CN102652164B - Resin composition for aqueous adhesive, aqueous adhesive, adhesive sheet, and method for producing composition for aqueous adhesive - Google Patents

Resin composition for aqueous adhesive, aqueous adhesive, adhesive sheet, and method for producing composition for aqueous adhesive Download PDF

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CN102652164B
CN102652164B CN201080055686.4A CN201080055686A CN102652164B CN 102652164 B CN102652164 B CN 102652164B CN 201080055686 A CN201080055686 A CN 201080055686A CN 102652164 B CN102652164 B CN 102652164B
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vinylite
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aqueous binder
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CN102652164A (en
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佐藤浩司
桥口恒则
辻川敦子
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Disclosed are: a resin composition for an aqueous adhesive, which exhibits excellent adhesion to a porous body that has a small area in contact with the adhesive or to an object to be adhered that has low surface polarity; and an aqueous adhesive using the resin composition for an aqueous adhesive. Specifically disclosed is a resin composition for an aqueous adhesive, which is characterized by containing (A) a vinyl resin, (B) an esterified product of a disproportionated rosin acid and (C) an aqueous medium. The resin composition for an aqueous adhesive is also characterized in that the esterified product of a disproportionated rosin acid (B) has a structure represented by general formula (1). Also specifically disclosed are an aqueous adhesive that contains the resin composition for an aqueous adhesive; and an adhesive sheet that uses the aqueous adhesive.

Description

The manufacture method of composition for resin combination, aqueous binder, adhesive sheet and aqueous binder for aqueous binder
Technical field
The present invention relates to can be used in for example take the various adherends that automobile inside member is representative laminating aqueous binder, for the manufacture of the aqueous binder of this aqueous binder with resin combination and use its adhesive sheet obtaining and duplexer.
Background technology
In recent years, tackiness agent is used to take in the manufacture of the various mechanicalss that trolley part, electric product are representative.
For example, at the manufacturing site location of automobile, use tackiness agent when automobile inside member is fixed to automotive interior etc.In addition,, at the manufacturing site location of electronicss such as mobile phone, liquid-crystal display etc., avoiding the object of impacting for protection electronic products, be arranged on use tackiness agent in exterior member fixing etc. of fixing, electronic products of cushioning material etc. of electronic products inside.
As the tackiness agent using in such use, use solvent is tackiness agent all the time, but from the viewpoint of reduction carrying capacity of environment in recent years, and expectation converts water system to by above-mentioned solvent system.
For example, as can be used in the aqueous binder of manufacturing above-mentioned adhesive sheet, known have following water system pressure-sensitive adhesive composite (for example, with reference to patent documentation 1.): it is to comprise to take the water system pressure-sensitive adhesive composite that acrylic acid polymer that (methyl) alkyl acrylate or ester ring type ester be principal monomer composition and the solvable composition of solution in all solids composition be 20 quality %～90 quality %, wherein, as the solvable composition of solution, contain second-order transition temperature for-20 ℃ of following and weight-average molecular weight be that more than 100,000 acrylic acid polymer and second-order transition temperature is 40 ℃ of above and weight-average molecular weight is 300～50000 acrylic acid polymer.
On the other hand, the in-built member using as the manufacturing site location at above-mentioned automobile, from also give the viewpoint of resiliency, vibrationproof etc. except giving designability etc., the low member of surface polarity that sometimes use as the porous inseries such as polyurethane foam the member little with the contact area of tackiness agent, is formed by polyolefine (polyethylene, polypropylene etc.) or rubber etc.In addition,, at the manufacturing site location of above-mentioned electric product, sometimes also use the porous inseries such as polyurethane foam as above-mentioned buffer reagent etc.
But, even bonding by the adhesive sheet that uses such aqueous binder of recording in above-mentioned patent documentation 1 to obtain etc. for the bonding of above-mentioned porous insert or base material that surface polarity is low, sometimes bonding strength that also cannot long term maintenance excellence, through time at the interface of above-mentioned adherend and binder layer, cause and peel off.
In addition, the adhesive sheet in the past using is owing to conventionally in the supporting body surface consisting of non-woven fabrics or porous insert, binder layer being set, so when described binder layer forms with aqueous binder in the past, sometimes form the binder layer of above-mentioned adhesive sheet and the interface of above-mentioned supporter through time cause and peel off.
Like this, from industrial community, require exploitation can embody the caking agent of excellent bonding force for above-mentioned porous insert or the low adherend of surface polarity etc., but practical situation are not yet to find.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-105298 communique
Summary of the invention
Invent problem to be solved
The problem that the present invention will solve is, provides the excellent bonding force of aqueous binder have to(for) the little porous insert of the contact area with tackiness agent, adherend that surface polarity is low with resin combination and uses its aqueous binder.
For the scheme of dealing with problems
The inventor etc. are in the process of studying in order to solve above-mentioned problem, and the ethene base system tackiness agent for the tackiness agent of water system was studied as basis in the past.Particularly, having studied at aqueous vinyl is in the past in tackiness agent, to be used in combination various additives.
For example, studied dry delayed-action activators such as mixing the film coalescence aid such as Texanol, ethylene glycol butyl ether, butyl poly glucoside in containing the tackiness agent of above-mentioned Vinylite, there is the acrylic resin (ARUFONUC-3510, Tg-50 ℃, East Asia synthetic (strain) system) etc. of lower glass transition temperatures as the tackiness agent of additive, the bonding force of above-mentioned adherend has been existed to the tendency reducing.
The inventor etc. are as mentioned above by the process of various additives and the research of ethene base system binder combination, discovery when having the carboxylate of nilox resin acid of the structure shown in following general formula (1) and Vinylite and be used in combination, obtains porous insert or the low adherend of surface polarity etc. to possess the aqueous binder of excellent bonding force.
In addition, the inventor etc. are in the process of the manufacture method of the above-mentioned aqueous binder of research, discovery is compared with the aqueous binder that the carboxylate of the composition that contains Vinylite and water-medium of manufacturing in advance and above-mentioned nilox resin acid is obtained by mixing, under the carboxylate of above-mentioned nilox resin acid and the existence of reactive surfactant and water-medium, mixture of vinyl monomer is carried out to Vinylite is manufactured in letex polymerization and the aqueous binder that obtains can be given more excellent bonding force.
; the present invention relates to a kind of resin combination, the aqueous binder that contains it and use its adhesive sheet for aqueous binder; it is characterized in that; the carboxylate (B) that contains Vinylite (A), nilox resin acid and water-medium (C), the carboxylate of above-mentioned nilox resin acid (B) has the structure shown in following general formula (1).
[Chemical formula 1]
Figure BDA00001741795700031
(n in above-mentioned general formula (1) represents 10～30 integer.)
In addition, the present invention relates to disposable in the mixture by the carboxylate (B) to reactive surfactant and above-mentioned nilox resin acid and water-medium (C) or gradation and supply with mixture of vinyl monomer and polymerization starter, utilize emulsion polymerization to manufacture Vinylite (A) and the manufacture method of resin combination for the aqueous binder that obtains.
The effect of invention
If aqueous binder resin combination of the present invention, can access the aqueous binder that porous insert that the contact area to tackiness agent that cannot reach with aqueous binder is in the past little or the low adherend of surface polarity have excellent bonding force.In addition, if aqueous binder resin combination of the present invention can access the water-fast bonding force of the level with the reduction that can not cause because of the impact of water or heat etc. bonding force or the aqueous binder of heat-resistance adhesion.
Aqueous binder of the present invention and use its adhesive sheet obtaining can be used in such as with automobile interior material fixing, particularly automobile ceiling material or vehicle door interior trim panel is fixed as representative, buffer reagent, sealing agent, for electronicss such as protection mobile phone or liquid-crystal display etc., avoids the object of impacting and be arranged in the manufacture of fixing and furniture etc. of exterior member of fixing, electronic products of fender etc. of electronic products inside.
Embodiment
Aqueous binder of the present invention contains Vinylite (A), has the carboxylate (B), water-medium (C) of the nilox resin acid of the structure shown in following general formula (1) and other additive as required with resin combination.
[Chemical formula 2]
Figure BDA00001741795700041
(n in above-mentioned general formula (1) represents 10～30 integer.)
Carboxylate (B) solubilized of above-mentioned Vinylite (A) and above-mentioned nilox resin acid or be scattered in above-mentioned water-medium (C).Particularly, above-mentioned Vinylite (A) by can be present in the wetting ability base in resin (A), reactive surfactant described later stably disperses or dissolves and exists in water-medium (C).
The carboxylate of above-mentioned nilox resin acid (B) can be dissolved or dispersed in water-medium (C) by the nonionic structure shown in above-mentioned general formula (1).
In addition, while polymerization of vinyl monomer being manufactured to Vinylite (A) under the existence of the carboxylate (B) of reactive surfactant and above-mentioned nilox resin acid as described later, the carboxylate of above-mentioned nilox resin acid (B) is present on the shell of Vinylite (A) particle, contributes to this Vinylite (A) dispersion of particles stability.
In the present invention, above-mentioned Vinylite (A) and the carboxylate (B) of above-mentioned nilox resin acid are used in combination, and are important at the aqueous binder that obtains the surperficial grade of the few porous insert of the contact area with tackiness agent to have excellent bonding force aspect resin combination.
First, above-mentioned Vinylite (A) is described.
As above-mentioned Vinylite (A), can use the various vinyl polymerization bodies that in the past used as binder constituents.
As above-mentioned Vinylite (A), preferably use for example has the Vinylite of the weight-average molecular weight of 500,000～1,000,000 scope, and use 500,000～800,000 Vinylite is preferred at the aqueous binder that obtains porous insert or the low adherend of surface polarity to possess excellent bonding force aspect resin combination.In addition, the weight-average molecular weight of above-mentioned Vinylite (A) refers to, when the tetrahydrofuran (THF) of above-mentioned Vinylite (A) and 25 ℃ is mixed and stirs 24 hours, use gel permeation chromatography (GPC) to measure the Vinylite (A) dissolving in above-mentioned tetrahydrofuran (THF) and the value obtaining.
As above-mentioned Vinylite (A), preferably use the Vinylite of the second-order transition temperature with-10 ℃～-60 ℃, uses the Vinylite of-30 ℃～-60 ℃ is preferred at the aqueous binder that obtains porous insert or the low adherend of surface polarity to possess the water-fast bonding force of excellent bonding force and excellence aspect resin combination.In addition, above-mentioned second-order transition temperature refers to by the calculated value of the formula derivation of FOX.
The second-order transition temperature of each polymerizable monomer that calculates the second-order transition temperature of polymkeric substance for formula based on FOX for example can adopt the numerical value of record in VI/213～258 page of " POLYMERHANDBOOK, THIRD EDITION " or " synthetic resins introduction for new peak molecular library the 7th volume coating (Bei Gang association three works, meeting of polymer publication, capital of a country, 1974) " 168～169 pages.In addition, the reactive surfactant that has free-radical polymerised unsaturated group in above-mentioned calculating is not included in polymerizable monomer.
As above-mentioned Vinylite (A), from porous insert or the low adherend of surface polarity being given to excellent bonding force, the viewpoint of excellent throwing anchor especially, preferably use the Vinylite of the median size with 150nm～500nm, the more preferably scope of 200nm～400nm.Here, above-mentioned median size refers to the value obtaining by dynamic light scattering determination.
As above-mentioned Vinylite (A), the viewpoint that the adherend forming from the little porous insert of the contact area to by with tackiness agent is given excellent bonding force, is preferably used the straight chain aliphatic ethylene base resin as far as possible without branched structure.
As above-mentioned Vinylite (A), particularly, can use the Vinylite that vinyl monomer described later is carried out to radical polymerization and obtain.
As above-mentioned vinyl monomer, can use vinyl monomer such as (methyl) alkyl acrylate, carboxylic vinyl monomer, hydroxyl etc.
As above-mentioned (methyl) alkyl acrylate, such as using (methyl) methyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) cyclohexyl acrylate etc.Wherein, in the use choosing group that freely (methyl) methyl acrylate, 2-EHA, butyl acrylate and vinylformic acid ester in the ninth of the ten Heavenly Stems form a kind is above owing to can reducing the second-order transition temperature of gained Vinylite (A), consequently, can give excellent bonding force, water-fast bonding force to porous insert or the low adherend of surface polarity, therefore preferably.On the other hand, by using (methyl) cyclohexyl acrylate, (methyl) methyl acrylate, ethyl propenoate etc. as above-mentioned (methyl) acrylic acrylate, also can give to aqueous binder the bond propertiess such as excellent heat-resistance adhesion, bonding confining force.
In addition; as can be used in the above-mentioned carboxylic vinyl monomer of manufacturing above-mentioned Vinylite (A), such as can using separately (methyl) vinylformic acid, (methyl) propenoic acid beta-carboxyl ethyl ester, 2-(methyl) acryl propionic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, methylene-succinic acid half ester, toxilic acid half ester, maleic anhydride, itaconic anhydride, β-(methyl) acryloxy ethyl hydrogenation succinate, β-(methyl) hydroxyethyl hydrogenated phthalates and their salt etc. or combining two or more use.Wherein, as above-mentioned carboxylic vinyl monomer, preferably use (methyl) vinylformic acid.
Above-mentioned carboxylic vinyl monomer, import carboxyl or carboxylic acid ester groups in gained Vinylite (A), is given the aspect of good dispersion stability and is preferably used.In addition, at aqueous binder of the present invention when being used in combination oil soluble epoxy compounds described later (D) in resin combination, carboxyl in the epoxy group(ing) that this compound (D) has and above-mentioned Vinylite (A) occurs crosslinked, thereby can form the bonding coat of the bond properties excellences such as heat-resistance adhesion or bonding confining force.
In addition, vinyl monomer as can be used in the above-mentioned hydroxyl of manufacturing above-mentioned Vinylite (A), can be used (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, polyethyleneglycol (methyl) acrylate, glycerine list (methyl) acrylate etc.
By using the vinyl monomer of above-mentioned hydroxyl, can in Vinylite (A), import hydroxyl.When being used in combination polyisocyanate crosslinking agent etc., the isocyanic ester radical reaction that described hydroxyl and this linking agent have.Thus, can form the bonding coat of the bond properties excellences such as heat-resistance adhesion or bonding confining force.
As the vinyl monomer for the manufacture of above-mentioned Vinylite (A), except above-mentioned substance, also can use as required other vinyl monomer.
As other vinyl monomer, for example also can use (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N-alkyl monosubstituted amino alkyl ester, (methyl) vinylformic acid N, the vinyl esters such as N-dialkyl aminoalkyl ester, (methyl) acrylamide, N-isopropylacrylamide, propenal, two acetone (methyl) acrylamide, vinyl-acetic ester, propionate, tertiary monocarboxylic acid (versatic acid) vinyl acetate; The vinyl ethers such as methylvinylether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl group vinyl ether, hexyl vinyl ether; The ethene base system nitriles such as (methyl) vinyl cyanide; Vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl phenylmethylether, alpha-halo ethene, vinyl naphthalene etc. have the ethene base system monomer of aromatic ring; Isoprene, divinyl, ethene etc. do not have the ethene base system monomer of functional group; The hetero ring type ethene base system monomers such as vinyl pyrrolidone etc.
As the Vinylite using in the present invention (A), preferably use the mixture of vinyl monomer polymerization of carboxylic vinyl monomer of above-mentioned (methyl) alkyl acrylate that the total amount of the mixture with respect to being comprised of above-mentioned vinyl monomer is comprised to 45 quality %～99 quality % and 1～5 quality % and the Vinylite that obtains, the Vinylite that use obtains the mixture of vinyl monomer polymerization of the carboxylic vinyl monomer of above-mentioned (methyl) alkyl acrylate that comprises 70 quality %～99 quality % and 1～5 quality %, obtain to porous insert or the low adherend of surface polarity possess excellent bonding force or water-fast bonding force aqueous binder aspect more preferably.In addition, above-mentioned " total amount of mixture of vinyl monomer " refers to that above-mentioned (methyl) alkyl acrylate, above-mentioned carboxylic vinyl monomer, other vinyl monomer described later etc. are commonly referred to as the total quality of the material of vinyl monomer, but while using reactive surfactant described later as tensio-active agent, also comprise the usage quantity of this reactive surfactant." total amount of mixture of vinyl monomer " below recorded also represents the same meaning.
Above-mentioned Vinylite (A) for example can be manufactured by above-mentioned vinyl monomer is carried out to letex polymerization under the existence of polymerization starter and water-medium (C) and tensio-active agent as required.
Here, while using 2-EHA as above-mentioned vinyl monomer, gained Vinylite easily forms branched structure.In addition,, while probably using aforesaid propylene acid 2-ethylhexyls more than 70 quality %, there is the tendency of the Vinylite that obtains further multiple-limb.In the present application, owing to preferably using as mentioned above the aliphatic ethylene base resin of unbranched as far as possible straight chain shape, so preferably manufacture Vinylite (A) by above-mentioned branch being suppressed to the manufacture method of irreducible minimum.
In order to suppress above-mentioned branched structure, form, letex polymerization temperature is adjusted to the scope of above-mentioned 45 ℃～60 ℃, and use azo initiator as polymerization starter, it is that the scope of 0.005 quality %～0.05 quality % is effective that the usage quantity of this azo initiator is adjusted to total quality with respect to above-mentioned mixture of vinyl monomer.
As above-mentioned azo initiator, from suppress above-mentioned Vinylite (A) branched structure formation and prevent the viewpoint that the production efficiency of above-mentioned Vinylite (A) reduces, preferably using 10 hours half life temperatures is " above-mentioned emulsion polymerization temperature-5 ℃ " following azo initiator.Particularly, preferably use choosing freely 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane dihydrochloride and 2, two [the a kind of above material in the group that 2-(2-tetrahydroglyoxaline-2-yl) propane dithionate forms of 2 '-azo.
Commercially available product as above-mentioned azo initiator, for example can use " VA-044 (with 44 ℃ of the pure pharmaceutical worker's industry of light, 10 hours half life temperatures, 2; two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2-azo) ", " VA-046B (with 46 ℃ of the pure pharmaceutical worker's industry of light, 10 hours half life temperatures, 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dithionate dihydrates of 2-azo) " etc.
In addition, as can be used in the tensio-active agent of manufacturing above-mentioned Vinylite (A), such as using anionic surfactant, nonionic surfactant, cationic surfactant, two ionic surfactants etc.Wherein, use anionic surfactant improve tackiness agent mechanical stability aspect be preferred.
As above-mentioned anionic surfactant, such as can using separately the sulfuric ester, alkylbenzene sulfonate, polyoxyethylene alkyl benzene sulfonate etc. of higher alcohols or combining two or more use.
As above-mentioned tensio-active agent, use can carry out together with above-mentioned vinyl monomer the tensio-active agent with free-radical polymerised unsaturated double-bond of letex polymerization, so-called reactive surfactant prevent from resulting from this tensio-active agent the bonding force oozing out etc. reduction aspect be preferred.
As above-mentioned reactive surfactant, for example, can list " Latemul S-180 " " the PD-104 " (trade mark with sulfonic group and salt thereof; Kao Corp's system), " Eleminol JS-2 " " RS-30 " (trade mark; Sanyo Chemical Industries, Ltd.'s system) etc.; " Acualon KH-05 " " KH-10 " " the KH-1025 " (trade mark with sulfate and salt thereof; Di-ichi Kogyo Seiyaku Co., Ltd.'s system), " ADEKA REASOAP SE-10 " " SE-20 " (trade mark; Asahi Denka Kogyo K. K's system) etc.; " New Frontier the A-229E " (trade mark with phosphate; Di-ichi Kogyo Seiyaku Co., Ltd.'s system) etc.; " Acualon RN-10 " " RN-20 " " RN-30 " " the RN-50 " (trade mark with nonionic hydrophilic group; Di-ichi Kogyo Seiyaku Co., Ltd.'s system), " Latemul PD-420 " " PD-430 " " PD-450 " (trade mark; Kao Corp's system) etc., they may be used singly or in combination of two or more.
The usage quantity of above-mentioned tensio-active agent is according to kind of tensio-active agent etc. and different, but the in the situation that of above-mentioned nonionic surfactant for example, total amount with respect to above-mentioned mixture of vinyl monomer, be preferably the scope of 1.0 quality %～5.0 quality %, more preferably the scope of 1.5 quality %～3.5 quality %.
In addition, above-mentioned tensio-active agent is in anionic surfactant, cationic surfactant, two ionic surfactants' situation, the usage quantity of above-mentioned tensio-active agent is with respect to the total amount of above-mentioned mixture of vinyl monomer, be preferably the scope of 0.5 quality %～3.0 quality %, more preferably the scope of 1.0 quality %～2.5 quality %.
Then, the carboxylate (B) of the nilox resin acid of using in the present invention is described.
The carboxylate of above-mentioned nilox resin acid (B) is characterised in that, it is that nilox resin acid is carried out esterification with the polyvalent alcohol with the structure shown in following general formula (1) and the material that obtains, and the repeating unit of the ethylene oxide structure shown in following general formula (1) (n in general formula (1)) is the integer of 10～30 scope.
[chemical formula 3]
Figure BDA00001741795700091
(n in above-mentioned general formula (1) represents 10～30 integer.)
Here, the carboxylate (B) that replaces above-mentioned nilox resin acid, for the aqueous binder that the carboxylate of the nilox resin acid that is 8 with regard to use said n obtains, the softening temperature of this aqueous binder reduces, and sometimes causes the reduction to the bonding force of the adherend of porous insert and low surface polarity or heat-resistance adhesion, water-fast bonding force.The aqueous binder that the carboxylate of the nilox resin acid that on the other hand, use said n is 40 obtains also causes the reduction to the bonding force of the adherend of porous insert and low surface polarity or water-fast bonding force sometimes.
In order to obtain the little porous insert of the contact area with aqueous binder, adherend that surface polarity is low to possess the aqueous binder resin combination of further excellent bonding force, suitable use said n is preferably the carboxylate of the nilox resin acid of 10～20, more preferably 14～18 integer.
Nilox resin acid as the carboxylate for the manufacture of above-mentioned nilox resin acid (B), can use the material that abietic acid, neoabietic acid, palustric acid etc. is had to the sylvic acid disproportionation of conjugated double bond and obtain, particularly, such as dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid etc., is wherein preferably used dehydroabietic acid.
In addition, as the polyvalent alcohol with above-mentioned nilox resin acid-respons, for example preferably use the polyoxyethylene glycol of the scope that the repeating unit that consists of Oxyerhylene is 10～30, can use the polyoxyethylene glycol of the repeating unit of the scope more preferably with 10～20, particularly preferably 14～16.
The carboxylate of above-mentioned nilox resin acid (B) for example can carry out condensation by the hydroxyl that utilizes known customary way that carboxyl that above-mentioned nilox resin acid has and above-mentioned polyvalent alcohol are had and manufacture.The end of the carboxylate of resulting nilox resin acid (B) can be hydroxyl, can be also alkoxyl group etc.
The carboxylate of above-mentioned nilox resin acid (B) is preferably used with the scope of 0.1 quality %～5 quality % with respect to the total amount of above-mentioned Vinylite (A), with the scope of 0.5 quality %～3 quality %, use owing to can maintaining the excellent bonding force of porous insert or the low adherend of surface polarity etc., and suppress nilox resin acid esters compound (B) to the oozing out of adherend surface, therefore preferably.
Then, the water-medium using in the present invention (C) is described.
As above-mentioned water-medium (C), can make water, with the mixed hydrophilic organic solvent of water and their mixture.As above-mentioned hydrophilic organic solvent, such as using the alcohols such as methyl alcohol, ethanol, n-propyl alcohol and Virahol; The ketone such as acetone, methyl ethyl ketone; The poly-alkyl diol classes such as ethylene glycol, glycol ether, propylene glycol; The alkyl ether of poly-alkyl diol; The lactams such as METHYLPYRROLIDONE etc. are general as the known organic solvent of high boiling solvent.In the present invention, can only make water, can make in addition water and with the mixture of the mixed organic solvent of water, also can only use the organic solvent mixed with water.From security, aspect to the load of environment, preferably only make water or water and with the mixture of the mixed organic solvent of water, particularly preferably only make water.
Above-mentioned water-medium (C) preferably comprises 30 quality %～70 quality % with respect to aqueous binder of the present invention by the total amount of resin combination, more preferably comprises 40 quality %～60 quality %.
Then, the oil soluble epoxy compounds (D) that can use in the present invention is described.
Oil soluble epoxy compounds (D) has and can wait the carboxyl reaction that can have with above-mentioned Vinylite (A) to form the epoxy group(ing) of crosslinking structure by heating.
As above-mentioned oil soluble epoxy compounds (D), for example can use Denacol EX-622 (NAGASE KASEI KOGYO KK system), Denacol EX-201 (NAGASE KASEI KOGYO KK system), Denacol EX-212 (NAGASE KASEI KOGYO KK system), Denacol EX-922 (NAGASE KASEI KOGYO KK system), Denacol EX-2000 (NAGASE KASEI KOGYO KK system), Denacol EX-4000 (NAGASE KASEI KOGYO KK system), Denacol EX-721 (NAGASE KASEI KOGYO KK system), Denacol EX-221 (NAGASE KASEI KOGYO KK system), TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system), TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's system) etc.Use TETRAD-X, the TETRAD-C wherein with amido more can promote crosslinking reaction, therefore preferably.
From adjusting the gel fraction of binder layer, porous insert or the low adherend of surface polarity being given to the viewpoint of excellent bonding force, water-fast bonding force sets out, above-mentioned oil soluble epoxy compounds (D) is preferably used with the scope of 0.01 quality %～3 quality % with respect to the total amount of above-mentioned Vinylite (A), more preferably the scope of 0.01 quality %～1 quality %.
Then, the rosin series resin (E) that can use in the present invention is described.
In the present invention, the rosin series resin (E) of softening temperature and the carboxylate (B) of above-mentioned nilox resin acid with 150 ℃～200 ℃ are used in combination, improve to aspect porous insert or the heat-resistance adhesion of the low adherend of surface polarity, water-fast bonding force particularly preferably.
As above-mentioned heat-resistance adhesion, particularly, require the duplexer that uses aqueous binder laminating adherend of the present invention to obtain in the situation that long-term characteristic of placing the level that also can not cause peeling off of adherend etc. under the hot environment of general 80 ℃ of left and right.In addition, the softening temperature of above-mentioned rosin series resin (E) refers to by JIS K-5902 method and measures the value obtaining.
As above-mentioned rosin series resin (E), such as using the rosin series resin in natural rosin, rosin ester, polymerized rosin, polymerized rosin ester, staybelite, hydrogenated wood rosin glycerol ester, nilox resin, nilox resin ester etc. with the softening temperature of 150 ℃～200 ℃.Wherein preferably use polymerized rosin ester etc.
From the little porous insert of the contact area to tackiness agent, adherend that surface polarity is low, give excellent bonding force and excellent heat-resistance adhesion and the viewpoint of water-fast bonding force, above-mentioned rosin series resin (E) is preferably used with the scope of 10 quality %～35 quality % with respect to the total amount of above-mentioned Vinylite (A), more preferably 10 quality %～20 quality %.
In addition,, in the present invention, except above-mentioned, can further use other rosin series resin.Particularly, can use the material having in natural rosin, rosin ester, polymerized rosin, polymerized rosin ester, staybelite, hydrogenated wood rosin glycerol ester, nilox resin, nilox resin ester etc. lower than the softening temperature of 150 ℃.
In addition, aqueous binder of the present invention is with in resin combination, except carboxylate (B), water-medium (C), oil soluble epoxy compounds (D) or the rosin series resin (E) of above-mentioned Vinylite (A), nilox resin acid, also can contain as required other additive etc.
As above-mentioned other additive, such as using the bonding imparting agent resins of terpenic series such as α pinene resin, beta-pinene resin, terpene phenolic resin, hydriding terpene phenol resins.
In addition,, as above-mentioned additive, can use the property base oils such as resin of aliphatics hydrocarbon system resin or fatty family ring type structure is resin.For example, also can be used in combination usually used as C5 is that resin or C9 are that resin, Dicyclopentadiene (DCPD) are the known petroleum line resins such as resin.
Then, aqueous adhesive of the present invention is described by the manufacture method of resin combination.
Aqueous adhesive of the present invention with resin combination for example can by by the water system dispersion of Vinylite (A) of manufacturing in advance as mentioned above, the carboxylate (B) of nilox resin acid and oil soluble epoxy compounds (D) as required and above-mentioned rosin series resin (E) mix, stirring is manufactured.
In addition, in order to obtain the porous insert little to the contact area with tackiness agent, the adherend that surface polarity is low possesses further excellent bonding force, the aqueous binder resin combination of water-fast bonding force, for example preferably adopt following methods: in the mixture of the carboxylate (B) with above-mentioned same reactive surfactant and above-mentioned nilox resin acid and water-medium (C), mixture and polymerization starter and the chain-transfer agent as required of other above-mentioned vinyl monomer supplied with in disposable or gradation, above-mentioned mixture of vinyl monomer is reacted by emulsion polymerization, thereby manufacture the aqueous binder resin combination that contains Vinylite (A).
Particularly, mixture of vinyl monomer or polymerization starter etc. are to the preferred disposable supply of supply in the carboxylate (B) of above-mentioned reactive surfactant and above-mentioned nilox resin acid and the mixture of water-medium (C) or successively supply with.
After above-mentioned supply, preferably in the temperature range of general 0 ℃～80 ℃ of left and right, react about approximately 3 hours～10 hours, by emulsion polymerization, carry out the radical polymerization of above-mentioned mixture of vinyl monomer.From ethene suppressing base resin (A), become the viewpoint of branched structure, the temperature of reaction after above-mentioned supply is preferably carried out at general lower temperature below 65 ℃.
As mentioned above, under existence by carboxylate in above-mentioned nilox resin acid (B) etc., manufacture Vinylite (A) and obtain aqueous binder composition of the present invention, thereby the carboxylate of above-mentioned nilox resin acid (B) generation office on the shell of the particle of Vinylite (A) is changing, consequently, can access the aqueous binder resin combination that can show further excellent bonding force and water-fast bonding force, heat-resistance adhesion to the little porous insert of the contact area with tackiness agent, adherend that surface polarity is low.
The aqueous binder obtaining by aforesaid method, with in resin combination, also can be used in combination above-mentioned oil soluble epoxy compounds (D), above-mentioned rosin series resin (E) as required.Particularly, resin combination for the aqueous binder obtaining by aforesaid method and above-mentioned oil soluble epoxy compounds (D), above-mentioned rosin series resin (E) mixing, stirring can be obtained.
As the chain-transfer agent using in above-mentioned method for making, such as using terpenic series compound, vinyl carbinol, the α-methylstyrenedimers etc. such as mercaptan based compound, α-pinene, limonene, terpinolene such as lauryl mercaptan.
Above-mentioned chain-transfer agent with respect to the total amount of above-mentioned vinyl monomer preferably with 0.01 quality %～0.5 quality %, more preferably use with the scope of 0.01 quality %～0.2 quality %.
The aqueous adhesive of the present invention obtaining by aforesaid method etc. completely can be in aqueous binder with resin combination.
Above-mentioned aqueous binder for example can have for the one or two sides at supporter in the manufacture of adhesive sheet of bonding coat.
By the one or two sides at for example supporter, apply above-mentioned aqueous binder, remove water-medium (C), the gel fraction that is simultaneously cured to overlay forms bonding coat till reaching general 25 quality %～55 quality % left and right, thereby can manufacture above-mentioned adhesive sheet.
As above-mentioned supporter, such as using polyester, polypropylene, polyethylene, PVC and their layered product etc.Wherein preferably use the film being formed by polyethylene terephthalate.
Viewpoint from raising with the adaptation of above-mentioned bonding coat, the surface of above-mentioned supporter also can utilize the easy gluing of surfaces of enforcement such as corona treatment to process in advance.
In addition,, as above-mentioned supporter, also can use the non-woven fabrics that the blending product such as by cotton, fiber crops, artificial silk or polyester and cotton, fiber crops, artificial silk of the core that is generally used for double-sided adhesive tape form or weave cotton cloth and the porous insert such as polyurethane foam.
As the method at above-mentioned supporting body surface coating aqueous binder, such as listing the method for using roller coating machine, intaglio plate coating machine, reverse coating machine, lip coating machine (Lip Coater), Bracewell coater, Kohler coater, mould painting machine etc.
The thickness that is formed at the bonding coat of above-mentioned supporting body surface is not particularly limited, and is preferably the scope of 1 μ m～100 μ m, more preferably the scope of 15 μ m～70 μ m.
Adhesive sheet obtained above is owing to especially the surface of the porous inseries such as foam also being had to excellent bonding force, so can be suitable for such as in the forming of the bonding or duplexer of the adherend consisting of porous inseries such as polyurethane foams.
In addition, adhesive sheet of the present invention is because the low adherend of effects on surface polarity has excellent bonding force, so can be in the adherend such as consisting of the polyolefine such as polypropylene or polyethylene, chloroprene or EPDM rubber etc. and metal etc. bonding.
Adhesive sheet obtained above is such as being suitable for the automobile inside member such as fixed table leather material on vehicle door interior trim panel in Automobile or pillar etc.
Above-mentioned automobile inside member as adherend, for example can use by weaving cotton cloth or non-woven fabrics, thermoplastic polyolefin resin, soft PVC, the leather-like sheet such as artificial leather or synthetic leather, polyurethane foam, polystyrene foam, ABS is foam, rubber (neoprene, EPDM etc.) be foam, vinyl chloride foam, polyethylene-based foam, polypropylene-based foam, phenol is foam, the porous inseries such as Urea Series foam, the polyolefine such as polypropylene or polyethylene, the automobile inside member that chloroprene or EPDM rubber etc. and metal etc. form.
In addition, above-mentioned adhesive sheet such as being suitable for cushioning material etc. fixing that is arranged on the electronic products inside such as mobile phone terminal more.In addition, can be in bonding, the wiring of the exterior member of above-mentioned electronic products fixing etc.
As above-mentioned cushioning material, such as using polyurethane foam, polystyrene foam, ABS, be that foam, rubber (neoprene, EPDM etc.) are that foam, vinyl chloride foam, polyethylene-based foam, polypropylene-based foam, phenol are the porous inseries such as foam, Urea Series foam.
In addition, as above-mentioned exterior member, such as using the plastic basis material that formed by the polyolefine such as polypropylene or polyethylene, chloroprene or EPDM rubber etc., metal base etc.
In addition,, as wiring, can use the surrounding of the metal wires such as copper cash by coated wirings such as vinyl chloride resins.
Embodiment
Below, by embodiment and comparative example, the present invention is further illustrated.
[preparation of Vinylite]
(synthesis example 1)
In container, drop into the Latemul PD-104 (polyoxybutylene-polyoxyethylene alkenyl ether ammonium sulfate as reactive surfactant, Kao Corp's system, solids component 20 quality %) 30 mass parts and Acualon KH-1025 (polyoxyethylene alkenyl ether ammonium sulfate, Di-ichi Kogyo Seiyaku Co., Ltd.'s system, solids component 25 quality %) 24 mass parts, 2-EHA 435 mass parts, butyl acrylate 120 mass parts, methyl methacrylate 30 mass parts and vinylformic acid 15 mass parts, lauryl mercaptan 0.21 mass parts and ion exchanged water 90 mass parts as chain-transfer agent, and stir, thereby prepare emulsion.
By possessing in the aggregation container of thermometer, dropping funnel, reflux condensing tube and whipping appts with nitrogen replacement, drop into ion exchanged water 373.2 mass parts, interior temperature is warming up to 52.5 ℃.
In above-mentioned aggregation container, with respect to the total amount of above-mentioned emulsion, drop into after the emulsion of 1 quality %, add Sodium Pyrosulfite 0.15 mass parts and ammonium persulphate 0.18 mass parts, initiated polymerization.
Keep after 30 minutes, by remaining emulsion (99 quality %) and 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dihydrochloride aqueous solution (nonvolatile component 0.5 quality %) 10 mass parts of 2 '-azo were added drop-wise in above-mentioned aggregation container with 6 hours.
After dropping finishes, aggregation container is kept 1 hour at 52.5 ℃ of interior temperature, then, aggregation container is cooled to after approximately 25 ℃, content is filtered with 200 order filter clothes (polyester), thereby obtain the Vinylite latex 1 of solids component 53.0 quality %, viscosity 250mPas, pH2.5, particle diameter 280nm, weight-average molecular weight 700,000.
In addition, the above-mentioned viscosity of above-mentioned Vinylite latex 1 is used Brookfield viscometer (VISCOMETER TV-10, TOKI SANGYO GO., LTD.) measure, above-mentioned particle diameter is used Microtrac UPA (Honeywell company) to measure, and above-mentioned weight-average molecular weight is used HLC-8220 (TOSOH Co., Ltd) to measure.
(embodiment 1)
Solids component 100 mass parts with respect to the Vinylite latex 1 obtaining in above-mentioned synthesis example 1, after ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 15 moles) 1 mass parts of mixing as the carboxylate (B) of nilox resin acid, further mixing ammoniacal liquor 4.2 mass parts, Boncoat 3750-E (thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.5 mass parts and ion exchanged water 2 mass parts of 12.5 quality %, is the Vinylite latex 1-1 that 10000mPas (#4 * 12), pH are 8 thereby obtain BM viscosity.
Then, using above-mentioned Vinylite latex 1-1 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, with 200 object filter clothes (polyester), filter, thereby obtain the resin combination 1 that aqueous binder is used.
(embodiment 2)
To dropping into Latemul PD-104 (Kao Corp's system, solids component 20 quality %) 45 mass parts as reactive surfactant in container, as ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 15 moles) 6 mass parts, 2-EHA 435 mass parts, butyl acrylate 120 mass parts, methyl methacrylate 30 mass parts and vinylformic acid 15 mass parts of the carboxylate (B) of nilox resin acid, as lauryl mercaptan 0.21 mass parts and ion exchanged water 108 mass parts of chain-transfer agent, and stir, thereby prepare emulsion.
By possessing in the aggregation container of thermometer, dropping funnel, reflux condensing tube and whipping appts with nitrogen replacement, drop into ion exchanged water 364.8 mass parts, interior temperature is warming up to 52.5 ℃.
In above-mentioned aggregation container, with respect to the total amount of above-mentioned emulsion, drop into after the emulsion of 1 quality %, add Sodium Pyrosulfite 0.15 mass parts and ammonium persulphate 0.18 mass parts, initiated polymerization.
Keep after 30 minutes, by remaining emulsion (99 quality %) and 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dihydrochloride aqueous solution (nonvolatile component 0.5 quality %) 10 mass parts of 2 '-azo were added drop-wise in above-mentioned aggregation container with 6 hours, further aggregation container is kept after 1 hour at 52.5 ℃ of interior temperature, be cooled to approximately 25 ℃, thereby obtain Vinylite latex 2-1.
Solids component 100 mass parts with respect to above-mentioned Vinylite latex 2-1, ammoniacal liquor 2.0 mass parts, Boncoat 3750-E (thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.5 mass parts and ion exchanged water 1.8 mass parts of mixing 12.5 quality % are the Vinylite latex 2-2 that 10000mPas (#4 * 12), pH are 8 thereby obtain BM viscosity.
Then, using above-mentioned Vinylite latex 2-2 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, this mixture is filtered with 200 order filter clothes (polyester), thereby obtain the resin combination 2 that the aqueous binder of the carboxylate that contains Vinylite, nilox resin acid, ion exchanged water and the oil soluble epoxy compounds of solids component 52.5 quality %, viscosity 242mPas, pH2.6, particle diameter 285nm, weight-average molecular weight 650,000 is used.
(embodiment 3)
With respect to above-described embodiment 2 in solids component 100 mass parts of the same Vinylite latex 2-1 that uses, mixing is as Super ester E-865-NT (Arakawa Chemical Industries, Ltd.'s system of rosin series resin (E), 160 ℃ of softening temperatures, nonvolatile component 50 quality %, polymerized rosin ester) 30 mass parts, then, to ammoniacal liquor 1.9 mass parts of mixing 12.5 quality % in this mixture, Boncoat 3750-E (the thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 0.6 mass parts and ion exchanged water 0.6 mass parts, thereby obtain BM viscosity, be 10000mPas (#4 * 12), pH is 8 Vinylite latex 3-1.
Using above-mentioned Vinylite latex 3-1 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, this mixture is filtered with 200 order filter clothes (polyester), thereby obtain the resin combination 3 that the aqueous binder of the carboxylate that contains Vinylite, nilox resin acid, ion exchanged water and the oil soluble epoxy compounds of solids component 52.5 quality %, viscosity 242mPas, pH2.6, particle diameter 285nm, weight-average molecular weight 650,000 is used.
(embodiment 4)
In container, drop into Latemul PD-104 (the Kao Corp's system as reactive surfactant, solids component 20 quality %) 45 mass parts, ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 15 moles) 6 mass parts as the carboxylate (B) of nilox resin acid, 2-EHA 435 mass parts, butyl acrylate 90 mass parts, ethyl propenoate 30 mass parts, methyl methacrylate 30 mass parts and vinylformic acid 15 mass parts, lauryl mercaptan 0.21 mass parts and ion exchanged water 108 mass parts as chain-transfer agent, and stir, thereby prepare emulsion.
By possessing in the aggregation container of thermometer, dropping funnel, reflux condensing tube and whipping appts with nitrogen replacement, drop into ion exchanged water 364.8 mass parts, interior temperature is warming up to 52.5 ℃.
In above-mentioned aggregation container, with respect to the total amount of above-mentioned emulsion, drop into after the emulsion of 1 quality %, add Sodium Pyrosulfite 0.15 mass parts and ammonium persulphate 0.18 mass parts, initiated polymerization.
Keep after 30 minutes, by remaining emulsion (99 quality %) and 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dihydrochloride aqueous solution (nonvolatile component 0.5 quality %) 10 mass parts of 2 '-azo were added drop-wise in above-mentioned aggregation container with 6 hours, further aggregation container is kept after 1 hour at 52.5 ℃ of interior temperature, be cooled to approximately 25 ℃, thereby obtain Vinylite latex 4-1.
Solids component 100 mass parts with respect to above-mentioned Vinylite latex 4-1, mixing is as Super ester E-865-NT (Arakawa Chemical Industries, Ltd.'s system of rosin series resin (E), 160 ℃ of softening temperatures, nonvolatile component 50 quality %, polymerized rosin ester) solid type divides 30 mass parts, further mix ammoniacal liquor 2.1 mass parts of 12.5 quality %, Boncoat 3750-E (the thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.6 mass parts and ion exchanged water 1.1 mass parts, thereby obtain BM viscosity, be 10000mPas (#4 * 12), pH is 8 Vinylite latex 4-2.
Using above-mentioned Vinylite latex 4-2 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, with 200 order filter clothes (polyester), filter, thereby obtain the resin combination 4 that the aqueous binder of the carboxylate that contains Vinylite, nilox resin acid, ion exchanged water and the oil soluble epoxy compounds of solids component 52.2 quality %, viscosity 208mPas, pH2.6, particle diameter 318nm, weight-average molecular weight 620,000 is used.
(embodiment 5)
Except spent glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 18 moles) is replaced ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 15 moles), the method by similarly to Example 1 obtains the resin combination 5 that aqueous binder is used.
(embodiment 6)
To dropping into Latemul PD-104 (Kao Corp's system, solids component 20 quality %) 45 mass parts as reactive surfactant in container, as ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 18 moles) 6 mass parts, 2-EHA 435 mass parts, butyl acrylate 120 mass parts, methyl methacrylate 30 mass parts and vinylformic acid 15 mass parts of the carboxylate (B) of nilox resin acid, as lauryl mercaptan 0.21 mass parts and ion exchanged water 108 mass parts of chain-transfer agent, and stir, thereby prepare emulsion.
By possessing in the aggregation container of thermometer, dropping funnel, reflux condensing tube and whipping appts with nitrogen replacement, drop into ion exchanged water 364.8 mass parts, interior temperature is warming up to 52.5 ℃.
In above-mentioned aggregation container, with respect to the total amount of above-mentioned emulsion, drop into after the emulsion of 1 quality %, add Sodium Pyrosulfite 0.15 mass parts and ammonium persulphate 0.18 mass parts, initiated polymerization.
Keep after 30 minutes, by remaining emulsion (99 quality %) and 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dihydrochloride aqueous solution (nonvolatile component 0.5 quality %) 10 mass parts of 2 '-azo were added drop-wise in above-mentioned aggregation container with 6 hours, further aggregation container is kept after 1 hour at 52.5 ℃ of interior temperature, be cooled to approximately 25 ℃, thereby obtain Vinylite latex 6-1.
Solids component 100 mass parts with respect to above-mentioned Vinylite latex 6-1, further mixing ammoniacal liquor 2.2 mass parts, Boncoat 3750-E (thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.2 mass parts and ion exchanged water 0.8 mass parts of 12.5 quality %, is the Vinylite latex 6-2 that 10000mPas (#4 * 12), pH are 8 thereby obtain BM viscosity.
Using above-mentioned Vinylite latex 6-2 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, with 200 order filter clothes (polyester), filter, thereby obtain the resin combination 6 that the aqueous binder of the carboxylate that contains Vinylite, nilox resin acid, ion exchanged water and the oil soluble epoxy compounds of solids component 52.4 quality %, viscosity 314mPas, pH2.8, particle diameter 297nm, weight-average molecular weight 640,000 is used.
(embodiment 7)
To dropping into Latemul PD-104 (Kao Corp's system, solids component 20 quality %) 45 mass parts as reactive surfactant in container, as ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 30 moles) 6 mass parts, 2-EHA 435 mass parts, butyl acrylate 120 mass parts, methyl methacrylate 30 mass parts and vinylformic acid 15 mass parts of the carboxylate (B) of nilox resin acid, as lauryl mercaptan 0.21 mass parts and ion exchanged water 108 mass parts of chain-transfer agent, and stir, thereby prepare emulsion.
By possessing in the aggregation container of thermometer, dropping funnel, reflux condensing tube and whipping appts with nitrogen replacement, drop into ion exchanged water 364.8 mass parts, interior temperature is warming up to 52.5 ℃.
In above-mentioned aggregation container, with respect to the total amount of above-mentioned emulsion, drop into after the emulsion of 1 quality %, add Sodium Pyrosulfite 0.15 mass parts and ammonium persulphate 0.18 mass parts, initiated polymerization.
Keep after 30 minutes, by remaining emulsion (99 quality %) and 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dihydrochloride aqueous solution (nonvolatile component 0.5 quality %) 10 mass parts of 2 '-azo were added drop-wise in above-mentioned aggregation container with 6 hours, further aggregation container is kept after 1 hour at 52.5 ℃ of interior temperature, be cooled to approximately 25 ℃, thereby obtain Vinylite latex 7-1.
Solids component 100 mass parts with respect to above-mentioned Vinylite latex 7-1, further mixing ammoniacal liquor 2.2 mass parts, Boncoat 3750-E (thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.2 mass parts and ion exchanged water 1.8 mass parts of 12.5 quality %, is the Vinylite latex 7-2 that 10000mPas (#4 * 12), pH are 8 thereby obtain BM viscosity.
Using above-mentioned Vinylite latex 7-2 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, with 200 order filter clothes (polyester), filter, thereby obtain the binder composition 7 for automobile inside of the carboxylate that contains Vinylite, nilox resin acid, ion exchanged water and the oil soluble epoxy compounds of solids component 52.1 quality %, viscosity 620mPas, pH2.8, particle diameter 281nm, weight-average molecular weight 640,000.
(comparative example 1)
Solids component 100 mass parts with respect to the Vinylite latex 1 obtaining in above-mentioned synthesis example 1, further mixing ammoniacal liquor 2.2 mass parts, Boncoat 3750-E (thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.0 mass parts and ion exchanged water 0.8 mass parts of 12.5 quality %, is the Vinylite latex 8-1 that 10000mPas (#4 * 12), pH are 8 thereby obtain BM viscosity.
Using above-mentioned Vinylite latex 8-1 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, with 200 order filter clothes (polyester), filter, thereby obtain the resin combination 8 that the aqueous binder that contains Vinylite, ion exchanged water and oil soluble epoxy compounds of solids component 53.0 quality %, viscosity 250mPas, pH2.5, particle diameter 280nm, weight-average molecular weight 700,000 is used.
(comparative example 2)
Solids component 100 mass parts with respect to the Vinylite latex 1 obtaining in above-mentioned synthesis example 1, mix Noniosid B-15 (the butyl poly glucoside as dry delayed-action activator, Di-ichi Kogyo Seiyaku Co., Ltd.'s system, solids component 50 quality %) after 1 mass parts, further mix ammoniacal liquor 2.5 mass parts of 12.5 quality %, Boncoat 3750-E (the thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.1 mass parts and ion exchanged water 0.9 mass parts, thereby obtain BM viscosity, be 10000mPas (#4 * 12), pH is 8 Vinylite latex 9-1.
Using above-mentioned Vinylite latex 9-1 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.02 mass parts of oil soluble epoxy compounds, mix, with 200 order filter clothes (polyester), filter, thereby obtain the resin combination 9 that the aqueous binder that contains Vinylite, ion exchanged water, oil soluble epoxy compounds and dry delayed-action activator of solids component 53.0 quality %, viscosity 250mPas, pH2.5, particle diameter 280nm, weight-average molecular weight 700,000 is used.
(comparative example 3)
To dropping into Latemul PD-104 (Kao Corp's system, solids component 20 quality %) 45 mass parts as reactive surfactant in container, as ethylene glycol dehydroabietic acid ester (the addition mole number of oxyethane (EO): 8 moles) 6 mass parts, 2-EHA 435 mass parts, butyl acrylate 120 mass parts, methyl methacrylate 30 mass parts and vinylformic acid 15 mass parts of the carboxylate of nilox resin acid, as lauryl mercaptan 0.21 mass parts and ion exchanged water 108 mass parts of chain-transfer agent, and stir, thereby prepare emulsion.
By possessing in the aggregation container of thermometer, dropping funnel, reflux condensing tube and whipping appts with nitrogen replacement, drop into ion exchanged water 364.8 mass parts, interior temperature is warming up to 52.5 ℃.
In above-mentioned aggregation container, with respect to the total amount of above-mentioned emulsion, drop into after the emulsion of 1 quality %, add Sodium Pyrosulfite 0.15 mass parts and ammonium persulphate 0.18 mass parts, initiated polymerization.
Keep after 30 minutes, by remaining emulsion (99 quality %) and 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dihydrochloride aqueous solution (nonvolatile component 0.5 quality %) 10 mass parts of 2 '-azo were added drop-wise in above-mentioned aggregation container with 6 hours, then aggregation container is kept after 1 hour at 52.5 ℃ of interior temperature, be cooled to approximately 25 ℃.
Solids component 100 mass parts with respect to above-mentioned polymkeric substance, further mixing ammoniacal liquor 2.2 mass parts, Boncoat 3750-E (thickening material of Dainippon Ink Chemicals's system, nonvolatile component 23 quality %) 1.4 mass parts and ion exchanged water 1.0 mass parts of 12.5 quality %, is the Vinylite latex 10-1 that 10000mPas (#4 * 12), pH are 8 thereby obtain BM viscosity.
Using above-mentioned Vinylite latex 10-1 with as TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system) 0.01 mass parts of oil soluble epoxy compounds, mix, content is filtered with 200 order filter clothes (polyester), thereby obtain the resin combination 10 that Vinylite, the carboxylate of nilox resin acid and the aqueous binder of ion exchanged water are used that contains of solids component 52.1 quality %, viscosity 234mPas, pH2.7, particle diameter 287nm, weight-average molecular weight 600,000.
[making of adhesive sheet]
The aqueous binder that uses above-mentioned aqueous binder to obtain with resin combination is coated on release paper with applicator, makes dry film thickness reach 60 μ m.
Then, above-mentioned painting application is dried to 3 minutes in the drying oven of 100 ℃, the polyurethane foam (Inoac Corporation system, ECS polyurethane foam) that is 5mm at this coated surfaces mounting thickness, till the thickness that is forced into this polyurethane foam reaches 2.5mm, above-mentioned coated surfaces and above-mentioned polyurethane foam is bonding, thus duplexer obtained.
Resulting duplexer is placed under the atmosphere of 40 ℃ and within 48 hours, carried out above slaking, thereby the gel fraction that obtains above-mentioned binder layer is the adhesive sheet of the present invention of the scope of 30 quality %～50 quality %.
[making of two sides adhesive sheet]
Above-mentioned aqueous binder is coated to respectively on 2 release papers with applicator with resin combination, makes dry film thickness reach 60 μ m.
Then, above-mentioned painting application after dry 3 minutes, is loaded to artificial silk non-woven fabrics (per unit grammes per square metre 14g/m an applicator surface that is coated with application in the drying oven of 100 ℃ 2), then the product applicator surface that loads another painting application on this artificial silk non-woven fabrics being formed, the roller that its use is adjusted to 100 ℃ carries out crimping with the pressure of 4000gf/cm, the hot and humid indoor placement of 40 ℃ * 50RH% 2 days, thereby obtains two sides adhesive sheet.
[evaluation method to the bonding force of porous insert (throwing anchor)]
< utilizes visual evaluation method >
By the adhesive sheet severing obtaining by aforesaid method, for its section, use microscope (50 times of KEYENCE CORPORATION, multiplying powers), the state at the contact site of visual observation binder layer and polyurethane foam (bonding position).
[determinating reference]
◎: there is no space or clear and definite interface between polyurethane foam and binder layer.
Zero: in 10% scope of the contact site integral body lower than polyurethane foam and binder layer, confirm space or clear and definite interface.
△: at more than 10% and in lower than 30% scope of the contact site of polyurethane foam and binder layer integral body, confirm space or clear and definite interface.
*: in more than 30% scope of the contact site of polyurethane foam and binder layer integral body, confirm space or clear and definite interface.
[evaluation method of the bonding force of the adherend that effects on surface polarity is low]
The only one side side of the two sides adhesive sheet obtaining by aforesaid method is removed release paper, and at the polyester film of this adhesive layer surface mounting thickness 25 μ m, portion comes and goes the roller of 2kg and applies load 2 times from it, by they crimping, thereby obtains duplexer.
Then, remove the release paper of the another side side of the test film that the duplexer consisting of above-mentioned two sides adhesive sheet and above-mentioned polyester film is cut into the size of width 20mm * length 100mm and obtain, at this adhesive layer surface mounting polypropylene base, portion applies and makes 2kg roller come and go the load of 1 time from it, thereby by they laminatings.
Then,, according to JISZ 0237, the stripping strength when peeling off with the speed of 300mm/min along 180 degree directions, evaluates the bonding strength between above-mentioned bonding coat and polypropylene base.
In addition, except using stainless steel (SUS) base material to replace above-mentioned polypropylene base, by with above-mentioned same method, evaluate the bonding strength between binder layer and stainless steel substrate.
Above-mentioned stripping strength is all probably evaluated as to the bonding force excellence of the adherend that effects on surface polarity is low for all base materials for the above person of 14N/20mm.
[evaluation method of heat-resistance adhesion]
< utilizes the evaluation > of heat-resisting creep test
The above-mentioned adhesive sheet of having removed release paper is pasted on the polypropylene base of area of wide 25mm * long 50mm, use the roller of 5kg to come and go and carry out crimping 1 time, thereby obtain duplexer.
Under the environment of 80 ℃, use simple type confining force trier (TESTER SANGYO CO, .LTD. make), at the supporter that forms the adhesive sheet of above-mentioned duplexer, be that polyurethane foam part applies the weight of 100g for No. #360 across sand paper, under above-mentioned polyurethane foam part state down, fix above-mentioned polypropylene base, place 30 minutes.
After 30 minutes, measure adhesive sheet and from polypropylene base, peel off the distance of (mm).In addition, before through 30 minutes, the supporter that forms adhesive sheet is that polyurethane foam and binder layer are peeled off, in the situation that above-mentioned polyurethane foam comes off, mensuration to the needed time till coming off (minute).
In addition, except replace above-mentioned polypropylene base with stainless steel substrate, by with above-mentioned same method, carry out the evaluation of heat-resistance adhesion.
Even by within above-mentioned 30 minutes, take the interior situation that does not come off or come off down to the needed time till coming off also as more than 10 minutes person is evaluated as heat-resistance adhesion excellence.
< utilizes the evaluation > of softening temperature
The above-mentioned adhesive sheet of having removed release paper is pasted on the adherend being formed by polypropylene of area of wide 25mm * long 25mm, with the roller of 5kg, come and go and carry out crimping 1 time, thereby obtain duplexer.
Under the environment of 23 ℃, with simple type confining force trier (TESTER SANGYO CO, .LTD. make), at the supporter that forms the adhesive sheet of above-mentioned duplexer, be that polyurethane foam part applies the weight of 310g for No. #360 across sand paper, vertically fixing under the state of above-mentioned duplexer, from 23 ℃ of speed with 3 ℃/5 minutes, heat up, measure the temperature that adhesive sheet comes off from polypropylene base.
In addition, except replace above-mentioned polypropylene base with stainless steel substrate, by with above-mentioned same method, carry out the mensuration of softening temperature.
Above-mentioned softening temperature is to 60 ℃ of above persons for all base materials and is evaluated as heat-resistance adhesion excellence.
[evaluation method of gel fraction]
The two sides adhesive sheet of making by aforesaid method is cut into the size of vertical 20mm and horizontal 100mm, as test film.With precision balance, measure the quality (W1) of having removed the binder layer of release paper from above-mentioned test film.
Then, above-mentioned binder layer is flooded in the toluene of 50cc after 24 hours, in the drying oven of 100 ℃, be dried 2 hours.With precision balance, measure the quality (W2) of dried binder layer.
Gel fraction is calculated according to (quality of quality (W2)-non-woven fabrics)/(quality of quality (W1)-non-woven fabrics) * 100.In addition, the quality of above-mentioned non-woven fabrics is 0.028g.
[evaluation method of water-fast bonding force]
The only one side side of the two sides adhesive sheet obtaining by aforesaid method is removed release paper, at this adhesive layer surface mounting thickness, is the polyester film of 25 μ m, and portion comes and goes the roller of 2kg and applies load 2 times from it, thereby by they crimping.
Then, remove the release paper of the another side side of the test film that the duplexer consisting of above-mentioned two sides adhesive sheet and above-mentioned polyester film is cut into the size of wide 20mm * long 100mm and obtain, at this adhesive layer surface mounting polypropylene base, portion applies the load that 2kg roller comes and goes 1 time from it, thereby by they laminatings.
Then, the duplexer consisting of above-mentioned polyester film and above-mentioned two sides adhesive sheet and above-mentioned polypropylene base is flooded after 72 hours in the warm water of 75 ℃, wipe the water that is attached to this duplexer surface, according to JIS Z 0237, stripping strength when peeling off with the speed of 300mm/min along 180 degree directions, evaluates and forms the bonding coat consisting of above-mentioned two sides adhesive sheet of above-mentioned duplexer and the bonding strength between above-mentioned polypropylene base.
Above-mentioned stripping strength is all probably evaluated as to the water-fast bonding force excellence of the adherend that effects on surface polarity is low for all base materials for the above person of 6N/20mm.
[table 1]
Figure BDA00001741795700241
[table 2]
Figure BDA00001741795700251

Claims (9)

1. an aqueous binder resin combination, it is characterized in that, the carboxylate (B) that contains Vinylite (A), nilox resin acid and water-medium (C), the carboxylate of described nilox resin acid (B) has the structure shown in following general formula (1), the end of the carboxylate of described nilox resin acid (B) is hydroxyl or alkoxyl group
Figure FDA0000417265820000011
N in described general formula (1) represents 10～30 integer.
2. aqueous binder resin combination according to claim 1, wherein, the weight-average molecular weight of described Vinylite (A) is 500,000～1,000,000.
3. aqueous binder resin combination according to claim 1, wherein, described Vinylite (A) have select in the group that free carboxyl group and carboxylic acid ester groups form more than a kind.
4. aqueous binder resin combination according to claim 1, wherein, described Vinylite (A) obtains the mixture of vinyl monomer polymerization of the carboxylic vinyl monomer of (methyl) alkyl acrylate that the total amount with respect to mixture of vinyl monomer contains 45 quality %～99 quality % and 1 quality %～5 quality %.
5. aqueous binder resin combination according to claim 1, wherein, the integer that the n in the structure shown in the described general formula (1) that the carboxylate of described nilox resin acid (B) has is 10～20.
6. aqueous binder resin combination according to claim 1, wherein, the hydroxyl reaction that the carboxyl that the carboxylate of described nilox resin acid (B) dehydroabietic acid has and polyoxyethylene glycol have obtains.
7. aqueous binder resin combination according to claim 1, wherein, with respect to the total amount of described Vinylite (A), the carboxylate (B) of the described nilox resin acid that contains 0.1 quality %～5 quality %.
8. aqueous binder resin combination according to claim 1, wherein, further contains oil soluble epoxy compounds (D).
9. according to the aqueous binder resin combination described in claim 1 or 8, wherein, further contain softening temperature and be the rosin series resin (E) of 150 ℃～200 ℃.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5196504A (en) * 1991-10-15 1993-03-23 Avery Dennison Corporation Repulpable pressure-sensitive adhesive compositions
JPH08301950A (en) * 1995-04-27 1996-11-19 Arakawa Chem Ind Co Ltd Aqueous rosin-based resin dispersion and its production
CN1145051A (en) * 1994-03-07 1997-03-12 艾弗里·丹尼森公司 Repulpable splicing tape
JP2002011337A (en) * 2000-06-28 2002-01-15 Harima Chem Inc Emulsifying dispersant for aqueous emulsion
JP2007217594A (en) * 2006-02-17 2007-08-30 Dainippon Ink & Chem Inc Acrylic water-based adhesive
WO2007067404A3 (en) * 2005-12-08 2007-11-22 Eastman Chem Co Emulsifiers for use in water-based tackifier dispersions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5751744A (en) * 1980-09-12 1982-03-26 Toho Chem Ind Co Ltd Novel liquid tackifier
JPH01292082A (en) * 1988-05-20 1989-11-24 Toho Chem Ind Co Ltd Method for preventing aqueous emulsion type tackifier from skinning
JP2002146315A (en) * 2000-11-16 2002-05-22 Chuo Rika Kogyo Corp Aqueous contact adhesive composition and method for producing the same
JP2005248056A (en) * 2004-03-05 2005-09-15 Sumitomo Rubber Ind Ltd Rubber composition and tire given by using the same
JP2006111669A (en) * 2004-10-13 2006-04-27 Toho Chem Ind Co Ltd Emulsion polymerization emulsifier
JP5190668B2 (en) * 2007-12-28 2013-04-24 荒川化学工業株式会社 Tackifier, sticky / adhesive composition and sticky / adhesive film label

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5196504A (en) * 1991-10-15 1993-03-23 Avery Dennison Corporation Repulpable pressure-sensitive adhesive compositions
CN1145051A (en) * 1994-03-07 1997-03-12 艾弗里·丹尼森公司 Repulpable splicing tape
JPH08301950A (en) * 1995-04-27 1996-11-19 Arakawa Chem Ind Co Ltd Aqueous rosin-based resin dispersion and its production
JP2002011337A (en) * 2000-06-28 2002-01-15 Harima Chem Inc Emulsifying dispersant for aqueous emulsion
WO2007067404A3 (en) * 2005-12-08 2007-11-22 Eastman Chem Co Emulsifiers for use in water-based tackifier dispersions
JP2007217594A (en) * 2006-02-17 2007-08-30 Dainippon Ink & Chem Inc Acrylic water-based adhesive

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"一种新型的松香聚氧乙烯蔗糖酯的合成与性能研究";周文富等;《日用化学工业》;20010630(第3期);第66-68页 *
"松香改性研究概述";曹祺风等;《广州化工》;20071031;第35卷(第5期);第10-13 *
周文富等."一种新型的松香聚氧乙烯蔗糖酯的合成与性能研究".《日用化学工业》.2001,(第3期),第66-68页.
实施例2.
曹祺风等."松香改性研究概述".《广州化工》.2007,第35卷(第5期),第10-13.

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