JPH08325307A - Particle, copolymer, tacky agent composition and tacky material and production of aqueous dispersion and production of tacky agent composition - Google Patents

Abstract

PURPOSE: To obtain the tacky agent composition capable of exhibiting excellent adhesive performance under low load even if substrate surface of wrap film of polyethylene, polyvinyl chloride, etc., is kept in dew condensation state or wet state. CONSTITUTION: This tacky agent composition is obtained by carrying out suspension copolymerization or emulsion copolymerization of an allyl compound expressed by a general formula R-CH=CH-CH2 -SO3 -M (R is hydrogen or >=1C monovalent hydrocarbon group; M is hydrogen or a monovalent metal) with an alkyl acrylate or an alkyl methacrylate in a mixed solvent of an organic solvent with water controlled in balance of hydrophilic property to hydrophobic property. The tacky agent composition exhibits excellent adhesiveness under low load even if substrate surface of wrap film of polyethylene, vinyl chloride, etc., is kept in dew condensation state or wet state and free from soaking of paste into the substrate and exhibits excellent performance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adherend (base,
The present invention relates to particles, a copolymer, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive that exhibit excellent adhesiveness on the surface of a substrate, a substrate) under a low load. Furthermore, the present invention is an aqueous system that exhibits excellent adhesiveness at a low load on the surface of the adherend (base, substrate, base material) that is polar or non-polar at a low temperature in a wet or condensed state. The present invention relates to a method for producing a dispersion and an adhesive composition.

The present invention can be used at low temperatures, such as on the surface of frozen food packaging taken from a freezer to room temperature,
Adhesive (base, substrate, substrate) surface that is in a wet or condensed state and is polar (for example, polyvinyl chloride, polyvinylidene chloride, etc.) or non-polar (for example, polyethylene, polypropylene, etc.) In addition, the present invention relates to particles, a copolymer, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive that exhibit excellent adhesiveness under a low load.

The particles, the copolymer, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive according to the present invention are polar or non-polar adherends (base, substrate, base material) in a wet or condensed state at low temperature.
Adhesive properties (an index of stickiness during adhesion. An index of how large an adhesive force can be obtained with a small pressure load and a short time) by simply applying a low load to the surface. An index of adhesive force after adhesion. Immediately, an index of bond strength that resists the force of pulling in a direction perpendicular to the adhesive surface. And a shear resistance property (index of cohesive force after adhesion. Immediately.
An index of cohesive force after adhesion that resists the force of tearing parallel to the adhesive surface. ) Good balance is exhibited.

[0004]

2. Description of the Related Art Today, wrap films made mainly of polyethylene, poly- or copoly-vinyl chloride, poly- or copoly-vinylidene chloride, etc. are often used in various distribution stages such as food production, distribution, retail and household. in use.

Such wrap films are particularly useful for frozen foods, chilled foods, partially frozen foods, frozen desserts (ice cream, frozen yogurt, shakes, sherbets, cakes, etc.), refrigerated foods, soft drinks, dairy products (milk, milk, Butter, etc., fermented foods (natto, pickles, kimchi, cheese, lactic acid beverages, yogurt, etc.), pastry products (kamaboko, bamboo rings, etc.), processed meat products, seafood processed foods, daily foods (tofu, shirataki, konjac, etc.) Manufacture and distribution of dumplings, shimai, etc.) and retort pouch foods at low temperature
It is also widely used for packaging and containers of foods, etc. that are frozen and refrigerated.

When it is attempted to attach a price seal or a legal label (indicator of product name, manufacturer, date of manufacture, etc.) to the surface of a package or container of food that is maintained at a low temperature, the adhesive of the seal is If it is general, there is a problem that it is difficult to attach it to such a surface that is in a low temperature, a dew condensation state or a wet state, and is nonpolar (particularly in the case of a polyolefin wrap film such as polyethylene). It was

From such a background, by simply applying a low load to the surface of the adherend (base, substrate, substrate) which is low temperature, dew condensation or wet state, polar or non-polar, the adhesive property (at the time of adhesion) An index of how easily it sticks. An index of how large an adhesive strength can be obtained with a small pressure load and a short time.) Peel resistance (an index of adhesive strength after bonding. Immediately, perpendicular to the adhesive surface Of the binding force that resists the force of pulling apart) and the shear resistance property (the index of cohesive force after adhesion.
An index of cohesive force after adhesion that resists the force of tearing parallel to the adhesive surface. There has been a need for a pressure-sensitive adhesive having a good balance of (1) and excellent adhesion performance.

However, an adhesive which does not necessarily satisfy such a required performance has not been put on the market. Conventionally, an aqueous dispersion pressure-sensitive adhesive composition in which an aqueous solution of a hydrophilic polymer such as polyvinyl alcohol, a cellulose derivative, or an acrylic acid-based polymer has been used for the dewed or wetted surface has been used.

However, even with these compositions, the tackiness itself is insufficient, the tackiness on the dew condensation surface is insufficient, and the composition is separated and settled over time, and stored. It left many practical problems such as lack of stability.

(1) JP-A-63-227682 JP-A-63-227682 (inventor; Keitaro Iwasaki,
Applicant: Toyo Ink Mfg. Co., Ltd., (A): (meth) acrylic acid ester having an alkyl group having 4 to 12 carbon atoms (eg, 2-ethylhexyl acrylate, etc.), 60 to 99.8 weight. Part, (B); polymerizable unsaturated carboxylic acid (eg, acrylic acid, etc.), 0.2 to 10 parts by weight, (C); copolymerizable vinyl-based monomer other than (A) and (B) (eg, ; Methyl acrylate, etc.) 0 to 3
9.8 parts by weight, and a water content obtained by blending 100 parts by weight of an acrylic acid ester-based copolymer obtained by emulsion polymerization with 5 to 45 parts by weight of polyethylene glycol having an average molecular weight of 180 to 1100. A technique relating to an adhesive having good adhesiveness to a large number of adherends-especially useful in the frozen food industry-is disclosed.

However, regarding the adhesiveness of the above-mentioned adhesive composition to the dew condensation surface, the wet surface, and the low temperature non-polar surface, an excellent effect is recognized in the case of a high load, but in contrast, in the case of a low load. However, the effect was insufficient. Further, undesirable penetration of the pressure-sensitive adhesive composition into the adherend was observed.

(2) JP-A-2-138380 JP-A-2-138380 (inventor: Tadashi Sugiyama, Uozumi)
Hiroshi and Nobuyuki Miyaji, applicant; Nippon Carbide Industry
Co., Ltd., a resin 100 of an aqueous dispersion of a pressure-sensitive adhesive resin.
Based on parts by weight, at least one or more salts selected from metal salts or ammonium salts of sulfuric acid or nitric acid (eg;
A technique relating to an aqueous pressure-sensitive adhesive composition excellent in adhesiveness to a dew condensation surface obtained by containing 1 to 5 parts by weight of Na ₂ SO ₄ etc. is disclosed.

Here, as a preferred embodiment of the resin, for example, (A); the glass transition point of the homopolymer is −
Acrylic acid or methacrylic acid alkyl ester monomer that can be 20 ° C. or lower, 50 to 99.9% by weight,
(B); α, β-unsaturated mono- or di-carboxylic acid monomer having 3 to 5 carbon atoms (eg acrylic acid) 0.1 to 5% by weight, (C); (A) ( Acrylic monomer mixture composed of 100% by weight of (A) and (B) other than (A) and (B) and 100% by weight of a total of 100% by weight of a monomer other than (A) and (B). The thing polymerized is mentioned.

However, regarding the adhesiveness of the above-mentioned adhesive composition to the dew condensation surface, the wet surface, and the low temperature non-polar surface, an excellent effect is recognized in the case of a high load, but in contrast, in the case of a low load. However, the effect was insufficient. Further, undesirable penetration of the pressure-sensitive adhesive composition into the adherend was observed.

[0015]

DISCLOSURE OF THE INVENTION The present invention provides an adhesive property by simply applying a low load to the surface of the adherend (base, substrate, base material) which is low temperature, dew condensation or wet state, polar or non-polar. (Indicator of stickiness during adhesion. Small pressure load ・
An index of how much adhesive strength can be obtained in a short time. ), Peel resistance (index of adhesive force after adhesion. Immediately, index of bond strength that resists the force of pulling in a direction perpendicular to the adhesive surface.) And shear resistance property (index of cohesive force after adhesion). Immediately, there is provided a pressure-sensitive adhesive having excellent adhesion performance and a pressure-sensitive adhesive using the same, which has a good balance of the cohesive force index after adhesion that resists the force of tearing parallel to the pressure-sensitive adhesive surface. With the goal.

[0016]

In view of the above-mentioned problems of the prior art, the inventors of the present invention have taken into consideration the inherent performance as an adhesive, that is, even on a surface under adverse conditions of low temperature, dew condensation state and non-polarity, that is, Just by applying a low load, adhesive properties (index of stickiness at the time of adhesion. Index of how large adhesive strength can be obtained with small pressure load and short time), peeling resistance (after adhesion) An index of the adhesive force. Immediately, an index of the binding force that resists the force of separating in the direction perpendicular to the adhesive surface. And a shear resistance property (an index of the cohesive force after adhesion.
An index of cohesive force after adhesion that resists the force of tearing parallel to the adhesive surface. ), The excellent adhesive performance is exhibited, and as a result of diligent research to obtain an aqueous pressure-sensitive adhesive composition having excellent storage stability, for example, sodium methallyl sulfonate and alkyl acrylate And / or a water-dispersed PSA composition obtained by emulsion-copolymerizing a monomer system containing an alkyl methacrylic acid ester in a mixed solvent system containing isopropyl alcohol and water has the finding that the above problems can be solved. Heading out, the present invention has been completed.

The adhesive is generally glue or adhesive (adhesive).
It is used for the manufacture and application of products such as tapes and adhesive labels, which can be easily combined with two members or combined with an indication by only applying a weak pressure such as finger pressure.

The adhesive (adhesive) performance of the adhesive is as follows (1)
It consists of the balance of the three elements of (3). (1) Adhesive property (index of how easily it adheres during adhesion. An index of how large an adhesive force can be obtained with a small pressure load and short time). (2) Peel resistance (an index of adhesive strength after bonding. Immediately, an index of bonding strength that resists the force of pulling in the direction perpendicular to the adhesive surface). (3) Shear resistance characteristics (index of cohesive force after adhesion. Immediately, index of cohesive force after adhesion that resists a tearing force parallel to the adhesive surface).

As a rule of thumb for those skilled in the art, regarding the prior art,
In general, attempts to improve performance with respect to peel resistance and adhesion properties tend to be accompanied by a decrease in performance with respect to shear resistance properties. Similarly, improvement in performance related to shear resistance characteristics tends to be accompanied by deterioration in performance related to peel resistance characteristics and adhesive characteristics. The performance of the adhesive is (1) above.
In addition to the adhesive performance consisting of a balance of the three characteristics (3) to (3), the storage stability before adhesion, temporal stability after adhesion, transparency, stability of color tone, etc. are also important. is there.

[0020]

[Means for Solving the Problems]

1. Technical idea which is the basis of completion of the present invention The present inventors have excellent adhesiveness to non-polar adherends such as polyethylene, and excellent transfer to a surface dewed or wetted at low temperature by a low load. As a result of earnest research to obtain an adhesive, for example, in the presence of isopropyl alcohol and sodium methallyl sulfonate, an ethylenically unsaturated monomer having a functional group mainly composed of alkyl (meth) acrylate , A monomer having two or more ethylenically unsaturated double bonds as necessary, and other monoethylenically unsaturated monomers (hereinafter referred to as an acrylic monomer)
We have found that a water-dispersed pressure-sensitive adhesive composition obtained by copolymerizing the above can solve the above-mentioned problems, and have reached the present invention.

2. The concept of the word used in the claims and specification of the present application (1) The concept of the word "polymer" The term "polymer" used in the claims and specification of the present application includes a polymer ( Macromolecules, macromolecules, polymers), homopolymers and copolymers. The arrangement of the copolymer (copolymer) may be any of random copolymer, alternating copolymer, block copolymer, graft copolymer and the like. The macromolecule is
Any structure such as linear, macrocyclic, branched, star-shaped or three-dimensional mesh-like may be used.

(2) Concept of the word "derivative" The concept of the word "derivative" used in the claims and specification of the present application includes a hydrogen atom of a specific compound,
Including those substituted by another atom or atomic group R. Here, R is a monovalent hydrocarbon group containing at least one carbon atom, and more specifically, an aliphatic group, an alicyclic group having substantially low aromaticity, a group combining these, or These are hydroxyl group, carboxyl group, amino group,
It may be a divalent residue bound by nitrogen, silicon sulfide, phosphorus or the like, and among these, those having an aliphatic structure in a narrow sense are particularly preferable.

R is the above-mentioned one substituted with, for example, a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, an alkoxyl group, a cycloalkoxyl group, an allyloxyl group, a halogen (F, Cl, Br, etc.) group. It may be a group. By appropriately selecting these substituents, various properties of the copolymer according to the present invention (heat resistance, toughness, degradability, strength properties, elongation properties, flexibility, plasticity, shapeability, transparency,
Adhesiveness, gas barrier property, degradability, etc.) can be controlled.

(3) Concept of the word "particle" The concept of the word "particle" used in the claims and the specification of the present application is completely defined by the concept that these words generally have in polymer chemistry. Include, but not necessarily equivalent. As for the aspect of the scanning electron microscopic morphology of the “particle” used in the claims and the specification of the present application, for example, an aspect having many protrusions in the shape of raspberry or corn-rice (confeito in Portuguese). , Erythrocyte-like flat aspect, rugby ball-like spheroidal aspect, E. coli-like spindle-like aspect, hollow particle aspect having one or more voids (voids) inside, like bell An embodiment in which hollow particles further include non-hollow particles, such as Russian folk art matryoshka, one more hollow particle inside the hollow particle
It also includes a mode having one or more. As used in the claims and specification of this application, the concept of the term "particle" also includes, for example, polymer emulsions, latices, and microspheres that make up polymer suspensions. Thus, the term "particles" as used in the claims and specification of this application, although not necessarily equivalent to the concepts these terms commonly have in polymer chemistry, It will be used conveniently for the occasional reference to the essential "aspect" of the heteropolymer system according to the invention.

(3) Adhesives The concept of the term "adhesives" used in the claims and specification of the present application is pressure-sensi.
It is mutually equivalent to the concept of the term "tive adhesive" (pressure-sensitive adhesive, pressure-sensitive adhesive), has adhesiveness (tack, tackiness) at a use temperature, and has a weak pressure (10 ² to 10 ⁴ ) which is a degree of finger pressure. In Pa), it includes an adhesive having a function of exhibiting a constant binding force that resists the force of separating by contacting the adherend instantaneously (0.01 to 1 second).

The term "adhesive" used in the claims and specification of the present application refers to, for example, New Polymer Dictionary (edited by The Polymer Society of Japan, published by Asakura Shoten, Tokyo, 1988), 3
The concept of "adhesive" described in the section "adhesive" in the right column of page 41 is included. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

The term "adhesive" used in the claims and specification of the present application includes, for example, "MA".
RUZEN Macromolecule Dictionary-Concise Encyc
lopedia of Polymer Science
e and Engineering (Kroschw
(edited by itz, translated by Tatsu Mita, Maruzen, Tokyo, 1994) "
Includes the concept of "adhesive" described in the section "Adhesive and its applied products" in the left column of 246 to the right column of page 248. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

(4) The concept of the term "release material" The term "release material" used in the claims and the specification of the present application means "release line".
It is mutually equivalent to the word "r", and by adhering to the adhesive layer, it protects the adhesive layer from contact with external objects and atmosphere until use, and it has good workability and is easily removed from the adhesive layer immediately before use. By peeling, it means a material having a function of exposing the adhesive layer and having a strength suitable for various manufacturing processes and uses.

The basic structure of the release material is generally a multi-layer structure in which a release layer is provided on at least one side of a sheet-like support layer, optionally with an undercoat layer (primer layer), on the surface. It has a laminated structure. The characteristics required of the release material include, for example, barrier properties of the release layer (property of the release agent of the release layer not permeating to other adjacent layers, adhesive of the adhesive layer to be bonded, adhering through the release layer, and the like). Of the release layer), the adhesiveness of the release layer (the release layer does not easily fall off from the release material support), heat resistance, heat shrinkage resistance and the like.

Specific examples of the support layer of the release material include, for example, film base materials such as polymers, tape base materials such as polymers, and the like.
Examples thereof include metal foil base materials such as aluminum and paper base materials. As a specific example of the paper base material, for example, weigh 30 to 30
Examples include kraft paper having a thickness of 30 to 400 μm, a high-quality paper, and a white board having a thickness of 0 g / m ² .

Specific examples of the polymer film substrate include polyolefin polymers such as polyethylene, polypropylene, polybutene, polymethylpentene, and methylpentene copolymer having a thickness of 3 to 200 μm, polyethylene terephthalate and polybutylene terephthalate. Halogenated (eg, chlorinated, fluorinated, etc.) polymers such as polyester-based polymers such as poly-vinyl halides, poly-vinylidene halides, vinyl halide / vinylidene halide copolymers, polytetra-halogenated ethylene System, 6
Examples thereof include polyamide-based polymers such as nylon and 6,6-nylon, and films of bisphenol A type polycarbonate and the like.

Specific examples of the metal foil substrate include copper foil, aluminum foil, tin foil and the like having a thickness of 3 to 200 μm. The release layer of the release material generally has the properties of being inert, of low polarity, of low surface energy and of low contact angle. Specific examples of the release layer of the release material include layers having inertness, low polarity, low surface energy, and low contact angle, such as silicone compounds, halogenated polymers such as PTFE, and waxes. To be

(5) Concept of the word "adhesive material" The concept of the word "adhesive material" used in the claims and specification of the present application is "pressure-sen".
sitve adhesive product
The term "(s)" is mutually equivalent and includes the concepts of "single-sided adhesive material" and "double-sided adhesive material".

The term "single-sided pressure-sensitive adhesive" used in the claims and the specification of the present application includes a pressure-sensitive adhesive layer and a support layer as essential components, and the support layer has one surface. The pressure-sensitive adhesive layer is provided only on the above, and if necessary, a primer layer may be provided between the pressure-sensitive adhesive layer and the support layer,
A release agent layer (back surface treatment agent layer) is bonded to the other surface of the support layer on which the pressure-sensitive adhesive layer is not provided, and a release material is bonded to the surface of the pressure-sensitive adhesive layer to form a multilayer structure or a laminated structure provided respectively. Include.

The term "double-sided pressure-sensitive adhesive" used in the claims and the specification of the present application has a pressure-sensitive adhesive layer and a support layer as essential components, and the support layer is adhesive on both sides. An adhesive layer is provided, and if necessary, a primer layer is provided between the pressure-sensitive adhesive layer and the support layer, and a release material is bonded to the surface of the pressure-sensitive adhesive layer to provide a multilayer structure or a laminated structure, respectively. Includes.

Specific examples of the support to be used for the support layer of the pressure-sensitive adhesive include, for example, film base materials such as polymers, foam base materials such as polymers, textile base materials such as polymers, and polymers such as polymers. Examples include tape base materials, metal foil base materials such as aluminum, and paper base materials. Specific examples of the paper substrate include kraft paper having a basis weight of 30 to 300 g / m ² and a thickness of 30 to 400 μm, high quality paper, white paperboard, art paper, coated paper, thermal paper, and the like.

Specific examples of the polymer film substrate include polyolefin polymers such as polyethylene, polypropylene, polybutene, polymethylpentene and methylpentene copolymer having a thickness of 3 to 200 μm, polyethylene terephthalate and polybutylene terephthalate. Halogenated (eg, chlorinated, fluorinated, etc.) polymers such as polyester-based polymers such as poly-vinyl halides, poly-vinylidene halides, vinyl halide / vinylidene halide copolymers, polytetra-halogenated ethylene System, 6
Examples thereof include polyamide-based polymers such as nylon and 6,6-nylon, films of bisphenol A-type polycarbonate and the like, or laminated films in which these are combined.

Other specific examples of the polymer film substrate include, for example, cellulose having a thickness of 3 to 200 μm, cellulose nitrate, cellulose acetate, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cuprammonium rayon, cupro. Examples thereof include films of cellulose derivatives such as fans and Bemberg, and laminated films in which these are combined.

Specific examples of the polymer foam base material include foams such as polyethylene, polypropylene, polybutene, and other polyolefins having a thickness of 100 μm to 10 mm, polystyrene, polyurethane, acrylonitrile, and the like.

Specific examples of the polymer textile base material include polyolefin polymers such as polyethylene, polypropylene, polybutene, polymethylpentene and methylpentene copolymer having a thickness of 100 μm to 10 mm, polyethylene terephthalate and polybutylene terephthalate. Halogenated (eg, chlorinated, fluorinated, etc.) polymers such as polyester-based polymers such as poly-vinyl halides, poly-vinylidene halides, vinyl halide / vinylidene halide copolymers, polytetra-halogenated ethylene Examples thereof include polyamide-based polymers such as 6-nylon and 6,6-nylon, and textiles such as acrylonitrile.

Specific examples of the metal foil substrate include copper foil, aluminum foil, tin foil and the like having a thickness of 3 to 200 μm. The release agent (back treating agent) layer of the pressure-sensitive adhesive material is generally inert, has low polarity, has low surface energy, and has a small contact angle. Specific examples of the release agent layer (back surface treating agent) of the pressure-sensitive adhesive include, for example, the above-mentioned halogenated polymers such as silicone compounds and PTFE, which have characteristics of inertness, low polarity, low surface energy, and low contact angle. And layers such as waxes.

Specific examples of the adhesive material include adhesive paper, adhesive film, adhesive sheet, adhesive tape, adhesive label, adhesive sticker, adhesive sticker, adhesive patch, adhesive hook, adhesive hanger, which has at least one adhesive surface. Examples of the adhesive tape include carpet fixing adhesive tape, earthquake-resistant furniture fixture fixing adhesive tape, medical adhesive tape, coating adhesive tape, masking adhesive tape, electronic industry adhesive tape, marking adhesive tape / film, and the like.

(6) Concept of the word "foam" The term "foam" used in the claims and specification of the present application includes many voids (air bubbles, voids, microvoids) inside the resin. , Including cavity)
Exists in the continuous phase of the resin having a small apparent density,
It includes a resin structure having a two-phase structure or a multi-phase structure, in which a void phase (both continuous and independent voids) is mixed, and for example, a polymer having a cell structure, a foamed polymer,
It includes general materials recognized as structural bodies such as expanded polymers, polymer foams, and polymer foams, and includes soft ones and hard ones.

The foam containing the degradable polymer composition of the present invention can be produced by a known / publicly used method. For example, "Maruzen High Polymer Dictionary-Concise
Encyclopedia of Polymer
Science and Engineering (K
roschwitz edition, translated by Tatsuta Mita, Maruzen, Tokyo, 1
1994) ", and the foaming agents and foaming techniques described on pages 811 to 815 can be preferably used. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

(7) Concept of the word "textile" The term "textile" used in the claims and specification of the present application includes woven fabric, knitted fabric, non-woven fabric,
Braid including rope and rope, cotton-like high bulk staple, sliver,
It generally includes those recognized as fibrous structures such as porous sponge, felt, paper and net. Generally, a textile is a thread processed by a suitable processing method.

(8) Concept of the word "thread" The concept of the word "thread" used in the specification of the present application is as follows.
Textile Handbook and Processing (edited by Textile Society, Maruzen, Tokyo, 1969)
Years) -including the concept of "original yarn" described on pages 393 to 421, for example, monofilament, multifilament, staple fiber (suf), tow, high bulk tow, high bulk tow, spun yarn, blended yarn, processed yarn , False twisted yarn, modified cross-section yarn, hollow yarn, conjugate yarn,
POY (partially oriented yarn), DTY (drawn yarn), POY
-Includes DTY, sliver and the like. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

(9) “Continuous emulsion polymerization or suspension polymerization”,
Concept of "multistep continuous polymerization" or "continuous polymerization""Continuous emulsion polymerization or suspension polymerization", "multistep continuous polymerization" or "continuous polymerization" used in the specification of the present application
The described concept consists in applying pre-formed particles in an aqueous continuous phase (aqueous medium), i.e. seed polymer particles, in one or more subsequent steps by application with monomers to polymerize, One of two or more polymer layers is laminated on the seed polymer by depositing one or more polymers, and the particle diameter is increased. Including technology. Here, the concept of the "monomer" includes one or more kinds of monomers, and the concept of the "polymer" includes a homopolymer and a copolymer. The arrangement of the copolymer (copolymer) may be any of random copolymer, alternating copolymer, block copolymer, graft copolymer and the like.

(10) Concept of "unimodal continuous polymerization heteropolymer" In a multi-step continuous polymerization, from one step to another,
In the next step, if no additional surfactant is added, the micelles are not substantially formed in the reaction system.
All monomers present in the reaction system of that stage are entrapped on the particles obtained from the reaction system of the immediately preceding stage and are physically and / or chemically intimately bound.

If such a reaction mode is consistently adopted in the process of producing particles, theoretically, regardless of actual results, particles having only one kind of core / shell structure or polymer deposition structure are obtained. You should be able to.

Such a particle is referred to as "unimodality (uni
modal) "continuously polymerized heteropolymer. Regarding the single-mode continuous polymerization heteropolymer, for example, Japanese Patent Publication No. 3-9124 (Kowalski et al.)
Further details are described in column 10, line 31 to column 11, line 8. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

(12) Polymodal Continuous Polymerization Heteropolymer On the other hand, the amount of micelles that can be formed in a step immediately following the one step, that is, CMC (critical micelle formation concentration) or more. The additional addition of the surfactant, with respect to the monomers present in the reaction system of that stage, some of the monomers are incorporated on the particles obtained from the reaction system of the immediately preceding stage, and are physically and / or chemically The remaining part of the monomer is not incorporated onto the particles obtained from the reaction system of the immediately preceding step, but is incorporated into additional micelles to form additional particles.

When such a reaction mode is adopted in the process of producing particles, theoretically, it should be possible to obtain particles having a wide variety of core / shell structures or polymer deposition structures regardless of actual results. Is. Such particles are referred to as “polymodal”-
For example, "binary mode", "ternary mode" or "multimodal" -continuously polymerized heteropolymer. Regarding the polymorphic continuous polymerization heteropolymer, for example, Japanese Patent Publication No. 3-9124 (Ko
Walski et al.), column 10, line 31 to column 11, line 8 for more details. The description is based on the matters or disclosures described in the present specification by reference,
Items or disclosures that can be derived directly and unambiguously by those skilled in the art.

Intended “single-modality” or “multimodality”
In order to realize the generation of particles having the above, the kind, concentration, addition mode, timing and period of addition of the surfactant, and the relative ratio of the surfactant and the monomer may be appropriately set.

(4) Multimodality of Particles According to the Present Invention The particles according to the present invention may be monomorphic or polymorphic. In the case of polymorphism, binary modality is generally preferred. In the case of polymorphism, it is generally preferred that the primary aspect make up about 60% to about 90%, more preferably about 75% to about 85%.

(5) Seed Polymer The concept of the term “seed polymer” as used in the specification of the present application is a preformed polymer particle, which is the polymer particle of the first stage in the polymerization, or It may be a polymer particle produced at any stage except the last stage of continuous polymerization. Thus, a polymer particle intended to be provided with a shell by one or more successive steps may then be used by itself in the next step of depositing the shell-forming polymer on the seed polymer particle. Called. Thus, the seed polymer or core can be manufactured in a single stage or continuous polymerization process.

(6) Adhesive Layer Forming Mechanism of Emulsion Type Adhesive Composition Regarding the adhesive layer forming (film forming, film forming, film forming) mechanism of the adhesive composition of the emulsion type paint, particles existing in the emulsion are Touch each other on the lower ground,
It is considered that a uniform adhesive layer is formed only after the thermal fusion between particles is developed. In addition to the importance of Tg, MFT is important in the theory of the adhesive layer forming mechanism of emulsion type adhesive compositions.

(7) MFT (Minimum Film-Forming Temperature) MFT is a value obtained when the adhesive composition is spread on an adherend.
It is the minimum film formation temperature of the particles contained in the composition. MF
T is for Resin Review
It can be easily evaluated by the modified method described in Vol. 16, No. 2 (1966). The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference. The principle of this evaluation method is that the temperature gradient bar (tempera)
The composition in which particles are dispersed on a pure gradient-bar is applied thinly, and the temperature at which a thin film starts to be formed is evaluated very simply and quickly.

The temperature at which the thin film starts to be formed is, for example, the boundary between the temperature zone in which the opaque particle-dispersed composition which is not coated is continuously present and the temperature zone in which the transparent film coated is continuously present. Can be visually confirmed with the naked eye. Further, the temperature at which the thin film starts to be formed, using a spatula, a temperature zone in which the undispersed particle-dispersed composition that can be scraped is continuously present, and a film that cannot be scraped and has a film formed are continuous. It is also possible to physically confirm the boundaries of the temperature zones that exist in the background.

MFT is the Tg of the polymer that constitutes the particles.
In addition to being affected by the above, it may be affected by additives (film-forming auxiliary, plasticizer, hydrophilic emulsifier, thickener, binder, etc.), plastic effect by water, organic solvent and the like.

The monomers used in the polymerization reaction of the copolymer according to the present invention will be described in detail below. [Monomer (a1)] (1) Monomer (a1) The monomer (a1) contains at least one sulfonic acid group and / or a metal salt thereof and at least one unsaturated double bond in the molecule. The monomer is one kind or two or more kinds selected from the group consisting of monoethylenically unsaturated monomers.

(2) Specific Examples of Monomer (a1) Specific examples of the monomer (a1) include monoethylenic ones having 3 or more carbon atoms such as sodium allylsulfonate and sodium methallylsulfonate. Unsaturated monomers are mentioned, and these compounds can be used alone or in combination of two or more kinds.

(3) Amount of the monomer (a1) used The amount of the monomer (a1) used is the amount of the monomer (a1) 1 described below.
0.1 to 10.0 parts by weight is preferable, and 0.5 to 5.0 parts by weight is more preferable, relative to 00 parts by weight. 0.0
If it is less than 1 part by weight, the adhesion performance to the dew condensation surface tends to decrease, and if it exceeds 10.0 parts by weight, the adhesion performance to the non-polar surface tends to decrease.

[Monomer (a2)] (1) Monomer (a2) The monomer (a2) has no sulfonic acid group and its metal salt in the molecule and contains at least one unsaturated double bond. It is one or more monomers selected from the group consisting of monoethylenically unsaturated monomers having a bond in the molecule.

(2) Specific Examples of Monomer (a2) i) Acrylic Acid Derivatives and Methacrylic Acid Derivatives Specific examples of the monomer (a2) include, for example, methyl-,
Ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, tert-butyl-, n-amyl-, isoamyl-, n-hexyl-, cyclohexyl-, heptyl-, 2- Ethylhexyl-, octyl-, 2-ethyloctyl-, decyl-,
Dodecyl-, octadecyl-, lauryl-, stearyl-, cyclohexyl-, hydroxyethyl-, 2-hydroxypropyl-, 3-hydroxypropyl-, 2-hydroxybutyl-, 3-hydroxybutyl-, 4-hydroxybutyl-, polyethylene Glycol mono-1,
Aliphatic (alkyl) acrylic acid derivatives or aliphatic (alkyl) methacrylic acid derivatives containing acrylic acid esters or methacrylic acid esters such as 4-butanediol mono- and dimethylamino-, benzyl-, phenyl-
Examples thereof include an aromatic acrylic acid derivative or an aromatic methacrylic acid derivative containing an acrylic acid ester or a methacrylic acid ester, and these can be used alone or in combination of two or more kinds.

Ii) Monomer Having Carboxyl Group Other specific examples of the monomer (a2) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid and citraconic acid. And monoethylenically unsaturated monomers having at least one carboxyl group and at least one unsaturated double bond in the molecule,
These may be used alone or in combination of two or more. Derivatives such as esters of these monomers having a carboxyl group can also be used alone or in combination of two or more.

Iii) Monomer having glycidyl group or epoxy group As other specific examples of the monomer (a2), for example, glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, N -Monoethylene having at least one epoxy group such as glycidyl acrylic acid amide, allyl glycidyl ether, glycidyl vinyl sulfonate, glycidyl cinnamate, vinyl cyclohexene monoeposide or the like and an epoxy group and at least one unsaturated double bond in the molecule And unsaturated unsaturated monomers, which may be used alone or in combination of two or more.

Iv) Amide-based monomer Other specific examples of the monomer (a2) include, for example, vinylamide, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide, diacetone. Examples thereof include amides such as methacrylamide, and these can be used alone or in combination of two or more kinds.

V) Monomer Having Two or More Ethylenically Unsaturated Bonds Other specific examples of the monomer (a2) include, for example, butadiene, divinylbenzene, (poly) ethylene glycol diacrylate and (poly). ) Ethylene glycol dimethacrylate, trimethylolpropane triacrylate,
Examples include monoethylenically unsaturated monomers having at least two unsaturated double bonds in the molecule, such as trimethylolpropane trimethacrylate, which may be used alone or
Combinations of more than one species can be used.

Vi) Aromatic monomer Other specific examples of the monomer (a2) include, for example, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole and vinylnaphthalene. , And aromatic vinyls such as divinylbenzene. These can be used alone or in combination of two or more kinds.

Vii) Halogen-based monomer etc. Other specific examples of the monomer (a2) include halogen such as vinyl chloride, vinylidene chloride, vinyl fluoride, monochlorotrifluoroethylene, tetrafluoroethylene, chloroprene and the like. There may be mentioned monoethylenically unsaturated monomers, which may be used alone or in combination of two or more kinds.

Other specific examples of the monomer (a2) include, for example, nitriles such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl acetate and vinyl propionate, ethylene, propylene, isoprene, butadiene and carbon number. Ethylenically unsaturated monomers including α-olefins such as 4 to 20 α-olefins, alkyl vinyl ethers such as lauryl vinyl ether, nitrogen-containing vinyls such as vinylpyrrolidone and 4-vinylpyrrolidone, and the like. These can be used alone or in combination of two or more.

(3) Amount of Monomer (a2) Used The amount of the monomer (a2) used is the amount of the monoethylenically unsaturated monomer based on the monomer (a1) and the monomer (a2) ( The glass transition temperature (hereinafter referred to as “Tg” in the specification of the present application) of the polymer produced by copolymerizing A) is preferably set to −40 to −65 ° C. This T
If g is -40 ° C or higher, the adhesive strength tends to decrease at low temperatures. If this Tg is less than -65 ° C, the cohesive force tends to decrease.

The polymerization reaction system of the copolymer according to the present invention will be described in detail below. [Organic solvent (s1)] (1) Specific examples of hydroxyl compound The organic solvent (s1) is at least one selected from the group consisting of hydrocarbons having at least one hydroxyl group (hydroxyl group) in the molecule and derivatives thereof. Organic solvent (hereinafter, referred to as “hydroxyl compound” in the specification of the present application), which is substantially uniformly mixed with the water solvent (s2), and has a hydrophilic / hydrophobic balance of the mixed solvent system (S). There is no particular limitation as long as it can control.

Specific examples of the hydroxyl compound used in the present invention include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, secondary amyl alcohol, and 2-amyl alcohol. Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2
-Hydroxypropyl methacrylate and the like,
These are used alone or in combination of two or more.

(2) Amount of Hydroxyl Compound Used The hydroxyl compound used in the present invention is preferably one which is substantially uniformly mixed with distilled water at 20 ° C. in an amount of 5.0% by weight or more. It is more preferable to mix them substantially uniformly at any ratio.

Regarding the weight fraction of the hydroxyl compound in the water / hydroxyl compound-mixed homogeneous solvent, if it is less than 5% by weight, the molecular weight of the polymer forming the emulsion particles tends to decrease, and the cohesive force tends to decrease accordingly. To be The amount of the hydroxyl compound in the water / hydroxyl compound mixed homogeneous solvent is 0.01 based on 100 parts by weight of the acrylic monomer dispersed in the mixed homogeneous solvent.
To 5.0 parts by weight,
It is more preferable that the amount is 0.5 to 3.0 parts by weight. If it is less than 0.01 part by weight, the adhesiveness to the dew condensation surface tends to be reduced, and if it exceeds 5.0 parts by weight, the cohesive force is reduced or stains (penetration) occur inside the adherend. It tends to be easy.

[Polymerization Method] The method for preparing the copolymer of the present invention is not particularly limited.

The copolymer according to the present invention can be preferably prepared by a radical polymerization method including, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and a bulk polymerization method. For the method for preparing the copolymer according to the present invention, generally, no special method is required, and a known / publicly used polymerization method can be adopted.

[Preparation Method of Copolymer Particles] When the emulsion polymerization method or the suspension polymerization method is adopted as the preparation method of the copolymer according to the present invention, the obtained copolymer is usually particles. .
In such a case, at the end of the copolymerization reaction, the reaction system usually becomes an aqueous dispersible composition having the characteristics of emulsion, latex or suspension, which contains the copolymer particles as a dispersed phase and water as a continuous phase. There is. The pressure-sensitive adhesive water-based composition can be prepared by using the water-based dispersible composition as a main component and adding other components as necessary.

As described above, an emulsion polymerization method or a suspension polymerization method is generally adopted as a method for preparing the copolymer particles according to the present invention. There is no particular limitation as long as it is a means that can substantially realize a hollow structure, a hollow structure, a morphology, a particle size, a particle size distribution, a single mode property / a multi mode property, and the like.

[Emulsion Polymerization Method] When the emulsion polymerization method is adopted in the method for preparing the copolymer according to the present invention, the reaction system is
It contains water, the above-mentioned mixed solution of monoethylenically unsaturated monomer (A), a surfactant, a chain transfer agent (polymerization degree modifier), a radical polymerization initiator and the like.

[Surfactant used in emulsion polymerization method]
The surfactant used in the emulsion polymerization method is not particularly limited as long as it can stably and uniformly form the dispersed phase containing the monomer in the aqueous continuous phase during the reaction. As the surfactant used in the emulsion polymerization method, known surfactants used in ordinary emulsion polymerization can be preferably used alone or in combination.

In a preferred embodiment, an anionic surfactant and / or an anionic surfactant is used as a mixture with a nonionic surfactant. In such a preferred embodiment, the amount of the surfactant used is preferably in the range of 0.01 to 10% by weight based on the monomer mixture. Hereinafter, specific examples of nonionic surfactants, anionic surfactants and cationic surfactants are listed,
These can be suitably used alone or in combination.

(1) Anionic surfactant As specific examples of the anionic surfactant used in the method for producing an aqueous dispersion according to the present invention, sodium dodecylbenzene sulfonate (DBS, SDS), sodium lauryl sulfate, Sodium alkyl diphenyl ether disulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene Alkyl phenyl ether sulfate sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, tert-octyl Phenoxyethoxy poly- (40) -ethoxyethyl sulfate sodium salt, fatty acid soap, rosin acid soap, alkyl sulfonate, alkylbenzene sulfonate, dialkylaryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, poly Examples thereof include oxyethylene alkylaryl sulfate, and these can be used alone or in combination.

(2) Nonionic Surfactant Specific examples of the nonionic surfactant used in the method for producing the aqueous dispersion according to the present invention include polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene. Oleyl phenyl ether, polyoxyethylene nonyl phenyl ether,
Oxyethylene / oxypropylene block copolymer, tert-octylphenoxyethyl poly- (3
9) -ethoxyethanol, nonylphenoxyethyl poly- (40) -ethoxyethanol, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, oxyethyleneoxypropylene block copolymer, and the like. Can be used alone or in combination.

(3) Cationic Surfactant Specific examples of the cationic surfactant used in the method for producing an aqueous dispersion according to the present invention include lauryltrimethylammonium chloride and stearyltrimethylammonium chloride. They can be used alone or as a mixture.

[Amount of Surfactant Used in Emulsion Polymerization Method] The amount of the surfactant used in the emulsion polymerization method is the amount which substantially forms micelles in the reaction system, or a single amount in the aqueous continuous phase. There is no particular limitation as long as it is an amount that forms a dispersed phase containing a monomer substantially continuously and stably and uniformly. Generally, the type and concentration of the surfactant are CMC (critical micelle formation concentration) value peculiar to the surfactant and H
Conditions that can substantially realize the desired particle characteristics (layer structure, hollow structure, morphology, particle size, particle size distribution, single mode / multimode, etc.) while considering the LB (hydrophilic / hydrophobic balance) value. Is appropriately selected.

In one embodiment, the amount of the surfactant used may be 0.01 to 10% by weight based on the total weight of all the monomers supplied to the reaction system. In such an embodiment, the amount of surfactant used is
If the amount is reduced to 0.01% by weight or less, the polymerization stability is lowered, and gelation tends to occur during the polymerization.

On the other hand, when the amount of the surfactant used is increased to 10% by weight or more, the water resistance of the coating when it is formed tends to decrease. In another embodiment using a persulfate polymerization initiator, the amount of the surfactant used is 0 to 2% by weight based on the total weight of all the monomers present in the reaction system. be able to.

[Amount of Surfactant Used in Multi-Stage Continuous Polymerization] The multi-stage continuous polymerization can be carried out by using the copolymer particles polymerized in the stage prior to a certain stage as a seed polymer. Regarding the amount of the surfactant used in the multi-stage continuous polymerization, a persulfate-based polymerization initiator is used. In one embodiment, the amount of the surfactant used is the unit amount supplied in the first stage of the polymerization. It may be 0 to 2.0% by weight based on the total weight of the whole body.

By carrying out emulsion polymerization while maintaining low levels of surfactant usage, a continuous stage of polymer formation is obtained by producing the most recently formed polymer in the preceding stage. It can be deposited on dispersed polymer particles. Here, "to carry out emulsion polymerization while maintaining the amount of surfactant used at a low level" generally means that the amount of surfactant used is more than the amount corresponding to the CMC value in the reaction system at that stage. Also means keeping low.

The limitation of the condition that "the emulsion polymerization is carried out while maintaining the amount of the surfactant used at a low level" is generally preferable, and the single-modal product is obtained. However, in the reaction system of an embodiment, even if an amount of the surfactant corresponding to the CMC value or more is used, the amount of the dispersed micelles having preferable properties or not excessive is obtained. It has been found to involve the formation of granules.

The limitation of such a condition that "the emulsion polymerization is carried out while maintaining the amount of the surfactant used at a low level" controls the number of micelles in each step of the multi-step continuous polymerization, and as a result, The effect of depositing the polymer produced in that stage on the granules or micelles produced in the previous stage.

[Polymerization Temperature] The polymerization temperature used in the method for producing an aqueous dispersion according to the present invention is not particularly limited as long as the polymerization reaction rate can be substantially maintained. The polymerization temperature is set in consideration of the type of monomer used, the type of polymerization initiator, etc., and generally, a temperature range of about 10 to about 100 ° C. is preferable, and a temperature of about 30 to about 90 ° C. A range is more preferable.

Suitable polymerization temperatures for various polymerization initiators are, for example, Chemical Monograph, Volume 15, Chemistry of Polymer Synthesis (Takayuki Otsu, Kagaku Dojin, Kyoto, 1968), page 63, Table 3-
As described in 2 "Classification of Initiator", such conditions can be suitably adopted also in the method for producing an aqueous dispersion according to the present invention. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

When a persulfate type polymerization initiator is used,
Generally, a temperature range of about 60 to about 90 ° C is preferred.
When using a redox polymerization initiator, a temperature range of about 30 to about 70 ° C. is generally preferable, a temperature range of about 30 to about 60 ° C. is more preferable, and a temperature range of about 30 to about 45 ° C.
Is more preferable.

[Type of Polymerization Initiator] Specific examples of the polymerization initiator used in the method for producing an aqueous dispersion according to the present invention include hydrogen peroxide, tertiary butyl peroxide, ammonium persulfate and alkali metal persulfate ( Metal; sodium, potassium or lithium) persulfates, azo compounds such as 2,2-azobisisobutyronitrile, organic peroxides such as benzoyl peroxide, cumene hydroperoxide and tert-butyl hydroperoxide Examples thereof include water-soluble free radical initiators commonly used in emulsion polymerization, such as substances, and these can be used alone or as a mixture.

Among these, in general, persulfates of alkali metal persulfate (metal; sodium, potassium or lithium) are particularly preferably used. Another specific example of the polymerization initiator is a redox polymerization initiator that forms a redox system by using a reducing agent together with the polymerization initiator.

Examples of the reducing agent include metabisulfite, hydrosulfite, salts of sulfite such as alkali metal hyposulfite (eg, sodium salt, potassium salt, etc.), bisulfite and salts thereof (eg, sodium salt, potassium salt, etc.). ), Sodium formaldehyde sulfoxylate, sodium pyrosulfite, L-ascorbic acid and salts thereof (for example, sodium salt, potassium salt, etc.), metal ions such as iron ions,
Rongalit and the like can be mentioned, and these can be used alone or as a mixture.

In the method for producing an aqueous dispersion according to the present invention, for example, Chemical Monograph, Volume 15, Chemistry of Polymer Synthesis (Takayuki Otsu, Kagaku Dojin, Kyoto, 1968) 62.
The compounds listed in the section "Initiator of radical polymerization" on page 72 to 72 can be preferably used alone or as a mixture. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

[Polymerization Initiator Addition Method] The polymerization initiator may be added all at once or continuously. [Amount of Polymerization Initiator] The amount of the polymerization initiator used in the method for producing an aqueous dispersion according to the present invention is not particularly limited as long as the reaction rate can be substantially ensured. Generally, the amount of the polymerization initiator used is preferably in the range of 0.01 to 4 parts by weight based on 100 parts by weight of the total amount of the monomers supplied. Also, the amount of the reducing agent used in the redox system is preferably 0.01 to 4 parts by weight based on 100 parts by weight of the total amount of the supplied monomers.

[Chain Transfer Agent] In the method for producing an aqueous dispersion according to the present invention, a chain transfer agent such as a mercaptan may be used if necessary. Specific examples of the chain transfer agent include mercaptans including lower alkyl mercaptans such as secondary butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, carbon tetrachloride and the like. Examples thereof include halogenated hydrocarbons, and these can be used alone or in combination. By controlling the amount of the chain transfer agent used, the toluene insoluble content of the produced copolymer can be adjusted arbitrarily.

[Polymerization regulator] If necessary, a polymerization regulator such as a pH regulator such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate or sodium carbonate can be added to the reaction system. Regarding the copolymer according to the present invention,
The details will be described below.

[Glass Transition Temperature (Tg) of Copolymer] (1) Tg of Copolymer Tg of the polymer according to the present invention is preferably -40 to -65 ° C. If this Tg is -40 ° C or higher, the adhesive strength tends to decrease at low temperatures. This Tg
However, when the temperature is lower than -65 ° C, the cohesive force tends to decrease.

(2) Fox's Formula The Tg of a polymer having a specific monomer composition can be calculated by the Fox's formula.
Here, the Fox equation is for calculating the Tg of the copolymer based on the Tg of the homopolymer of the individual monomers forming the copolymer,
For more details, see Bulletin of the American Physical Society, Series 2 (Bulletin).
of the American Physical
Society, Series 2) Volume 1, Issue 3, 12
3 pages (1956). The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

(3) T for ethylenically unsaturated monomer
Data for g Tg for various ethylenically unsaturated monomers that form the basis for evaluating the Tg of a copolymer by Fox's equation.
Is, for example, New Polymer Bunko, Volume 7, Introduction to Synthetic Resins for Paints (Kyozo Kitaoka, Polymer Publishing Association, Kyoto, 1974) 1
The numerical values described in Table 10-2 (main raw material monomers of acrylic resin for paints) on pages 68 to 169 can be adopted. The description is a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the present specification by reference.

[Weight Average Molecular Weight of Copolymer] The weight average molecular weight of the copolymer of the present invention is generally about 3,000.
It is about 50,000 to about 100,000 and about 100,000 or less when a chain transfer agent is used. If cross-linking occurs in the course of polymerization, the molecular weight of the polymer can increase significantly. For example, in some embodiments where a relatively low weight average molecular weight, such as about 500,000 to about 20,000 is desired, the amount of monoethylenically unsaturated monomer used is suppressed and a chain transfer agent is used instead. Use from 0.05 to 2% or more.

[Toluene-insoluble matter of copolymer] The toluene-insoluble matter of the copolymer is preferably 30 to 70%, and 4
0 to 55% is more preferable. If it is less than 30%, the cohesive force tends to decrease, and if it exceeds 70%, the adhesive force tends to decrease.

[Particle Diameter] The average diameter of the copolymer particles of the present invention is substantially stable and uniform in the composition system, and substantially sufficient storage stability and workability are ensured. If it is done, it is not particularly limited. [Core Polymer / Shell Polymer Weight Ratio] When the copolymer particles of the present invention are core / shell type particles, the core polymer / shell polymer weight ratio is the desired core /
There is no particular limitation as long as the shell structure can be substantially secured. Generally, a weight ratio of core polymer / shell polymer of 5:95 to 90:10 is preferred.

[Additives] The copolymer and the water-based pressure-sensitive adhesive composition of the present invention may optionally contain additives used in ordinary polymer emulsion compositions. Specific examples of the additive include, for example, a tackifier, a crosslinking agent, an antifoaming agent, a dispersant, a thickener, a pigment, a pigment dispersant, a bath agent, a film-forming auxiliary agent, an organic solvent, a plasticizer, and a preservative. , Antibacterial agents, anticorrosive agents, thixotropic agents (additives that suppress thixotropy or thixotropy), and the like, and these can be used alone or in combination.

(1) Tackifier The tackifier that can be used in the copolymer of the present invention and the aqueous pressure-sensitive adhesive composition is not particularly limited as long as it can substantially exhibit the function of tackifying. Specific examples of the tackifier that can be used in the copolymer and the aqueous pressure-sensitive adhesive composition of the present invention include, for example, natural or polymerized rosin, modified rosin, methyl ester, glycerin ester, pentaerythritol ester, and triethylene glycol. Rosin-based tackifying resins represented by esters and hydrogenation thereof, α-pinene, β-pinene, camphor,
A terpene-based tackifying resin typified by dipentene and terpene phenol, an aliphatic system containing a C5 (5 carbon atoms) fraction as a main raw material, and an aroma containing a C9 (9 carbon atoms) fraction as a main raw material Coumarin-based indene-based adhesives containing petroleum-based tackifier resins represented by group-based and their copolymerization systems, alicyclic systems, styrenes of tar naphtha fraction, indene, coumarone, and other dicyclopentadiene The imparting resin, an alkylphenol tackifying resin represented by a condensate of pt-butylphenol and acetylene, a xylene tackifying resin obtained by reacting o-xylene, p-xylene, m-xylene with formalin, and the like, These may be used alone or in combination of two or more.

(2) Crosslinking Agent The crosslinking agent that can be used in the copolymer and the aqueous pressure-sensitive adhesive composition of the present invention is not particularly limited as long as it can substantially exhibit the function of crosslinking. As the cross-linking agent that can be used in the copolymer and the aqueous pressure-sensitive adhesive composition of the present invention, for example, a cross-linking agent that can cross-link with a functional group-containing monomer can be preferably used. Specific examples of the cross-linking agent that can be used in the copolymer and the aqueous pressure-sensitive adhesive composition of the present invention include, for example, an isocyanate compound, a melamine compound, an epoxy compound, a metal compound, a functional group-containing monomer such as an aziridinyl compound. Examples thereof include those that undergo a crosslinking reaction with, and these can be used alone or in combination of two or more kinds. As the cross-linking agent, one that meets the required adhesive properties
It is appropriately selected.

[Adherend (Substrate, Substrate, Substrate) Suitable for Water-Based Adhesive Composition of the Present Invention] The copolymer and water-based adhesive composition of the present invention are at low temperature in a wet or condensed state. Yes,
It exhibits excellent adhesiveness with a low load on the surface of the adherend (base, substrate, substrate) that is polar or non-polar.

The copolymer and the water-based pressure-sensitive adhesive composition of the present invention are, for example, in a wet or condensed state at a low temperature, as in the case of the surface of a frozen food package taken out from a freezer at room temperature, and have a polar property. Excellent adhesion at low load to the surface of the adherend (base, substrate, substrate) that is non-polar (for example, polyethylene, polypropylene, etc.) (for example, polyvinyl chloride, polyvinylidene chloride, etc.) Express.

The pressure-sensitive adhesive using the copolymer and the water-based pressure-sensitive adhesive composition of the present invention is an adherend (base, substrate, substrate) which is in a wet or dew state at low temperature and is polar or non-polar.
Adhesive properties (an index of stickiness during adhesion. An index of how large an adhesive force can be obtained with a small pressure load and a short time) by simply applying a low load to the surface. An index of adhesive force after adhesion. Immediately, an index of bond strength that resists the force of pulling in a direction perpendicular to the adhesive surface. And a shear resistance property (index of cohesive force after adhesion. Immediately.
An index of cohesive force after adhesion that resists the force of tearing parallel to the adhesive surface. ) Has a good balance and excellent adhesive performance. The copolymer and the water-based pressure-sensitive adhesive composition of the present invention are, for example, on the surface of any base such as wood, paper, synthetic resin, glass, metal, ceramics, gypsum, or leather, at low temperature, in a wet state or a dew condensation state. Under the conditions described above, excellent adhesion can be exhibited under a low load.

[Uses of the adhesive composition according to the present invention] Specific examples of the adhesive material using the adhesive composition of the present invention include the following. The term “release material” used below has a function of protecting the adhesive layer until use and also having a function of easily peeling from the adhesive layer immediately before use to expose the adhesive layer, for example, silicone treatment. And sheets that have been laminated with PTFE (paper,
Includes cloth, film, tape and the like. ) Means.

(1) Labels An adhesive layer is formed by applying the copolymer or water-based pressure-sensitive adhesive composition of the present invention onto a release material, and drying it if necessary to remove moisture, organic solvent, etc. Remove and transfer to one side of support (paper base such as high-quality paper, art paper, coated paper, thermal paper, film base such as polyester, polypropylene and vinyl chloride, foam base such as urethane and acrylic) This makes it possible to manufacture pressure sensitive adhesive sheets and pressure sensitive adhesive labels.

(2) Single-sided or double-sided pressure-sensitive adhesive tape The copolymer or the water-based pressure-sensitive adhesive composition of the present invention is applied to a support (for example, woven cloth / nonwoven cloth / brassie cloth / film such as rayon, nylon, polyester, polypropylene). A single-sided or double-sided adhesive tape can be produced by applying a single-sided coating or a double-sided coating to form an adhesive layer on one side or both sides, and attaching a release paper sheet to the adhesive layer. Further, the release paper sheet, one-side coating or both-side coating, to form an adhesive layer on one side or both sides, by sticking this adhesive layer, further release paper / release film,
Single-sided or double-sided adhesive transfer tapes can be manufactured.

[0119] In the specification of the present application, the examples, production examples and modes are for helping understanding of the content of the invention according to the present application, and the description does not limit the invention in any way. Not a thing. In order to more specifically describe the present invention, examples and comparative examples will be described below. "Parts" and "%" used in the following description are
Unless otherwise specified, it means "parts by weight" and "% by weight", respectively.

[0120]

EXAMPLES Examples of the present invention will be specifically described below.
The invention is not limited to the examples. In addition, the part in an example represents a weight part, and% represents weight%, respectively. Examples 1 to 14 96 parts of distilled water, sodium dodecylbenzenesulfonate in a reactor with a nitrogen inlet tube and a stirrer, the temperature of which was adjustable,
2 parts and 1.0 part of potassium persulfate were charged, and the mixture was put under a nitrogen stream to give 7
After the temperature was raised to 0 ° C., 0.8 parts of sodium dodecylbenzenesulfonate was added to the monomer mixture shown in Table 1 and 68 parts of distilled water.
Of the monomer emulsion, which was emulsified and dispersed, was continuously added in 3 hours, and the reaction was continued at 80 ° C. for 3 hours to complete the polymerization and then cooled, and the pH was adjusted to 7 to 7.5 with ammonia water. After the adjustment, an acrylic aqueous copolymer was obtained by filtering with a wire mesh or the like. The nonvolatile content, toluene insoluble content, and glass transition temperature of this acrylic aqueous copolymer were measured by the following methods. The measurement results are shown in Table-1.

[Non-volatile content] The non-volatile content [%] was accurately measured by transferring approximately 2 g of the acrylic aqueous copolymer to a petri dish and weighing it.
After drying at 5 ° C. for 3 hours, the sample was precisely weighed again and calculated by the following formula. Nonvolatile matter [%] = (A−B) / A × 100 Here, A is the weight before drying, and B is the weight after drying at 105 ° C. for 3 hours.

[Toluene-insoluble matter] Toluene-insoluble matter [%] was measured by weighing an acrylic aqueous copolymer dried under reduced pressure at 30 ° C., and weighing 2 g of toluene per 1 g of this polymer.
After adding 00 ml and immersing at 30 ° C. for 24 hours, it was filtered by a glass filter (No. 3) and calculated by the following formula. Toluene-insoluble matter [%] = (C−D) / C × 100 Here, C is the weight of the acrylic aqueous copolymer dried under reduced pressure at 30 ° C., and D is filtered by a glass filter (No. 3). Copolymer weight. [Glass transition temperature] It was measured using a differential scanning calorimeter.

Comparative Examples 1 to 9 96 parts of distilled water, 0.2 part of sodium dodecylbenzenesulfonate and 1.0 part of potassium persulfate were charged in the same apparatus as in Production Example 1 and heated to 70 ° C. under a nitrogen stream. Thereafter, a monomer emulsion obtained by emulsifying and dispersing the acrylic monomer mixture consisting of Table 2 in 0.8 part of sodium dodecylbenzenesulfonate and 68 parts of distilled water was continuously added for 3 hours, and further 80 ° C. After the reaction was continued for 3 hours to complete the polymerization, the mixture was cooled, the pH was adjusted to 7 to 7.5 with aqueous ammonia, and the mixture was filtered with a wire mesh or the like to obtain an acrylic aqueous copolymer.

Nonvolatile matter, toluene insoluble matter and glass transition temperature of this acrylic aqueous copolymer were measured in the same manner as in Examples. Table 2 shows the measurement results. The acrylic aqueous copolymers obtained in the above Examples and Comparative Examples were treated with Primal AS.
A small amount of E-60 (thickener: manufactured by Nippon Acrylic Co., Ltd.) was added to increase the viscosity to about 5000 cps. This was coated on release paper so that the dry weight was about 20 g / m ² , dried at 100 ° C. for 3 minutes, and then transferred to high-quality paper to prepare a sample for measuring adhesive physical properties.

The physical properties were measured by the following methods. [Measurement of physical properties] (1) Initial tack force A weight (in increments of 50 g) with a polyethylene plate adherend attached to the upper horizontal surface, a looped width of 25 mm, and a length of 2
Adhesion area of 25 mm for 50 mm test piece
Initially, the weight of the maximum weight capable of holding the adhesive for 20 seconds or more was taken as the initial adhesive force after being pressed for 3 seconds under a load of 25 mm and a load of 10 g for 3 seconds.

(2) Adhesive strength A test piece having a width of 25 mm and a length of 150 mm was used in an atmosphere of 20 ° C. and a rubber roll weighing 50 g, and a thickness of 5 m.
m × width 50 mm × length 125 mm, a polyethylene plate, a polyvinyl chloride wrap film wrapped around a wrap surface was pressure-bonded at a speed of 300 mm / min, and the 180-degree peeling strength of this adhesive sample was applied for 30 minutes after pressure bonding. 0
The sample was placed in an atmosphere of 0 ° C., and the tensile speed was 300 mm / min in a 0 ° C. atmosphere using a Tensilon tensile tester.

(3) Adhesive force on dew condensation surface: A stainless steel plate having a thickness of 5 mm, a width of 50 mm and a length of 125 mm and a wrap film of polyethylene or polyvinyl chloride wound around the plate was left in a thermostatic chamber at -20 ° C. for 3 hours or more. , 20 ° C. × 65% RH, taken out in a room, allowed to condense for 60 seconds, and immediately, a test piece was pressure-bonded to the lap surface with a roll of 50 gr at a speed of 300 mm / minute, and a peeling speed of 300 mm / minute after 60 seconds. It was measured at.

(4) Cohesive force A test piece having a width of 25 mm and a length of 150 mm was bonded to a stainless steel plate (SUS304) with an area of 25 mm × 25 mm in a 20 ° C. atmosphere using a rubber roll weighing 2 kg.
The adhesive sample that was crimped to
The test piece was hung vertically in an atmosphere of ° C, a weight of 1 kg was placed on the lower end of the test piece, and the test piece was allowed to stand still, and the time until the weight fell was measured.

(5) Paste soaking 5 kg / cm on a test piece with a width of 200 mm and a length of 200 mm
^While the pressure of ² was being applied, it was left to stand at 40 ° C.-85% RH in a constant temperature and constant humidity for 72 hours and then visually observed. Table 3 shows the measurement results. The abbreviations in Table 1 or 2 mean the following contents. 2EHA: 2-ethylhexyl acrylate nBA: n-butyl acrylate St: Styrene HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid t-DM: t-dodecyl mercaptan IPA: i-propyl alcohol SMS: sodium methacryl sulfonate

Abbreviations in Table 3 have the following meanings. PE: polyethylene wrap film (Mitsubishi Petrochemical Co., Ltd.)
Manufactured by Yuka Wrap F-61A) PVC: polyvinyl chloride wrap film (manufactured by Mitsui Toatsu Chemicals Inc., Hilap CMA) The unit of initial tack force and adhesive force is [g / 25 mm ² ].

[0131]

[Table 1]

[0132]

[Table 2]

[0133]

[Table 3]

[0134]

[Table 4]

[0135]

[Table 5]

[0136]

[Table 6]

[0137]

[Table 7]

[0138]

[Table 8]

[0139]

EFFECTS OF THE INVENTION According to the present invention, the adhesive strength to non-polarity such as polyethylene, which has not been achieved in the prior art in the pressure-sensitive adhesive, and the dewed or wetted surface of the wrap film made of polyethylene, polyvinyl chloride, etc. A pressure-sensitive adhesive having excellent adhesiveness and cohesive force due to transfer with a low load to a film is achieved.

That is, Comparative Examples 1 and 8 which are out of the scope of the present invention have good cohesive force and paste penetration, but are significantly inferior in initial tack force, adhesive force and adhesive force on dew condensation surface. Comparative Example 4 and Comparative Example 7 have an initial tack force, an adhesive force,
Condensation surface adhesion is good, but cohesion and / or paste penetration is poor. In addition, Comparative Example 3 and Comparative Example 5 have an initial tack force,
Adhesive strength, cohesive strength, and paste penetration are good, but the dew condensation surface adhesion is extremely poor, and in Comparative Example 6, adhesive strength, cohesive strength, and paste penetration are good for wrap films made from polyvinyl chloride. However, the adhesive strength to a wrap film made of polyethylene as a raw material and the initial tack strength are remarkably poor. Further, in Comparative Example 9, the initial tack force and the adhesive force are good,
The dew condensation surface adhesive strength and cohesive strength are remarkably inferior and are not satisfactory. On the other hand, Examples 1 to 14 are excellent in all adhesive performance. Therefore, by using the pressure-sensitive adhesive of the present invention, polyethylene, a wrap film made of polyvinyl chloride or the like as a dew condensation or adhesiveness due to low weight transfer to a wet surface, a pressure-sensitive adhesive label excellent in cohesive force, It enables the production of adhesive tapes, and can be expanded to other fields where adhesives could not be used in the past.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 141/00 JDF C09J 141/00 JDF

Claims (14)

[Claims] 1. A group consisting of a monomer (a1); a monoethylenically unsaturated monomer having at least one sulfonic acid group and / or a metal salt thereof, and at least one unsaturated double bond in the molecule. At least one kind of monomer selected from: and a monomer (a2); a monomer having no sulfonic acid group and a metal salt thereof in the molecule and at least one unsaturated double bond in the molecule Monoethylenically unsaturated monomer system (A) containing at least one kind of monomer selected from the group consisting of ethylenically unsaturated monomers, organic solvent (s1); at least one hydroxyl group in the molecule Containing at least one organic solvent selected from the group consisting of hydrocarbons and derivatives thereof, and a water solvent (s2); water, and controlling the hydrophilic / hydrophobic balance, and mixing them substantially uniformly. Mixed solvent system ( S)
Particles obtained by emulsion polymerization or suspension polymerization in the presence of 2. A monomer (a1); a group consisting of at least one sulfonic acid group and / or a metal salt thereof, and a monoethylenically unsaturated monomer having at least one unsaturated double bond in the molecule. At least one kind of monomer selected from: and a monomer (a2); a monomer having no sulfonic acid group and a metal salt thereof in the molecule and at least one unsaturated double bond in the molecule Monoethylenically unsaturated monomer system (A) containing at least one kind of monomer selected from the group consisting of ethylenically unsaturated monomers, organic solvent (s1); at least one hydroxyl group in the molecule Containing at least one organic solvent selected from the group consisting of hydrocarbons and derivatives thereof, and a water solvent (s2); water, and controlling the hydrophilic / hydrophobic balance, and mixing them substantially uniformly. Mixed solvent system ( S)
A copolymer obtained by polymerization in the presence of 3. The monomer (a1) has the general formula “R—CH═
CH-CH ₂ -SO ₃ -M "(R is hydrogen or C 1 or more monovalent hydrocarbon group having a carbon, M is hydrogen or a monovalent metal) compound and a derivative thereof represented by Containing at least one monomer selected from the group consisting of:
The particle according to claim 1 or the copolymer according to claim 2. 4. The monomer (a1) has the general formula “CH ₂ ═C”.
H-CH ₂ —SO ₃ —M ”(M is hydrogen or a monovalent metal) and contains at least one monomer selected from the group consisting of allylsulfonic acid compounds and derivatives thereof. The particle according to claim 1 or the copolymer according to claim 2, which is a product. 5. The particle according to claim 1, wherein the monomer (a2) contains at least one monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate. Or a copolymer. 6. The organic solvent (s1) at 20 ° C.,
The particle or copolymer according to any one of claims 1 to 5, which can be mixed substantially uniformly at a ratio of at least 5% by weight with respect to the water solvent (s2). 7. A glass transition temperature of about -40 to about -6.
The particle or copolymer according to claim 1, which has a temperature of 5 ° C. 8. A pressure-sensitive adhesive composition comprising the particle or copolymer according to claim 1. 9. The pressure-sensitive adhesive composition according to claim 8, which has a toluene insoluble content of 30 to 70%. 10. A pressure-sensitive adhesive material comprising the pressure-sensitive adhesive composition according to claim 8 or 9 in an adhesive layer. 11. A pressure-sensitive adhesive material, which comprises the pressure-sensitive adhesive composition according to claim 8 or 9 in an adhesive layer and exhibits tackiness to a wet state surface or a dew-condensed surface. 12. A pressure-sensitive adhesive material, which comprises the pressure-sensitive adhesive composition according to claim 8 in an adhesive layer and exhibits tackiness on the surface of a frozen food packaging material. 13. A monomer (a1); a group consisting of a monoethylenically unsaturated monomer having at least one sulfonic acid group and / or a metal salt thereof and at least one unsaturated double bond in the molecule. At least one kind of monomer selected from: and a monomer (a2); a monomer having no sulfonic acid group and a metal salt thereof in the molecule and at least one unsaturated double bond in the molecule A monoethylenically unsaturated monomer system (A) containing at least one kind of monomer selected from the group consisting of ethylenically unsaturated monomers is added at a temperature of about 10 ° C. to about 100.
C., organic solvent (s1); at least one organic solvent selected from the group consisting of hydrocarbons having at least one hydroxyl group in the molecule and derivatives thereof, and water solvent (s2); water and radicals Emulsion polymerization or suspension polymerization is carried out in a substantially uniform mixed solvent system (S) having a hydrophilic / hydrophobic balance controlled and containing a polymerization initiator, thereby forming copolymer particles. And a water-insoluble copolymer particle as a disperse phase, and a mixed solvent system (S) as a continuous phase, which is an emulsion, latex, or suspension. 14. A group consisting of a monomer (a1); a monoethylenically unsaturated monomer having at least one sulfonic acid group and / or a metal salt thereof and at least one unsaturated double bond in the molecule. At least one kind of monomer selected from: and a monomer (a2); a monomer having no sulfonic acid group and a metal salt thereof in the molecule and at least one unsaturated double bond in the molecule A monoethylenically unsaturated monomer system (A) containing at least one kind of monomer selected from the group consisting of ethylenically unsaturated monomers is added at a temperature of about 10 ° C. to about 100.
C., organic solvent (s1); at least one organic solvent selected from the group consisting of hydrocarbons having at least one hydroxyl group in the molecule and derivatives thereof, and water solvent (s2); water and radicals Emulsion polymerization or suspension polymerization is carried out in a substantially uniform mixed solvent system (S) having a hydrophilic / hydrophobic balance controlled and containing a polymerization initiator, thereby forming copolymer particles. And a water-insoluble dispersible pressure-sensitive adhesive composition having the characteristics of an emulsion, a latex or a suspension, which comprises water-insoluble copolymer particles as a dispersed phase and contains a mixed solvent system (S) as a continuous phase. Production method.