WO2005082953A1

WO2005082953A1 - Modified petroleum resin emulsion and acrylic pressure -sensitive adhesive compositions containing the same

Info

Publication number: WO2005082953A1
Application number: PCT/JP2005/003274
Authority: WO
Inventors: Sadaharu Hashimoto; Haruo Yanase
Original assignee: Zeon Corporation
Priority date: 2004-03-01
Filing date: 2005-02-28
Publication date: 2005-09-09
Also published as: CN1910209A; TWI357910B; TW200613350A; JP4940946B2; CN100503656C; JPWO2005082953A1

Abstract

The invention relates to a modified petroleum resin emulsion containing a modified petroleum resin which comprises 10 to 100 % by mass of C4-6 olefinic unsaturated hydrocarbon monomer units and 0 to 90 % by mass of C7-11 olefininc unsaturated hydrocarbon monomer units and has a softening point of 30˚C or above and an acid value of 0.1 to 100 KOHmg/g, and provides acrylic pressure-sensitive adhesive compositions which are excellent both in the peel adhesion to polyolefin resin adherends and in the balance between initial tack and holding power and a modified petroleum resin emulsion useful as the tackifier for the compositions.

Description

Specification

Modified petroleum resin emulsion and acrylic pressure-sensitive adhesive composition using the same

The present invention relates to a modified petroleum resin emulsion and an acrylic pressure-sensitive adhesive composition using the same, and more particularly, to a polyolefin-based resin adherend having excellent peel adhesive strength, and The present invention relates to an acrylic pressure-sensitive adhesive composition having an excellent balance between adhesion and holding power, and a modified petroleum oil emulsion suitable as a tackifier for the pressure-sensitive adhesive composition.

Background art

[0002] Aqueous pressure-sensitive adhesive compositions containing an acrylic polymer emulsion as a main component are widely used because they are colorless and transparent, have excellent aging resistance, and are unlikely to cause environmental problems due to volatilization of organic solvents. Such acrylic pressure-sensitive adhesive compositions usually include a rosin-based tackifying resin, a terpene-based tackifying resin, and a petroleum resin for the purpose of improving the adhesive properties such as peel adhesion, initial adhesion, and holding power. A tackifying resin such as a system tackifying resin is blended.

[0003] For example, Patent Document 1 discloses that an acrylic polymer emulsion contains 10 to 60% by mass of an aromatic vinyl monomer unit such as styrene or a-methylstyrene, and has a softening point of 10 to 120 ° C. An aqueous acrylic pressure-sensitive adhesive composition containing an emulsion composed of petroleum resin is disclosed. In Patent Document 2, the aromatic ring of an aromatic hydrocarbon resin obtained by polymerizing a C9 fraction such as vinyl toluene and indene on an acrylic polymer emulsion is partially hydrogenated. An aqueous acrylic pressure-sensitive adhesive composition containing an emulsion comprising a tackifying resin is disclosed. However, the pressure-sensitive adhesive composition as described above was inferior in peel adhesion to a non-polar adherend such as polyethylene.

[0004] Further, Patent Document 3 discloses that a liquid tackifying resin is 3-45 parts by mass with respect to 100 parts by mass of a solid content of an acrylic polymer emulsion having a glass transition temperature of 60--30 ° C. And an aqueous acrylic pressure-sensitive adhesive composition comprising a crosslinking agent. However, such a pressure-sensitive adhesive composition had poor holding power. Patent Document 1: JP-A-61-275363

Patent Document 2: JP-A-9-188864

Patent Document 3: JP-A-2000-319618

Disclosure of the invention

[0006] In view of the above circumstances, an object of the present invention is to provide an acrylic pressure-sensitive adhesive composition having excellent peel adhesion to a polyolefin resin adherend and excellent balance between initial adhesion and holding power, and It is an object of the present invention to provide a modified petroleum oil emulsion suitable as a tackifier for the pressure-sensitive adhesive composition.

The present inventors have conducted intensive studies to achieve the above object, and as a result, found that 10 to 100% by mass of unitary unsaturated unsaturated hydrocarbon monomer units having 416 carbon atoms and 7 to 11 carbon units of olefinic unsaturated hydrocarbon monomer units. When a modified petroleum resin emulsion containing 0 to 90% by mass of an insoluble unsaturated hydrocarbon monomer unit and having a specific softening point and an acid value is used, a polyolefin resin is used.

The present inventors have found that an acrylic pressure-sensitive adhesive composition having excellent peel adhesion to an adherend and excellent balance between initial adhesion and holding power can be obtained, and based on this finding, have completed the present invention.

Thus, according to the present invention, there is provided a olefinic unsaturated hydrocarbon monomer having 4 to 6 carbon atoms in an amount of 10 to 100% by mass and an olefinic unsaturated hydrocarbon monomer having 7 to 11 carbon atoms. Provided is a modified petroleum oil emulsion comprising a modified petroleum oil having a unit of 0 to 90% by mass, a softening point of 30 ° C. or more, and an acid value of 0.1 to 0.1 OOKOHmgZg.

Further, according to the present invention, there is provided an acrylic pressure-sensitive adhesive composition containing the acrylic polymer emulsion and the above-mentioned modified petroleum resin emulsion.

Further, according to the present invention, there is provided a pressure-sensitive adhesive tape obtained by applying the acrylic pressure-sensitive adhesive composition on a substrate.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

(Modified petroleum fat emulsion)

The modified petroleum resin emulsion of the present invention is a olefinic unsaturated hydrocarbon having 416 carbon atoms. Monomeric unit 10-100% by mass and C 7-11 olefinic unsaturated hydrocarbon monomer unit 0-90% by mass, softening point 30 ° C or more, and acid value 0 1-Contains 100KOH mgZg of modified petroleum resin.

[0008] The modified petroleum榭脂is Orefuin unsaturated hydrocarbon monomer units 10- 100 mass ^_0/0 of 4 one 6 carbons, preferably 40- 95 weight ^_0/0, more preferably 50- 85 mass ^_0/0 and Orefuin unsaturated hydrocarbon monomer units 0- 90 wt% of carbon number 7-11, preferably 5- 60 wt%, and more preferably is made of 15 50 wt%. When the content of the olefinic unsaturated hydrocarbon monomer unit having 416 carbon atoms is small, the peel adhesion to the polyolefin resin adherend is poor, and the initial adhesion is also reduced. Modified petroleum resin containing olefinic unsaturated hydrocarbon monomer units having 7 to 11 carbon atoms in order to further enhance the peel adhesion and holding power to polyolefin resin adherends. preferable

[0009] Examples of the olefinic unsaturated hydrocarbon monomer having 416 carbon atoms used as a raw material include monoolefinic unsaturated hydrocarbons and olefinic unsaturated hydrocarbons having 416 carbon atoms.

Examples of the monoolefinic unsaturated hydrocarbon having 416 carbon atoms include linear monoolefins such as isobutene, 1-butene, 2-butene, 1-pentene, 2-pentene, methylbutene, methylpentene and hexene; cyclopentene, methyl Cyclic monoolefins such as cyclopentene and cyclohexene; and the like.

[0010] Examples of the diolefinic unsaturated hydrocarbon monomer having 416 carbon atoms include a chain conjugated diene such as 1,3-butadiene, isoprene, 1,3 pentadiene and 1,3-hexadiene; Cyclic conjugated gens such as cyclopentadiene and methylcyclopentadene; non-conjugated gens such as 1,2-butadiene and 1,4 pentadene;

[0011] The amount of the olefinic unsaturated hydrocarbon monomer having 416 carbon atoms used in the production of the modified petroleum resin is preferably at least 10% by weight, more preferably at least 10% by weight, based on the total amount of the monomer. It is from 45 to 95% by mass, particularly preferably from 55 to 85% by mass. If the amount is too small, the peel adhesion to the polyolefin-based resin adherend is inferior, and the initial adhesion is also reduced.

[0012] A monoolefinic unsaturated hydrocarbon monomer having 416 carbon atoms and a diolefin having 416 carbon atoms The ratio with the unsaturated unsaturated hydrocarbon monomer is preferably 20Z80-80Z20, more preferably 30-70-70-30, and particularly preferably 35-65-65-35 by mass ratio.

[0013] In the present invention, it is preferable to use a diolefinic hydrocarbon having 416 carbon atoms containing 70% by mass or more, more preferably 90% by mass or more of isoprene and Ζ or 1,3 pentadiene.

[0014] The olefinic unsaturated hydrocarbon monomer having 7 to 11 carbon atoms optionally used as a raw material includes, for example, aromatic aromatic compounds such as styrene, α-methylstyrene, ρ-methylstyrene, ethylstyrene, and t-butylstyrene. Bull monomer; 2,4,4 trimethyl-1 pentene, 2,4,4 trimethyl-2 pentene, heptene, otaten, etc., chain monoolefins having 7-11 carbon atoms; methylcyclohexene, dicyclopentadiene, indene, Examples include cyclic olefins having 7 to 11 carbon atoms such as coumarone. Of these, styrene, which is preferably an aromatic vinyl monomer, is more preferably used.

The amount of the olefinic unsaturated hydrocarbon monomer having 7 to 11 carbon atoms used in the production of the modified petroleum resin is preferably 90% by mass or less, more preferably 5 to 5% by mass, based on the total amount of the monomers. It is 5% by mass, particularly preferably 15-45% by mass. When used in the above range, an acrylic pressure-sensitive adhesive composition having excellent peel adhesion and holding power to a polyolefin resin adherend can be obtained.

[0015] The soft petroleum point of the modified petroleum resin is 30 ° C or more, preferably 50 to 130 ° C, more preferably 80 to 120 ° C. When the softening point is less than 30 ° C, the pressure-sensitive adhesive composition has poor holding power.

[0016] The acid value of the modified petroleum resin is 0.1-lOOKOHmgZg, preferably 0.3-50KOHmgZg, more preferably 1-120KOHmgZg. When the acid value is low or high, the peel adhesion to a polyolefin resin adherend is poor.

[0017] The weight average molecular weight of the modified petroleum resin is preferably in the range of 1,000 to 4,000, more preferably in the range of 1,500 to 3,500. When the weight average molecular weight is in the above range, an acrylic pressure-sensitive adhesive composition having excellent peel adhesion and holding power to a polyolefin resin adherend can be obtained.

[0018] The above modified petroleum resin is usually obtained by subjecting the above monomer to cationic polymerization using an acidic metal halide catalyst in a polymerization solvent to obtain a petroleum resin, and then obtaining the obtained petroleum resin. Etile on resin Obtained by an addition reaction of an unsaturated carboxylic acid.

[0019] The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Examples thereof include fatty acids such as pentane, hexane, heptane, cyclopentane, cyclohexane, isopentane, and methylpentane. Aromatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and the like. These polymerization solvents can be used alone or in combination of two or more.

The amount of the polymerization solvent to be used is generally 40 to 200 parts by mass, preferably 60 to 100 parts by mass, based on 100 parts by mass of the total amount of the monomers.

[0020] The acidic halogenated metal catalyst used as the polymerization catalyst is not particularly limited as long as it is a Friedel-Crafts type catalyst. Representative examples include fluorides, chlorides, bromides and iodides of metals such as aluminum, boron and iron. Among them, aluminum chloride, which is preferably aluminum halide such as aluminum chloride and aluminum bromide, can be more preferably used.

The amount of the acidic metal halide catalyst to be used is generally 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total amount of the monomers.

[0021] In the polymerization, it is preferable to previously contact the acidic halogenated metal catalyst with the cyclic monoolefin. As the cyclic monoolefin, cyclopentene, which is preferably a cyclic monoolefin having 5 to 6 carbon atoms, can be more preferably used. The amount of the cyclic monoolefin used herein is preferably at least 5 times the amount of the acidic halogenated metal catalyst.

As the polymerization operation, a conventionally known method can be employed.

The polymerization temperature is usually in the range of 20 ° C to 100 ° C, preferably 0 ° C to 80 ° C.

After the polymerization reaction is started, when a predetermined polymerization conversion ratio is reached, a polymerization terminator is added to stop the polymerization reaction. The polymerization conversion when terminating the polymerization reaction is usually 50 to 95% by mass, preferably 60 to 90% by mass.

After terminating the polymerization reaction, unreacted monomers and the polymerization solvent are distilled off, and if desired, low-molecular-weight oligomer components are removed by steam distillation at a high temperature to obtain a petroleum resin. Can be

[0025] Next, the obtained petroleum resin is subjected to an addition reaction with an ethylenically unsaturated carboxylic acid, Modifies oils and fats.

Examples of the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; and ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; Ethylenically unsaturated polycarboxylic anhydrides such as maleic anhydride and itaconic anhydride; partial esters of ethylenically unsaturated polycarboxylic acids such as monomethyl maleate and monoethyl fumarate; and the like. Of these, ethylenically unsaturated polycarboxylic acids and ethylenically unsaturated polycarboxylic anhydrides are preferred, and ethylenically unsaturated polycarboxylic anhydrides are more preferred, and maleic anhydride is particularly preferred. Can be used.

[0026] The amount of the ethylenically unsaturated carboxylic acid to be used is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the petroleum resin obtained above. Parts, particularly preferably 0.5-5 parts by weight.

[0027] Conditions for the addition reaction of the ethylenically unsaturated carboxylic acid are usually 50 to 300 ° C, preferably 200 to 270 ° C, preferably for 5 minutes to 20 hours, more preferably for 10 minutes to 13 hours. It is. At the time of the addition reaction, a diluent, an anti-gelling agent, a reaction accelerator and the like can be added as necessary.

[0028] The modified petroleum resin emulsion of the present invention is obtained by emulsifying the modified petroleum resin obtained as described above in an aqueous medium.

As the aqueous medium, an aqueous solution of a water-soluble organic solvent such as ethanol, ethylene glycol, and dalyserin, which is usually used in water, can also be used.

The amount of the aqueous medium to be used is generally 50 to 200 parts by mass, preferably 60 to 150 parts by mass, per 100 parts by mass of the modified petroleum resin.

[0029] The method of emulsification is not particularly limited. For example, (1) a method of wet-dispersing a modified petroleum resin in an aqueous medium at a temperature lower than the softening point of the modified petroleum resin, (2) an aqueous medium , A method in which the modified petroleum resin is emulsified while being heated to a temperature at which the modified petroleum resin is fluidized; (3) a method in which an organic solvent solution of the modified petroleum resin is emulsified in an aqueous medium; A method in which an aqueous medium is added to a modified petroleum resin heated to a temperature at which the modified petroleum resin is heated while stirring, and phase inversion emulsification is performed. And then subjecting the mixture to phase inversion emulsification. Among them, the point that it is easy to adjust the volume average particle diameter of the modified petroleum resin particles in the modified petroleum resin emulsion to a preferable range,

The method (3) or (5) can be preferably employed. When an organic solvent is used, it is preferable to distill the organic solvent from the emulsified emulsion.

[0030] The method of emulsifying the modified petroleum resin of the present invention includes (a) a high-pressure impact type (Gaulin homogenizer: manufactured by Gorin), and ( _b ) a rotor stator method (Ebara Milder: manufactured by Ebara Corporation). ), (C) Internal shear (liquid-liquid shear) method (for example, CLEARMIX, manufactured by Emtechnik), (d) Static tube method (static mixer), (e) Anchor type stirring method, (f) Line mill method , (G) vibration type, (h) membrane emulsification type, (i) centrifugal thin film contact type, and the like. Among them, the method (a), (b) or (c) is preferred in that the volume average particle diameter of the modified petroleum resin particles in the modified petroleum resin emulsion is preferably adjusted to a range. The method (a) can be particularly preferably employed.

[0031] The organic solvent for dissolving the modified petroleum resin is not particularly limited as long as it can dissolve the resin, and examples thereof include aromatic hydrocarbons such as benzene and toluene; pentane, hexane, heptane and the like. Aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclopentane and cyclohexane; and the like. Considering the safety in the emulsification process and the ease with which the organic solvent is distilled off, an organic solvent having a boiling point of 30 to 120 ° C can be preferably used.

The solution concentration is usually from 10 to 90% by mass, preferably from 50 to 80% by mass.

[0032] In emulsifying, the emulsifying agent is excellent in the storage stability of the obtained modified petroleum oil emulsion which is easy to adjust the volume average particle diameter of the modified oil oil particles in the modified oil emulsion to a preferable range. It is preferable to use.

Examples of the narcotics include, but are not limited to, sulfonated α-olefin sulphonates, alkyl sulfates, alkyl phenol sulfates, polyoxyethylene alkyl phenol ether sulfates, and polyoxyethylene alkyl phenol ether sulfo phenols. Acid-based emulsifiers such as acid half-ester salts and rosin stones; and non-ionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenol ethers.

The amount of the emulsifier to be used is generally about 110 parts by weight, preferably 115 parts by weight, per 100 parts by weight of the modified petroleum resin. [0033] The volume average particle diameter of the modified petroleum resin particles in the modified petroleum resin emulsion is preferably 0.1-, more preferably 0.2-0.6 m. When the volume average particle size is in the above range, an acrylic pressure-sensitive adhesive composition having a better balance of pressure-sensitive adhesive properties can be obtained.

In the modified petroleum resin emulsion of the present invention, it is preferable that the modified petroleum resin particles having a particle diameter of 30 μm or more are small. If the number of particles having a particle diameter of 30 m or more is too large, the surface of the pressure-sensitive adhesive composition becomes rough when the resulting pressure-sensitive adhesive composition is applied to a substrate, and the appearance becomes poor. A film may not be obtained, resulting in product defects and reduced peel adhesion. The number of modified petroleum resin particles having a particle diameter of 30 m or more can be measured in a specific particle size range using a precision particle size distribution analyzer. The number of modified petroleum resin particles having a particle diameter of 30 m or more is determined by measuring the number of all modified petroleum resin particles having a particle diameter in the range of 4-164 μm. Is relatively evaluated as a ratio of the number of modified petroleum resin particles in the above.

The ratio of the number of modified petroleum resin particles having a particle diameter of 30 μm or more in the modified petroleum resin particles having a particle diameter of 4-164 μm is preferably 1% or less 0.1% It is more preferable that the particle diameter is not more than 0.05%, and it is particularly preferable that there is no particle having a particle diameter of 30 μm or more.

[0035] The method for controlling the particle number distribution of the modified petroleum resin particles at a particle diameter of 4-164 µm to the above range is not particularly limited. And a method of removing modified petroleum resin particles having a particle diameter of 30 μm or more after emulsifying the volatile petroleum resin. The conditions adjusted when emulsifying the modified petroleum resin include temperature, pressure, stirring intensity and the like, and these conditions are adjusted as necessary. As a method for removing the modified petroleum resin particles having a particle diameter of 30 m or more after emulsifying the modified petroleum resin, filtration using a mesh filter under its own weight or pressure, and a filtration device equipped with a membrane filter are available. It is preferable to perform filtration under pressure using a mesh filter because the removal device and the operation are simple. The filtration operation can be repeated so that the particle number distribution of the modified petroleum resin particles at a particle diameter of 4 to 64 m falls within the above range.

[0036] The solid content of the modified petroleum fat emulsion is preferably 30% by mass or more. More preferably, it is 40 to 70% by mass.

[0037] To the modified petroleum oil emulsion, if necessary, compounding agents such as an antifoaming agent, a thickening agent, a filler, an antioxidant, a preservative, and an antibacterial agent can be added.

(Acrylic pressure-sensitive adhesive composition)

The acrylic pressure-sensitive adhesive composition of the present invention contains an acrylic polymer emulsion and the above-mentioned modified petroleum resin emulsion.

The acrylic polymer constituting the acrylic polymer emulsion contains, as a main component, an alkyl (meth) acrylate monomer unit.

Examples of the alkyl (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2- (meth) acrylate. And ethyl hexyl. These monomers can be used alone or in combination.

The acrylic polymer may be a copolymer of an alkyl (meth) acrylate monomer and another monomer copolymerizable therewith.

Other monomers copolymerizable with the alkyl (meth) acrylate monomer include, for example, (meth) acrylic acid, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) acrylonitrile, butyl acetate, styrene and the like.

[0040] The glass transition temperature of the acrylic polymer is not particularly limited, but is usually -80-0 ° C, preferably -60-10 ° C. If the glass transition temperature is too high, the initial adhesive strength tends to decrease, while if it is too low, the holding power tends to decrease.

[0041] The acrylic polymer emulsion is usually produced by emulsion polymerization of the above monomers.

. The method of emulsion polymerization is not particularly limited, and a conventionally known method can be employed.

[0042] The volume average particle diameter of the acrylic polymer particles in the acrylic polymer emulsion is not particularly limited, but is usually 0.05 to 1 µm, preferably 0.1 to 0.6 µm. .

[0043] The solid concentration of the acrylic polymer emulsion is usually from 40 to 70% by mass.

[0044] The acrylic pressure-sensitive adhesive composition of the present invention comprises a modified petroleum resin emulsion at a solid content of 100 parts by mass of an acrylic polymer emulsion, preferably 0.1 to 50 mass%. Parts, more preferably 2 to 40 parts by mass, particularly preferably 5 to 30 parts by mass. When the amount of the modified petroleum resin emulsion is within the above range, a pressure-sensitive adhesive composition having excellent peel adhesion to a polyolefin resin adherend and excellent initial adhesion and holding power can be obtained.

[0045] The acrylic pressure-sensitive adhesive composition may further include a plasticizer, a wax, an ultraviolet absorber, an antifoaming agent, a thickener, a filler, an antioxidant, a preservative, an antibacterial agent, and a water-resistant agent, if necessary. A compounding agent such as an agent or a film-forming aid can be added. In addition, an emulsion composed of a conventionally known tackifying resin may be added as long as the effects of the present invention are not substantially impaired.

[0046] (Adhesive tape)

The pressure-sensitive adhesive tape of the present invention is obtained by applying the acrylic pressure-sensitive adhesive composition on a substrate.

Examples of the substrate include, but are not particularly limited to, papers such as kraft paper, Japanese paper, high-quality paper, synthetic paper; cloths such as cotton cloth, soft cloth, and polyester cloth; cellophane, polyester film, polyamide film, and polyvinyl chloride film. And resin films such as polypropylene films and polyethylene films; metal foils such as aluminum foil and copper foil; nonwoven fabrics such as nonwoven fabrics made of polyester and nonwoven fabrics made of rayon. These substrates may be those whose surfaces have been subjected to corona discharge treatment or primer application in advance.

The thickness of the substrate is usually about 10 m-2 mm.

As the coating device, a conventionally known coating device can be used, and for example, a die coater, a comma coater, a roll coater, or the like can be used.

[0048] The coating amount of the acrylic pressure-sensitive adhesive composition is generally 200 µm, preferably 5 to 100 µm, as the thickness after drying.

[0049] After applying the acrylic pressure-sensitive adhesive composition on the substrate, the aqueous medium in the composition is volatilized to obtain a pressure-sensitive adhesive tape.

[0050] The pressure-sensitive adhesive tape of the present invention is particularly suitable as a pressure-sensitive adhesive tape for non-polar polyolefin-based resin products because it has excellent peel adhesion to non-polar polyolefin-based resin adherends. Of course, it can also be suitably used as an adhesive tape using a non-polar polyolefin resin as a substrate. Here, the polyolefin-based resin mainly refers to a homopolymer or copolymer of an olefin monomer such as ethylene, propylene, butene, and isobutene. In addition, polyolefin-based resins include those having a very small amount of polar groups.

Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the examples, “%” and “parts” are all by mass unless otherwise specified.

[0052] The evaluation was performed as follows.

(1) Styrene unit amount (%) in resin: determined by NMR analysis.

(2) Weight average molecular weight: It was determined as a standard polystyrene conversion value by gel permeation 'chromatography.

(3) Soft point (° C): Measured by a ring and ball method according to JIS K 2531.

(4) Acid value (mgKOHZg): Measured according to JIS K0070.

(5) Volume average particle diameter of emulsion: Measured using a light scattering particle diameter measuring device (LS-230: manufactured by Beckman Co., Ltd.).

(6) Proportion of the number of modified petroleum grease particles having a particle size of 30 μm or more: Modified petroleum grease emulsion 0.2 g (solid content: 50%), 200 ml of electrolyte solution (Isothon-Π), stirring and measurement Sample. Using a precision particle size distribution analyzer (Multisizer 1-3: manufactured by Beckman Coulter, Inc.), the number of modified petroleum resin particles having a particle diameter of 30 μm or more within a particle diameter of 4-64 μm in increments of 2 m It was measured. An aperture of 140 m was used for the measurement.

The ratio of the number of the modified petroleum resin particles having a particle diameter of 30 m or more is the percentage of the modified petroleum resin particles having a particle diameter of 4-164 m in the modified petroleum resin particles having a particle diameter of 30-64 m. It is shown by the ratio of the number.

(7) Peel adhesion (NZm): Measured at 23 ° C according to PSTC-1 (180 ° peel adhesion test by Adhesive Tapes Committee (US)) using polyethylene as an adherend. The higher the value, the better.

(8) Holding force (min): PSTC-6 (adhesive tape committee) using stainless steel as adherend (Retention force test method using (US)), using adhesive tape with a width of 25mm, at 25 × 25mm at the adhesive part, at a load of 3.92 × 104Pa, at a temperature of 50 ° C, and the time until peeling (minutes) Was measured. The longer the time, the better.

(9) Initial adhesion (mm): Rolling ball tack was measured at 23 ° C according to PSTC-6 (Initial adhesion test method by Adhesive Tapes Committee (US)). The smaller the value, the better.

(Synthesis example 1)

The reactor was charged with 86 parts of cyclopentane, 14 parts of cyclopentene and 1 part of Shiridani aluminum, and then heated to 50 ° C. Subsequently, the remaining monomer mixture consisting of 14 parts of cyclopentene, 44 parts of 1,3 pentadiene, 18 parts of styrene and 10 parts of a chain monoolefin having 4 to 16 carbon atoms (including 1 pentene, 2-butene, methylbutene, etc.) Was continuously added to the reactor over a period of 60 minutes to carry out polymerization. After continuing the reaction at 50 ° C. for 10 minutes, a mixture of methanol and aqueous ammonia was added to the reactor to stop the polymerization reaction. At this point, the polymerization conversion ratio was 85%.

After removing the precipitate generated by terminating the polymerization by filtration, the obtained polymer solution was charged into a distillation still and heated under a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers. Next, low-molecular-weight oligomer components were removed while blowing saturated steam at 240 ° C or higher.

Next, 2.97 parts of maleic anhydride was added to 100 parts of the molten resin, and

After an addition reaction at 1 ° C for 1 hour, 2,6-di-t-butyl-p-talesol

0.3 parts were added and mixed.

Thereafter, the resin in a molten state was taken out and allowed to cool to room temperature to obtain a modified petroleum resin A. The styrene unit amount, weight average molecular weight, softening point and acid value of the modified petroleum resin A were measured, and the results are shown in Table 1.

(Synthesis Example 2)

A modified petroleum resin B was obtained in the same manner as in Synthesis Example 1 except that the monomer composition and the amount of maleic anhydride shown in Table 1 were changed. The styrene unit amount, weight average molecular weight, softening point and acid value of the modified petroleum resin B were measured, and the results are shown in Table 1.

(Synthesis example 3) The reactor was charged with 86 parts of cyclopentane, 14 parts of cyclopentene and 1 part of Shiridani aluminum, and then heated to 50 ° C. Subsequently, the remaining monomer mixture consisting of 14 parts of cyclopentene, 44 parts of 1,3 pentadiene, 18 parts of styrene, and 10 parts of a chain monoolefin having 4 to 16 carbon atoms (including 1 pentene, 2-butene, methylbutene, etc.) Was continuously added to the reactor over a period of 60 minutes to carry out polymerization. After continuing the reaction at 50 ° C. for 10 minutes, a mixture of methanol and aqueous ammonia was added to the reactor to stop the polymerization reaction. At this point, the polymerization conversion ratio was 85%.

Next, 0.3 part of 2,6-di-t-butyl-P talesol as an antioxidant was added to 100 parts of the molten resin, and mixed. Thereafter, the resin in a molten state was taken out and allowed to cool to room temperature to obtain petroleum resin C. The styrene unit amount, weight average molecular weight, softening point and acid value of petroleum resin C were measured, and the results are shown in Table 1.

(Synthesis example 4)

The reactor was charged with 86 parts of cyclopentane, 14 parts of cyclopentene and 1 part of Shiridani aluminum, and then heated to 50 ° C. Subsequently, the remaining monomer mixture consisting of 7 parts of cyclopentene, 22 parts of 1,3 pentadiene, 18 parts of styrene, and 39 parts of a chain monoolephine having 416 carbon atoms (including 1 pentene, 2-butene, methylbutene, etc.) Was continuously added to the reactor over a period of 60 minutes. After continuing the reaction at 50 ° C for 10 minutes, a mixture of methanol and aqueous ammonia was added to the reactor to stop the polymerization reaction. The polymerization transfer ratio at this point was 76%.

After removing the precipitate generated by terminating the polymerization by filtration, the obtained polymer solution was charged into a distillation still and heated under a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers.

[0060] Next, 100 parts of the molten resin were added to 3.49 parts of maleic anhydride, and the mixture was subjected to an addition reaction at 230 ° C for 1 hour. —0.3 parts of g-ptyl-p-taresol was added and mixed. Thereafter, the resin in a molten state was taken out and allowed to cool to room temperature to obtain a modified petroleum resin D. The styrene unit amount, weight average molecular weight, softening point and acid value of the modified petroleum resin D were measured, and the results are shown in Table 1.

[table 1]

(Example 1)

To a solution of 100 parts of modified petroleum resin A dissolved in 60 parts of toluene, add an aqueous solution of 4 parts of an ionic emulsifier (sodium dodecylbenzenesulfonate) in 100 parts of water, and mix at 80 ° C. The mixture was emulsified at 1500 rpm for 1 hour using a homogenizer. Further, the obtained emulsion was emulsified at 90 ° C. for 10 minutes using a Gaulin homogenizer to obtain an emulsion having a uniform particle diameter.

Then, the toluene in the emulsion was removed by distillation under reduced pressure, followed by filtration through a 150-mesh stainless steel wire mesh, followed by filtration using a 500-mesh stainless steel wire mesh. A modified petroleum resin A having a concentration of 50% was obtained. The volume average particle diameter of the resin emulsion A1 and the ratio of the number of modified petroleum resin particles having a size of 30 μm or more were measured, and the results are shown in Table 2.

[0063] To 100 parts of the solid content of an acrylic polymer emulsion (Water Base Adhesive: ACHEM TECHNOLOGY CORPORATION) having a solid content concentration of 50% and containing butyl acrylate as a main component, the resin emulsion A was solidified. In 15 minutes, the mixture was mixed to prepare an acrylic pressure-sensitive adhesive composition.

The obtained acrylic pressure-sensitive adhesive composition was applied on a 25-m-thick polyester film using an applicator so that the thickness after drying was 25 m, and dried to obtain a pressure-sensitive adhesive tape.

The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

(Example 2)

A resin emulsion B1 was obtained in the same manner as in Example 1, except that the modified petroleum resin B was used instead of the modified petroleum resin A. The volume average particle diameter of the fat emulsion B1 and the ratio of the number of modified petroleum fat particles having a size of 30 m or more were measured, and the results are shown in Table 2.

An adhesive tape was obtained in the same manner as in Example 1 except that resin emulsion B1 was used instead of resin emulsion A1. The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

(Example 3)

粘着 An adhesive tape was obtained in the same manner as in Example 2 except that the amount of the fat emulsion B1 was changed as shown in Table 2. The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

(Example 4)

The fat emulsion A1 was again filtered through a stainless steel mesh of 500 mesh to obtain a fat emulsion A2 containing no modified petroleum fat particles of 30 / zm or more. The volume average particle diameter of the resin emulsion A2 and the ratio of the number of modified petroleum resin particles having a size of 30 μm or more were measured, and the results are shown in Table 2. An adhesive tape was obtained in the same manner as in Example 1, except that resin emulsion A2 was used instead of resin emulsion Al. The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

(Comparative Example 1)

A resin emulsion C1 was obtained in the same manner as in Example 1 except that petroleum resin C was used instead of modified petroleum resin A. The volume average particle diameter of the fat emulsion C1 and the ratio of the number of modified petroleum fat particles having a size of 30 m or more were measured, and the results are shown in Table 2.

An adhesive tape was obtained in the same manner as in Example 1 except that resin emulsion C1 was used instead of resin emulsion A1. The peel adhesive strength, holding power and initial adhesive strength of these adhesive tapes to polyethylene were measured. Table 2 shows the results.

(Comparative Example 2)

A resin emulsion D1 was obtained in the same manner as in Example 1, except that the modified petroleum resin A was used instead of the modified petroleum resin A. The volume average particle diameter of the fat emulsion D1 and the ratio of the number of modified petroleum fat particles having a size of 30 m or more were measured, and the results are shown in Table 2.

An adhesive tape was obtained in the same manner as in Example 1 except that resin emulsion D1 was used instead of resin emulsion A1. The peel adhesive strength, holding power and initial adhesive strength of these adhesive tapes to polyethylene were measured. Table 2 shows the results.

(Comparative Example 3)

A resin emulsion E1 was obtained in the same manner as in Example 1, except that an aromatic hydrocarbon resin ("High Resin # 90", manufactured by Toho Chemical Co., Ltd.) was used instead of the modified petroleum resin A. . The volume average particle size of the resin emulsion E1 and the ratio of the number of modified petroleum resin particles having a size of 30 μm or more were measured. The results are shown in Table 2.

An adhesive tape was obtained in the same manner as in Example 1 except that resin emulsion E1 was used instead of resin emulsion A1. The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

(Comparative Example 4)

A resin emulsion F1 was obtained in the same manner as in Example 1 except that rosin-based hydrocarbon resin (“Super Ester-A100”, manufactured by Arakawa Chemical Co., Ltd.) was used instead of the modified petroleum resin A. It was. The volume average particle diameter of the resin emulsion Fl and the ratio of the number of modified petroleum resin particles of 30 m or more were measured, and the results are shown in Table 2.

An adhesive tape was obtained in the same manner as in Example 1 except that resin emulsion F1 was used instead of resin emulsion A1. The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

(Comparative Example 5)

In producing the fat emulsion C1, a fat emulsion C2 was obtained in the same manner as in Comparative Example 1 except that the step of filtering with a wire mesh was not performed. The volume average particle size of the resin emulsion C2 and the ratio of the number of modified petroleum resin particles having a size of 30 μm or more were measured. The results are shown in Table 2.

An adhesive tape was obtained in the same manner as in Example 1, except that resin emulsion C2 was used instead of resin emulsion A1. The peel adhesive strength, holding power and initial adhesive strength of the pressure-sensitive adhesive tape to polyethylene were measured. Table 2 shows the results.

[Table 2]

Table 2 shows the following.

The acrylic pressure-sensitive adhesive composition of Comparative Example 1 to which the fatty acid emulsion C1 having an acid value of less than 0.1% was added had slightly poor holding power and initial adhesive strength, and poor peel adhesive strength to polyethylene. I'm wearing

The acrylic pressure-sensitive adhesive composition of Comparative Example 2 to which the resin emulsion D1 having a softening point of 30 ° C. or less was added had extremely low holding power and poor peel adhesion to polyethylene. The acrylic pressure-sensitive adhesive composition of Comparative Example 3 to which a resin emulsion E1 composed of a commercially available aromatic hydrocarbon resin was added had relatively excellent holding power, but had poor peel adhesion to polyethylene and initial adhesion. Is not enough.

The acrylic pressure-sensitive adhesive composition of Comparative Example 4 to which a resin emulsion F1 composed of a commercially available rosin hydrocarbon resin was added, although the initial adhesive strength was relatively excellent, the peel adhesive strength to polyethylene and the holding power were poor.

The acid value is less than 0.1% and the ratio of the number of modified petroleum resin particles having a length of 30 m or more is high.The acrylic pressure-sensitive adhesive composition of Comparative Example 5 to which resin emulsion C2 was added was coated on a substrate. As a result, the surface of the pressure-sensitive adhesive composition becomes rough, fish eyes are generated and a uniform film cannot be obtained, and the peel adhesion and initial adhesion are poor.

[0074] In contrast to these comparative examples, the acrylic pressure-sensitive adhesive compositions of Examples 1, 2 and 4 in which the resin emulsion Al, B1 or A2 of the present invention was added were used to improve the peel adhesion to polyethylene. Excellent, excellent balance between holding power and initial adhesive strength. Further, even when the amount of the resin emulsion B1 added is reduced, an acrylic pressure-sensitive adhesive composition having excellent peel adhesion to polyethylene and excellent retention and initial adhesion can be obtained. Example 1 1 3).

Industrial applicability

[0075] The acrylic pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape of the present invention include, for example, sanitary articles such as used garbage, disposable diapers, and sanitary napkins; Packaging of components such as mechanical parts; Packaging of electrical products such as TVs, audio products, refrigerators, etc .; Binding of slips, books, catalogs, etc .; Packaging of craft bags, polypropylene bags, polyethylene bags, etc .; It can be applied to clothing uses such as stoppers, lamination of leather or fabric, and adhesion of interlining.

Claims

The scope of the claims

[1] Consisting of olefinic unsaturated hydrocarbon monomer units having 4 to 6 carbon atoms, 10 to 100% by mass, and 0 to 90% by mass of olefinic unsaturated hydrocarbon monomer units having 7 to 11 carbon atoms, A modified petroleum emulsion containing a modified petroleum resin having a softening point of 30 ° C. or higher and an acid value of 0.1-lOOKOHmgZg.

[2] The modified petroleum resin is a olefinic unsaturated hydrocarbon monomer unit having 4 to 6 carbon atoms, 40 to 95 mass% and an olefinic unsaturated hydrocarbon monomer unit having 7 to 11 carbon atoms. 2. The modified petroleum oil emulsion according to claim 1, comprising 60% by mass.

[3] The modified petroleum resin emulsion according to claim 1 or 2, wherein the volume average particle diameter of the modified petroleum resin particles is 0.1—: Lm.

[4] The ratio of the number of modified petroleum resin particles in the range of 30-64 μm in the modified petroleum resin particles in the particle diameter range of 4-64 μm is 1% or less. Modified petroleum oil emulsion described in any one of 1-3.

[5] An acrylic pressure-sensitive adhesive composition comprising the acrylic polymer emulsion and the modified petroleum resin emulsion according to any one of claims 14 to 14.

6. The acrylic pressure-sensitive adhesive composition according to claim 5, comprising 0.1 to 50 parts by mass of a modified petroleum resin emulsion based on 100 parts by mass of the solid content of the acrylic polymer emulsion.

[7] An adhesive tape obtained by applying the acrylic pressure-sensitive adhesive composition according to claim 5 on a substrate.