JP2001146581A - Water-redispersible pressure-sensitive adhesive emulsion composition and pressure-sensitive adhesive article obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pressure-sensitive adhesive emulsion composition improved in redispersibility of its film into water and in at least one of its three pressure- sensitive adhesive characteristics. SOLUTION: This emulsion composition is obtained by polymerizing 100 pts.wt. acrylic monomer in the presence of 5-50 pts.wt. polymer which is obtained by the polymerization of a monomer mixture containing a polyalkylene oxide (meth)acrylate: CH2=CR1COO-(R2O)n-R3 (Rl is H or methyl; R2 is a 2-3C alkylene; R3 is H or a 1-3C branched alkyl optionally having a branch; and (n) is an integer of 1-17) and an ethylenically unsaturated carboxylated monomer followed by neutralization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging tape, an office tape, a masking tape, a double-sided tape, an anticorrosion tape, a surface protection sheet, a medical adhesive product, a building / building material tape, an adhesive label, a fastening for a paper diaper. A pressure-sensitive adhesive emulsion composition used for tapes, slippage prevention of sanitary goods such as paper diapers and napkins, and pressure-sensitive adhesive products such as carpet rolls, especially when used paper is recycled into pulp again in a recycling process. A pressure-sensitive adhesive emulsion composition that is used so that it can be recovered, or is used so that the label attached to the container can be easily peeled when the container is recycled, and a film formed from the pressure-sensitive adhesive emulsion composition is easily formed. As a pressure-sensitive adhesive emulsion composition having the property of being redispersible in water (water redispersibility) .

[0002]

2. Description of the Related Art In recent years, tapes,
Recycling of paper products and containers (bottles) such as sheets and labels is becoming important. Well, containers (bottles)
Adhesive products such as labels, adhesive tapes, adhesive films and adhesive sheets are usually composed of an adhesive and a base material of the adhesive product, and the adhesive is used for the adhesive product. Thus, the presence of the adhesive considers the recycling of paper products and containers, since adhesives are frequently used with paper products such as tapes, sheets, and labels, and are used to label containers. This is extremely important. In order to obtain an adhesive product suitable for recycling of paper products and containers, it is considered that the adhesive preferably has the following properties. In this specification, the term "adhesive product" refers to a packaging tape, an office tape, a masking tape, a double-sided tape, an anticorrosion tape, a surface protection sheet, a medical adhesive product, a building / building material tape,
It refers to adhesive labels, fastening tapes for disposable diapers, sanitary articles such as disposable diapers and napkins, and carpet rolls, and refers to products having adhesiveness.

[0003] First, the desired pressure-sensitive adhesive has good adhesion 3 properties. The adhesion 3 property is generally required for an adhesive, and refers to adhesive strength, tack, and cohesive strength. It is preferable that these three characteristics have a good balance and all of the values are large. Second, the film formed from the intended adhesive can be (again) dispersed in water due to the presence of water. Hereinafter, this property is also referred to as “water redispersibility”. However, it is not always preferable that the film has high solubility in water. This is because the adhesive dissolved in water can be discharged to the surrounding environment together with the wastewater, so that the global environment can be polluted. Therefore, it is preferable that the film is physically recovered by dispersing in water using a method such as filtration. Furthermore, it is also required that the production cost of the pressure-sensitive adhesive is low. As such a pressure-sensitive adhesive, a water-dispersible emulsion-type pressure-sensitive adhesive composition (not a solvent type) has been studied in various ways.

JP-A-8-12727 discloses that a monomer mixture containing a carboxylated rosin ester-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and a water-soluble vinyl monomer is copolymerized. Discloses a water-redispersible pressure-sensitive adhesive comprising a vinyl copolymer. But,
Since the reactivity (copolymerization) of the above-mentioned monomer mixture is not sufficient, the polymerization rate of the monomer mixture is not sufficient, and the water redispersibility of a film formed from this pressure-sensitive adhesive is insufficient. Furthermore,
There is a problem that the production cost of the desired water redispersible pressure-sensitive adhesive is high.

JP-A-9-328666 discloses an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms, vinyl acetate, (meth) acrylic acid, and a caprolactone adduct of (meth) acrylic acid. A water redispersible pressure-sensitive adhesive composition obtained by converting a part or all of the carboxyl groups of a resin obtained by copolymerizing a monomer mixture containing the same into an alkali metal salt and then adding a sugar alcohol is disclosed. JP-A-10-110,149 discloses a monomer mixture containing an alkyl (meth) acrylate, (meth) acrylic acid, a caprolactone adduct of (meth) acrylic acid, and an alkoxyalkyl (meth) acrylate. A water-redispersible pressure-sensitive adhesive composition obtained by adding a tertiary amino alcohol to a resin obtained by copolymerizing the resin is disclosed. However, these water redispersible pressure-sensitive adhesive compositions can maintain good adhesion 3 properties (adhesion, tack, and cohesion), but the water redispersibility of a film formed from these pressure-sensitive adhesive compositions is low. There is a problem that it is insufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a film having a water re-dispersibility and an adhesive, tack and cohesive force. It is an object of the present invention to provide a pressure-sensitive adhesive emulsion composition having at least one of improved properties, a pressure-sensitive adhesive product using such a pressure-sensitive adhesive emulsion composition, and a method for producing a pressure-sensitive adhesive product using such a pressure-sensitive adhesive emulsion composition.

[0007]

SUMMARY OF THE INVENTION The present inventors have conducted various studies on improving at least one of the three properties of adhesion, tack, and cohesion and the water redispersibility of a formed film. , As described in detail below,
Polyalkylene oxide (meth) acrylate represented by the general formula (I) CH ₂ ＣＲCR ¹ COO— (R ² O) _n —R ³ (I) [In the formula (I), R ¹ is a hydrogen or methyl group; ^Two
Is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a branch, and n is an integer of 1 to 17. And (B) a polymer mixture obtained by polymerizing and neutralizing a monomer mixture containing a monomer having an ethylenic double bond and a carboxyl group.
By using a pressure-sensitive adhesive emulsion composition obtained by polymerizing 100 parts by weight of an acrylic monomer mixture in the presence of parts by weight, the three properties of adhesiveness, tackiness, and cohesive force and the water of the resulting film are obtained. The inventors have found that at least one of the redispersibility can be improved, and have completed the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

According to the present invention, a monomer mixture containing a specific monomer, that is, a “monomer mixture containing (A) and (B)” is polymerized and then neutralized. The pressure-sensitive adhesive emulsion composition obtained by polymerizing an acrylic monomer in the presence of a specific polymer to be obtained has an adhesive force, tack, and cohesion that cannot be achieved by a conventional pressure-sensitive adhesive composition. It can improve at least one of the cohesive properties of the force and the redispersibility of the resulting film in water.

In the present invention, the “specific polymer” is
(A) polyalkylene oxide (meth) acrylate represented by the general formula (I) CH ₂ CR ¹ COO— (R ² O) _n —R ³ (I) [In the formula (I), R ¹ is hydrogen or methyl Group, R ²
Is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a branch, and n is an integer of 1 to 17. And (B) a polymer obtained by polymerizing and neutralizing a monomer mixture containing a monomer having an ethylenic double bond and a carboxyl group.

Here, "(A) polyalkylene oxide (meth) acrylate" refers to a compound represented by the general formula (I), wherein R ¹ is hydrogen or a methyl group. (A), if R ¹ is hydrogen acrylate, R ¹
Is methacrylate when is a methyl group. In this specification, acrylate and methacrylate are also collectively described as “(meth) acrylate”, and acrylic acid and methacrylic acid are also collectively described as “(meth) acrylic acid”.

[0011] and R ² in formula (I) refers to an alkylene group having 2 or 3 carbon atoms, -C ₂ H ₄ is an alkylene group having 2 carbon atoms - when used internally, the alkylene group of 3 carbon atoms -
C ₃ H ₆ - refers to. As R ² , one molecule of (A) may have a combination of an alkylene group having 2 carbon atoms and an alkylene group having 3 carbon atoms, and a combination of an alkylene group having 2 carbon atoms and an alkylene group having 3 carbon atoms may be present. The arrangement may be random or block. Further, in the formula (I), R ³ may be, for example, hydrogen, a methyl group, an ethyl group, a propyl group or the like, and particularly preferably, hydrogen. Further, in the formula (I), n
Is a number in which one molecule of (A) has R ² , and n is 1
Preferred is an integer of ~ 17.

(A) Polyalkylene oxide (meth)
In formula (I), R ¹ is preferably hydrogen, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen, and n is preferably an integer of 1 to 17. When R ² is an alkylene group having 2 carbon atoms, the number n in which one molecule has R ² is from 1 to 1.
An integer of 7 is preferable, and an integer of 5 to 11 is more preferable.
Particularly preferred is an integer from 7 to 9. When R ² is an alkylene group having 3 carbon atoms, the number n of one molecule having R ² is 1 to 17
Is preferably an integer of 5 to 13, more preferably 6 to 13.
An integer of from 10 to 10 is particularly preferred.

These (A) can be used alone or in combination. When (A) is a combination, an arithmetic average can be adopted as the value of n obtained by the combination. In this case, the value of n is not always an integer. It should be noted that the above range of n can be applied to the value of n obtained in combination, except that n is an “integer”. That is, when (A) is a combination, in Formula (I), n is preferably 1 to 17. (A) In formula (I), R ¹ is preferably hydrogen, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen, and n is preferably 1 to 17. When R ² is an alkylene group having 2 carbon atoms, the number n in which one molecule has R ² is preferably 1 to 17, more preferably 5 to 11, and particularly preferably 7 to 9. When R ² is an alkylene group having 3 carbon atoms, the number n in which one molecule has R ² is preferably 1 to 17, more preferably 5 to 13, and particularly preferably 6 to 10.

These (A) are produced by using a known method.
It is possible to use a commercially available product.
For example, polyethylene glycol monoacrylate
(AE350 (trade name) made by Nippon Yushi, formula (I)
And R¹Is hydrogen, R^TwoIs an ethylene group having 2 carbon atoms, R^ThreeIs water
Element, and n ≒ 8) and polypropylene glycol monoa
Crylate (AP400 manufactured by NOF Corporation (product
Name), in the formula (I), R ¹Is hydrogen, R^TwoHas 3 carbon atoms
Propylene group, R^ThreeIs hydrogen, and n 、 6)
You. Here, n of these commercial products is n ≒ 8, n ≒ 6.
And n is not necessarily an integer. these
Are all mixtures, and AE350 is R^Two
Is a mixture mainly composed of 8 ethylene groups having 2 carbon atoms
And AP400 is R^TwoIs a propylene group having 3 carbon atoms.
Since the number is a mixture mainly composed of 6, the value of n becomes an integer.
It is considered not.

The above-mentioned “monomer mixture containing (A) and (B)” is based on the monomer mixture containing (A) and (B) (100% by weight). (A) is preferably contained in an amount of 5 to 70% by weight,
%, More preferably 20 to 50% by weight.

The term “(B) a monomer having an ethylenic double bond and a carboxyl group” is not particularly limited as long as it is a monomer having a polymerizable ethylenic double bond and a carboxyl group. Not something. As such (B), for example, acrylic acid, methacrylic acid, maleic acid,
Fumaric acid, maleic acid, itaconic acid, crotonic acid, hydroxyethyl monomaleate, hydroxypropyl monomaleate, and half-alkyl esters of maleic acid, fumaric acid, and itaconic acid, 2- (meth) acryloyloxyethyl succinic acid, And 2- (meth) acryloyloxyethyl phthalic acid. (B) As a monomer having an ethylenic double bond and a carboxyl group,
Particularly, acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl succinic acid are preferable. These (B) can be used alone or in combination.

The term "monomer mixture comprising (A) and (B)" refers to such a monomer mixture containing (A) and (B) (100% by weight). B) preferably contains 0.1 to 20% by weight, and 1 to 15% by weight.
More preferably, the content is particularly preferably 2 to 12% by weight.

Further, the "monomer mixture comprising (A) and (B)" is intended to include (C) another monomer which can impart not-improper properties to a specific polymer of interest. Can be.
Such “(C) other monomer” is not limited to the above (A) and (B), and is not particularly limited as long as it has at least one ethylenic double bond. Never.

As such “(C) other monomer”,
The following can be exemplified: (C1) unsaturated chain hydrocarbon compounds such as ethylene, propylene, isobutylene, butadiene and isoprene; (C2) styrene such as styrene and α-methylstyrene and derivatives thereof; (C3) ) Vinyl compounds such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyral; (C4) vinyl chloride, vinylidene chloride, chloroprene,
And compounds having a chlorine atom and an ethylenic double bond, such as and α-chlorostyrene; (C5) methyl (meth) acrylate, ethyl (meth)
Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate,
And 1 to 18 carbon atoms such as dodecyl (meth) acrylate
(C6) (meth) acrylic acid derivatives having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate (C7) dimethylaminoethyl (meth) acrylate;
Acrylamide, N-methylolacrylamide, N-
Monomers having a nitrogen atom and an ethylenic double bond such as methylol methacrylamide, t-octylacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylonitrile, N-vinylpyrrolidone and vinylpyridine; (C8) ethylene glycol di (meth) acrylate,
Ethylenic double bonds such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and tetramethylolmethanetetra (meth) acrylate (C9) other monomers having at least one ethylenic double bond, such as glycidyl (meth) acrylate, dioctyl maleate, vinyl sulfonic acid, and sodium vinyl sulfonic acid . These "(C) other compounds"
Can be used alone or in combination.

The "monomer mixture comprising (A) and (B)" is defined as such a monomer mixture comprising (A) and (B) (100% by weight). C) to 2
It is preferably contained in an amount of 5 to 80% by weight, more preferably 35 to 70% by weight, and particularly preferably 45 to 60% by weight.

The (C) other compound is represented by (C5) having 1 to 18 carbon atoms based on the (C) other compound (100% by weight).
50 to 100% by weight of a (meth) acrylic acid alkyl ester compound having an alkyl group which may have a substituent
It is preferably contained, more preferably 70 to 100% by weight, and particularly preferably 90 to 100% by weight.

In the present invention, the above-mentioned "(A) and (B)"
(Addition polymerization or radical polymerization) of the "monomer mixture comprising" can be carried out by a conventional method using a solvent or an aqueous medium as a solvent, and by appropriately using a polymerization initiator. When using an aqueous medium, an emulsifier can be used. In the polymerization reaction, a reducing agent and a chain transfer agent can be used in combination with the polymerization initiator, if necessary. The reaction temperature, the reaction time, the composition and concentration of the monomer mixture in the solvent, the type and concentration of the polymerization initiator, the reducing agent, the chain transfer agent, and the like, and the polymerization reaction conditions such as the stirring speed are controlled by the specific polymer of interest. And it can be appropriately selected depending on the characteristics of the pressure-sensitive adhesive emulsion composition of the present invention and the like.

In the present invention, the "solvent" is a solvent usually used for polymerization of a monomer mixture, and is an organic solvent having a low reactivity with a specific polymer of the present invention and a raw material of the pressure-sensitive adhesive emulsion composition. Solvent, for example, methanol,
Refers to ethanol, isopropyl alcohol, acetone, ethyl acetate and the like. Further, the “solvent” may include a small amount of an aqueous medium described below, and may further include a monomer, an oligomer, and the like. As will be described further below, "solvent"
Is an emulsifier, a polymerizable emulsifier, a polymerization reaction initiator, a reducing agent, a chain transfer agent, a pH adjuster and / or various additives which are usually used in producing a specific polymer and pressure-sensitive adhesive emulsion composition. May be included.

Here, in the present invention, the “aqueous medium” is
General water, for example, refers to distilled water or ion-exchanged water, but is a water-soluble or water-dispersible organic solvent, and reacts with the specific polymer and the raw material of the PSA emulsion composition according to the present invention. Poor organic solvents, such as acetone,
It may contain a small amount of ethyl acetate, toluene, xylene and the like. Further, the “aqueous medium” may contain a water-soluble or water-dispersible monomer, oligomer, or the like. As will be described later, the `` aqueous medium '' is usually used when producing a specific polymer and pressure-sensitive adhesive emulsion composition, an emulsifier, a polymerizable emulsifier, a polymerization initiator, a reducing agent, a chain transfer agent, p
An H adjuster and / or various additives may be included.

The "polymerization initiator" used in the present invention is a compound capable of causing a polymerization reaction of a monomer mixture by adding a small amount thereof, and is used in a solvent or an aqueous medium. What can be done is preferred.
Examples of such a polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and organic peroxides such as t-butyl hydroperoxide and t-butyl peroxybenzoate and benzoyl peroxide. Hydrogen peroxide; azobisnitrile such as 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis-2,4-dimethylvaleronitrile. As a polymerization initiator,
When polymerizing in a solvent, azobisnitrile such as AIBN is particularly preferable. Further, as a polymerization initiator, when polymerizing in an aqueous medium, particularly, ammonium persulfate,
Sodium and potassium persulfates are preferred.

When polymerizing in an aqueous medium, emulsion polymerization can be carried out using an emulsifier. Where "emulsifier"
Means that when polymerized in an aqueous medium, the aqueous medium and (A)
And a surfactant used for forming an emulsion with a monomer mixture containing (B), preferably a surfactant that does not adversely affect the polymerization reaction.
The “emulsifier” is not particularly limited as long as it is usually used for an emulsion polymerization reaction.

Examples of the surfactant include the following: Examples of the anionic surfactant include alkali metal salts of higher fatty acids such as sodium oleate and potassium oleate, sodium dodecyl sulfate, sodium dodecyl benzenesulfonate, dialkyl sulfo succinate. Sulfonic acid derivatives and sulfates such as sodium oxalate, sodium polyoxyethylene alkylphenol ether sulfate, and formalin condensate of naphthalenesulfonic acid; ammonium salts such as dodecyltrimethylammonium chloride and stearyltrimethylammonium chloride as cationic surfactants; As nonionic surfactants, polyoxyethylene dodecyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol Ethers, and polyoxyethylene derivatives such as polyoxyethylene sorbitan mono dodecanoate.

In the emulsion polymerization, a polymerizable emulsifier can be used as an emulsifier. Here, "polymerizable emulsifier" refers to a compound having a polymerizable unsaturated bond and capable of functioning as an emulsifier capable of forming an emulsion of an aqueous medium and a monomer mixture, and includes a sulfonic acid group and a sulfonate group. And ethylenically unsaturated monomers having a sulfuric ester group or an ethyleneoxy group, and mixtures thereof.
Further, the sulfonic acid group or the sulfonate group of the above-mentioned polymerizable emulsifier may be in the form of a salt, and as a counter cation of the sulfonic acid group or the sulfonate group, an ammonium ion or an alkali metal ion is preferable, and particularly, an ammonium ion or potassium ion. Ions and sodium ions are preferred. Examples of the polymerizable emulsifier include sodium styrenesulfonate, sodium vinylsulfonate, and sodium allylalkyl sulfosuccinate. Examples of the polymerizable emulsifier containing the polymerizable emulsifier include Sanyo Chemical Co., Ltd. JS-2 (product name) and the like can be exemplified. These emulsifiers are
They may be used alone or in combination.

As described above, the mixture obtained by polymerizing the “monomer mixture containing (A) and (B)” is neutralized to obtain the desired specific polymer. .
When a solvent is used as the solvent for the above-mentioned polymerization, it is preferable to neutralize the solvent after converting the solvent into an aqueous medium by adding the aqueous medium after removing the solvent.

Here, the "neutralization" can be carried out by adding an alkaline substance usually used for neutralization. As a result, in particular, the carboxyl group in the system is neutralized, and water solubility can be imparted to the intended specific polymer. Therefore, this specific polymer can function as a protective colloid in the polymerization of an acrylic monomer described later.
However, this particular polymer need not be completely water-soluble. It is sufficient that the specific polymer has the necessary water solubility within a range that does not deteriorate the properties of the intended pressure-sensitive adhesive emulsion composition, that is, within the range of the desired predetermined properties. In addition, it is sufficient that this specific polymer exhibits a necessary function as a protective colloid.

Here, the term "alkaline substance" refers to a substance which exhibits a pH of greater than 7 when dissolved in water, and is not particularly limited as long as it is usually called an alkaline substance. The form of the alkaline substance is not limited to gas, liquid and solid, but the form of an aqueous solution dissolved in water can be handled, and the neutralization reaction can be easily controlled, and it is preferable. Examples of such an “alkaline substance” include an alkali metal such as ammonia, sodium and potassium, an alkaline earth metal such as calcium and magnesium, and the like, and aqueous ammonia, an aqueous sodium solution and an aqueous potassium solution are preferable. The addition of the alkaline substance is preferably performed so that the pH of the mixture containing the specific polymer becomes 8 or more, more preferably the pH is adjusted to 8 to 10, and the pH is adjusted to 8 to 9. Is particularly preferred.

The pressure-sensitive adhesive emulsion composition of the present invention can be obtained by polymerizing 100 parts by weight of an acrylic monomer in the presence of 5 to 50 parts by weight of the above specific polymer. Here, the amount of the specific polymer to be present is preferably 5 to 50 parts by weight, more preferably 6 to 30 parts by weight, and particularly preferably 7 to 20 parts by weight. In this specification, "parts by weight"
And "% by weight" are based on the weight without solvent.
Therefore, as the weight part of the specific polymer, the weight part based on the value of the weight of the solid content calculated based on the dry weight% is used.

Here, the “acrylic monomer” refers to a monomer selected from so-called acrylic acid derivatives and methacrylic acid derivatives, which is usually used for producing a pressure-sensitive adhesive composition, and an acrylic acid derivative and a methacrylic acid derivative. It may be a monomer having an ethylenic double bond capable of polymerizing (addition polymerization or radical polymerization) with a monomer selected from methacrylic acid derivatives, or a mixture containing a plurality of the monomers. Good.

Further, a polymer obtained by directly polymerizing the “acrylic monomer” under the condition that the above-mentioned specific polymer does not exist (hereinafter, also referred to as “polymer of acrylic monomer”)
At room temperature (20 to 30 ° C.) alone preferably has practical tackiness, and more preferably has sufficiently high tackiness. For this purpose, the glass transition temperature (Tg) of the polymer of the acrylic monomer is preferably −20 ° C. or lower, more preferably −70 to −40 ° C., and −50 to −60.
C is preferred. In the present invention, the “glass transition temperature (Tg)” is represented by the formula of Fox (Fox),
A theoretical value calculated based on the glass transition temperature of the homopolymer of each monomer constituting the “acrylic monomer” (Seika Okamura, Introduction to Polymer Chemistry, 2nd ed., P. 172, 1
(See February 1, 981 issued by Kagaku Doujin Co., Ltd.)

Examples of such acrylic monomers include the following monomers: (D1) methyl (meth) acrylate, ethyl (meth)
Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (D2) alkyl (meth) acrylate compounds having an alkyl group which may have a substituent having 1 to 18 carbon atoms, such as isooctyl (meth) acrylate, isononyl (meth) acrylate, and dodecyl (meth) acrylate; (D3) dimethylaminoethyl (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
(D4) ethylene glycol di (meth) acrylate; nitrogen-containing (meth) acrylic acid derivatives such as N-methylolacrylamide, N-methylolmethacrylamide, t-octylacrylamide, and diethylaminoethyl (meth) acrylate;
Ethylenic double bonds such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and tetramethylolmethanetetra (meth) acrylate (D5) other (meth) acrylic acid derivatives such as glycidyl (meth) acrylate; (D6) acrylic acid and methacrylic acid; (D7) maleic acid, fumaric acid , Maleic acid, itaconic acid, crotonic acid, hydroxyethyl monomaleate,
(D8) hydroxypropyl monomaleate and carboxylic acids having an ethylenic double bond such as maleic acid, fumaric acid, half-alkyl esters of itaconic acid, polycaprolactone monoacrylate, hydroxyethyl phthalate, and acrylic acid dimer; Unsaturated chain hydrocarbon compounds such as ethylene, propylene, isobutylene, butadiene and isoprene; (D9) styrene such as styrene and α-methylstyrene and derivatives thereof; (D10) vinyl acetate, vinyl propionate, benzoic acid Vinyl compounds such as vinyl and vinyl butyral; (D11) compounds having a chlorine atom and an ethylenic double bond such as vinyl chloride, vinylidene chloride, chloroprene and α-chlorostyrene; (D12) acrylamide, acrylonitrile Monomers having a nitrogen atom and an ethylenic double bond such as ril, N-vinylpyrrolidone and vinylpyridine; (D13) divinylbenzene, divinylsilane, diallylphthalate, cyclopentadiene, methylenebisacrylamide, diallylmalate, tetra Monomers having at least two ethylenic double bonds, such as allyloxyethane and γ-methacryloxypropyltrimethoxysilane, and monomers having at least one ethylenic double bond and another crosslinkable functional group (D14) dioctyl maleate, vinyl sulfonic acid,
And other monomers having at least one ethylenic double bond such as sodium vinyl sulfonate. These acrylic monomers can be used alone or in combination.

The acrylic monomer is (D1) having 1 to 1 carbon atoms.
Having an alkyl group which may have 18 substituents (meth)
It preferably comprises an alkyl acrylate compound. The acrylic monomer is (D1) an alkyl (meth) acrylate compound having an alkyl group which may have a substituent having 1 to 18 carbon atoms, based on the acrylic monomer (100% by weight). , 65-99.49% by weight
It is preferably contained, more preferably 79 to 98.95% by weight, and particularly preferably 84.5 to 98.4% by weight.

The (D1) alkyl (meth) acrylate compound having an alkyl group which may have a substituent having 1 to 18 carbon atoms has a monomer homopolymer having a glass transition temperature of -90 to 20 ° C. It is preferable to include
More preferably, those containing -20 to -40 ° C,
It is particularly preferred to include those having a temperature of -70 to -50C.
Such (D1) alkyl (meth) acrylate compounds having an alkyl group which may have a substituent having 1 to 18 carbon atoms include, for example, 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, t- Examples include at least one selected from butyl acrylate, n-octyl acrylate, isooctyl acrylate, and isononyl acrylate. The acrylic monomer preferably contains these alone or in combination.

The acrylic monomer preferably comprises (D6) acrylic acid and / or methacrylic acid. The acrylic monomer is based on the acrylic monomer (1
(D6) acrylic acid and / or methacrylic acid is preferably contained in an amount of 0.5 to 30% by weight, more preferably 1 to 20% by weight, and 1.5 to 1% by weight.
It is particularly preferred to contain 5% by weight.

The acrylic monomer is (D13) a monomer having at least two ethylenic double bonds and / or a monomer having at least one ethylenic double bond and another crosslinkable functional group. It preferably comprises monomers. The acrylic monomer is based on the acrylic monomer (1
(D13) a monomer having at least two ethylenic double bonds and / or a monomer having at least one ethylenic double bond and another crosslinkable functional group. , Preferably 0.01 to 5% by weight, more preferably 0.05 to 0.1% by weight, particularly preferably 0.1 to 0.5% by weight.

Further, it is preferable to add a tackifier resin to the “acrylic monomer”. Here, the "tackifying resin" refers to a substance capable of imparting a property of improving the adhesive force to various substrates to the obtained adhesive emulsion composition. Examples of the tackifying resin include the following: (E1) raw rosin, hydrogenated rosin, hydrogenated rosin ester,
Rosin resins such as disproportionated rosin, disproportionated rosin ester, and polymerized rosin ester; (E2) polyterpene resins such as α-pinene resin, β-pinene resin, dipentene resin, and terpene-phenol resin (E3) Hilets (trade name) manufactured by Mitsui Chemicals, Quinton (trade name) manufactured by Zeon Corporation, Tackiroll (trade name) manufactured by Sumitomo Chemical Co., Ltd., and Estecolletz 1000 (trade name) manufactured by Esso Chemical Co., Ltd. (E4) Neopolymer S (trade name) manufactured by Nippon Synthetic Resin;
Aromatic petroleum resins such as Petrozine (trade name) manufactured by Mitsui Chemicals and Petrite (trade name) manufactured by Toyo Soda; (E5) Hiresin (trade name) manufactured by Toho Petrochemical; Tack Ace manufactured by Mitsui Chemicals (trade name) (E6) Arakawa Chemical's Alcon (trade name) and Esso Chemical's EsteCollets (product) (E7) Polyamide resins such as Tomide (trade name) manufactured by Fuji Kasei Kogyo; (E8) Epicoat (trade name) manufactured by Shell Chemical Co., Ltd., manufactured by Mitsui Petrochemical Epoxy. Epoxy resins such as EPOMIC (trade name) and EPOTOT (trade name) manufactured by Toto Kasei; (E9) Natural rubber, isoprene rubber, styrene butadiene rubber, styrene-butadiene block resin Mer, styrene - isoprene block polymer, ethylene - isoprene - elastomers such as styrene block polymer. As the tackifying resin, (E1) rosin-based resins and (E1)
2) Polyterpene resins are preferred, and polymerized rosin pentaerythritol resin and disproportionated rosin pentaerythritol resin are particularly preferred.

These tackifying resins can be used alone or in combination. It is preferable to add 1 to 15 parts by weight of such a tackifier resin to the acrylic monomer based on 100 parts by weight of the acrylic monomer.
The amount is more preferably 0 parts by weight, and particularly preferably 3 to 6 parts by weight.

In the present invention, the polymerization (addition polymerization or radical polymerization) of an acrylic monomer in the presence of a specific polymer is carried out by an ordinary method using an aqueous medium as a solvent and appropriately adding a polymerization initiator. It can be performed by using. It is preferable to use an emulsifier, if necessary. In the polymerization reaction, a reducing agent and a chain transfer agent can be used in combination with the polymerization initiator, if necessary. The polymerization reaction conditions such as the reaction temperature, the reaction time, the composition and concentration of the acrylic monomer in the aqueous medium, the type and concentration of the polymerization initiator, the reducing agent, the chain transfer agent, etc., and the stirring speed are determined by the specific polymer used It can be appropriately selected depending on the characteristics and the like of the intended pressure-sensitive adhesive emulsion composition of the present invention. Here, the above-mentioned aqueous medium, polymerization initiator, and emulsifier can be used as the “aqueous medium”, “polymerization initiator”, and “emulsifier”.

The thus obtained pressure-sensitive adhesive emulsion composition of the present invention further comprises a pressure-sensitive adhesive composition,
Various additives and the like can be included. As such additives, thickeners, thickeners, pigments, fillers, plasticizers, anti-binders, rust inhibitors, freeze stabilizers, antioxidants, ultraviolet absorbers,
Preservatives, neutralizing agents, leveling agents, anti-blocking agents, crosslinking agents, surfactants, antistatic agents, flame retardants, tackifiers,
Lubricants, fluorescent whitening agents, fragrances and the like can be exemplified. These additives can be appropriately selected depending on the intended properties of the pressure-sensitive adhesive emulsion composition, and can be used alone or in combination.

In the pressure-sensitive adhesive emulsion composition of the present invention obtained as described above, the water re-dispersibility of the formed film, and the adhesive strength, tackiness and cohesion, are higher than those of the conventional pressure-sensitive adhesive composition. At least one of the three properties of force adhesion is improved. The film formed from the pressure-sensitive adhesive resin emulsion composition of the present invention preferably has practical tackiness at room temperature (20 to 30 ° C), and more preferably has sufficiently high tackiness.

The pressure-sensitive adhesive emulsion composition of the present invention can be prepared by a method usually applied to a pressure-sensitive adhesive composition.
Adhesive products can be manufactured. Thus, the present invention
For example, the present invention provides a pressure-sensitive adhesive product by applying the pressure-sensitive adhesive emulsion composition of the present invention to a substrate or the like of a pressure-sensitive adhesive product and then drying.

Here, "apply" means that an appropriate amount of the pressure-sensitive adhesive composition is made to exist on a substrate or the like of a pressure-sensitive adhesive product, and examples thereof include coating and coating. The application is usually preferably performed uniformly over the entire surface of the substrate or the like of the adhesive product. Furthermore, “coating” can be used without any limitation as long as it is a coating method usually used as a method for coating the pressure-sensitive adhesive composition. In addition, “application” can be used without any limitation as long as it is an application method generally used as a method for applying the pressure-sensitive adhesive composition. Further, “drying” can be used without limitation as long as it is a drying method generally used as a method for drying to remove moisture. For example, warm air drying, reduced pressure drying, natural drying, and the like can be exemplified.

Accordingly, the present invention improves the water redispersibility of a film formed from a pressure-sensitive adhesive composition used for a pressure-sensitive adhesive product and at least one of the three adhesive properties of a pressure-sensitive adhesive composition used for a pressure-sensitive adhesive product. To provide adhesive products that are easier to recycle and more environmentally friendly. Further, the present invention provides a method of producing a tacky product having such improved properties, being easier to recycle, and environmentally friendly.

The pressure-sensitive adhesive emulsion composition of the present invention exhibits excellent properties of improving the water redispersibility of a film to be formed and at least one of the three adhesive properties of adhesion, tack and cohesion. I do. This is considered for the following reasons. The pressure-sensitive adhesive emulsion composition of the present invention is produced by emulsion polymerization of an acrylic monomer in the presence of the above-mentioned specific polymer having water solubility. At this time, the polymer functions as a protective colloid, and the acrylic monomer is polymerized using the protective colloid as an adsorption layer. Therefore, the specific polymer having water solubility and the polymer of the acrylic monomer are physically or chemically integrated particles, and the particles include the polymer of the acrylic monomer. It is believed that there is a rich portion and a particular polymer rich portion.

It is considered that such adhesive 3 properties of the adhesive emulsion composition of the present invention are mainly exhibited by a polymer-rich portion of an acrylic monomer. By the way, when the film of the present invention is left in water, a portion rich in a specific polymer having water solubility can become a water passage at an interface between portions rich in a polymer of an acrylic monomer. Therefore,
It is considered that the water-soluble polymer-rich portion present in the coating has an effect of causing the splitting of the coating by water more easily and improving the redispersibility of the coating in water. Therefore, it is considered that at least one of the adhesion 3 property and the film redispersibility can be improved.

According to the present invention, the protective colloid comprises (A) a polyalkylene oxide (meth) acrylate represented by the general formula (I) CH ₂ ＣＲCR ¹ COO- (R ² O) _n -R ³ (I) In (I), R ¹ is hydrogen or a methyl group, R ²
Is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a branch, and n is an integer of 1 to 17. And (B) a polymer obtained by polymerizing and neutralizing a monomer mixture comprising a monomer having an ethylenic double bond and a carboxyl group,
In the presence of 5 to 50 parts by weight of its protective colloid, 100
A method for producing the above-mentioned pressure-sensitive adhesive emulsion composition, which comprises polymerizing an acrylic monomer in parts by weight.

Further, the pressure-sensitive adhesive emulsion composition of the present invention can be prepared by converting the above-mentioned acrylic monomer into the acrylic monomer in advance by using ordinary emulsion polymerization or the like in the absence of the above-mentioned specific polymer. It can also be produced by mixing with the above-mentioned specific polymer after forming the polymer. If necessary, additional physical means such as heating and ultrasonic irradiation can be used.

[0052]

EXAMPLES Hereinafter, the present invention will be described more specifically and in detail with reference to Examples and Comparative Examples. However, these Examples are merely one embodiment of the present invention, and the present invention is not limited by these Examples. Not something. In this example, "parts by weight"
And "% by weight" are based on the weight without solvent. Therefore, for example, the parts by weight of the specific polymer are described based on the value of the weight of the solid content calculated based on the dry weight%.

Example 1 (1) Production of Specific Polymer 1 500 g of butyl acrylate (BA) and 400 g of polyethylene glycol monoacrylate (AE350 (trade name) manufactured by NOF Corporation; in the formula (I), R ¹ is hydrogen ,
R ² is an ethylene group having 2 carbon atoms, R ³ is hydrogen, and n ≒
8) and 100 g of acrylic acid (AA) were weighed and stirred to obtain a monomer mixture (1). In a four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, and a dropping funnel, 250 g of isopropyl alcohol (I
PA), 10 g of n-dodecyl mercaptan (NDM) as a chain transfer agent, and 9 g of azobisisobutyronitrile (AIBN) as a catalyst were heated with stirring. When the temperature of the mixture reached 50 ° C., about 10% by volume of the monomer mixture (1) was added to a four-necked flask, and an initial polymerization reaction was performed while further raising the temperature. When the liquid temperature reached 80 ° C., dropping of about 90% by volume of the remaining monomer mixture (1) from the dropping funnel was started.

While maintaining the reaction temperature at 80 ° C., the monomer mixture (1) was added dropwise over 3 hours. After completion of the dropwise addition, 50 g of IPA and 1 g of AIBN were added dropwise over 1 hour while stirring while maintaining the temperature of the reaction mixture at 80 ° C. Then, while maintaining the temperature of the reaction mixture at 80 ° C.,
The reaction was continued for a time to complete the polymerization reaction, after which the reaction mixture was cooled. 320g of water and 25% ammonia water 19
4 g was added to the reaction mixture, and the reaction mixture was dissolved in water to obtain an aqueous solution. 300 g of IPA was recovered from this aqueous solution using an evaporator to obtain an aqueous solution of a specific polymer 1.

The concentration of the obtained aqueous solution of the specific polymer 1 was 65% by weight, the viscosity was 5000 mPa · s (30 ° C.), and p
H was 8. Here, the concentration of the aqueous solution of the specific polymer 1 was determined by weighing the aqueous solution of the specific polymer 1 in an aluminum cup, and then heating and drying at 100 ° C. for 3 hours. The weight after drying was shown as a percentage by weight based on the weight put in an aluminum cup. The viscosity of the aqueous solution of the specific polymer 1 was measured at 30 ° C. using a BH type viscosity type. P of aqueous solution of specific polymer 1
H was measured using a pH meter.

(2) Preparation of pressure-sensitive adhesive emulsion composition of Example 1 79.7 g of 2-ethylhexyl acrylate (2EH)
A) 10 g of butyl acrylate (BA), 10 g of methyl methacrylic acid (MAA), 0.3 g of γ-methacryloxypropyltrimethoxysilane (A174), and 0.05 g of n-dodecyl mercaptan as a chain transfer agent ( NDM) is weighed and stirred, and the monomer mixture (2) is stirred.
I got Stirrer, temperature controller, thermometer, reflux condenser,
And a four-necked flask equipped with a dropping funnel, 60 g of water, 0.4 g of 25% aqueous ammonia, 0.35 g of sodium persulfate, and 5 g of an aqueous solution of the above specific polymer 1 with 5 g of protective colloid 1 ( (Equivalent to dry amount), and the mixture was heated and heated while stirring.

When the temperature of the mixture in the system reached 50 ° C., about 5% by volume of the above monomer mixture (2) was dropped into a four-necked flask. An initial reaction was performed while further heating and raising the temperature of the reaction mixture. When the temperature of the reaction mixture is 75
When the temperature reached ° C, the remaining about 95% by volume of the monomer mixture (2) was dropped into the four-necked flask over 4 hours from the dropping funnel. The remaining about 9% of this monomer mixture (2)
When 5% by volume was added dropwise, an aqueous solution in which 0.3 g of sodium persulfate was dissolved in 10 g of water was simultaneously added for 4 hours.
Dropped over minutes. After completion of the dropwise addition, the temperature of the reaction mixture was reduced to 7
Stirring was continued for 2 hours while maintaining the temperature at 5 ° C. to complete the polymerization reaction. Thereafter, the reaction mixture is cooled and 2
The mixture was neutralized to pH 7 by adding 5% aqueous ammonia. The reaction mixture was filtered using a 200-mesh filter cloth to remove water-insoluble substances, thereby obtaining a PSA emulsion composition of Example 1.

(3) Physical properties of the pressure-sensitive adhesive emulsion composition of Example 1 Regarding the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1, the concentration was 58.7% by weight and the viscosity was 6,100 mPa ·
s (30 ° C.), pH was 7.0, and the particle size of the emulsion was 0.20 μm. The physical properties were measured using the same method as described in the above-mentioned method for producing the aqueous solution of the specific polymer 1. However, the particle size of the emulsion of the water-redispersible pressure sensitive adhesive emulsion composition was measured using a laser particle analyzer (PAR I manufactured by Otsuka Electronics Co., Ltd.).
II (trade name)). Physical properties are summarized in Table 1.
It was shown to.

(4) Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1 The pressure-sensitive adhesive emulsion composition of Example 1 was adjusted to have a coating thickness of 5 by adjusting the slit width of the table coater.
After coating on a PET film to a thickness of 0 μm,
Dry at 5 ° C. for 5 minutes. A polylaminate type release paper was adhered to the coated surface (adhesive surface) obtained on the PET film to obtain an adhesive product (hereinafter, this is referred to as "test specimen of Example 1").

(A) Evaluation of Adhesive Strength Adhesive strength to a stainless steel plate (hereinafter also referred to as “SUS adhesive strength”) was determined by the method (1) described in JISZ0237.
Evaluation was made by measuring the 180-degree peeling adhesion to SUS using an 80-degree peeling method. The 180 degree peeling adhesive strength was measured using Tensilon (RTM250 (trade name) manufactured by Orientec). It is preferable that the 180 degree peeling adhesive strength is large because the SUS adhesive strength is large. S of the pressure-sensitive adhesive emulsion composition of Example 1
US adhesive strength was 7.15 N / 25 mm. Adhesion to a polyethylene plate (hereinafter also referred to as “PE adhesion”) can be determined by using the same method except that a polyethylene plate is used instead of a stainless steel plate in the above-described measurement of SUS adhesion. evaluated. The PE adhesive strength of the pressure-sensitive adhesive emulsion composition of Example 1 was 3.26 N / 25.
mm.

(B) Evaluation of tack The evaluation of the ball tack was performed using the method described in JISZ0237. Was measured. Ball No. The larger the value is, the larger the ball tack is. Ball No. of the pressure-sensitive adhesive emulsion composition of Example 1 Was 10. (C) Evaluation of Holding Force The evaluation of the holding force was performed by measuring the time until the test piece dropped from the test plate using the method described in JISZ0237. The longer the time, the more preferable the holding power is.
The holding power of the pressure-sensitive adhesive emulsion composition of Example 1 was 14
40 minutes.

(D) Water redispersibility of a film formed by the pressure-sensitive adhesive emulsion composition of Example 1 The water redispersibility of the film was evaluated as follows. 1 g of the film obtained by drying the pressure-sensitive adhesive emulsion composition of Example 1 at 50 ° C. for 48 hours was finely cut, and 1000 g
Juicer mixer with water (Matsushita Electric Industrial Co., Ltd.)
MX-M3 (brand name)). After stirring at 30 ° C. for 10 or 20 minutes at the maximum stirring speed,
The mixture was filtered through a 50-mesh filter paper, and the film not redispersed in water collected on the filter paper was dried and weighed. The difference between the weight% of the film not redispersed in water and 100% by weight with respect to 1 g of the film used for evaluation (this is the weight% of the film redispersed in water) was calculated, and the redispersibility of the film was calculated. And
The larger the weight% of the film dissolved in water, the higher the water redispersibility of the film is, which is preferable. The water redispersibility of the film of the pressure-sensitive adhesive emulsion composition of Example 1 was 40% by weight when stirred for 10 minutes, and 70% by weight when stirred for 20 minutes. The evaluation results of the pressure-sensitive adhesive emulsion composition of Example 1 are collectively shown in Table 1.

Example 2 The adhesive emulsion of Example 1 was used, except that the aqueous solution of the specific polymer 1 was weighed so that the specific polymer 1 became 10 g (equivalent to dry amount) in Example 1. Example 2 was prepared using a method similar to that described for the preparation of the composition.
Pressure-sensitive adhesive emulsion composition was produced. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 2 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. The evaluation of the pressure-sensitive adhesive emulsion composition of Example 2 was performed using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1.

Example 3 The pressure-sensitive adhesive emulsion of Example 1 was used, except that the aqueous solution of the specific polymer 1 was weighed so that the specific polymer 1 became 50 g (in terms of dry amount). Example 3 was prepared using a method similar to that described for the preparation of the composition.
Pressure-sensitive adhesive emulsion composition was produced. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 3 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. The evaluation of the pressure-sensitive adhesive emulsion composition of Example 3 was performed using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1.

Comparative Example 1 The pressure-sensitive adhesive emulsion of Example 1 was used, except that an aqueous solution of the specific polymer 1 was weighed and added so that the specific polymer 1 became 3 g (equivalent to dry amount). A PSA emulsion composition of Comparative Example 1 was produced using the same method as described in the production of the composition. The physical properties of the pressure-sensitive adhesive emulsion composition of Comparative Example 1 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. Comparative Example 1
Of the pressure-sensitive adhesive emulsion composition of Example 1 was evaluated using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2.

Comparative Example 2 The pressure-sensitive adhesive emulsion of Example 1 was used, except that an aqueous solution of the specific polymer 1 was weighed and added so that the specific polymer 1 became 70 g (equivalent to dry amount). Comparative Example 2 was prepared using a method similar to that described in the preparation of the composition.
Pressure-sensitive adhesive emulsion composition was produced. The physical properties of the pressure-sensitive adhesive emulsion composition of Comparative Example 2 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. The evaluation of the pressure-sensitive adhesive emulsion composition of Comparative Example 2 was performed using the same method as that described in the evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. When the amount of the specific polymer 1 is 5 parts by weight or less with respect to 100 parts by weight of the monomer mixture (2), the water redispersibility of the film is reduced, and
At 0 parts by weight or more, the holding power was reduced.

Example 4 (1) Preparation of Specific Polymer 2 In the preparation of the specific polymer 1 described in Example 1, 480 g of 2-ethylhexyl acrylate (2EHA) was used instead of the monomer mixture (1). ), 400 g of polypropylene glycol monoacrylate (AP400 (trade name) manufactured by NOF Corporation, in the formula (I), R ¹ is hydrogen, R ² is a propylene group having 3 carbon atoms, R ³ is hydrogen, and n
# 6) Same as the method described in Example 1 except that a monomer mixture (3) obtained by weighing 20 g of 100 g of acrylic acid (AA) and 20 g of methacrylic acid (MAA) was used. An aqueous solution of the specific polymer 2 was produced using the method described in (1). (2) Production of pressure-sensitive adhesive emulsion composition of Example 4 In the production of the pressure-sensitive adhesive emulsion composition of Example 1 described in Example 1, 7 was used instead of the monomer mixture (2).
5.9 g of 2-ethylhexyl acrylate (2EH
A) 10 g of butyl acrylate (BA), 4 g of methyl methacrylate (MMA), 10 g of acrylic acid (AA), 0.1 g of γ-methacryloxypropyltrimethoxysilane (A174), 0.0 as a chain transfer agent
1 g of n-dodecyl mercaptan (NDM) and a polymerized rosin pentaerythritol resin (D125 (trade name) manufactured by Arakawa Chemical Co., Ltd.) as a solid tackifier were weighed and stirred to obtain a monomer mixture ( Using 4)
Instead of weighing and adding the aqueous solution of the specific polymer 1 so that the specific polymer 1 becomes 5 g (dry conversion amount), the specific polymer 2 is converted to the aqueous solution of the specific polymer 2 by 5 g (dry conversion amount). The pressure-sensitive adhesive emulsion composition of Example 4 was obtained by using the same method as that described in Example 1 except that it was weighed and added so as to be as in Example 1. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 4 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. (3) Evaluation of PSA Emulsion Composition of Example 4 Evaluation of the PSA emulsion composition of Example 4 was carried out using the same method as described in Evaluation of PSA Emulsion Composition of Example 1. evaluated. The results are shown in Table 1.

Example 5 The pressure-sensitive adhesive emulsion of Example 4 was used, except that an aqueous solution of the specific polymer 2 was weighed and added so that the specific polymer 2 became 10 g (equivalent to dry amount). Example 5 was prepared using a method similar to that described for the preparation of the composition.
Pressure-sensitive adhesive emulsion composition was produced. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 5 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. The evaluation of the pressure-sensitive adhesive emulsion composition of Example 5 was performed using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1.

Example 6 The pressure-sensitive adhesive emulsion of Example 4 was used, except that the aqueous solution of the specific polymer 2 was weighed and added so that the specific polymer 2 became 50 g (in terms of dry amount). Example 6 was prepared using a method similar to that described for the preparation of the composition.
Pressure-sensitive adhesive emulsion composition was produced. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 6 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. The evaluation of the pressure-sensitive adhesive emulsion composition of Example 6 was performed using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1.

Comparative Example 3 The pressure-sensitive adhesive emulsion of Example 4 was used, except that an aqueous solution of the specific polymer 2 was weighed and added so that the specific polymer 2 became 3 g (equivalent to dry amount). A PSA emulsion composition of Comparative Example 3 was produced using the same method as described in the production of the composition. The physical properties of the pressure-sensitive adhesive emulsion composition of Comparative Example 3 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. Comparative Example 3
Of the pressure-sensitive adhesive emulsion composition of Example 1 was evaluated using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2.

Comparative Example 4 The pressure-sensitive adhesive emulsion of Example 4 was used, except that an aqueous solution of the specific polymer 2 was weighed so that the specific polymer 2 became 70 g (in terms of dry amount). Comparative Example 4 was made using a method similar to that described for the preparation of the composition.
Pressure-sensitive adhesive emulsion composition was produced. The physical properties of the pressure-sensitive adhesive emulsion composition of Comparative Example 4 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. The evaluation of the pressure-sensitive adhesive emulsion composition of Comparative Example 4 was performed using the same method as that described in the evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. 100
The specific polymer 2 was added to the monomer mixture (2) in parts by weight.
However, when the amount is less than 5 parts by weight, the water redispersibility of the film decreases, and
If the amount is more than the weight part, the holding power is reduced.

Example 7 In the preparation of the pressure-sensitive adhesive emulsion composition of Example 1 described in Example 1, 4 g (in terms of dry amount) of an emulsifier (Neopelle No. 6 (trade name) manufactured by Kao Corporation) was further added. ) And 2 g (dry equivalent) of an emulsifier (Perex OTP (trade name) manufactured by Kao Corporation) together with an aqueous solution of the specific polymer 1 in a four-necked flask, except that The adhesive emulsion composition of Example 7 was produced using the same method. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 7 were measured using the same method as that described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. The evaluation of the pressure-sensitive adhesive emulsion composition of Example 7 was performed using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1.

Example 8 In the preparation of the pressure-sensitive adhesive emulsion composition of Example 1 described in Example 1, 4 g (in terms of dry amount) of an emulsifier (Neopele No. 6 (trade name) manufactured by Kao Corporation) was further added. ) And 4 g (dry equivalent) of an emulsifier (Perex OTP (trade name) manufactured by Kao Corporation) together with an aqueous solution of the specific polymer 1 in a four-necked flask, except that A pressure-sensitive adhesive emulsion composition of Example 8 was produced using the same method. The physical properties of the pressure-sensitive adhesive emulsion composition of Example 8 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1. The evaluation of the pressure-sensitive adhesive emulsion composition of Example 8 was performed using the same method as the method described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 1.

Comparative Example 5 In the preparation of the pressure-sensitive adhesive emulsion composition of Example 1 described in Example 1, 4 g (in terms of dry amount) of an emulsifier (Kao ( No. 6 (trade name) manufactured by Kao Corporation and 2 g (dry equivalent) of an emulsifier (Perex OT manufactured by Kao Corporation)
P (trade name) was charged into a four-necked flask, and a pressure-sensitive adhesive emulsion composition of Comparative Example 5 was produced using the same method as that described in Example 1. The physical properties of the pressure-sensitive adhesive emulsion composition of Comparative Example 5 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. The evaluation of the pressure-sensitive adhesive emulsion composition of Comparative Example 5 was performed using the same method as that described in the evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2.

Comparative Example 6 In the preparation of the pressure-sensitive adhesive emulsion composition of Example 1 described in Example 1, 4 g (in terms of dry amount) of an emulsifier (Kao ( Neoperet No. 6 (trade name) manufactured by Kao Corporation and 4 g (dry equivalent) of an emulsifier (Perex OT manufactured by Kao Corporation)
P (trade name) was charged into a four-necked flask, and a pressure-sensitive adhesive emulsion composition of Comparative Example 6 was produced using the same method as that described in Example 1. The physical properties of the pressure-sensitive adhesive emulsion composition of Comparative Example 6 were measured using the same method as described in the measurement of the physical properties of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2. Evaluation of the pressure-sensitive adhesive emulsion composition of Comparative Example 6 was performed using the same method as that described in Evaluation of the pressure-sensitive adhesive emulsion composition of Example 1. The results are shown in Table 2.

When an emulsifier is further used in addition to the specific polymer 1, the adhesive strength, tackiness,
Further, the water redispersibility of the obtained film could be improved without lowering the holding power. On the other hand, the specific polymer 1
When the monomer mixture was polymerized using only the emulsifier without using the emulsifier, the water redispersibility of the film formed from the obtained pressure sensitive adhesive emulsion composition was not sufficient.

[0077]

[Table 1] a) The unit of concentration is% by weight. The viscosity is measured at 30 ° C. and its unit is mPa · s. The unit of the particle size is μm. b) The unit of the adhesive force is N / 25 mm. c) The ball tack is the ball No. Indicated by d) The unit of holding power is minutes. e) Water redispersibility is expressed in terms of% by weight of the film redispersed in water.

[0078]

[Table 2] a) The unit of concentration is% by weight. The viscosity is measured at 30 ° C. and its unit is mPa · s. The unit of the particle size is μm. b) The unit of the adhesive force is N / 25 mm. c) The ball tack is the ball No. Indicated by d) The unit of holding power is minutes. e) Water redispersibility is expressed in terms of% by weight of the film redispersed in water.

[0079]

Since the present invention is configured as described above, it has the following effects.

The pressure-sensitive adhesive emulsion composition of the present invention comprises:
(A) A polyalkylene oxide (meth) acrylate represented by the general formula (I) and (B) a monomer mixture containing a monomer having an ethylenic double bond and a carboxyl group are polymerized and neutralized. In the presence of 5 to 50 parts by weight of the obtained polymer, it is obtained by polymerizing 100 parts by weight of an acrylic monomer, so that compared with a conventional pressure-sensitive adhesive composition,
Water redispersibility of the formed film, as well as adhesion, tack,
And at least one of the cohesive three properties of cohesion is improved.

Further, (A) the polyalkylene oxide (meth) acrylate represented by the general formula (I) is a compound of the formula (I) wherein R ¹ is hydrogen and R ² is 2 or 3 carbon atoms.
Alkylene group, R ³ is hydrogen, and n is from an integer of 1 to 17, water-redispersible of film formed is further improved.

Further, since the monomer (B) having an ethylenic double bond and a carboxyl group is acrylic acid and / or methacrylic acid, the water redispersibility of the formed film is further improved. Further, the acrylic monomer has a glass transition temperature of a polymer obtained by polymerizing the acrylic monomer of −20 ° C. or lower, so that at least one of the adhesive strength and the tack of the formed film is higher. Be improved. Furthermore, since the acrylic monomer mixture contains acrylic acid and / or methacrylic acid, the water redispersibility of the formed film is further improved. Furthermore, since a tackifier resin, particularly a polymerized rosin pentaerythritol resin, is added to the acrylic monomer mixture, at least one of the adhesion and the tack of the formed film is further improved.

Since the pressure-sensitive adhesive product of the present invention is manufactured by applying the above-mentioned pressure-sensitive adhesive emulsion composition to a substrate and then drying, the pressure-sensitive adhesive product manufactured by using the conventional water-redispersible pressure-sensitive adhesive composition is manufactured. In comparison with the above, the ease of recycling and the friendliness to the global environment are improved.

In the method for producing a pressure-sensitive adhesive product of the present invention, since the above-mentioned pressure-sensitive adhesive emulsion composition is applied to a substrate and then dried, it is compared with a conventional method for producing a pressure-sensitive adhesive product using a water-dispersible pressure-sensitive adhesive composition. As a result, an adhesive product having improved recyclability and environmental friendliness can be produced.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J040 BA202 DF041 DF051 DF062 DL121 DL161 DN062 DN072 EL012 GA07 GA08 JA03 JA09 JB09 KA26 KA38 LA02 LA06 LA11 NA02 NA05 NA06 NA12 QA01

Claims (10)

[Claims] (A) a polyalkylene oxide (meth) acrylate represented by the general formula (I): CH ₂ 1CR ¹ COO— (R ² O) _n —R ³ (I) wherein, in the formula (I), ¹ is hydrogen or methyl, R ²
Is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a branch, and n is an integer of 1 to 17. And (B) a polymer mixture obtained by polymerizing and neutralizing a monomer mixture containing a monomer having an ethylenic double bond and a carboxyl group.
An adhesive emulsion composition obtained by polymerizing 100 parts by weight of an acrylic monomer in the presence of parts by weight. 2. A polyalkylene oxide (meth) acrylate (A) wherein R ¹ is hydrogen,
R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen,
The pressure-sensitive adhesive emulsion composition according to claim 1, wherein n is an integer of 1 to 17. 3. The pressure-sensitive adhesive emulsion composition according to claim 1, wherein (B) the monomer having an ethylenic double bond and a carboxyl group is acrylic acid and / or methacrylic acid. . 4. The acrylic monomer has a glass transition temperature of a polymer obtained by polymerizing the acrylic monomer of −20.
The pressure-sensitive adhesive emulsion composition according to any one of claims 1 to 3, wherein the temperature is lower than or equal to 0C. 5. An acrylic monomer comprising acrylic acid and / or
5. The pressure-sensitive adhesive emulsion composition according to claim 1, further comprising methacrylic acid. 6. 6. The pressure-sensitive adhesive emulsion composition according to claim 1, wherein a tackifier resin is added to the acrylic monomer. 7. The pressure-sensitive adhesive emulsion composition according to claim 6, wherein the tackifying resin is a polymerized rosin pentaerythritol resin. 8. A pressure-sensitive adhesive product produced by applying the pressure-sensitive adhesive emulsion composition according to any one of claims 1 to 7 to a base material of the pressure-sensitive adhesive product, followed by drying. 9. A method for producing a pressure-sensitive adhesive product, comprising applying the pressure-sensitive adhesive emulsion composition according to claim 1 to a substrate of the pressure-sensitive adhesive product, followed by drying. 10. The protective colloid comprises: (A) a polyalkylene oxide (meth) acrylate represented by the general formula (I) CH ₂ ＣＲCR ¹ COO— (R ² O) _n —R ³ (I) [Formula (I) )), R ¹ is hydrogen or a methyl group, R ²
Is an alkylene group having 2 or 3 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a branch, and n is an integer of 1 to 17. And (B) a polymer obtained by polymerizing and neutralizing a monomer mixture comprising a monomer having an ethylenic double bond and a carboxyl group, and 5 to 50 parts by weight of the polymer The method for producing a pressure-sensitive adhesive emulsion composition according to any one of claims 1 to 7, wherein 100 parts by weight of an acrylic monomer is polymerized in the presence of a protective colloid.