimethylketoximate) methylsilane,
Bis (cyclohexyl ketoximate) methylsilane,
Ketoximate silanes such as bis (diethylketoximate) trimethylsiloxysilane; dimethylsilane,
Trimethylsiloxymethylsilane, 1,1-dimethyl-3,3
Examples thereof include hydrosilanes such as dimethyldisiloxane; alkenyloxysilanes such as methyldi (isopropenyloxy) silane, but are not limited thereto.

In the method of reacting an alkylene oxide polymer having an unsaturated group represented by the general formula (3) with the hydrogenated silicon compound represented by the general formula (2), after reacting them, part or all of The X group may be further converted into another hydrolyzable group or a hydroxyl group. For example, when the X group is a halogen group or a hydride group, it is preferably converted into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group or the like before use.

In the general formula (3), R ³ is a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group, and particularly hydrogen. It is preferably an atom. Z is a divalent organic group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, (In the formula, R is a divalent hydrocarbon group having 1 to 20 carbon atoms,
When two are included, they may be the same or different, and a methylene group is particularly preferable.

As a specific method for producing an alkylene oxide polymer having an unsaturated group represented by the general formula (3), the method disclosed in JP-A-54-6097, or ethylene oxide, an epoxy compound such as propylene oxide A method of introducing an unsaturated group into a side chain by adding an olefin group-containing epoxy compound such as allyl glycidyl ether and copolymerizing at the time of polymerization is exemplified.

In the present invention, instead of the alkylene oxide polymer which is the organic polymer (A), a vinyl polymer, a vinyl copolymer or a gen polymer as a main chain (A) an organic polymer May be used. Specific examples of the organic polymer having at least one hydrolyzable silicon-containing group in these molecules include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer,
Acrylic ester-butadiene copolymer, ethylene-
Butadiene copolymer, vinyl pyridine-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, polyisoprene, styrene-isoprene copolymer,
A polymer having rubber properties such as isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic acid ester, and polymethacrylic acid ester, Any polymer may be used as long as it is a polymer obtained by introducing a hydrolyzable silicon-containing group into the polymer. Particularly, 50% (% by weight, the same applies below) of acrylic acid ester or methacrylic acid ester is polymerized in the organic polymer of (A) containing acrylic acid ester or methacrylic acid ester as a main component, that is, in the organic polymer of (A). An organic polymer (A) containing a selected portion is preferable, and specifically, n-butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, ethyl acrylate, propyl acrylate, isobutyl (meth)
A straight chain having 2 to 12 carbon atoms such as acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, and n-decyl (meth) acrylate;
The organic polymer (A) produced from a polymer or copolymer mainly composed of branched (alicyclic) alcohol (meth) acrylic acid esters is preferable. If the carbon number of the alcohol is smaller or larger than this, the tackiness of the organic polymer (A) becomes poor, which is not preferable.

Above all, the organic polymer (A) containing n-butyl acrylate or 2-ethylhexyl acrylate as a main component is preferable.

As a method of introducing a hydrolyzable silicon-containing group in the molecule, a method of copolymerizing a polymerizable monomer having a hydrolyzable silicon-containing group, a method of using a polymerization initiator having a hydrolyzable silicon-containing group, A method using a chain transfer agent having a hydrolyzable silicon-containing group, a method combining these methods, or a hydrolyzable silicon-containing group after the completion of the polymerization of a monomer having no hydrolyzable silicon-containing group. Examples thereof include a method of reacting a compound which has a reactive group capable of reacting with the polymer, but is not limited to these methods.

The polymerizable monomer having a hydrolyzable silicon-containing group, However, the present invention is not limited to these. Of these, especially Is preferred.

The vinyl polymer having a hydrolyzable silicon-containing group, which is the organic polymer (A) used in the present invention, contains 50% in the polymer.
Other copolymerizable monomers may be incorporated by copolymerization in the range of less than 40%, preferably less than 40%, and more preferably less than 20%.

Specific examples of the other copolymerizable monomer include methacrylic acid, methyl methacrylate, acrylic acid, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, acrylic acid amide, styrene, hydroxyethyl acrylate, Hydroxyethyl methacrylate, N,
Examples thereof include N-dimethylaminoethyl acrylate, vinyl acrylate and allyl acrylate. These other copolymerizable monomers exemplified are preferred to be copolymerized within the above range because they have an effect of improving adhesive force and cohesive force, but when the amount of copolymerization is 50% or more, tack ( The initial adhesive strength) has a large fixed price, which is not preferable.

Examples of the polymerization initiator having the hydrolyzable silicon-containing group include: Azobis-2- (6-methyldimethoxysilyl-2-cyanohexane) Azo compounds such as azobis-2- (6-trimethoxysilyl-2-cyanohexane) and azobis-2- (6-methyldiacetoxysilyl-2-cyanohexane), Examples thereof include, but are not limited to, peroxide compounds.

Examples of the chain transfer agent having the hydrolyzable silicon-containing group include However, the present invention is not limited to these.

Polymerization of the vinyl polymer having a hydrolyzable silicon-containing group, which is the organic polymer (A) used in the present invention, can be carried out by, for example, a method using a radical initiator, a method using ultraviolet ray, X-ray, or γ-ray irradiation. It can be done in the usual way.
Specific examples of the radical initiator include benzoyl peroxide, benzoyl hydroperoxide and di-t-
Peroxides such as butyl peroxide, di-t-butyl hydroperoxide, acetyl peroxide, lauroyl peroxide, hydrogen peroxide; azo compounds such as azobisisobutyronitrile; persulfates, diisopropyl peroxide Examples thereof include peroxides such as oxydicarbonate. In addition to the radical initiator,
Polymerization may be performed using a radical polymerization initiator having a hydrolyzable silicon-containing group.

In the polymerization, a solvent may be used if necessary.
Specific examples of such a solvent include ethers, hydrocarbons, acetic acid esters and the like.

The polymerization temperature is not particularly limited, and in the case of a polymerization method or a method using a radical initiator, the optimum temperature may be set depending on the kind of the initiator to be used, and is usually 50 to 150.
It is preferable to carry out at ° C. If necessary, a chain transfer agent such as a mercaptan or a halogen-containing compound, or a chain transfer agent having a hydrolyzable silicon-containing group as described above is used to control the degree of polymerization of vinyl-based monomers. You may.

At the time of polymerization, the vinyl-based monomer and the like may be charged all at once, or may be charged separately in order to adjust the calorific value or may be charged continuously.

As the molecular weight of the vinyl polymer having a hydrolyzable silicon-containing group, those having a molecular weight of 500 to 100,000 can be used, and those having a molecular weight of 2000 to 500,000 are preferable. By the way, the molecular weight is 30
It is preferably from 00 to 15,000.

The organic polymer (A) used in the present invention may be a single polymer or a mixture of two or more polymers. For example, the alkylene oxide-based polymer may be used in combination with a vinyl-based polymer having a hydrolyzable silicon-containing group such as an acrylic acid alkyl ester-based polymer, or the alkylene oxide-based polymer may be used in combination. It may be a polymer having a hydrolyzable silicon-containing group obtained by polymerizing a vinyl monomer such as an alkyl acrylate in the presence.

In the present invention, a tackifying resin can be used for adjusting the tackiness property. The tackifying resin is not particularly limited, for example, a resin having a polar group such as a rosin ester resin, a phenol resin, a xylene resin, a xylene phenol resin, a terpene phenol resin, an aromatic resin having a relatively small polarity, or an aliphatic-aromatic resin. Various petroleum resins such as group copolymer system or alicyclic system, or coumarone resin,
Usual tackifying resins such as low molecular weight polystyrene resins and terpene resins can be used.

Specific examples of these resins include Petrosin 80 (manufactured by Mitsui Petrochemical Co., Ltd.), Neopolymer S (manufactured by Nippon Petrochemical Co., Ltd.), Tack Ace A100 (Mitsui Petrochemical Co., Ltd.).
Quinton 1500 (manufactured by Nippon Zeon Co., Ltd.), FTR6100
(Manufactured by Mitsui Petrochemical Co., Ltd.), Picolastek A75 (manufactured by Hercules Co., Ltd.), Kumaron G-90 (Nittetsu Chemical Co., Ltd.)
Resin) with a relatively small polarity such as YS Polystar-T
-115, YS Polystar-S-145 (above, Yasuhara Yushi Co., Ltd.
Examples thereof include resins having a polar group such as Steberite Ester 7 (manufactured by Hercules Co., Ltd.) and Neopolymer E-100 (manufactured by Nippon Petrochemical Co., Ltd.), but the invention is not limited thereto.

The number of copies of the tackifying resin (B) used depends on the type,
Up to 140 parts per 100 parts of the organic polymer (A), 1
If it exceeds 40 parts, it will be difficult to obtain a product with good tack characteristics.

Organozirconium or organoaluminum, which is the curing catalyst used in the present invention, is the essential point of the present invention, and by using these curing catalysts, the releasability of the pressure-sensitive adhesive composition of the present invention from silicone release paper is significantly improved. It

The organic zirconium or organic aluminum in the present invention has the general formula: Or (In the formula, n is 0, 1, 2, 3 or 4, l is 0, 1, 2 or 3, R is
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and Y is 1 to 8 carbon atoms
A hydrocarbon group, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same. Zirconium or aluminum alkoxide compounds, chelate compounds and organic acid salts represented by zirconium or aluminum represented by the formula (1) may be different from each other. It doesn't matter if it is something like this. Examples of the alkoxy group serving as Y include groups such as methoxy group, ethoxy group, propoxy group and butoxy group.

Specific examples of such compounds include (C ₂ H ₅ O) ₄
Zr, (iso-C ₃ H ₇ O) ₄ Zr, (nC ₄ H ₉ O) ₄ Zr, (C ₈ H ₁₇ O) ₄ Zr, (iso-C ₃ H ₇ O) ₃ Al, (iso-C ₃ H ₇ O) ₂ Al (sec-C ₄ H ₉ O), (sec-C ₄ H ₉ O) ₃ Al and other alkoxide compounds, Zr (acac)
₄ (zirconium tetraacetylacetonate, the same meanings below mean the same), (nC ₄ H ₉ O) ₃ Zr (acac), (nC ₄ H ₉ O) ₂ Zr (acac) ₂ , (nC ₄ H ₉ 0) Zr (acac) ₃ , (iso-C ₃ H ₇ O) ₂ Al (acac), Al (acac) ₃ , (iso-C ₃ H ₇ O) ₂ Al (ethyl acetoacetate, (iso- C ₃ H ₇ O) ₂ Al (methylacetoacetate), (iso-C ₃ H ₇ O) ₂ Al (propylacetoacetate), Al (ethylacetoacetate) ₃ , Al (methylacetoacetate) ₃ , Al (propyl Chelate compounds such as acetoacetate) ₃ and (CH ₃ CO ₂ ) ₂ ZrO (C ₇ H
₁₅ CO _{2) 2} ZrO, and organic acid salts such as _{(C 15 H 31 CO 2)} 2 ZrO , but not limited thereto. Further, these organozirconium or organoaluminum can be used even when forming an aggregate in the form of, for example, a trimer or tetramer. The above-mentioned curing catalyst may be used alone or in combination of two or more kinds.

The amount of these curing catalysts used is 0.01 to 20 parts, preferably 0.1 to 10 parts, relative to 100 parts of the organic polymer (A). If the amount used is less than 0.01 part, the catalytic effect is small, and if it exceeds 20 parts, the curing is too fast, and the workability of applying to the support becomes poor.

The curing catalyst used in the present invention has a curing activity which is not inferior to that of organic tin compounds which have been often used conventionally, and the adhesive is colored as in the case where an alkyl titanate compound is used as a catalyst. There is no problem,
It is a curing catalyst that is also excellent in terms of productivity and appearance.

In the present invention, if necessary, a plasticizer or a softening agent such as dioctyl phthalate, butyl benzyl phthalate, polypropylene glycol, chlorinated paraffin, liquid polybutadiene, etc .; calcium carbonate, clay, talc, titanium oxide, zinc white, silica, Fillers such as diatomaceous earth and barium sulfate; antioxidants, ultraviolet absorbers, pigments, surfactants and the like can be added as appropriate.

A solvent may be added for the purpose of improving workability and decreasing viscosity. For example, an aromatic hydrocarbon solvent such as toluene or xylene, an ester solvent such as ethyl acetate, butyl acetate, amyl acetate or cellosolve acetate. Examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone.

In the method of the present invention, using the adhesive composition, for example, a film made of synthetic resin or modified natural product, paper, cloth of all kinds, metal foil, metallized plastic foil, asbestos or glass fiber cloth etc. as a substrate Manufacture adhesive tapes, sheets, labels or foils. That is, a solvent-free liquid type, a solvent type, an emulsion type or a hot melt type or the like is applied to these substrates with the pressure-sensitive adhesive composition, exposed to moisture or water, and then room temperature curing or heat curing is performed, Manufacture adhesive tapes, sheets, labels or foils.

Hereinafter, the present invention will be described in more detail with reference to examples.
The test methods used in the examples are as follows.

(Peeling resistance to silicone release paper) The produced adhesive tape was adhered to a commercially available silicone release paper, taken out after adhering by the accelerated method at 50 ° C for 7 days, 14 days and 21 days, and returned to room temperature, and then a pulling speed of 300 mm / Peel 180 ° in minutes and measure the resistance at that time.

(Residual Adhesion Rate) After sticking the produced adhesive tape to a commercially available silicone release paper and leaving it at 50 ° C, measure the adhesive strength of the adhesive tape peeled off from the silicone release paper, and measure its size to the initial adhesive strength. It is shown as a relative ratio (percentage).

(Adhesive strength) The prepared adhesive tape was attached to a stainless steel plate adherend, and the temperature was 23 ° C.
After standing for 60 minutes at 23 ° C, measure 180 ° peel strength at a pulling speed of 300 mm / min.

Synthesis Example 1 Polypropylene oxide having an average molecular weight of 8,000 and having an allyl ether group at a ratio of 98% among all terminals (manufactured from polypropylene glycol as a starting material) 80
In a pressure resistant reactor equipped with a stirrer, 0 g was added with 20 g of methyldimethoxysilane, followed by a catalyst solution of chloroplatinic acid (H ₂
0.34 ml of a solution prepared by dissolving 8.9 g of PtCl ₆ .6H ₂ O in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran was added, and the mixture was reacted at 80 ° C. for 6 hours.

The amount of unreacted silane was determined by gas chromatography and infrared analysis to determine the reaction rate.
You can see that% is reacting, A polypropylene oxide terminated with groups was obtained.

Synthesis Example 2 Tetra-n-butoxyzirconium (38.3 g, 0.1M) was dissolved in toluene (88 g), and acetylacetone (10.0 g, 0.1M) was added thereto.
(M) is gradually added with stirring to generate heat, and tri-n-
Butoxyzirconium acetylacetonate was produced. Hereinafter, the obtained mixed toluene solution is referred to as Synthesis Example 2 catalyst.

Synthesis Example 3 Tetra-n-butoxyzirconium (38.3 g, 0.1M) was dissolved in 87 g of toluene, and 20.0 g (0.2
When M) was gradually added with stirring, heat was generated and di-n-butoxyzirconium bisacetylacetonate was obtained. Hereinafter, this mixed toluene solution is referred to as Synthesis Example 3 catalyst.

Synthesis Example 4 38.3 g (0.1M) of tetra-n-butoxyzirconium was dissolved in 86 g of toluene, and 30.0 g (0.3
When M) was gradually added with stirring, heat was generated and di-n-butoxyzirconium trisacetylacetonate was obtained. Hereinafter, the obtained mixed toluene solution is referred to as Synthesis Example 4 catalyst.

Synthesis Example 5 n-butyl acrylate 128 g (1.0 M), γ-methacryloxypropylmethyldimethoxysilane 3.48 g (0.015 M), γ
-Mercaptopropylmethyldimethoxysilane 2.46 g (0.
015M) and α, α′-azobisisobutyronitrile 0.2
5 g were mixed and dissolved. 30 g of this mixed solution was placed in a 300 ml four-necked flask substituted with nitrogen gas, placed in an oil bath at 70 ° C. and gradually heated with stirring. Polymerization soon started, and heat generation and thickening were observed, but the remaining mixture was gradually added dropwise from a dropping funnel over 2.5 hours while continuing stirring. After completion of the dropwise addition, the mixture was stirred for 1 hour as it was to complete the polymerization, and a colorless transparent viscous substance having a polymerization rate of 97% and a viscosity of 350 p (23 ° C.) was obtained.

Examples 1 to 10 100 parts of the polyalkylene oxide having the hydrolyzable silicon-containing group obtained in Synthesis Example 1 was mixed with 80 parts of the tackifying resin shown in Table 1 to prepare a toluene solution having a solid content concentration of 80%. did. To this solution was added the curing catalyst shown in Table 1, and the thickness
A 25 μm polyester base material (Lumirror film manufactured by Toray Industries, Inc.) was coated with a coater so that the paste thickness after drying would be 25 μm, and cured in a dryer at 120 ° C. for 1 to 10 minutes. The releasability of the obtained adhesive tape to a commercially available silicone release paper (EK-130R manufactured by Soken Kako Co., Ltd.) was measured. The results are shown in Table 1.

Note that YS Polystar T-115 in Table 1 is a terpene phenol resin manufactured by Yasuhara Yushi Kogyo Co., Ltd., YS Polystar S145.
Is a terpene phenol resin manufactured by Yasuhara Yushi Kogyo Co., Ltd., and steberite ester 7 is a hydrogenated rosin ester resin manufactured by Hercules.

Further, in Table 1, for example, Zr (acac) ₄ is zirconium tetraacetylacetonate.

Comparative Examples 1 to 3 Adhesive tapes were produced in the same manner as in Example 1 except that the organotin compound shown in Example 1 was used as the curing catalyst, and the peelability was measured. The results are also shown in Table 1.

From the results shown in Table 1, it can be seen that the pressure-sensitive adhesive tape using the composition of the present invention has superior releasability to silicone release paper as compared with the comparative example.

Examples 10 to 16 To 100 parts of the acrylic acid copolymer having a hydrolyzable silicon-containing group obtained in Synthesis Example 5, 50 parts of YS Polystar T-115 was added to prepare a toluene solution having a solid content concentration of 80%. The curing catalyst shown in Table 2 was added to this, and it was coated on a 25 μm-thick polyester base material (Lumirror film manufactured by Toray Industries, Inc.) so that the paste thickness after drying would be 25 μm. It was cured for a minute to give an adhesive tape.

The releasability of the obtained adhesive tape from silicone release paper was measured in the same manner as in Example 1. The results are second
Shown in the table.

Comparative Examples 4 to 5 Adhesive tapes were produced in the same manner as in Example 10 except that the organotin compound shown in Table 2 was used as the curing catalyst, and the peelability was measured. The results are also shown in Table 2.

From the results shown in Table 2, it can be seen that the pressure-sensitive adhesive tape produced using the composition of the present invention has a better silicon peeling property than the comparative example.

[Advantages of the Invention] The adhesive tape, sheet, label or foil produced by the present invention has a specific organozirconium or organoaluminum specific to the condensation reaction between the hydrolyzable silicon-containing groups contained in the organic polymer (A). Since it uses a curing catalyst, it has good releasability to silicone release paper or silicone release film, and is suitable for fields requiring double-sided tape, label, sheet, etc. release properties to silicone release paper or silicone release film. Available.

Claims (4)

[Claims] 1. A general formula which is (A) 100 parts by weight of an organic polymer having at least one hydrolyzable silicon-containing group in a molecule, (B) 10 to 140 parts by weight of a tackifying resin, and (C) a curing catalyst. : (In the formula, n is 0, 1, 2, 3 or 4, l is 0, 1,
2, or 3, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Y is a hydrocarbon group having 1 to 18 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, A group selected from the group consisting of a cyanoalkoxy group and an amino group, which may be the same or different) and a composition comprising 0.01 to 20 parts by weight of organozirconium or organoaluminum. Adhesive tapes, sheets, which are applied to materials and cured by exposure to moisture or water,
Label or foil manufacturing method. 2. The organic polymer of (A) essentially has the following general formula as a main chain: --R ¹ --O-- (wherein R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms). The process according to claim 1, which is an alkylene oxide polymer having a repeating unit represented by 3. The production method according to claim 1, wherein the organic polymer (A) has a hydrolyzable silicon-containing group at the terminal of the molecule and has a molecular weight of 3000 to 15000. 4. The main chain of the organic polymer (A) has 2 to 1 carbon atoms.
The production method according to claim 1, which is obtained by polymerizing an alkyl acrylate monomer consisting of alcohol and acrylic acid of 2 as a main component.