DE10244087A1 - Emulsion type adhesive composition is obtained by polymerizing ethylenically unsaturated monomer in presence of resin emulsion obtained by polymerizing emulsification liquid obtained from fat soluble component - Google Patents

Abstract

An emulsion type adhesive composition is obtained by polymerizing an ethylenically unsaturated monomer (E) having alkyl (meth)acrylate (e1) as main component, in presence of a resin emulsion (II) obtained by polymerizing an emulsification liquid (I). The emulsification liquid (I) is obtained by emulsifying a fat-soluble component containing ethylenically unsaturated monomer (A) and tackifier (B). An emulsion type adhesive composition is obtained by polymerizing an ethylenically unsaturated monomer (E) having alkyl (meth)acrylate (e1) as main component, in presence of a resin emulsion (II). The resin emulsion (II) is obtained by polymerizing an emulsification liquid (I) in the presence of a polymerization initiator (D). The emulsification liquid (I) is obtained by emulsifying a fat-soluble component containing ethylenically unsaturated monomer (A) having alkyl (meth)acrylate (a1) as main component, and tackifier (B) using an emulsifier (C) in an aqueous medium. The average particle diameter of the fat soluble component is 1 mum or less.

Description

Background of the Invention Field of the Invention

The present invention relates to a method for producing a Emulsion of a pressure sensitive adhesive composition. In particular, it relates to a method for producing an emulsion of a pressure sensitive adhesive composition which is a excellent adhesiveness (especially adhesiveness to Polyolefin), adhesive strength, adhesion to a base material and Water resistance (especially resistance to white coloring or fading when immersed in water).

Description of the Prior Art

The emulsion of an acrylic ester copolymer can differ in their Balance between stickiness (or stickiness) and Cohesiveness can change by changing their composition and can therefore used as an adhesive and a tackifying agent become. In this case it is common to use a tackifying resin add to improve the adhesiveness (or stickiness).

Due to the water insolubility of the tackifying resin, the Method of addition after dissolving in a solvent or the method of addition in the form of an emulsion made by Emulsifying in water is applied. However, at first-mentioned method the advantage of the aqueous system is not can be exploited and in the latter method, the Particles of the tackifying resin and the particles of the Acrylate ester emulsion should not be mixed evenly.

Accordingly, problems often arise because of the adhesiveness the resulting adhesive or adhesive is reduced and the Water resistance is also reduced.

In order to solve these problems, the following suggestions have been made.

(1) JP-A-54-23641
An emulsion comprising an acrylic monomer, a copolymerizable monomer having a crosslinking functional group, a polymeric compound dissolved in at least one of the monomers, and a surfactant is subjected to emulsion polymerization to form an aqueous dispersion of the adhesive composition.

(2) JP-A-58-185668
A composition obtained by dissolving or dispersing a tackifying resin in a mixture of a crosslinking monomer and a (meth) acrylate, or an emulsion composition obtained by dispersing the above composition in water containing an emulsifier, continuously becomes a polymerization solution containing water, contains an emulsifier and a polymerization catalyst, so that polymerization takes place, whereby a copolymer-emulsion adhesive is obtained.

In addition to the above recommendations (1) and (2) will also suggested the following.

(3) JP-A-2000-313865
0.5 to 5 parts by weight of a tackifying resin and an oil-soluble polymerization initiator are dissolved in 100 parts by weight of a mixed monomer which contains 50 to 99.5% by weight of an alkyl (meth) acrylate with 9 to 14 carbon atoms in the alkyl group and Contains 5 to 2.5% by weight of a monomer having a carboxyl group, a hydroxyl group or an amide group, and the resulting solution is subjected to an emulsion dispersion in an aqueous solution of an emulsifier, thereby obtaining monomer oil droplets having an average particle diameter of 1 µm or less, which are then polymerized to obtain an emulsion of an adhesive.

However, there are no studies on an emulsion Dispersion method of the mixed solution with a solution in it or dispersed tackifier resin for the in literature (1) and (2) techniques. Based on detailed research in the context of the present invention it was found that a Problem occurs if the polymerization is carried out using a Emulsion solution is carried out by dispersing the emulsion in is usually obtained because the polymerization becomes unstable when the amount of tackifying agent used is increased and the shelf life of the resulting emulsion is reduced.

In addition, in the references (1), (2) and (3) procedures described the adhesiveness (especially the Adhesion to polyolefin), the holding force, the adhesion to one Base material and water resistance (especially the Resistance to fading or white coloring when immersed in Water) is insufficient and there is a need for improvement.

Description of the invention

Under these circumstances, an object of the present invention is Providing a process for producing an emulsion of a pressure sensitive adhesive composition which is a excellent adhesiveness (especially adhesiveness to Polyolefin), holding or adhesive force, adhesion to a base material and Water resistance (especially resistance to fading or whitening when immersed in water).

The invention was completed as part of extensive investigations by the present inventors. It is the process for producing an emulsion of a pressure-sensitive adhesive, which according to the invention comprises the following steps:
Emulsifying an oil-soluble component comprising an ethylenically unsaturated monomer (A) mainly comprising an alkyl (meth) acrylate ester (a1) and a tackifying agent (B) in an aqueous medium; using an emulsifier (C) to form an average particle diameter of the oil-soluble component of 1.0 µm or less to prepare an emulsion (I),
Polymerization of the emulsion (I) in the presence of a polymerization initiator (D) to obtain a resin emulsion (II) and
Polymerization of an ethylenically unsaturated monomer (E), which mainly comprises an alkyl (meth) acrylate ester (e1), in the presence of the resin emulsion (II) to obtain an emulsion of an adhesive composition.

According to the invention, it is from the standpoint of adhesion to one Base material and water resistance (especially the Resistance to fading or white coloring when immersed in Water) is preferred if the ethylenically unsaturated monomer (E) in addition to the alkyl (meth) acrylate ester (e1) Unsaturated monomer (e2) containing carboxyl groups or alternatively a carboxyl group-containing unsaturated monomer (e2) and an unsaturated monomer containing a crosslinking group (e3) (which is the carboxyl group-containing unsaturated monomer (e2) excludes) contains.

According to the invention, it is also preferred if the emulsion of pressure sensitive adhesive composition beyond Contains crosslinking agent (F), because the effect of the invention more clearly occurs.

Description of the preferred embodiments

The invention is described in more detail below.

The ethylenically unsaturated monomer (A) according to the invention is used mainly comprises an alkyl (meth) acrylate ester (a1) as Main component. Examples of the alkyl (meth) acrylate ester (a1) include an alkyl (meth) acrylate ester having a carbon number in the Alkyl group from 1 to 8, such as methyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate and n-octyl (meth) acrylate and an alkyl (meth) acrylate ester with a Carbon number of the alkyl group of 9 or more, such as Nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate, Tridecyl (meth) acrylate, isotridecyl (meth) acrylate and Tetradecyl (meth) acrylate. Among them is an alkyl (meth) acrylate ester a carbon number of the alkyl group of 1 to 8 is preferred and in particular, methyl (meth) acrylate, ethyl (meth) acrylate, n- Butyl (meth) acrylate and 2-ethylhexyl acrylate are preferably used.

The ethylenically unsaturated monomer (A) can also be a crosslinking monomer (a2) in addition to the alkyl (meth) acrylate ester (a1) included. Examples of the crosslinking monomer (a2) include (1) a monomer containing the carboxyl group, (2) a Monomer containing hydroxyl group, (3) an epoxy group containing monomer, (4) one containing the alkoxysilyl group Monomer, (5) a monomer that is at least one of the groups Amide group, methylol group and keto group (the "keto group" here means a carbonyl group of the ketone type or keto enol Tautomer type) and (6) a polyfunctional monomer. This Crosslinking monomers (a2) can be used alone or in combination of two or more of them can be used.

Examples of the carboxyl group-containing monomer under (1) include acrylic acid, an acrylic acid dimer, methacrylic acid, crotonic acid, Itaconic acid and maleic acid.

Examples of the hydroxyl group-containing monomer under (2) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Examples of the epoxy group-containing monomer under (3) include glycidyl (meth) acrylate and acrylic glycidyl ether.

Examples of the alkoxysilyl group-containing monomer under (4) include γ- (meth) acryloxyethyltrimethoxysilane, γ- (Meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (Meth) acryloxypropyltriethoxysilane, γ- (Meth) acryloxypropylmethyldimethoxysilane, γ- (Meth) acryloxypropyldimethylmethoxysilane, γ- (Meth) acryloxypropylmethyldiethoxysilane, γ- (Meth) acryloxypropyldimethylethoxysilane (Meth) acryloxypropyltrichlorosilane, γ- (Meth) acryloxypropylmethyldichlorosilane, γ- (Meth) acryloxypropyldimethylchlorosilane, γ- (Meth) acryloxypropyl tripropioxysilane, γ- (Meth) acryloxypropylmethyldipropioxysilane, γ- (Meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ- (Meth) acryloxypentyltrimefihoxysilane, γ- (meth) acryloxyhexyltrimethoxysilane, γ- (meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- (meth) acrloxydecyltrimethoxysilane, γ- (Meth) acryloxydodecyltrimethoxysilane, γ- (Meth) acryloxyoctadecyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, Vinylmethyldiethoxysilane and vinylmethyldipropoxysilane.

Examples of the monomer having at least one group selected from an amide group, a methylol group and a keto group under (5) contains include acrylamide and methacrylamide containing one amide group; N-methylolacrylamide and butoxy-N-methylolacrylamide, containing an amide group and a methylol group; Diacetone acrylamide containing an amide group and a keto group; and containing 2- (acetoacetoxy) ethyl (meth) acrylate and allylacetoacetate a keto group.

Examples of the polyfunctional monomer under (b) include Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3- Butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Hexyanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tetramethylolmethane tri (meth) acrylate, Tetramethylol methane tetra (meth) acrylate, glycerol methacrylate, acrylate, Tris (meth) acryloyloxyphosphate, glycerol di (meth) acrylate, Diallyl terephthalate, tetraallyloxyethane, divinylbenzene and Tri (meth) allyl isocyanurate.

Among the examples of the crosslinking monomer (a2) particularly preferably uses acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, γ- Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ- methacryloxypropyl, Methacryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, N- Methylolacrylamide, diacetone acrylamide, 2- (Acetoacetoxy) ethyl methacrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, diallyl terephthalate and divinylbenzene. According to the invention, the ethylenically unsaturated monomer (A) in addition a further copolymerizable monomer (a3) in addition to the alkyl (meth) acrylate ester (a1) or to the alkyl (meth) acrylate ester (a1) and the crosslinking monomer (a2). Examples of that copolymerizable monomer (a3) include acrylonitrile, methacrylonitrile, Styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, Alkyl vinyl ether, dimethylaminoethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate and Methoxytriethyleneglycol (meth) acrylate.

In the ethylenically unsaturated monomer (A), the ratio is from Alkyl (meth) acrylate ester (a1), the crosslinking monomer (a2) and the copolymerizable monomer (a3) preferably 50 to 100 wt .-% of Alkyl (meth) acrylate ester (a1), 0 to 20 wt .-% of the crosslinking Monomer (a2) and 0 to 50% by weight of the copolymerizable monomer (A3). The proportions are more preferably 70 to 100% by weight of the Alkyl (meth) acrylate ester (a1), 0 to 10 wt .-% of the crosslinking Monomer (a2) and 0 to 30% by weight of the copolymerizable monomer (A3). The amount is particularly preferably 80 to 100 wt .-% of Alkyl (meth) acrylate ester (a1), 0 to 5% by weight of the crosslinking monomer (a2) and 0 to 20% by weight of the copolymerizable monomer (a3).

If the amount of the alkyl (meth) acrylate ester (a 1) is less than 50% by weight is not preferred because in some cases none sufficient adhesiveness and stickiness can be achieved and the Transparency of the coated film is reduced. If the amount of crosslinking monomer (a2) exceeds 20% by weight, this is not preferred because in some cases the transparency of the coated film is reduced and the polymerization becomes unstable. It is not preferred that the amount of the copolymerizable monomer (a3) is 50% by weight exceeds, because in some cases insufficient adhesive ability and stickiness can be achieved and the transparency of the coated film is reduced.

The tackifying agent (B) used in the present invention is not subject to any limitation, provided it is in the ethylenically unsaturated Monomer (A) can be dissolved or dispersed, and examples thereof are a rosin ester such as "Super Ester A-75" (manufactured by Arakawa Chemical Industries, Ltd.), "Super Ester A-100" (manufactured by Arakawa Chemical Industries, Ltd.) and "Super Ester A-125" (manufactured from Arakawa Chemical Industries, Ltd.); a polymerized Rosin esters such as "Pensel D125" (manufactured by Arakawa Chemical Industries, Ltd.), "Pensel D160" (manufactured by Arokawa Chemical Industries, Ltd.) and "Rikatack PCJ" (manufactured by Rika Finetec Industries, Ltd.); a xylene resin such as "Nikanol HP-100" (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and, "Nikanol HP-150 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and "Nikanol HP-80" (manufactured by Mitsubishi Gas Chemical Co., Ltd.); a terpene phenol resin such as "YS Polyster T-115 "(manufactured by Yasuhara Chemical Co., Ltd.) and "Mightyace G125" (manufactured by Yasuhara Chemical Co., Ltd.); on Petroleum resin or petroleum resin such as "FTR-6120" (manufactured by Mitsui Petrochemical Industries, Ltd.) and "FTR-6100" (manufactured by Mitsui Petrochemical Industries, Ltd.); as well as other resins, such as a coumaron Inden resin, a terpene resin, a styrene resin and an ethylene vinyl acetate Resin.

In addition, a styrene Butadiene block polymer, a styrene-isoprene block polymer Ethylene isoprene-styrene block polymer, a vinyl chloride-vinyl acetate copolymer and Acrylic rubber can be used, which are called elastomers.

According to the ethylenically unsaturated monomer (A) and the tackifying agent (B) mixes to form an oil-soluble one Component. The mixing ratio therein is preferably 5 to 400 parts by weight of the tackifying agent (B) per 100 Parts by weight of the ethylenically unsaturated monomer (A). The relationship of the tackifying agent (B) is more preferably 8 to 300 Parts by weight and particularly preferably 10 to 200 parts by weight. It is not preferred that the amount of the tackifying agent (B) is less than 5% by weight since there is insufficient adhesive power, in particular adhesion to polyolefin can be achieved, and if the Amount of the tackifying agent (B) 400 parts by weight exceeds, this is also not preferred because the polymerization becomes unstable and does not achieve sufficient adhesive strength and stickiness can be.

The the ethylenically unsaturated monomer (A) and the tackifying Oil-soluble component containing agent (B) is in the aqueous Medium using an emulsifier (C) to prepare the Emulsion (I) emulsified. The emulsifier (C) is not subject to any particular one Restriction, provided that it has the function that the respective Components are emulsified in the aqueous medium and For example, a reactive (ionic or nonionic) surfactant and a non-reactive (ionic or nonionic) surfactant used alone or in combination become. Of these, taking into account the water resistance preferably a reactive surfactant is used.

The reactive surfactant can be an ionic or nonionic surfactant that has a radical reactivity with the ethylenically unsaturated monomer (A). Examples of the reactive surface active agent include those structures represented by the general formulas (1) to (9) below.

In the general formulas (1) to (9), R _{1 represents} an alkyl group, R _{2 represents} a hydrogen atom or a methyl group, R _{3 represents} an alkylene group, n represents an integer of 1 or more, m and 1 each represent an integer Number of 1 or more, provided that m + l 3, and X represents a hydrogen atom, SO ₃ NH ₄ or SO ₃ Na.

Examples of commercially available products for the surfactant include "Adeka Reasoap SE-20N" (anionic), "Adeka Reasoap SE-10N" (anionic), "Adeka Reasoap NE-10" (non-ionic), "Adeka Reasoap NE- 20 "(non-ionic)," Adeka Rerasoap NE-30 "(non-ionic)," Adeka Reasoap NE-40 "(non-ionic)," Adeka Reasoap SDX-730 "(anionic), "Adeka Reasoap SDX-731" (anionic), "Adeka Reasoap ER-10" (non- ionic), "Adeka Reasoap ER-20" (non-ionic), "Adeka Reasoap ER-30" (non-ionic), "Adeka Reasoap ER-40" (non-ionic), "Adeka Reasoap SR-10N "(anionic) and" Adeka Reasoap SR-20N "(anionic), respectively manufactured by Asahi Denka Kogyo K.K .; "Eleminol JS-2" (anionic) and "Eleminol RS-30" (anionic), each manufactured by Sanyo Chemical Industries, Ltd .; "Latemul S-180A" (anionic) and "Latemul S180" (anionic), each manufactured by Kao Corporation; "Aqualon BC-05" (anionic), "Aqualon BC-10" (anionic), "Aqualon BC-20" (anionic), "Aqualon HS-05" (anionic), "Aqualon HS-10" (anionic), "Aqualon HS- 20 "(anionic)," Aqualon RN-10 "(non-ionic)," Aqualon RN-20 "(non- ionic), "Aqualon RN-30" (non-ionic), "Aqualon RN-50" (non-ionic), "New Frontier S-510" (anionic), "Aqualon KH-05" (anionic) and "Aqualon KH-10" (anionic), all of which are from the Dai-ichi Kogyo Seiyaku Co "Ltd, and" Phosphinol TX "(anionic), the by Toho Chemical Industry Co., Ltd. will be produced.

The mixing amount of the emulsifier (C) is preferably 0.5 to 10 Parts by weight per 100 parts by weight of the total ethylenically unsaturated monomers (A) and tackifying agents (B). The The amount is more preferably 0.8 to 7 parts by weight and particularly preferably 1 to 5 parts by weight. It is not preferred if the amount of the emulsifier (C) is less than 0.5 part by weight because the Particle diameter of the oil-soluble component difficult 1 µm or may be less and the polymerization becomes unstable. It is also not preferred that the amount of emulsifier is 10 parts by weight exceeds, because the polymerization can become unstable and the Water resistance of the coated film can be reduced.

Part of the emulsifier (C) can previously in the Polymerization vessel are inserted instead of added to the emulsion (I) to become.

A method for producing the emulsion (I) is described, the is obtained by emulsifying the oil-soluble component that the ethylenically unsaturated monomer (A) which is the alkyl (meth) acrylate ester (a1) or the alkyl (meth) acrylate ester (a1) with the crosslinking Monomer (a2) and / or the other copolymerizable monomer (a3) contains, as well as the tackifying agent (B) contains in the aqueous Medium using the emulsifier (C) to achieve a average or average particle diameter of the oil-soluble Component of 1 µm or less.

It is a method for loading the respective components preferred if the tackifying agent (D) previously in the ethylenically unsaturated monomer (A) is dissolved and then the other components.

The amount of water used is preferably 70 to 500 Parts by weight per 100 parts by weight of the total ethylenically unsaturated monomer (A) and tackifying agent (B). The The amount of water is more preferably 80 to 300 parts by weight and particularly preferably 85 to 200 parts by weight. It is not preferred use less than 70 parts by weight of water because the Emulsion (I) can have a high viscosity and the Polymerization stability can be reduced. It is not preferred that the amount of water exceeds 500 parts by weight because the Concentration of the emulsion (I) is reduced, reducing the concentration the emulsion of the tackifying agent composition; is obtained, is reduced and the drying properties at Layering (when a coated film is formed) is deteriorated.

The emulsion (I) is obtained by emulsifying the oil-soluble ones Component, the ethylenically unsaturated monomer (A) and contains tackifying agent (B) in the aqueous medium Application of the emulsifier. The oil-soluble component has preferably an average or average diameter of 1.0 µm or less, more preferably 0.05 to 0.7 µm and particularly preferably from 0.1 to 0.5 μm. If the average Particle diameter of the oil-soluble component in the emulsion (I) 1.0 µm exceeds a large amount of aggregated material formed during the polymerization and the shelf life of the emulsion is deteriorated, making the adhesive ability of a coated Foil, in particular the adhesiveness to olefin is deteriorated and the water resistance is reduced, thereby reducing the aim of present invention is not achieved.

The process of making the average or average Particle diameter of the oil-soluble component of 1.0 µm or less is not subject to any particular limitation and the particular Components can be mixed and emulsified with a arbitrarily chosen stirring device or emulsifying device be subjected. However, it is preferred according to the invention if an emulsion (I ') with an average particle diameter of Oil-soluble component that exceeds 1.0 microns, initially produced and then into the emulsion (I) with an average Particle diameter of the oil-soluble component of 1.0 µm or less is converted.

The emulsion (I ') is preferably obtained by mixing the respective components and subsequent preliminary emulsification using a stirrer equipped with stirrer blades is like a homodisperser and stirring blades, forming one Emulsion with an average particle diameter of oil-soluble component that exceeds 1.0 µm. The emulsion (I ') is also subjected to an emulsion treatment to form the Emulsion (I) with an average particle diameter of oil-soluble component of 1.0 µm or less.

The method for further dispersing the emulsion (I ') to obtain the emulsion (I) having an average particle diameter of the oil-soluble component of 1.0 µm or less is not particularly limited, and any method can be used. For example, treatment with an emulsifying device such as a high pressure homogenizer treatment, an ultrasonic wave treatment and a stirring treatment can be used. High-pressure homogenizer treatment is particularly preferred since an emulsion with a narrow particle diameter distribution can be effectively achieved. The pressure for using the high-pressure homogenizer is preferably 10 to 1500 kg / cm ² and particularly preferably 30 to 1000 kg / cm ² .

The temperature at the time of emulsification can be such that the Mix does not react during the emulsification and is in the generally at about 5 to 6000. The number of times the feed is repeated Emulsion into the emulsifying device, d. H. the number of passes, is preferably about 1 to 5 times.

After preparation of the emulsion (I), the emulsion (I) in the presence of a Polymerization initiator (D) polymerizes to form the resin emulsion (II). Examples of the method therefor include those in which (i) the Temperature of the total amount of emulsion (I) to effect the Polymerization is increased, (ii) the temperature of part of the emulsion (I) to initiate the polymerization is increased and the rest of the emulsion (I) is added dropwise or in stages (the polymerization initiator (D) is also added dropwise as necessary) to the polymerization and (iii) water is placed in a polymerization vessel (a Part of the emulsifier (C) and the polymerization initiator (D) can each be charged if necessary), the temperature will then increased and the total amount of emulsion (I) is dropwise or stepwise to effect the polymerization added. However, the procedure is not based on these methods limited.

The amount of the polymerization initiator (D) used is preferably 0.05 to 5 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer (A). The amount of Polymerization initiator (D) is more preferably 1 to 3 parts by weight. If the amount of the polymerization initiator used is less than Is 0.05 part by weight, so this is not preferable since the Polymerization rate is delayed. It is not preferred one Amount of the polymerization initiator of over 5 parts by weight use because the molecular weight of the resin becomes low and the Holding force is reduced.

The polymerization initiator (D) is not subject to any particular one Limitation and it can be both water-soluble and oil-soluble be used. Specific examples include an organic one Peroxide, such as alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p- Methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, t-butylcumyiperoxide, benzoyl peroxide, Dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t- butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5- Trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, Diisobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and t- Butyl peroxyisobutyrate, azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2- Azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile); Potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide; an ammonium (amine) salt of 4,4'-azobis-4- cyanoverlianoic acid, 2,2'-azobis (2-methylamidoxime) dihydrochloride, 2,2'- Azabis (2-methylbutanamide oxime) dihydrochloride tetrahydrate, 2,2'-azobis (2- methyl-N- (1,1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide), 2,2'- Azobis (2-methyl-N- (2-hydroxyethyl) propionamide) and various types of redox catalysts (example of a usable here Oxidizing agents include ammonium persulfate, potassium persulfate, Hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, Cumene hydroperoxide and p-menthane hydroperoxide, and examples of one Reducing agents which can be used here include sodium sulfite, acidic Sodium sulfite, rongalite and ascorbic acid).

The polymerization initiator (D) can previously in the Polymerization vessel added or immediately before initiating the Polymerization can be added and can also during the Polymerization can be added. Alternatively, it can be mixed Solution of the ethylenically unsaturated monomer (A) and sticky agent (B) before emulsification or can be added be added to the emulsion (I) after emulsification. The Polymerization initiator (D) Can be dissolved in a Solvent are added and the resulting solution of Polymerization initiator (D) can be emulsified and then added become.

A pH buffering agent can be added for the polymerization to adjust the pH of the polymerization as necessary adjust.

The polymerization conditions in the polymerization method are not subject to any particular restriction. With method (i) lies however, generally the temperature range is appropriate at about 40 to 100 ° C and the reaction will be useful over a period of time from 0.5 to 8 hours after the initial temperature increase carried out.

In method (ii) it is preferred that after the polymerization of 5 to 95 wt .-% of the emulsion (I) at a temperature of 40 ° to 90 ° C. for a period of 0.1 to 5 hours, or during the Polymerization, the rest of the emulsion (I) dropwise or stepwise is added over a period of about 0.1 to 5 hours and then the reaction mixture at this temperature during aged for a period of about 1 to 3 hours.

In method (iii), water is used in an amount of 5 to 300% by weight, based on the emulsion (I), followed by its temperature a range of 40 to 90 ° C is increased and then the emulsion (I) drop by drop or stepwise in the course of 0.5 to 5 hours is added, then at this temperature for a period of is aged for about 1 to 3 hours.

The resin emulsion (II) and the resin component can be obtained the resin emulsion (II) is preferably in the form of fine particles with an average or average particle diameter of 0.05 to 0.5 µm and particularly preferably 0.1 to 0.3 µm. The Resin concentration of the resin emulsion (II) is preferably 10 to 65% by weight and particularly preferably 20 to 55% by weight.

According to the invention, an ethylenically unsaturated is also Monomer (E), which is mainly an alkyl (meth) acrylate ester (e1) contains, further polymerized in the presence of the resin emulsion (II), whereby the emulsion of the composition of the tackifying Means is obtained.

The ethylenically unsaturated monomer (E) mainly contains that Alkyl (meth) acrylate ester (e1) and examples of the alkyl (meth) acrylate ester (e1) include those as examples of the alkyl (meth) acrylate ester (a1) were given. Among these are an alkyl (meth) acrylate ester a carbon number of the alkyl group of 1 to 8 is preferred and methyl (meth) acrylate, ethyl (meth) acrylate, n- Butyl (meth) acrylate and 2-ethylhexyl acrylate.

The ethylenically unsaturated monomer (E) preferably additionally contains to the alkyl (meth) acrylate ester (e1) containing the carboxyl group unsaturated monomer (e2) or alternatively it contains a Unsaturated monomer (e2) containing carboxyl group and a crosslinking group containing unsaturated monomer (e3) (which the unsaturated monomer (e2) containing the carboxyl group is not included).

Examples of the unsaturated monomer containing the carboxyl group (e2) include the components that are the same as or similar to the ones as examples of the monomer (1) containing the carboxyl group under the crosslinking monomers (a2) described for the ethylenic unsaturated monomer (A) have been specified.

Examples of the unsaturated containing the crosslinking group Monomer (e3) (which is different from the one containing the carboxyl group unsaturated monomer (e2)) include those for the monomer (2) containing the hydroxyl group, the epoxy group containing monomer (3), the alkoxysilyl group-containing monomers (4), the monomer having at least one group selected from the group Amide group, a methyl group and a keto group contains (5) and the polyfunctional monomer (6) for the crosslinking monomer (a2), described for the ethylenically unsaturated monomer (A) and the monomer containing a keto group among the Monomers (5) and the polyfunctional monomer (6) are preferred used. It is most preferred if that is a keto group containing monomer among the monomers (5) is used and in in this case, particularly preferred effects for adhesion on a base material (peel strength) and resistance to Fading or whitening when immersed in water can be achieved.

Another copolymerizable monomer (e4) are used and examples of the copolymerizable monomer (e4) include the same or similar compounds as those Examples were given for the copolymerizable monomer (a3), described for the ethylenically unsaturated monomer (A).

In the ethylenically unsaturated monomer (E), the proportion of Alkyl (meth) acrylate ester (e1), which contains the carboxyl group unsaturated monomer (e2) containing the crosslinking group unsaturated monomer (e3) (which is different from the carboxyl group containing unsaturated monomer (e2) differs and other copolymerizable monomer (e4) preferably 50 to 99% by weight of the alkyl (meth) acrylate ester (e1), 1 to 10% by weight of the Unsaturated monomer (e2) containing corboxyl group, 0 to 5% by weight of the unsaturated containing the crosslinking group Monomer (e3) and 0 to 49% by weight of the copolymerizable monomer (E4). The proportion is more preferably 70 to 98.45% by weight of the Alkyl (meth) acrylate ester (e1), 1.5 to 8 wt .-% of the carboxyl group containing unsaturated monomer (e2), 0.05 to 3 wt .-% of the crosslinking group containing unsaturated monomer (e3) and 0 up to 28.45% by weight of the copolymerizable monomer (e4). Especially the proportion is preferably 80 to 97.9% by weight of the Alkyl (meth) acrylate ester (e1), 2 to 6 wt .-% of the carboxyl group containing unsaturated monomer (e2), 0.1 to 2 wt .-% of the crosslinking group containing unsaturated monomer (e3) and 0 up to 17.9% by weight of the copolymerizable monomer (e4).

If the proportion of the alkyl (meth) acrylate ester (e1) is less than 50% by weight sufficient adhesiveness and stickiness cannot be achieved and if it exceeds 99% by weight, there is a tendency that the holding force, the adhesion to a base material and the Resistance to fading or white coloring when immersed in Water. If the proportion of the carboxyl group containing unsaturated monomer (e2) less than 1% by weight is sufficient adhesion, adhesion to one Base material and resistance to fading or white coloring cannot be achieved when immersed in water and if it is 10% by weight exceeds, there are cases where the adhesiveness to polyolefin is reduced and the polymerization becomes unstable. If the share of the crosslinking group-containing unsaturated monomer (e3) 5% by weight exceeds, there is a tendency that the adhesiveness and Tackiness can be reduced and the resistance to fading or white coloring when immersed in water is reduced. If the Proportion of copolymerizable monomer (e4) exceeds 49% by weight, there is a tendency that the adhesiveness and stickiness decrease become.

In the polymerization of the ethylenically unsaturated monomer (E) in Presence of the resin emulsion (II) as obtained above is from From the point of view of polymerization stability preferred without one Restriction to represent that an emulsion (P) initially through preliminary emulsification of the ethylenically unsaturated monomer (E), which contains components (e1) to (e4) in an aqueous medium is produced and the emulsion (P) in the presence of the resin emulsion (II) is polymerized.

In the preparation of the emulsion (P) by prior emulsification, an emulsifier is preferably used and compounds are the same or similar to those described for the emulsifier (C), can be used alone or in combination of two or more thereof Emulsifier can be used.

If the polymerization is accomplished by previously emulsifying the emulsion (P) obtained from ethylenically unsaturated monomer (E) is carried out, a polymerization initiator, the same or similar as described for the polymerization initiator (D).

The polymerization initiator (D) can previously in the Polymerization vessel to be added or immediately before initiating can be added to the polymerization and can also be added during be added to the polymerization as necessary. alternative it can be added to the ethylenically unsaturated monomer (E) before Emulsifying can be added or can be added to the emulsion (P) after the Emulsifying can be added. The addition of the polymerization initiator (D) can be done after separate dissolution in a solvent and the Solution of the polymerization initiator (D) thus obtained can be emulsified and then added.

The procedure for loading the respective components is subject to no particular limitation and it can be a procedure are used in which after dissolving the emulsifier (C) in Water the other components are charged, or alternatively after dissolving the emulsifier (C) in the mixed solution of the ethylenically unsaturated monomer (E) the other components be added.

The mixing amount of the emulsifier (C) is preferably 0.3 to 7 Parts by weight per 100 parts by weight of the ethylenically unsaturated Monomers (E). The range is more preferably 0.5 to 5 parts by weight. If the amount of emulsifier (C) is less than 0.3 part by weight the performance of the emulsification cannot are maintained, thereby reducing the polymerization stability becomes. If the mixing amount of the emulsifier (C) exceeds 7% by weight, on the other hand, there is a tendency that the adhesiveness that Adhesion to a base material and water resistance reduced become.

The amount of water used is preferably 25 to 200 Parts by weight per 100 parts by weight of the ethylenically unsaturated Monomers (E). The range is more preferably 30 to 150 Parts by weight. If the amount of water used is less than 25 Parts by weight, this is not preferred because the emulsion (P) can have a high viscosity and the polymerization stability can be reduced. If the amount of water is 200 parts by weight exceeds, there is a tendency that the concentration of the Emulsion is reduced, which reduces the drying properties when Coating will deteriorate.

The temperature of the emulsion (P) is then in the presence of the Resin emulsion (II) increased to initiate the polymerization. The the amount of the polymerization initiator (D) used is preferred 0.03 to 5 parts by weight, and more preferably 0.05 to 3 parts by weight per 100 Parts by weight of the ethylenically unsaturated monomer (E). If the Amount of the polymerization initiator (D) is less than the range the rate of polymerization will be delayed and if the Exceeds the range, the molecular weight tends to be of the resin is reduced, thereby reducing the holding force.

Examples of the polymerization method include methods in which the resin emulsion (II) and the emulsion (P) are mixed and the Temperature is then increased to effect the polymerization; mixing part of the emulsion (P) with the remaining emulsion (II) whereupon the temperature is increased to initiate the polymerization, and then the entire amount of the rest of the emulsion (P) is added dropwise, gradually or continuously to the Continue polymerization; and the drop by drop, step or continuous addition of the emulsion (P) in the presence of the resin emulsion (II) to effect polymerization, but is limited to these methods do not exist.

The polymerization temperature is not particularly limited and in general the polymerization is preferably carried out in one Temperature range of about 40 to 90 ° C performed.

After the polymerization, an alkaline solution, such as aqueous ammonia, various types of water-soluble amines, an aqueous solution of sodium hydroxide and an aqueous solution of Potassium hydroxide added to adjust the pH to a range from 5 to 9 and preferably set from 6 to 8, using an emulsion receives that is suitable as an emulsion of the composition of the sticky agent according to the invention.

The emulsion obtained preferably comprises fine particles with a Particle diameter from 0.10 to 0.35 µm, and more preferably from 0.13 to 0.25 µm.

The content of resin emulsion (II) in the resulting emulsion is preferably 10 to 80% by weight, expressed as solids content, based on total solids. The salary of the Resin emulsion (II) is more preferably 20 to 60% by weight and particularly preferably 25 to 50% by weight. It is not preferred that the content of Resin emulsion (II) is less than 10% by weight because of the adhesiveness polyolefin becomes insufficient and it is also not preferable that the Resin emulsion (II) content exceeds 80% by weight because of the holding force is reduced and the resistance to fading or Whitening when immersed in water is reduced.

The effect of the present invention can be considerably improved if a crosslinking agent (F) is also in the emulsion the composition of the tackifying agent of the invention Is mixed in.

The crosslinking agent (F) used here is not subject to any particular one Limitation and examples include a carbodiimide compound, an oxazoline compound, an aziridine compound, a hydrazine Compound, an isocyanate compound, a melamine compound, a Epoxy compound, a metal salt and a metal complex salt. Under these are at least one compound selected from the group of a carbodiimide compound, an oxazoline compound, an aziridine Compound and a hydrazine compound and especially one Carbodiimide compound and a hydrazine compound, preferred.

The carbodiimide compound can be a compound with at least two Be carbodiimide groups and examples of commercial products include "Carbodilite" (manufactured by Nisshinbo Industries, Inc.).

The oxazoline compound can be a compound with at least two Be oxazoline groups and examples of commercial products include "Epocros" (manufactured by Nippon Shokubai Co., Ltd.).

The aziridine compound can be a compound with at least two Be aziridine groups and include examples of commercial products "Chemitite" (manufactured by Nippon Shokubai Co., Ltd.).

The hydrazine compound can be a compound with at least two Be hydrazine groups and examples thereof include oxalic acid hydrazide, Malonic acid hydrazide, succinic acid hydrazide, glutaric acid hydrazide, Adipic acid hydrazide, sebacic acid hydrazide, maleic acid hydrazide, Fumaric acid hydrazide and itaconic acid hydsazide.

Examples of the isocyanate compound include an isocyanate Compound such as toloylene diisocyanate, 4,4'-diphenyimethane diisocyanate, Hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, Isophorone diisocyanate and tetramethylxylene diisocyanate; a Biuret polyisocyanate compound such as "Sumidur N" (manufactured by Sumitomo Bayer Urethane Co., Ltd.); a polyisocyanate compound with an isocyanurate ring such as "Desmodur IL" and "Desmodur HL" (made by Bayer AG) and "Coronate EH" (manufactured by Nippon Polyurethane Industry Co., Ltd.); an adduct-polyisocyanate compound, such as "Sumidur L" (manufactured by Sumitomo Bayer Urethane Co., Ltd.); and an adduct polyisocyanate compound such as "" Coronate HL " (manufactured by Nippon Polyurethane Industry Co., Ltd.). On Block isocyanate can also be used without any problems.

Examples of the melamine compound include (Hexamethoxy) methylolmelamine and methoxymethylolmelurea.

Examples of the epoxy compound include "Denacol" and "Denacast" (manufactured by Nagase Chemtex Corporation).

Examples of the metal salt and the metallic complex salt include an ethylenediaminetetraacetic acid (EDTA) chelate salt, an acetic acid Ammonium complex salt and an ammonium carbonate complex salt one polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, Nickel, antimony, magnesium, vanadium, chrome and zircon.

The mixing ratio of the crosslinking agent (F) is depending on the Species generally at 0.05 to 10 parts by weight, preferably 0.08 up to 5 parts by weight and particularly preferably 0.1 to 3 parts by weight per 100 parts by weight of the solids content of the emulsion. If the Mixing amount of the crosslinking agent (F) less than 0.05 Is by weight, it is difficult to have sufficient adhesive force and Resistance to fading or white coloring when immersed in Water to achieve. If the blended amount of crosslinking agent (F) exceeds 10 parts by weight, there is a tendency for the Adhesion and stickiness are reduced.

According to the invention, depending on the need Coating properties improving agent, a thickener, an antiseptic and antifungal agent, an antirust agent, a freezer Defrost stabilizer, a plasticizer, a solvent with high Boiling point, pigment, filler and the like to the like obtained emulsion can be added and can before polymerization and fed in the step during the polymerization.

The resulting emulsion of the composition of the pressure sensitive Adhesive of the invention essentially does not form aggregated Products in the polymerization and exhibits excellent Storage stability, excellent adhesiveness (especially Adhesion to polyolefin), holding power, adhesion to a base material and water resistance (especially resistance to fading or white coloring when immersed in water).

Examples

The invention is explained in more detail by means of the following examples. In in the examples, all percentages and parts relate to the weight, except the percentages for light transmission.

example 1 Preparation of the resin emulsion (II) (first stage, polymerization)

A mixture containing 55.8 parts of 2-ethylhexyl acrylate (a1), 30 parts of n- Butyl acrylate (a1), 10 parts methyl methacrylate (a1), 4 parts acrylic acid (a2), 0.2 parts tripropylene glycol diacrylate (a2) and 50 parts "Super Ester A-125" (a rosin ester tackifier manufactured by Arakawa Chemical Industries, Ltd.) (B) became an aqueous solution added, which was obtained by dissolving 1.0 parts of dibasic Sodium phosphate dodecahydrate and 4.5 parts of an emulsifier ("SE- 10N ", manufactured by Asahi Denka Kogyo K.K. (C) in 190 parts water and stirred and mixed with a homomixer, one previous emulsification was achieved. The oil-soluble component the resulting emulsion (I ') had an average Particle diameter of 5 µm. The average or average Particle diameter was calculated from the distribution of the Scattering intensity measured using a dynamic Light scattering photometer "DLS-700" (manufactured by Otsuka Electronics Co., Ltd.) (the same will be used hereinafter).

Then, the emulsion (I ') was run with one pass at a pressure of 50 kg / cm ² and then with three passes at a pressure of 300 kg / cm ² using a high pressure homogenizer ("Homogenizer" manufactured by Gaulin Corp .) treated to obtain 345.5 parts of an emulsion (I) with an average particle diameter of the oil-soluble component of 0.15 μm.

Separately, 1.0 part was used as the polymerization initiator Ammonium persulfate in 19.0 parts of water to make one Initiator solution solved.

50 parts of water and 172.8 parts of the emulsion (I) were mixed into one Polymerization vessel introduced and the temperature was increased. When the temperature reached 80 ° C, 25% (5 parts) of 20 parts the initiator solution is added to the polymerization vessel and after Polymerization was carried out at 80 ° C for 30 minutes the rest of the emulsion (I) and 25% (5 parts) of the initiator solution at 80 ° C was added dropwise over 30 minutes to carry out the polymerization. Careful polymerization was then carried out at 80 ° C. for 1 Hour carried out to obtain a resin emulsion (II) (Average particle diameter 0.14 µm, resin concentration 43.9%). The resin concentration was removed from the residue after drying of 1 g of the resin emulsion at 110 ° C for 3 hours (im following is done the same).

Preparation of an emulsion of a composition of a pressure sensitive adhesive (second stage of polymerization)

A mixture of 1 30.2 parts of 2-ethylhexyl acrylate (e1), 70.0 parts of n- Butyl acrylate (e1), 23.3 parts methyl methacrylate (e1), 9.3 parts acrylic acid (e2) and 0.47 parts of tripropylene glycol diacrylate (e3) became one added aqueous solution which was formed by dissolving 1.6 Sharing an emulsifier ("SE-10N", manufactured by Asahi Denka Kogyo K. K.) (C) in 110 parts of water and stirred and with a homomixer mixed to obtain a previous emulsification, whereby 344.9 parts of an emulsion (P) was obtained.

The emulsion (P) was added to the resin solution (II) along with 33% (6.6 Divide) of the initiator solution at 80 ° C for 3 hours and then The remaining 17% (3, 4 parts) of the Initiator solution added. Then a careful Polymerization continued for 2 hours at 80 ° C.

After the polymerization was complete, the reaction mixture was cooled and adjusted to pH 7.5 with 5% aqueous ammonia, where an emulsion with a non-volatile content of 49%, a viscosity of 1500 mPa.s and a particle diameter of Received 0.17 µm. The viscosity was determined using a type B viscometer measured under the conditions at a temperature of 25 ° C (in following is done the same).

Measure the amount of coarse particles

100 g of the resulting emulsion (Em) was passed through a sieve of 200 mesh filtered and the filtered residue (aggregated material, i.e. coarse particles) was dried at 100 ° C for 3 hours to obtain the Measure the weight (mg per 100 g Em) of the coarse particles.

Crosslinking agent (F) mixed with the emulsion of the composition of the tackifying agent

1.0 part of a carbodiimide compound ("V-04" manufactured by Nisshinbo Industries, Inc.) as a crosslinking agent (F), 0.05 part of a fluorine Wetting agent (the wetting improver) ("FT-100", manufactured by Neos Co., Ltd.) as the coating properties improver and an appropriate amount of a thickener ("UH-541", manufactured by Asahi Denka Kogyo K.K.) became 100 Parts of the resulting emulsion added and mixed with it and the Viscosity was set to 10000 mPa.s to achieve a Emulsion of a composition of a tackifying agent as Target product. The resulting emulsion of the composition of the Pressure sensitive adhesive was subjected to the following ratings.

Shelf Life

The emulsion of the composition of the pressure-sensitive adhesive thus obtained was left to stand at 40 ° C. for 6 months, and the occurrence of an increase in viscosity of deposits and deposits was observed and evaluated with the following evaluation levels.
1: Viscosity increase, deposits and deposits did not occur.
3: Viscosity increase, deposits and deposits occurred.

In addition, the resulting emulsion of the composition of the tackifying agent on a peelable paper piled up with a dry thickness of 20 µm and after Drying at 100 ° C for 5 minutes was carried out on a base material a PET (polyester) film with a thickness of 50 µm or on the side the aluminum vapor deposition of a base material, which by aluminum vapor deposition was obtained (base material PET Film) adhered to form an adhesive film, the following Reviews of its adhesive properties have been submitted.

adhesive force

The adhesive film (using a PET film as the base material), thus obtained was peeled from the releasing paper and each on a stainless steel plate (SUS304) and a plate made of polyethylene (PE) (standard test plate, manufactured by Nippon Testpanel Co., Ltd.) at 20 ° C and 65% RH and it became the 180 ° peel strength (gf per 25 mm) according to the measurement method for the Adhesive force measured according to JIS Z0237.

holding force

The adhesive film (using a PET film as the base material), thus obtained was peeled from the releasing paper and stuck on a stainless steel test plate (SUS304) under Achieving an adhesive surface of 25 mm × 25 mm. At a Load of 1 kg applied at 80 ° C and 50% RH the sliding (mm) of the adhesive films was measured after 24 hours or the time until the adhesive film has peeled off (minutes) determined according to the measuring method for the holding force in accordance with JIS Z0237. in the If there was no sliding (i.e., sliding of 0 mm), the adhesive sheet became not deducted.

Ball adhesive force

Using a Type J Ball Adhesive Test Machine Dow became the ball number of the ball with the maximum Diameter caused by the adhesive force of the test piece (25 mm × 100 mm) at an angle of 30 ° under conditions of 20 ° C and 65% RH was stopped, measured.

Adhesion to the base material

The adhesive sheet (using an aluminum vapor-coated plate as a base material) was subjected to the same measurement as the measurement for the adhesive strength on a stainless steel plate (SUS304), and the adhesive property on the base material was compared with the peel strength (g per 25 mm) and the formwork conditions for carrying out the comprehensive assessment as follows. Peeling conditions A: The peeling took place at an interface with the glued material or there was a cohesive break in the adhesive layer.
B: The peeling took place at an interface with the base material. Comprehensive evaluation 1: The peeling took place at an interface with the adhesive material or there was a cohesive break in the adhesive layer and the peel strength was 1000 g or more per 25 mm.
2: Peeling occurred at the interface with the base material, and the peel strength was 1000 g or more per 25 mm.
3: Peeling occurred at the interface with the base material and the peel strength was less than 1000 g per 25 mm.

Resistance to fading or white coloring when immersed in water

The adhesive film (using a PET film as the base material, Width 25 mm) was peeled from the trigger paper and onto a Glued on glass plate. After dipping the assembly in warm Water at 60 ° C for 3 days was taken out of the water and measured directly for light transmission (%). The measurement the light transmittance was carried out using an "SZ- Σ80 Color Measuring System ", manufactured by Nippon Denshoku Industries Co., Ltd. and a test piece that is not in warm water immersed (i.e. the assembly formed by sticking the Adhesive film on the glass plate) was used as a blank for the measurement used.

Example 2 Preparation of the emulsion (II) (first polymerization stage)

A mixed solution containing 30.9 parts of 2-ethylheyl acrylate (a1), 60 parts of n- Butyl acrylate (a1), 5 parts methyl methacrylate (a1), 4 parts acrylic acid (a2), 0.1 part tripropylene glycol diacrylate (a2) and 50 parts "Super Ester A-125" (a rosin ester tackifier manufactured by Arakawa Chemical Industries, Ltd.) (B) became an aqueous emulsion added, which was formed by dissolving 1.0 parts of one dibasic sodium phosphate dodecahydrate and 4.5 parts of one Emulsifiers ("SE-10N", manufactured by Asahi Denka Kogyo K.K.) (C) in 190 parts of water and stirred and mixed with a homomixer Achieve a previous emulsification. The oil-soluble component the resulting emulsion (I ') had an average Particle diameter of 5 µm.

Subsequently, the emulsion (I ') was carried out with one pass at a pressure of 50 kg / cm ² and then further with three passes at a pressure of 300 kg / cm ² using a high pressure homogenizer ("Homogenizer" manufactured by Gaulin Corp.) treated to obtain 345.5 parts of an emulsion (I) with an average particle diameter of the oil-soluble component of 0.15 μm.

Separately, 1.0 part was used as the polymerization initiator Ammonium persulfate in 19.0 parts of water to make one Initiator solution solved.

50 parts of water and 172.8 parts of the emulsion (I) were mixed into one Polymerization vessel added and the temperature was increased. If the Temperature reached 80 ° C, 25% (5 parts) of the initiator solution in the polymerization vessel added and after performing the Polymerization at 80 ° C for 30 minutes was the rest of the Emulsion (I) and 25% (5 parts) of the initiator solution at 80 ° C for 30 Dropped minutes to carry out the polymerization. Subsequently was careful polymerization at 80 ° C for 1 hour carried out to form a resin emulsion (II) (average Particle diameter 0.14 µm, resin concentration 43.9%).

Preparation of an emulsion of a composition of a pressure sensitive adhesive according to the invention (second polymerization)

A mixture of 72.1 parts of 2-ethylhexyl acrylate (e1), 140 parts of n- Butyl acrylate (e1), 11.7 parts of methyl methacrylate (e1), 9.3 parts of acrylic acid (e2) and 0.23 parts of tripropylene glycol diacrylate (e3) became one aqueous solution added by dissolving 1.6 parts of a Emulsifiers ("SE-10N", manufactured by Asahi Denka Kogyo K.K.) (C) in 110 parts of water and stirred and mixed with a homomixer to form a previous emulsification, giving 344.9 parts an emulsion (P).

The emulsion (P) was added to the resin solution (II) along with 33% (6.6 Divide) of the initiator solution at 80 ° C for 3 hours and then When the dropwise addition was complete, the remaining 17% (3.4 Parts) of the initiator solution are added. Then it was carefully continued Polymerized at 80 ° C for 2 hours.

After the polymerization was complete, the reaction mixture was cooled and adjusted to pH 7.5 with 5% aqueous ammonia, where an emulsion with a non-volatile content of 49%, a viscosity of 1800 mPa.s and a particle diameter of 0.1 7 µm was obtained. The resulting emulsion was the same Subjected to evaluations as in example 1.

To 100 parts of the resulting emulsion, 2 parts of an oxazoline Compound ("Epocros K-2010E" manufactured by Nippon Shokubai Co., Ltd.) as a crosslinking agent (F), 0.05 part of a fluorine wetting agent ("FT-100" manufactured by Neos Co., Ltd.) as an aid to Improve the coating properties and a suitable one Amount of thickener ("UH-541" manufactured by Asahi Denka Kogyo K.K.) was added and the viscosity was raised to 10000 mPa.s adjusted to obtain an emulsion of a composition of a tackifying agent as a targeted product.

The resulting emulsion of the composition of the pressure sensitive adhesive was given the same reviews for the Storage stability and the stickiness properties as in Example 1 subjected.

Example 3

The procedure was as in Example 1, except that Crosslinking agent (F) was exchanged with 0.3 part of 2.2- Bishydroxymethylbutanol-tris as one. Aziridine compound ("Chemitite PZ- 33 ", manufactured by Nippon Shokubai Co., Ltd.) to form a Emulsion of a composition of a tackifying agent. The resulting emulsion of the composition of the tackifying By means of the same ratings for shelf life and Tackiness as in Example 1 subjected.

Example 4

The procedure was as in Example 1, except that in first polymerization step the amount of 2-ethylhexyl acrylate (a1) was exchanged to 55.0 parts and 0.2 parts of tripropylene glycol diacrylate (a2) was exchanged for 1.0 part of diacetone acrylamide (a2) and in the second polymerization stage, the amount of 2- Ethyl hexyl acrylate (a1) exchanged for 128.3 parts and 0.47 parts Tripropylene glycol diacrylate (e3) became 2.3 parts of diacetone arylamide (e3) added to obtain an emulsion with a non-volatile part of 49%, a viscosity of 1600 mPa.s and one Particle diameter of 0.1 7 µm. The resulting emulsion of The composition of the pressure sensitive adhesive was the subjected to the same evaluations as in Example 1.

0.3 part was added to 100 parts of the resulting emulsion Adipic acid hydrazide as a hydrazine compound (manufactured by Otsuka Chemical Co., Ltd.) as a crosslinking agent (F) and 0.2 parts of a fluorine Crosslinking agent ("FT-100" manufactured by Neos Co., Ltd.) as an agent to improve the coating properties and a suitable Amount of thickener ("UH-541" manufactured by Asahi Denka Kogyo K.K.) was added and mixed and the viscosity was set to 10000 mPa.s to achieve an emulsion of a Composition of a tackifier. The resulting one Emulsion of the composition of the tackifying agent was the same rating for shelf life and the Tackiness properties as in Example 1 subjected.

Example 5

The same procedure as in Example 4 was carried out with except that 1.0 part of 2- (acetoacetoxy) ethyl acrylate (a2) instead of 1.0 part of diacetone acrylamide (a2) were used.

Example 6

The procedure was as in Example 4, but with 1.0 part Allylacetoacetate (a2) instead of 1.0 part of diacetone acrylamide (a2) were used.

Example 7

The procedure was as in Example 1, but "Pensel D125" (a polymerized rosin ester tackifier from Arakawa Chemical Industries, Ltd.) instead of "Super Ester A- 125 "(a rosin ester tackifier made by Arakawa Chemical Industries, Ltd.) (B) was used while achieving an emulsion with a non-volatile content of 49%, a viscosity of 1500 mPas and a particle diameter of 0.17 µm. The resulting emulsion was given the same ratings as in Example 1 subjected.

The emulsion of a composition of a tackifying agent was obtained using the resulting emulsion in the same Way as in Example 1 and the resulting emulsion of The composition of the tackifying agent was the same Reviews of shelf life and the Tackiness properties as in Example 1 subjected.

Example 8

The procedure was as in Example 1, but "YS Polyester N-125" (a terpene-phenolic resin tackifying agent) manufactured by the Yasuhara Chemical Co., Ltd.) was used instead of "Super Ester A-125 "(a rosin sulfate releasing agent manufactured by Arakawa Chemical Industries, Ltd.) (B) to achieve an emulsion with a non-volatile content of 49%, a viscosity of 1400 mPa.s and a particle diameter of 0.17 µm. The resulting emulsion was subjected to the same ratings as in Example 1.

The emulsion of a composition of the tackifying agent was obtained using the emulsion in the same manner as in Example 1 and the resulting emulsion of the composition of the Tackifier was given the same ratings for that Storage stability and the stickiness properties as in Example 1 subjected.

Example 9

The procedure was as in Example 1, with the exception that both in the first polymerization stage as well as in the second Polymerization step reduced the amounts of acrylic acid in half were and the amounts of 2-ethylhexyl acrylic according to the reduced amounts were increased to achieve an emulsion with a non-volatile content of 49.5%, a viscosity of 800 mPa.s and a particle diameter of 0.16 µm. The resulting emulsion was subjected to the same evaluations as in Example 1.

The emulsion of a composition of a tackifying agent was obtained in the same manner as in Example 1, but with the Amount of carbodiimide compound ("V-04" manufactured by Nisshinbo Industries, Inc.) as the crosslinking agent (F) was changed to 1.5 parts and the resulting emulsion of the composition of the Tackifier was given the same ratings for that Shelf life and stickiness properties as in Example 1 subjected.

Example 10

The procedure was as in Example 1, but both in the first and in the second polymerization stage the amounts of acrylic acid Were increased 1.5 times and the amounts of 2-ethylhexyl acrylate Amounts corresponding to the increased amounts were decreased below Achieving an emulsion with a non-volatile content of 47.5%, a viscosity of 2000 mPa.s and a particle diameter of 0.18 µm. The resulting emulsion was rated the same as in Subject to Example 1.

An emulsion of a composition of the pressure sensitive adhesive was obtained in the same manner as in Example 1, except that the amount of carbodiimide compound ("V-04" made by the Nisshinbo Industries, Inc.) as a crosslinking agent (F) to 0.75 parts was changed and the resulting emulsion of the composition of the adhesive the same ratings for shelf life and the stickiness properties were subjected as in Example 1.

Example 11

We worked in example 4, but both in the first as well as in the second polymerization stage Diacetone acrylamide were reduced to a third party and the amounts increased 2-ethylhexyl acrylate in amounts corresponding to the enlarged amounts were raised to form an emulsion with a non- volatile content of 49%, a viscosity of 1200 mPa.s and a Particle diameter of 0.17 µm. The resulting emulsion was the subject to the same ratings as in Example 1.

An emulsion of a composition of a pressure sensitive Adhesive was prepared in the same manner as in Example 1, with however, the amount of adipic acid hydrazide (manufactured by Otsuka Chemical Co., Ltd.) as crosslinking agent (F) changed to 0.5 parts and the resulting emulsion of the composition of the Adhesive received the same ratings for shelf life and subjected to the stickiness properties as in Example 1.

Example 12

The procedure was as in Example 4, but both in the first as well as in the second polymerization stage Diacetone acrylamide were increased twice and the amounts of 2- Ethyl hexyl acrylate in amounts corresponding to the increased amounts were reduced to achieve an emulsion with a non- volatile content of 49%, a viscosity of 1900 mPas and a Particle diameter of 0.17 µm. The resulting emulsion was the subject to the same ratings as in Example 1.

An emulsion of a composition of pressure sensitive adhesive in the same manner as in Example 1, wherein however, the amount of adipic acid hydrazide (manufactured by Otsuka Chemical Co., Ltd.) as crosslinking agent (F) changed to 0.15 parts and the resulting emulsion of the composition of the The adhesive was rated the same for storage stability and subjected to the stickiness properties as in Example 1.

Comparative experiment 1

The procedure was as in Example 1, but the treatment of Emulsion (I ') (with an average particle diameter of oil-soluble component of 5 µm) with the high-pressure homogenizer ("Homogenizer" manufactured by Gaulin Corp.) was not carried out but the polymerization (polymerization in the first stage) without it, to obtain a resin emulsion (Average particle diameter 0.1 2 µm, resin concentration 43.9%). The second stage polymerization was carried out using the resulting resin emulsion in the same manner as in. Example 1 carried out to obtain an emulsion with a non-volatile Proportion of 48.5%, a viscosity of 2000 mPa.s and a Particle diameter of 0.15 microns, with an emulsion Composition of a pressure sensitive adhesive obtained. The Emulsion and the emulsion of the composition of the tackifying By means of which one received the same ratings as in Subject to Example 1.

Comparative Example 2

A mixed solution containing 55.8 parts of 2-ethylhexyl acrylate (a1), 30 parts of n- Butyl acrylate (a1), 10 parts methyl methacrylate (a1), 4 parts acrylic acid (a2), 0.2 parts tripropylene glycol diacrylate (a2) and 50 parts "Super Ester A-125" (a rosin ester tackifier manufactured by Arakawa Chemical Industries, Ltd.) (B) became an aqueous one Solution added, which was obtained by dissolving 1.0 parts dibasic sodium phosphot dodecahydrate and 4.5 parts of one Emulsifier ("SE-10N", manufactured by Asahi Denka Kogyo K. K,) (C) in 190 Divide water and it was stirred and mixed with a homomixer mixed to form a previous emulsion. The oil-soluble Component of the resulting emulsion (I ') such as an average Particle size of 5 µm.

Subsequently, the emulsion was further processed by one pass at a pressure of 50 kg / cm ² and then three passes at a pressure of 300 kg / em ² using a high pressure homogenizer ("Homogenizer" manufactured by Gaulin Corp.) to obtain 345.5 parts of an emulsion (I) with an average particle diameter of the oil-soluble component of 0.15 μm.

Comparative experiment 3

The procedure was as in Example 1, but the amount of "Super Ester A-125" (a rosin-releasing agent, manufactured by Arakawa Chemical industries, Ltd.) (B) to 15 parts, the amount of water was changed to 97.2 parts, the Amount of dibasic sodium phosphate dodecahydrate per 0.3 part was changed and the amount of emulsifier ("SE-10N" manufactured by the Asahi Benk Kogyo K.K.) (C) was changed to 3.5 parts, below Formation of an emulsion (I) with an average Particle diameter of the oil-soluble component of 0.20 µm. The Polymerization was further carried out in the same manner, however the amount of water in the polymerization vessel to 10 parts was changed to form an emulsion with a non-volatile Share of 48.5%, a viscosity of 150 mPa.s and a Particle diameter of 0.20 µm.

The emulsion was obtained under an adhesive composition Use the resulting emulsion in the same way as in the example 1. The emulsion of the adhesive composition thus obtained was subjected to the same evaluations as in Example 1.

Comparative experiment 4

The first stage and the second stage of the polymerization were the same Performed as in Example 1, except that "Super Ester A-125" (a rosin ester tackifier manufactured by Arakawa Chemical Industries, Ltd.) (B) was left out achieving an emulsion with a non-volatile content of 43%, one Viscosity of 100 mPa.s and a particle diameter of 0.15 µm, whereupon "Super Ester A-125" which had been emulsified separately was added was in the same amount as in Example 1, forming an emulsion has been. The crosslinking agent (F), which has the coating properties improving agents were added in the same manner as in Example 1 to obtain an emulsion of an adhesive composition. The Emulsion and the emulsion of the adhesive composition so were obtained, were the same reviews in the same Way as in Example 1 subjected.

Summary and evaluation of the results

The evaluation results of Examples 1 to 12 and Comparative Experiments 1 to 4 are shown in Tables 1 to 3 below.

The emulsion of the composition of a pressure sensitive adhesive according to the invention is described in the specific above Process produced and thus has the advantages that in essentially no aggregated product formed during the polymerization and it has excellent storage stability as well as a excellent adhesiveness (especially adhesiveness to Polyolefin), holding force, adhesion to a base material and Water resistance (especially resistance to fading or white coloring when immersed in water).

Claims (8)

1. A method of making an emulsion of a pressure sensitive adhesive composition comprising the following steps:
Emulsifying an oil-soluble component comprising an ethylenically unsaturated monomer A mainly comprising an alkyl (meth) acrylate ester a1 and a tackifying agent B in an aqueous medium using an emulsifier C to form an average particle diameter of the oil-soluble component of 1 , 0 µm or less, for the preparation of an emulsion I,
Polymerizing the emulsion I in the presence of a polymerization initiator D to form a resin emulsion II and
Polymerization of an ethylenically unsaturated monomer E, which mainly comprises an alkyl (meth) acrylate ester e1, in the presence of resin emulsion II to form an emulsion of a pressure sensitive adhesive composition. 2. Process for the preparation of an emulsion of a pressure sensitive The adhesive composition of claim 1, wherein the is ethylenic unsaturated monomer E in addition Carboxyl group-containing unsaturated monomer e2 in addition to that Contains alkyl (meth) acrylate ester e1. 3. Process for the preparation of an emulsion of a pressure sensitive The adhesive composition of claim 2, wherein the content of the Carboxyl group-containing unsaturated monomers e2 1 to 10% by weight, based on the ethylenically unsaturated monomer E. is. 4. Process for the preparation of an emulsion of a pressure sensitive The adhesive composition of claim 1, wherein the is ethylenic unsaturated monomer E in addition Unsaturated monomer e2 containing carboxyl groups and a crosslinking one Group-containing unsaturated monomer e3 (which is the Carboxyl group-containing unsaturated monomer e2) in addition to the alkyl (meth) acrylate ester e1. 5. Process for the preparation of an emulsion of a pressure sensitive The adhesive composition of claim 4, wherein the content of the Carboxyl group-containing unsaturated monomers e2 1 to 10% by weight, based on the ethylenically unsaturated monomer E. is and the content of the containing a crosslinking group unsaturated monomer e3 (which contains the carboxyl group unsaturated monomer e2) 0.05 to 5 wt .-%, based on the ethylenically unsaturated monomer E. 6. Process for the preparation of an emulsion of a pressure sensitive The adhesive composition of claim 4, wherein the is the crosslinking Group-containing unsaturated monomer e3 (which is the Excludes carboxyl group-containing unsaturated monomer e2) is the unsaturated monomer containing the ket group. 7. Process for the preparation of an emulsion of a pressure sensitive The adhesive composition of claim 1, wherein the emulsion of the Adhesive composition also a crosslinking agent F contains. 8. Process for producing a pressure sensitive emulsion The adhesive composition of claim 7, wherein the Crosslinking agent F is at least one compound selected from the Group of a carbodiimide compound, an oxazoline compound, one Aziridine compound and a hydrazine compound.