JP5620320B2 - Adhesive laminate - Google Patents

Description

  The present invention relates to an adhesive laminate of a heat and pressure adhesive type.

  Various adhesives are known for bonding both paper and film by laminating another paper or film on a laminate in which an adhesive layer is formed on paper or film, etc., and then applying heat and pressure (heat sealing). Yes. When manufacturing and storing the laminate as described above, the adhesive applied to a long paper or film is usually taken up and stored in roll form after drying.

  Many of such adhesives are produced using an organic solvent, and there is a problem from the viewpoint of environmental load during production and storage. On the other hand, in recent years, for the purpose of reducing the environmental burden, it has been studied to use an aqueous emulsion without using an organic solvent (Patent Document 1).

  In addition, for the purpose of energy saving and labor saving, there is a demand for an adhesive that can be heat sealed at a low temperature.

JP-A-6-049315 ([0014])

  By the way, in order to improve the heat sealability at a low temperature, it is common to make the resin, which is the main agent of the adhesive, soft and easy to soften at a lower temperature. When a laminate using such a flexible resin as an adhesive is wound up and stored, the adhesive-uncoated surface (back surface) of the laminate will be in contact with the adhesive layer, but the flexible low-temperature softening property In the adhesive layer using resin, a phenomenon called “blocking” occurs in which both adhere to each other during storage, and tension is applied when unwinding from what was stored in a roll. There are problems that stable unwinding is difficult, workability is deteriorated, and adhesive is transferred to the back surface, and the quality of the heat-sealable laminate is deteriorated.

  In order to prevent blocking, it is generally known to add higher fatty acid amides such as fatty acid-based high melting point waxes and stearic acid amides. (Heat sealability) may be reduced.

  Then, this invention aims at providing the adhesive laminated body which has the characteristic that heat sealing property in low temperature is favorable and does not produce blocking easily.

In the present invention, a specific filler is contained in an adhesive resin composition containing an aqueous emulsion obtained by emulsifying an adhesive resin with a polymer emulsifier, and then applied to the surface of a film-like substrate or a sheet-like substrate. It is an adhesive laminate of the heat and pressure bonding type, and contains 2 to 40 parts by weight of the polymer emulsifier and 0.1 to 5 parts by weight of the filler with respect to 100 parts by weight of the adhesive resin. And the thickness L1 of the adhesive bond layer which consists of the said adhesive resin composition, and the volume average particle diameter L2 of a filler make the said subject by setting it as the adhesive laminated body which has the relationship of following formula (1). It was solved.
0.1 ≦ L1 / L2 <1 (1)

According to this invention, since the filler having a specific particle size is contained in the adhesive layer, the contact portion between the adhesive uncoated surface (back surface) and the adhesive layer of the laminate is only the top of the filler even during winding. The contact area between the two is reduced. For this reason, it can prevent that blocking arises.
In addition, when a film or sheet to be bonded (such as a sheet to be bonded) and an adhesive layer of the adhesive laminate according to the present invention are overlaid and heated and pressed, the sheet or the like to be bonded and the adhesive layer of the laminate Since the pressure concentrates on the contact portion with the top of the filler in the adhesive, the adhesive force is further improved. From these, in this invention, although it has a filler whose particle size is larger than the coating film thickness, the adhesion performance can be improved.

Schematic diagram of the cross section of the adhesive laminate according to the present invention

  An adhesive laminate according to the present invention comprises an adhesive resin composition containing an aqueous emulsion obtained by emulsifying an adhesive resin with a polymer emulsifier, a film-like substrate or sheet-like substrate (hereinafter referred to as “substrate”). It is referred to as a “sheet or the like”).

  As said adhesive resin, resin which has adhesiveness is said, According to the kind of base material or to-be-adhered body, a thermoplastic resin can be selected suitably and can be used. Examples thereof include homopolymers and copolymers of olefin monomers, vinyl esters, and (meth) acrylic monomers.

  Examples of the olefin monomer include α-olefins such as ethylene, propylene, butene, pentene, hexene, and octene. Examples of the vinyl esters include vinyl acetate and vinyl versatate.

  The (meth) acrylic monomer includes (meth) acrylic acid, methyl (meth) acrylate, (meth) acrylic acid such as lauryl (meth) acrylate and alkyl esters thereof, (meth) acrylic acid 2 -(Meth) acrylic acid alkoxyalkyl esters such as methoxymethyl, polymerizable dibasic acids such as maleic acid, maleic anhydride and itaconic acid, and alkylamino (meth) acrylic esters such as dimethylaminoethyl methacrylate .

  The said thermoplastic resin can be used individually or in combination of multiple. Moreover, an additive can be added in the range which does not impair the property of a thermoplastic resin. Examples of the additive include tackifiers, chlorinated polyolefins, styrenic block copolymers and derivatives thereof. In the present specification, “(meth) acryl” means “acryl or methacryl”.

  Examples of the tackifier include rosin and derivatives thereof, terpenes and derivatives thereof, aliphatic hydrocarbon resins and derivatives thereof. Examples of the chlorinated polyolefins include chlorinated polypropylene and chlorinated polyethylene. Examples of the styrene block copolymer and derivatives thereof include styrene-isoprene block copolymers, styrene-butadiene block copolymers, hydrogenated products thereof, and maleic anhydride-modified products.

  The method for producing the aqueous thermoplastic resin emulsion is not particularly limited as long as the thermoplastic resin can be emulsified and dispersed. For example, the following methods can be mentioned. That is, first, an adhesive resin as a substance to be dispersed is dissolved in an organic solvent such as toluene, and this is mixed with an emulsifier and an aqueous medium. And it stirs with a high-speed stirrer such as a homomixer to produce a content solvent dispersion of the substance to be dispersed. Next, a method of removing the organic solvent by an operation such as distillation under reduced pressure to obtain an aqueous emulsion can be mentioned. Further, an aqueous solution of an emulsifier is added and mixed while stirring the adhesive resin in a molten state, and then an aqueous medium such as water is added to disperse the dispersoid in the aqueous medium with an emulsifier, particularly a polymer emulsifier. A method for producing an emulsion can also be mentioned.

  At this time, when a thermoplastic resin containing a carboxyl group such as (meth) acrylic acid or maleic anhydride or an anhydride thereof is used as the adhesive resin, an amine or an alkali is used at a temperature equal to or higher than the softening point of the thermoplastic resin. The method of making it a dispersion liquid by making it contact in alkaline media, such as a metal hydroxide and an alkaline-earth metal hydroxide, in an aqueous medium is also mentioned.

  The above-mentioned aqueous medium refers to a mixed solution of water or water and an organic solvent compatible with water such as methanol or ethanol. Among these, it is particularly preferable to use water from the environmental aspect.

  The preferred weight average molecular weight of the polymer emulsifier used in the present invention is in the range of 5,000 to 1,000,000. If it is less than 5,000, it may be difficult to stably disperse the thermoplastic resin as the dispersoid. On the other hand, if it exceeds 1,000,000, the polymer emulsifier becomes difficult to dissolve in water, and the stability of the aqueous dispersion of the adhesive resin composition tends to deteriorate.

  Examples of the polymer emulsifier include an alkali neutralized polymer of anionic polymer, an acid neutralized polymer of a cationic polymer, and an amphoteric polymer emulsifier having anionic and cationic properties. Examples thereof include Japanese and nonionic water-soluble polymers.

  As the polymer emulsifier exhibiting anionic property, those having a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acidic phosphoric acid group and the like are used. For example, acrylamido-2-methylpropane sulfonic acid etc. are mentioned as a sulfonic acid group containing monomer. Moreover, mono (2-methacryloyloxyethyl) acid phosphate etc. are mentioned as an acidic phosphate ester group containing monomer.

Preferred monomers as the carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, crotonic acid, fumaric acid, maleic acid monoalkyl ester, and fumaric acid monoalkyl ester. .
In the present specification, “(meth) acryl” means “acryl or methacryl”.

  Particularly preferred as anionic polymer emulsifiers are monomers containing carboxyl groups, especially copolymers using maleic acid, such as styrene-maleic acid copolymers and their partial esters, and (meth) acrylic acid. For example, a (meth) acrylic copolymer is used.

  The content of the structural unit derived from the anionic monomer in the anionic polymer emulsifier is required to be 5 mol% or more as a copolymerization component, and preferably 10 mol% or more. When it is less than 5 mol%, the stabilizing effect as a polymer emulsifier is lowered. On the other hand, the upper limit of the content is preferably 80 mol%, and preferably 70 mol%. If the amount is more than 80 mol%, the stabilizing effect of the aqueous thermoplastic resin dispersion tends to decrease, and further, the water resistance of the resulting aqueous thermoplastic resin dispersion decreases, and the dry film becomes hard. The low temperature heat sealability is lowered, and the dry film becomes cloudy.

  Moreover, you may neutralize the functional group which shows the said anionicity with the neutralizing agent which consists of an alkaline substance. Examples of the neutralizing agent include ammonia and sodium hydroxide. The neutralizing agent is desirably used in an amount of 60 mol% to 150 mol% based on the functional group exhibiting anionic property. If the amount is less than this range or is used in excess of this range, the stability of the aqueous thermoplastic resin dispersion tends to deteriorate in any case.

  Among these, as the anionic polymer emulsifier, a particularly preferable one is a neutralizer having a high vapor pressure that hardly remains in the film from the viewpoint of water resistance of the film obtained from the aqueous dispersion of the thermoplastic resin, such as ammonia. (Meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer neutralized using These anionic polymer emulsifiers may be used in combination of two or more.

  Next, as the above-mentioned cationic polymer emulsifier, dialkylaminoalkyl (meth) acrylate-alkyl (meth) acrylate copolymer, dialkylaminoalkyl (meth) acrylamide- (meth) acrylic acid alkyl ester copolymer, etc. Can be given. In particular, the number of carbon atoms of the alkyl group substituted with the alkylamino group of the alkylaminoalkyl (meth) acrylate is preferably in the range of 1 to 6. Examples of such alkylaminoalkyl (meth) acrylates include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and the like.

  Among these, from the viewpoint of the water resistance of the film obtained from the thermoplastic resin dispersion, a (meth) acrylate alkyl neutralized with a neutralizer having a high vapor pressure that hardly remains in the film, for example, formic acid or acetic acid. An ester copolymer is more preferred as the cationic polymer emulsifier. The neutralizing agent is desirably used in an amount of 60 mol% to 150 mol% with respect to the functional group exhibiting cationic properties. If the amount is less than this range or is used in excess of this range, the stability of the aqueous thermoplastic resin dispersion tends to deteriorate in any case.

  The content of the structural unit derived from the cationic monomer in the cationic polymer emulsifier is required to be 1 mol% or more as a copolymerizable component, and preferably 2 mol% or more. When the amount is less than 1 mol%, the dispersion stability tends to decrease. On the other hand, the upper limit of the content is preferably 85 mol%, and preferably 80 mol%. When it is more than 85 mol%, the dispersion stabilizing effect may be lowered.

  Next, the amphoteric polymer emulsifier is a single amount containing an anionic monomer mainly composed of (meth) acrylic acid and a cationic monomer mainly composed of alkylaminoalkyl (meth) acrylate. It is an amphoteric polymer emulsifier obtained by copolymerizing a body mixture. By using an amphoteric system, the hardness as an anionic polymer emulsifier can be suppressed.

  The total molar ratio of the anionic monomer and the cationic monomer is preferably 25 to 50 mol% of the total monomers.

  When the molar ratio of the anionic monomer to the cationic monomer is not 50/50, the resulting polymer emulsifier exhibits liquidity derived from the larger monomer.

In amphoteric polymer emulsifiers, functional groups that exhibit anionic properties are neutralized with alkaline substances such as ammonia and sodium hydroxide, and cationic functional groups that are neutralized with acidic substances such as formic acid and acetic acid. Each may be neutralized with an agent. In any case, it is desirable that the neutralizing agent is used in an amount of 60 mol% to 150 mol% with respect to the anionic or cationic functional group. If it is less than this range or exceeds this range, the stability of the aqueous thermoplastic resin dispersion tends to deteriorate in any case.
Two or more of these amphoteric polymer emulsifiers may be used in combination.

Examples of the nonionic water-soluble polymer include partially saponified polyvinyl alcohol, a block copolymer of ethylene oxide and propylene oxide, and hydroxyethyl cellulose. In particular, the reactive emulsifier represented by the formula (1) is preferable.
R ^1- (C _n H _2n O) _m -R ² (1)
In the formula, R ¹ represents a group selected from the following two groups (a) and (b), R ² represents H or an alkyl group having 1 to 4 carbon atoms, and n represents 1 to 3 M represents an integer of 4 to 25.
(A) (meth) acryloyloxy groups _(CH 2 = CH-COO- or _{CH 2 = C (CH 3)} -COO-)
(B) (meth) acryloyloxy ethoxy _{(CH 2 = CH-COO-} CH 2 -CH 2 -O- or _{CH 2 = C (CH 3)} -COO-CH 2 -CH 2 -O-)

  Specific examples of the nonionic reactive emulsifier represented by the above formula (1) include methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n -Butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate tetrapropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (Meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentatetrapropylene glycol (me ) Acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate and the like. Among these, those having a polyethylene glycol chain having 2 to 25 repeating units of ethylene glycol groups are more preferable. When the number of repeating units is smaller than 2, the dispersion stability is lowered. When it is larger than 25, the hydrophilic group is solidified at a normal temperature, so that a sufficient dispersion stabilizing effect may not be obtained. Two or more of these nonionic reactive emulsifiers may be used in combination.

  The content of the structural unit derived from the nonionic monomer in the nonionic polymer emulsifier needs to be 5 mol% or more as a copolymerization component, and preferably 10 mol% or more. When it is less than 5 mol%, the stabilizing effect as a polymer emulsifier is lowered. On the other hand, the upper limit of the content is preferably 100 mol%.

  The copolymer constituting the above various polymer emulsifiers is weighed and then polymerized by adding each component individually to the polymerization vessel, or by mixing each monomer in advance. It can manufacture by adding to a polymerization vessel and polymerizing. This copolymerization reaction is performed in the presence of a polymerization initiator at 0 to 180 ° C., preferably at 40 to 120 ° C. for 0.5 to 20 hours. This copolymerization is preferably carried out using a hydrophilic solvent such as ethanol, isopropanol or cellosolve or water or a mixed solvent of water and the hydrophilic solvent as a medium.

  In the present invention, in addition to the polymer emulsifier, a low molecular weight emulsifier that does not satisfy the molecular weight range may be used as long as the effects of the present invention are not impaired. Examples of the low molecular weight emulsifier include anionic emulsifiers such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylsulfonate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate and the like. Examples of nonionic emulsifiers generally include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oxypropylene block copolymer, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid having a molecular weight of 5,000 or less. . Furthermore, examples of amphoteric emulsifiers include lauryl betaine and lauryl dimethylamine oxide.

  The amount of the polymer emulsifier used is preferably 2 to 40 parts by weight with respect to 100 parts by weight of the adhesive resin in terms of the stability of the resulting dispersion and the water resistance of the film. More preferably, it is 3 to 20 parts by weight. If it is less than 2 parts by weight, the stability of the aqueous thermoplastic resin dispersion may be lowered. If it exceeds 40 parts by weight, the water resistance is lowered and the heat sealability may be deteriorated.

  To the above adhesive resin composition, a filler having a specific particle size is added as an antiblocking agent, and other auxiliary agents are added as necessary to form a coating solution. And as shown in FIG. 1, by adding this filler 3, the unevenness | corrugation is formed in the surface of the adhesive bond layer 2 formed on the base material sheet 1 etc. after application | coating and drying. And the filler 3 itself is not exposed, and the surface and circumference | surroundings are covered with adhesive resin. Since the surface and periphery of the filler are covered with the adhesive resin, the film or sheet to be bonded (such as the sheet to be bonded) is covered with the adhesive resin that covers the periphery of the filler as well as the portion where the filler does not exist. It becomes possible to join.

  As the filler, inorganic fillers such as calcium carbonate, silica, titania, and alumina, and various granular polymers such as organic fillers such as acrylic beads, styrene beads, silicon beads, and urethane beads can be used. Among these, when forming a coating film, the shape is maintained, but at the time of pressure bonding by heating and pressing, an organic filler that exhibits a certain degree of flexibility and plasticity and can widen the adhesion area should be used as at least a part of the filler component. Is preferred.

  Among these, cross-linked polymethyl methacrylate (cross-linked PMMA) and cross-linked polystyrene (cross-linked PS) particles have a particle size adjustment, a balance between the flexibility and shape retention of the particles, or an affinity with an adhesive resin. Is particularly preferable.

The filler needs to form a convex portion when the adhesive layer is formed. For this reason, when the thickness of the adhesive layer is L1 and the volume average particle diameter of the filler is L2, it is necessary to have the relationship of the following formula (1).
0.1 ≦ L1 / L2 <1 (1)
When L1 / L2 exceeds 1, the convex portion becomes small or the filler is buried in the adhesive layer, and blocking tends to occur. On the other hand, if L1 / L2 is less than 0.1, the relative weight of the filler increases, and the coatability may deteriorate or streaking to the substrate may occur. More preferably, it is 0.25 or more.

  The volume average particle size of the filler was measured using SALD2200 (Laser diffraction scattering method) manufactured by Shimadzu Corporation.

  When the adhesive laminate according to the present invention is wound up, the filler is subjected to pressure, but if the filler is destroyed by this pressure, the effect of the present invention may not be sufficiently obtained. It is preferable to have a hardness that does not cause destruction by the pressure received during winding and storage.

  The amount of the filler used is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the adhesive resin. More preferably, it is 0.25 to 2.5 parts by weight. If it is less than 0.1 parts by weight, blocking may occur. If it exceeds 5 parts by weight, the coating appearance may be deteriorated. In the present invention, if necessary, adding a desired amount of a filler outside the above particle size range to the adhesive resin composition may be performed as long as the effects of the present invention are not impaired.

  The base sheet and the like are not particularly limited, and any film or sheet such as a film or sheet made of a synthetic resin such as paper, woven fabric, nonwoven fabric, or polyolefin can be used.

  The adhesive laminate according to the present invention can be produced by first preparing an adhesive resin composition containing a filler, then applying the composition to a base sheet and drying. The adhesive resin composition containing the filler is a method of mixing the filler after manufacturing the adhesive resin composition, the filler in the stage of manufacturing an aqueous emulsion by emulsifying and dispersing the adhesive resin using a polymer emulsifier. And the like.

  Hereinafter, the present invention will be described more specifically using examples. In addition, this invention is not limited to a following example, unless the summary is exceeded.

<Evaluation>
(Preparation of adhesive laminate)
The adhesive resin composition is applied to the corona surface-treated surface of the OPP film (Futamura Chemical Co., Ltd .: FOS, thickness: 50 μm, corona surface-treated) so as to have the predetermined film thickness described in Table 3 or Table 4. Was applied using a bar coater and dried under conditions of 80 ° C. × 1 minute to prepare an adhesive laminate.

(Blocking property)
The coated surface of the adhesive laminate prepared above and the non-corona-treated surface of the OPP film were bonded together and allowed to stand at 40 ° C. × 0.1 MPa · s × 48 hours to obtain a sample for evaluation. After standing to cool, it was peeled by 180 ° by hand, and the feeling of peeling at that time was evaluated.
Peeling feeling: ○: Peeling without resistance.
Δ: A little resistance and peeling sound.
X: A feeling of resistance is strong and a peeling sound is large.

(Sliding property (Static friction coefficient))
Using the above-mentioned adhesive laminate on a flat indenter and an OPP film on the ascending plate, the sliding property between the coated surface and the non-treated surface of the OPP film is measured by a static friction coefficient measuring instrument manufactured by Shinto Kagaku Co., Ltd .: Tribogear TYPE10. The coefficient of static friction was measured.

(Adhesive strength)
The above-mentioned adhesive laminate and the corona-treated surface of the OPP film were placed so as to overlap each other. Thereafter, heat sealing was performed using a heat seal tester (120 ° C. × 0.1 MPa × 1 second).
After the heat-sealed sample was allowed to cool to room temperature, it was cut into a width of 15 mm and subjected to a peel test under predetermined peel conditions (200 mm / min, peel angle 90 °) to measure the adhesive strength.

(appearance)
Using a turbidimeter (NDH5000) manufactured by Nippon Denshoku Industries Co., Ltd., the turbidity of the film was determined from the ratio of the diffuse transmitted light to the total light transmitted light.

<Raw materials>
((Meth) acrylic acid)
Acrylic acid: manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “AA”.
Methacrylic acid: Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as “MAA”.

((Meth) acrylic acid alkylaminoalkyl)
N, N-dimethylaminoethyl methacrylate: Sanyo Chemical Industries, Ltd., methacrylate DMA, hereinafter abbreviated as “DMA”.

(Other comonomer)
・ Methyl methacrylate: manufactured by Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as “MMA”.
Lauryl methacrylate: manufactured by Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as “SLMA”.
-Butyl methacrylate: Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as "BMA".
Methoxypolyethylene glycol (meth) acrylate Polyethylene glycol repeating unit number 9: manufactured by NOF Corporation, hereinafter abbreviated as “PME”.

[Anti-blocking agent]
(Filler)
Crosslinked PMMA beads (5 μm): Polymethylmethacrylate crosslinked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MBX-5, volume average particle diameter: 5 μm
Cross-linked PMMA beads (8 μm): Polymethylmethacrylate cross-linked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MBX-8, volume average particle size: 8 μm
Crosslinked PMMA beads (12 μm): Polymethylmethacrylate crosslinked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MBX-12, volume average particle diameter: 12 μm
Crosslinked PMMA beads (20 μm): polymethylmethacrylate crosslinked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MBX-20, volume average particle diameter: 20 μm
Crosslinked PMMA beads (50 μm): Polymethylmethacrylate crosslinked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MBX-50, volume average particle diameter: 50 μm

Crosslinkable PS beads (8 μm): polystyrene crosslinked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: SBX-8, volume average particle diameter: 8 μm
Crosslinkable PS beads (12 μm): polystyrene crosslinked polymer beads, manufactured by Sekisui Plastics Co., Ltd .: SBX-12, volume average particle diameter: 12 μm

(Lubricant)
Amide-based low-molecular lubricant: stearamide, manufactured by Nippon Kasei Co., Ltd .: Diamond 200 (trade name)

[Others]
Isopropanol: manufactured by Tokuyama Corporation: Tokuso IPA (registered trademark), hereinafter abbreviated as “IPA”.

<Adhesive resin composition>
(Production of polymer emulsifier) (EM1 to EM4)
A 150 L reactor equipped with a cooling pipe, a nitrogen introducing pipe, a stirrer, a monomer dropping funnel and a heating jacket was charged with the indicated amounts of each component listed in Table 1, and after replacing with nitrogen, the internal temperature was raised to 80 ° C. Polymerization was initiated by adding the amount of polymerization initiator (2,2'-azobisisobutyronitrile) listed in Table 1. After carrying out the polymerization for 4 hours while keeping the internal temperature at 80 ° C., neutralize the obtained copolymer with the neutralizing agent in the amount shown in the table, and then add water while distilling off isopropanol (IPA) Then, a cationic polymer emulsifier made of a viscous acrylic copolymer (Production Example 1), an anionic polymer emulsifier (Production Example 2), and an amphoteric polymer emulsifier (Production Example 3) (Hereinafter referred to as “EM1” (Production Example 1), “EM2” (Production Example 2), and “EM3” (Production Example 3)) (yield of 97%). . The nonionic polymer emulsifier does not require neutralization, and water is added while distilling off the IPA from the reaction solution to convert it into an aqueous system. The nonionic polymer emulsifier (hereinafter referred to as “EM4” (Production Example) 4)) was obtained (yield 97%).

(Production of aqueous thermoplastic resin dispersion) (EM1-1 to EM4-1)
Ethylene-vinyl acetate copolymer (Mitsui DuPont Polychemical Co., Ltd., trade name: Everflex 220, vinyl acetate content 28 wt%) 70 parts by weight, aliphatic saturated hydrocarbon resin (Arakawa Chemical Industries, Ltd.) Product name: Alcon P100 Mixing 30 parts by weight of softening point 100 ° C., 100 parts by weight from the hopper of a twin screw extruder (manufactured by Ikekai Co., Ltd .: model number PCM45L / D = 30, injection port: 2 places) It was continuously fed into the extruder at a rate of / hour.
Next, from the first inlet of the extruder, the polymer emulsifier aqueous solution shown in Table 1 was continuously supplied at 10 parts by weight / hour in terms of solid content, and 84 parts by weight of water / hour was continuously supplied from the second inlet, Extrusion was performed at a barrel temperature of 100 ° C. to obtain a milky white thermoplastic resin aqueous dispersion. Hot water was added to the obtained aqueous dispersion to adjust the solid content concentration shown in the table. The results are shown in Table 2.
The thermoplastic resin aqueous dispersions produced using the respective ionic polymer emulsifiers were respectively converted into a cationic system “EM1-1”, an anionic system “EM2-1”, an amphoteric system “EM3-1”, and a nonionic system “EM4”. -1 ".

(Examples 1-7 , Reference Examples 1-3 , Comparative Examples 1-10)
(Manufacture of adhesive resin composition)
The thermoplastic resin aqueous dispersion shown in Table 2 was put into a 500 ml glass beaker. The amount of antiblocking agent shown in Table 3 was added to the solid content of the thermoplastic resin dispersion while stirring with a 25 mm disperser type stirring blade (1500 rpm), followed by stirring for 5 minutes. In consideration of the desired coating thickness (after drying), adjust the solid content of the dispersion with the amount of IPA added so that the coating thickness of the composition is equal to or greater than the particle size of the added filler. Thus, an adhesive resin composition for coating was prepared.
Said evaluation was performed using the obtained adhesive resin composition. The results are shown in Tables 3 and 4.

1 Base sheet 2 Adhesive layer 3 Filler

Claims (3)

An adhesive resin composition containing an aqueous emulsion obtained by emulsifying an adhesive resin with a cationic polymer emulsifier is incorporated with an organic filler composed of a crosslinked granular polymer and applied to the surface of a film-like substrate or sheet-like substrate. It is an adhesive laminate of a heat and pressure adhesive type,
While containing 2-40 parts by weight of the polymer emulsifier with respect to 100 parts by weight of the adhesive resin, 0.1-5 parts by weight of the filler is contained,
And the adhesive laminated body in which the thickness L1 of the adhesive bond layer which consists of the said adhesive resin composition, and the volume average particle diameter L2 of a filler have the relationship of following formula (1).
0.1 ≦ L1 / L2 <1 (1) The adhesive laminate according to claim 1, wherein the filler is an organic filler made of granular crosslinked polymethyl methacrylate or crosslinked polystyrene . The adhesive laminate according to claim 1 or 2 , wherein the film-like substrate or sheet-like substrate is at least one selected from paper, woven fabric, nonwoven fabric, and a film or sheet of a synthetic resin film.

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