JPH081090A - Improving method of adhesion property - Google Patents

Abstract

PURPOSE:To improve adhesion property of a base body by using such a polymer as an adhesion improving material that contains a specified amt. or more of vinylcarboxylates of an alkylene oxide adduct of a cylic amine or non-cyclic amine having >=5 carbon number as the structural unit. CONSTITUTION:A polymer containing vinylcarboxylates of an alkylene oxide adduct of a cyclic amine or non-cyclic amine having >=5 carbon number by >=50wt.% as the structural unit is used as an adhesion improving material. By using this material, adhesion property of a base material can be improved without using a reaction type adhesion improving material which is unstable to temp., pH of the system or water content. Thereby, adhesion to glass, metal, plastics, paper, cloth, fiber, wood, concrete, gypsum board, brick, and ceramic can be improved. Since the material is nonreactive, the storage stability of a coating compsn. is good.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for improving adhesion of various base materials.

[0002]

2. Description of the Related Art Conventionally, an adhesion improver such as a silane coupling agent or an epoxy group-containing polymer or a coating composition containing the adhesion improver can be attached to a substrate to improve the adhesion. Are known.

[0003]

However, since the conventional adhesion improver has a highly reactive group such as a silyl group or an epoxy group, when it is contained in a paint or an adhesive, the temperature or Since it is unstable with respect to the pH and water content of the system, there has been a problem that the adhesiveness between the base material and the coating film is not sufficiently exhibited.

[0004]

[Means for Solving the Problems] The present inventors have found a method for improving the adhesion of a substrate without using a reaction type adhesion improver which is unstable with respect to temperature, pH of the system, moisture and the like. As a result of intensive studies, the present invention has been reached.

That is, the present invention provides a polymer (A) containing a vinyl carboxylic acid ester (a), which is an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms, as a structural unit in an amount of 50% by weight or more. It is a method for improving the adhesion of a substrate, which is characterized in that it is used as an adhesion improver.

The cyclic amine in the present invention is not particularly limited as long as it is a cyclic amine having active hydrogen for addition of alkylene oxide, and therefore, it may have an amine nitrogen inside and outside the ring. The active hydrogen group may be derived from an amino group, or may be derived from any group such as a hydroxyl group and a carboxyl group to which an alkylene oxide can be added.

Examples of such cyclic amines include:
Non-aromatic heterocyclic amines [having aziridine ring (aziridine, 2-methylaziridine, 2-
Those having a pyrrolidine ring (pyrrolidine, 2-methylpyrrolidine, 2-ethylpyrrolidine, 2-pyrrolidone, succinimide, 1,2-cyclohexanedicarboximide, etc.), those having a piperidine ring (piperidine, 2- Methyl piperidine,
3,5-dimethylpiperidine, 2-ethylpiperidine,
4-piperidinopiperidine, 2-methyl-4-pyrrolidinopiperidine, ethylpicolinate, etc.), those having a piperazine ring (1-methylpiperazine, 1-methyl-3-ethylpiperazine, etc.), morpholine ring Having (morpholine, 2-methylmorpholine, 3,
5-dimethylmorpholine, thiomorpholine, etc.),
Pyrolines (3-pyrroline, 2,5-dimethyl-3-pyrroline, 2-phenyl-2-pyrroline, etc.), pyrazolines (Pyrazoline, etc.), imidazoles (2-methylimidazole, 2-ethyl-4-methylimidazole) ,
2-phenylimidazole), pyrazoles (pyrazole, pyrazolecarboxylic acid, etc.), pyridones (α
-Pyridone, γ-pyridone and the like), and ε-caprolactam, pyridazinone, pyridaline, pyridoin and the like]; aromatic heterocyclic amine [2-hydroxypyridine, 2-hydroxy-3,5-ditertiarybutylpyridine, 2-carboxyl Pyridine, 4-pyridylcarbinol, 2-hydroxypyrimidine, pyrrole, 2-phenylpyrrole, etc.]; aromatic amine [aniline, 3-methylaniline, N-methylaniline, N-
Isopropylaniline, etc.] and the like.

Of these cyclic amines, non-aromatic cyclic amines are preferred. Among them, those having a piperidine ring and those having a morpholine ring are preferable, and those having a morpholine ring are most preferable.

The acyclic amine having 5 or more carbon atoms has 5 carbon atoms which has active hydrogen for addition of alkylene oxide.
The above non-cyclic amine is not particularly limited. For example,
Primary aliphatic acyclic amine having 5 or more carbon atoms (dimethylpropylamine, 2-ethylbutylamine, pentylamine, 2,2-dimethylbutylamine, hexylamine,
Cyclohexylamine, octylamine, 2-ethylhexylamine, isodecylamine, laurylamine, etc.), secondary aliphatic acyclic amine having 5 or more carbon atoms [methylbutylamine, methylisobutylamine, methyltertiarybutylamine, methylpentylamine, Methylhexylamine, methyl (2-ethylhexyl) amine,
Methyloctylamine, methylnonylamine, methylisodecylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine, ethylisobutylamine, ethyltertiarybutylamine, ethylpentylamine, ethylhexylamine, ethyl (2-ethylhexyl) amine, ethyloctyl Amine, dipropylamine, diisopropylamine, propylbutylamine, propylisobutylamine, propyltertiarybutylamine, propylpentylamine, propylhexylamine, propyl (2-ethylhexyl) amine, propyloctylamine, isopropylbutylamine, isopropylisobutylamine, isopropyltertiaryamine Ributylamine, isopropylpentylamine, isopropylhexylamine Isopropyl (2-ethylhexyl) amine, isopropyl octyl amine, dibutyl amine, diisobutyl amine, di-tert-butyl amine, butyl pentyl amine, dipentyl amine, such as dicyclohexylamine, and the like.

Among the acyclic amines having 5 or more carbon atoms, primary aliphatic acyclic amines having 5 to 8 carbon atoms are preferable.

Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide. Preferred of these are ethylene oxide or propylene oxide, and combinations of both.

The number of moles of alkylene oxide added is usually 1 to 50 moles, preferably 1 to 5 moles.

The vinyl carboxylic acid of the ester (a) in the present invention does not need to have a vinyl group and a carboxyl group directly bonded, and examples thereof include (meth) acrylic acid, (iso) crotonic acid, maleic acid, fumaric acid and Radical-polymerizable unsaturated aliphatic carboxylic acids such as itaconic acid; Radical-polymerizable aromatic carboxylic acids such as vinylbenzoic acid and 2-carboxy-4-isopropenyl-3-pyrrolidineacetic acid;
And ester-forming derivatives thereof (acid anhydride, acid halide or ester).

Of these, (meth) acrylic acid, maleic acid, vinyl benzoic acid and their ester-forming derivatives are preferable, and (meth) acrylic acid and (meth)
Ester-forming derivatives of acrylic acid are especially preferred.

The polymer (A) in the present invention may be a polymer consisting of the ester (a) alone or a copolymer of the ester (a) and another vinyl monomer (b). Is 50% by weight of ester (a) as a constituent unit.
It is necessary to contain at least the above, and it is desirable to contain at least 70% by weight.

The monomer (b) may be a hydrophilic vinyl monomer (b-1) [excluding (a)] or a lipophilic vinyl monomer (b-2).

As the monomer (b-1), a nonionic compound [hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth))
Acryloyloxypolyglycerol, vinyl alcohol, allyl alcohol, (meth) acrylamide, N-
Methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-vinyl-2-pyrrolidone, vinylimidazole, N-methylol-ε-caprolactam, N-methylolmaleimide, N-vinylsuccinimide, p-aminostyrene, N- Vinylcarbazole,
2-vinylpyridine, 2-cyanoethyl (meth) acrylate, etc .; anionic compound [(meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, (meth) acrylicsulfonic acid, styrene Acids such as sulfonic acid, vinyl benzoic acid, alkylallyl sulfosuccinic acid, (meth) acryloyl polyoxyalkylene sulfate and salts thereof]; cationic compounds [N, N-dimethylaminoethyl (meth) acrylate, N, N -Dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, vinylaniline and their acid salts ]; Having an amine imide group Thing [1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) Amine (meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide and the like].

Examples of the monomer (b-2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, Glycidyl (meta)
(Meth) acrylate derivative such as acrylate, N, N
-N-alkyl (meth) acrylamide derivatives such as dibutyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, (meth) acrylonitrile, styrene, 1-methylstyrene, vinyl acetate, butadiene,
Examples thereof include vinyl chloride and isoprene.

The weight average molecular weight of the polymer (A) is usually 1,
000 to 5,000,000, preferably 10,000
0-2,000,000, particularly preferably 100,000
It is 0 to 1,000,000.

Next, the method for producing the polymer (A) in the present invention will be described. The polymer (A) is an ester (a)
Further, it can be obtained by radical polymerization using the monomer (b) if necessary. The polymerization method is not particularly limited, and it is possible to use an ordinary thermal polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like. The polymer (A) can be obtained by initiating the polymerization by heating in the presence of an initiator or irradiation with light or radiation in the presence of a photosensitizer.

The polymerization temperature is usually 20 to 350 ° C., preferably 50 to 150 ° C., the reaction pressure is usually atmospheric pressure to 20 atmospheres,
The atmospheric pressure is preferably 10 atm.

As the radical polymerization initiator, usual ones can be used. For example, azo type initiators [2,2′-azobis (dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 4 , 4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-amidinopropane) hydrochloride, azobis (2-methyl-N-bishydroxymethyl-2-hydroxyethylpropionamide), azobis ( 2-methyl-N-hydroxyethylpropionamide), etc.], peroxide initiators [ammonium persulfate, sodium persulfate, hydrogen peroxide, benzoylperoxide, lauryl peroxide, tertiary butyl hydroperoxide, dicumyl peroxide,
Ditertiary butyl peroxide, cumene hydroperoxide, etc.] and the like. If necessary, a chain transfer agent (lauryl mercaptan, mercaptoethanol, etc.) may be used for the purpose of adjusting the weight average molecular weight of the polymer (A).

The polymer (A) of the present invention is also characterized in that it exhibits thermoreversible thickening. To further explain this point, the aqueous liquid containing the polymer (A) decreases in viscosity with increasing temperature up to a certain temperature, but when it exceeds this certain temperature, the viscosity increases with a high gradient. Has a different transition temperature, and this change in the temperature-viscosity relationship reversibly and repeatedly occurs with increasing and decreasing temperatures.

The transition temperature can be easily adjusted by changing the type of alkylene oxide in the ester (a) constituting the polymer (A) and the number of added moles. here,
The transition temperature means a temperature at which the polymer (A) changes from hydrophilicity to hydrophobicity or from hydrophobicity to hydrophilicity. For example, a 1 wt% aqueous solution of the polymer (A) is gradually heated. It can be determined by measuring the temperature at which the aqueous solution begins to become cloudy or by gradually increasing the temperature of the 20 wt% aqueous solution of the polymer (A) and measuring the temperature at which its viscosity begins to increase. it can.

Explaining the relationship between the type of alkylene oxide and the number of added moles and the transition temperature of the polymer (A), when ethylene oxide is used as the alkylene oxide in the polymer (A) and the number of added moles is increased, the transition temperature becomes higher. When propylene oxide or butylene oxide is used, the transition temperature becomes lower as the number of added moles increases. The number of moles of alkylene oxide added should be appropriately adjusted depending on the desired transition temperature, the type of amine, the type of alkylene oxide, etc., but is usually 1 to 50 mol, preferably 1 to 5 mol.

Further, it can be easily adjusted by changing the kind and amount of the above-mentioned monomer (b) used if necessary. Specifically, when the monomer (b-1) is used together with the ester (a), the transition temperature becomes high,
The higher the ratio in the polymer (A), the higher the transition temperature. Therefore, the higher the hydrophilicity of the polymer (A), the more remarkable the tendency. On the contrary, when the monomer (b-2) is used together with the ester (a), the transition temperature becomes low, and the transition temperature becomes lower as the proportion thereof increases. Therefore, the higher the hydrophobicity of the polymer (A), the more remarkable the tendency.

When the polymer (A) is composed of the ester (a) alone, when the temperature exceeds the transition temperature, the viscosity rapidly increases in a very narrow temperature range and gelation occurs, but the composition ratio of the ester (a) is As it approaches 50% by weight, the viscosity increases gradually over a wide temperature range as the temperature rises, so that the viscosity increasing property can be controlled according to the purpose of use.

Therefore, the polymer (A) can be used also as a thermoreversible thickener, and has a higher viscosity and a higher viscosity than the conventionally used polymers of methylcellulose and the proposed N-alkylacrylamide. It is excellent in reversibility and controllability of transition temperature.

The polymer (A) has a transition temperature of usually 5 to 95.
It is used by controlling it to be within the range of ° C.

When the polymer (A) is used as a thickener,
The polymer (A) may be used as it is, or may be used as a solution having an arbitrary concentration. To make a solution,
It may be mixed with a solvent such as water, acetone, methanol or isopropyl alcohol at a transition temperature or lower. However, since the transition temperature changes depending on the types and amounts of the components such as salt, surfactant and solvent in the solution, it is desirable to use the transition temperature in the solution. When the polymer (A) is used as a solution, the content of the polymer (A) varies depending on the type of solvent, the desired viscosity, etc., but is usually 0.1 with respect to the solution.
~ 80% by weight.

The polymer (A) is a paint, an ink, an adhesive,
Inorganic salt aqueous solutions, water-soluble resin aqueous solutions, aqueous slurry and colloidal dispersions of water-insoluble inorganic and organic substances, natural and synthetic latexes, which are commonly used in the fields of printing pastes, cosmetics, resin mortar, cement, etc. It is used by being contained in an aqueous liquid such as various resin emulsions and mixtures thereof. In this case, the amount of the polymer (A) used is
Although it varies depending on the type and viscosity of the aqueous liquid, it is usually 0.0001 to 30% by weight, preferably 0.
001 to 20% by weight.

When the polymer (A) is used as a thickener,
The polymer (A) may optionally contain an antioxidant, an ultraviolet absorber, a water resistant agent, a fragrance, an antifoaming agent, a dye and the like.

The polymer (A), when applied to an aqueous liquid,
When the transition temperature is exceeded in a wide temperature range, the viscosity rises steeply, and this temperature / viscosity change can be reversibly repeated. There is an advantage that the transition temperature can be easily and arbitrarily adjusted. Therefore, when the polymer (A) is used as a thickening agent, it has the effect of preventing penetration into the substrate or skinning on the surface in the heating and drying step, and increases in the drying step after coating. Since it is made to be viscous and gelled, it has the effect of preventing migration of the binder in the coating layer, and is also useful as a migration inhibitor such as a binder for non-woven fabrics and a coating agent for coated paper.

As the substrate in the present invention, glass, metal (iron, aluminum, copper, stainless steel, tin plate, zinc alloy, etc.), plastic (acrylic, nylon, polyester, polycarbonate, urethane, ABS, etc.),
Examples include paper, cloth, fibers, wood, concrete, gypsum board, bricks and pottery.

The polymer (A) can be used as it is or as a solution having an arbitrary concentration. Examples of the solvent for forming the solution include water, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, methanol, isopropyl alcohol, acetonitrile, toluene, xylene and the like.

The polymer (A) is usually used as an adhesion-improving composition obtained by containing it in a resin capable of forming a coating film. The amount used is 0.01 to 30% by weight, preferably 0.05 to 30% by weight based on the adhesion improving composition.
It is 20% by weight.

As the resin capable of forming a coating film, for example,
Acrylic resin, alkyd resin, melamine resin, urethane resin, SBR, NBR, epoxy resin, urea resin, phenol resin, α-olefin maleic anhydride resin, vinyl acetate resin, celluloses, vinyl acetate-acrylic copolymer, ethylene-acetic acid Examples thereof include vinyl copolymers, acrylic silicone resins, acrylic urethane resins, polyester resins, polyether resins, terpene resins and urea resins. These resins are usually solvents (water, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, methanol, isopropyl alcohol, acetonitrile,
(Toluene, xylene, etc.) or an aqueous dispersion.

Specific applications of the adhesion improving composition include paints, tacky adhesives, printing inks, paper coatings, concrete and ceramic binders, glass fiber binders, and the like. It is possible.

To produce the adhesion-improving composition, 100 parts of a resin capable of forming a coating film and, if necessary, a pigment (nitroso pigment, nitro pigment, azo pigment, phthalocyanine pigment,
Carbon black, iron oxide, titanium oxide, zinc white, cobalt blue, calcium carbonate, yellow lead, alumina white, zinc sulfide, vermilion, molybdenum red, clay, ultramarine blue,
Dark blue, etc.), pigment dispersant (sodium polyacrylate, etc.), curing agent (melamine resin, polyisocyanate, etc.), plasticizer (dioctyl phthalate), other additives (sag suppressant, thickener, antifreeze agent, Paint additives such as defoaming agents, preservatives, desiccants, leveling agents, etc.) and solvents (such as those mentioned above) dispersing equipment (ball mill, sand mill, high speed disperser, paint conditioner, etc.)
After uniformly mixing the polymer (A) with 0.01 ~
30 parts by weight may be added and mixed uniformly.

The adhesion-improving composition thus obtained is applied to the above-mentioned substrate with a brush coater, a roll coater, a curtain flow coater, an applicator or a sprayer to a thickness of 0.1 to 1000 μm, If necessary, the same or different base materials may be attached to each other at room temperature to 1
When dried at 50 ° C., a coating film having good adhesion to the substrate can be obtained.

[0041]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples are parts by weight. Production Example 1 100 parts of 2-morpholinoethyl methacrylate (ester of morpholine ethylene oxide 1 mol adduct and methacrylic acid) and 0.1 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule, It was freeze-deaerated, then sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 1.

Production Example 2 90 parts of 2- (2-morpholinoethoxy) ethyl methacrylate (2 mol adduct of morpholine with ethylene oxide and ester with methacrylic acid), 10 parts of methyl methacrylate and 2,2'-azobis (2,2) 4-Dimethylvaleronitrile) (0.1 part) was added to the ampoule, freeze-deaerated, sealed, and polymerized at 60 ° C. for 8 hours to obtain a polymer 2.

Production Example 3 80 parts of 2-morpholinopropyl methacrylate (an ester of 1 mol adduct of morpholine with propylene oxide and methacrylic acid), 5 parts of styrene, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl methacrylate and 2,2 '. -Add 0.1 part of azobis (2,4-dimethylvaleronitrile) to the ampoule, freeze degassing, and seal.
Polymerization was performed at 0 ° C. for 8 hours to obtain a polymer 3.

Production Example 4 80 parts of 2- (2-piperidinoethoxy) ethyl methacrylate, 10 parts of N, N-dibutylacrylamide, 10 parts of styrene and 2,2'-azobis (2,4-dimethylvaleronitrile) 0 Polymer (4) was obtained by adding 0.5 part to an ampoule, and freeze-deaeration, followed by sealing and polymerizing at 50 ° C. for 8 hours.

Production Example 5 80 parts of an acrylic acid ester of a 4 mol adduct of dimethylpropylamine with ethylene oxide, 20 parts of methyl methacrylate and 0.5 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were added to an ampoule. After freezing, degassing, sealing, and polymerizing at 50 ° C. for 8 hours, a polymer 5 was obtained.

Production Example 6 In a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 20 g of a sulfonate-type polymerizable emulsifier [Eleminol JS-2 manufactured by Sanyo Chemical Industry Co., Ltd.] and water. 600
g and 2.0 g of sodium persulfate were charged, the inside of the system was replaced with nitrogen gas under stirring, and the temperature was raised to 85 ° C. At the same temperature,
Methyl methacrylate 185 g, n-butyl methacrylate 143 g, n-butyl acrylate 70 g, acrylic acid 2
The mixture of g was added dropwise over 1 hour and reacted at the same temperature for 2 hours. After cooling to 30 ° C, pH is adjusted with 25% ammonia water.
Acrylic emulsion 1 (solid content 40.1%, hereinafter referred to as AcEM1) was obtained by adjusting to 8.5. Production Example 7 In the same manner as in Production Example 6, from a mixture of 65 g of n-butyl methacrylate, 188 g of n-butyl acrylate, 140 g of 2-ethylhexyl acrylate and 7 g of acrylic acid, an acrylic emulsion 2 (solid content 40.3 %, Hereinafter AcEM2
I got).

Examples 1 to 5 and Comparative Examples 1 and 2 0.5 parts of the polymer 1 obtained in Preparation Example 1, 25 parts of AcEM1 obtained in Preparation Example 6, 10 parts of titanium oxide, 2 parts of butyl cellosolve. , 5 parts of water and 0.1 part of a sodium polyacrylate-based dispersant (20% aqueous solution), and the glass beads 8
The white coating composition 1 of Example 1 was obtained by mixing together with 0 part by a paint conditioner for about 30 minutes. Similarly,
The white coating composition 2 of Example 2 was added to the polymer 2 by adding the polymer 3 to the polymer 2.
To white coating composition 3 of Example 3, polymer 4 to white coating composition 4 of Example 4, and polymer 5 to white coating composition 5 of Example 5 respectively. For comparison, in place of the polymer 1 in Example 1, an aqueous epoxy resin [Epicote DX-255 manufactured by Yuka Shell Epoxy Co., Ltd.] was used.
A white coating composition 6 of Comparative Example 1 was prepared using 5 parts and 0.5 parts of an aqueous curing agent [Epicure 3255 manufactured by Yuka Shell Epoxy Co., Ltd.] without using the polymer 1. A white coating composition 7 of Comparative Example 2 was obtained. Each of these white coating compositions 1 to 7 was applied onto a stainless steel plate with a wet film thickness of 100 μ by an applicator and dried at 60 ° C. for 30 minutes, and then the adhesiveness was evaluated by a cellotape peeling test.
Further, each of the white coating compositions 1 to 7 was stored in a closed container at 50 ° C for 2 weeks to evaluate the storage stability. The results are shown in Table 1.

[0049]

Adhesion: Evaluated according to JIS K5400. The number of unpeeled pieces out of 100 pieces of cross-cut cellophane tape peeled. Storage stability: State of white coating composition after standing at 50 ° C. for 2 weeks. [○: Good (immediately after creation, no change). X: Remarkably thickened. ]

Examples 6 to 10 and Comparative Examples 3 and 4 5 parts of Polymer 1 obtained in Production Example 1 and 25 parts of AcEM2 obtained in Production Example 7 were mixed and dissolved using a disper. The pressure-sensitive adhesive composition 1 of Example 6 was obtained. In the same manner, the polymer 2 to the pressure-sensitive adhesive composition 2 of Example 7, the polymer 3 to the pressure-sensitive adhesive composition 3 of Example 8, the polymer 4 to the pressure-sensitive adhesive composition 4 of Example 9, The pressure-sensitive adhesive composition 5 of Example 10 was obtained from the combined product 5. For comparison, in Example 6, instead of the polymer 1, 0.5 parts of an aqueous epoxy resin [Epicoat DX-255 manufactured by Yuka Shell Epoxy Co., Ltd.] and an aqueous curing agent [Okaka Shell Epoxy Co., Ltd.] were used. Made Epicure 3255]
The pressure-sensitive adhesive composition 6 of Comparative Example 3 was prepared using 0.5 parts of the polymer of Example 6 without using the polymer 1 to obtain the pressure-sensitive adhesive composition 7 of Comparative Example 4. Each of these pressure-sensitive adhesive compositions 1 to 7 was coated on a polyester film with an applicator to a wet film thickness of 50 μm and dried at 60 ° C. for 30 minutes to obtain a pressure-sensitive adhesive tape. The adhesive strength of the obtained adhesive tape to a stainless steel plate was evaluated. Each pressure-sensitive adhesive composition 1 to 7 was stored in a closed container at 50 ° C for 2 weeks to evaluate the storage stability. Table 2 shows the results.

[0052]

Adhesive strength: An adhesive tape was attached to a stainless steel plate and left at 25 ° C. for 60 minutes, and then 180 ° peel strength was measured at a pulling rate of 300 mm / min at room temperature. Storage stability: The state of the pressure-sensitive adhesive composition after standing at 50 ° C. for 2 weeks. [○: Good (immediately after creation, no change). X: Remarkably thickened. ]

Reference Example 1 2,2-Dimethylpropylamine ethylene oxide 4
95 parts of an acrylic acid ester of a mole addition product, 5 parts of methyl methacrylate and 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule, and the mixture was freeze-deaerated, then sealed, and then at 50 ° C. for 8 hours. Polymerization was performed to obtain a polymer A. The transition temperature of polymer A was 44 ° C. Polymer A
Was added to 20 parts of 80 parts of ion-exchanged water at 20 ° C., and mixed and dissolved uniformly. This aqueous solution was heated at a rate of 2 ° C./min to measure the viscosity (using a B-type viscometer and ST rotor). Table 1 shows the results. Next, the thickened aqueous solution was cooled from 55 ° C. to 30 ° C. at a rate of 2 ° C./min to measure the viscosity (using a B-type viscometer and ST rotor). The results are shown in Table 2.

[0056]

[Table 1]

[0057]

[Table 2]

Reference Example 2 98 parts of an acrylic acid ester of a 3 mol addition product of methylbutylamine with ethylene oxide, 2 parts of hydroxyethyl methacrylate and 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were added to an ampoule. After freezing, degassing, sealing, and polymerizing at 50 ° C. for 8 hours, a polymer B was obtained. The transition temperature of polymer B was 63 ° C. Polymer B
Was added to 20 parts of 80 parts of ion-exchanged water at 20 ° C., and mixed and dissolved uniformly. This aqueous solution was heated at a rate of 2 ° C./min to measure the viscosity (using a B-type viscometer and ST rotor). Table 3 shows the results. Next, the thickened aqueous solution was cooled from 75 ° C. to 45 ° C. at a rate of 2 ° C./min, and the viscosity was measured (B-type viscometer, ST rotor used). The results are shown in Table 4.

[0060]

[Table 3]

[0061]

[Table 4]

Reference Example 3 The polymer A of Reference Example 1 was mixed at 20 ° C. with a urethane emulsion (Sanprene UXA3004, Sanyo Kasei Kogyo Co., Ltd.) 9
0.2 part was added to 9.8 parts and uniformly mixed and dissolved.
The temperature of this mixture was raised at a rate of 2 ° C./min to measure the viscosity (B-type viscometer, using ST rotor). The results are shown in Table 5. Next, the thickened aqueous solution is heated at 55 ° C. to 30 ° C.
The temperature was lowered to 2 ° C. per minute up to 0 ° C. and the viscosity was measured (using a B-type viscometer and ST rotor). Table 6 shows the results.

[0063]

[Table 5]

[0064]

[Table 6]

[0065]

The adhesion improving method of the present invention has the following effects. (1) The adhesion to glass, metal, plastic, paper, cloth, fiber, wood, concrete, gypsum board, brick, pottery, etc. can be remarkably improved. (2) Since it is non-reactive, the storage stability of the coating composition is good. By exhibiting the above effects, the adhesion improving method of the present invention is useful in the fields of paints, adhesives, printing inks, paper coating materials, concrete, ceramics, and glass fiber binders.

Claims (2)

[Claims] 1. An adhesion improver comprising a polymer (A) containing, as a constituent unit, 50% by weight or more of a vinylcarboxylic acid ester (a) of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms. A method for improving adhesiveness of a base material, which is used as. 2. The method for improving adhesion according to claim 1, wherein the cyclic amine is piperidine or morpholine.