WO2008018589A1 - Résine réactive hydrocompatible et son procédé de production - Google Patents

Résine réactive hydrocompatible et son procédé de production Download PDF

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Publication number
WO2008018589A1
WO2008018589A1 PCT/JP2007/065723 JP2007065723W WO2008018589A1 WO 2008018589 A1 WO2008018589 A1 WO 2008018589A1 JP 2007065723 W JP2007065723 W JP 2007065723W WO 2008018589 A1 WO2008018589 A1 WO 2008018589A1
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Prior art keywords
water
resin
aqueous
urethane resin
reactive
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PCT/JP2007/065723
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English (en)
Japanese (ja)
Inventor
Tetsuo Sakurai
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National Starch And Chemical Investment Holding Corporation
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Publication of WO2008018589A1 publication Critical patent/WO2008018589A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than 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
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to an aqueous reactive resin containing a urethane resin and a bull resin (preferably an acrylic resin) and a method for producing the same, and the aqueous reactive resin is a base (or binder) such as an aqueous coating agent and an adhesive. ) Is preferably used.
  • an acrylic resin As an aqueous coating resin, an acrylic resin has been conventionally used for various coating applications due to its excellent weather resistance and toughness.
  • Water-based acrylic resins can be easily manufactured in various forms, from emulsion types to microemulsion types, and are generally excellent in weather resistance, gloss, alkali resistance, transparency, solvent resistance and adhesion.
  • it has the advantage of providing a film (coating or coating)
  • it is inadequate in terms of bending resistance, impact resistance, wear resistance, etc., and at the same time has good adhesion to both polyester and polyolefin substrates. There is also a problem that this is extremely difficult.
  • one of the resins used as coating resins is urethane resin.
  • Urethane resins have a problem that they are excellent in adhesion to both polyester and polyolefin substrates, are balanced and expensive, and have insufficient weather resistance.
  • Patent Document 1 discloses a urethane resin and its emulsion (aqueous solution or aqueous dispersion) blended in a water-based paint or water-based adhesive.
  • the urethane emulsion is excellent in storage stability and water resistance, but the urethane resin is insufficient in weather resistance and the like as compared with the acrylic resin.
  • urethane resin is cheaper than acrylic resin. Therefore, it is not preferable from the viewpoint of cost to contain a large amount of such urethane emulsion in the water-based paint.
  • Patent Document 2 discloses an adhesive composition in which a urethane resin and an acrylic resin are mixed. However, when the film is formed, the resulting mixture of urethane resin and acrylic resin is not sufficiently stable with time, phase separation may occur.
  • Patent Document 3 and Patent Document 4 disclose urethane polymer dispersions obtained by emulsion polymerization of acrylic monomers in the presence of water-based urethane resins. The urethane bur polymer dispersions disclosed in Patent Documents 3 and 4 are insufficient in terms of water resistance and solvent resistance capable of forming a film having excellent physical properties.
  • the urethane butyl polymer dispersion disclosed in Patent Documents 3 and 4 was coated on a substrate to form a film, and the film was whitened when immersed in water. Because the film is whitened, the film obtained from the urethane butyl polymer dispersion described in Patent Documents 3 and 4 cannot be said to have sufficient water resistance, and the solvent resistance, which is an advantage of acrylic resin, is the effect of urethane resin. It is recognized that it has declined.
  • Patent Document 1 Japanese Patent Laid-Open No. 9241349 (Patent No. 3618882)
  • Patent Document 2 Japanese Patent Laid-Open No. 5-117611
  • Patent Document 3 Japanese Patent Laid-Open No. 5-132535
  • Patent Document 4 Japanese Patent Laid-Open No. 6-80930
  • the present invention has been made to solve the above-described problems, and the object of the present invention is to obtain gloss, transparency, solvent resistance and adhesion from a conventional aqueous acrylic resin. While maintaining at least the same performance as film, it is water resistant, especially immersed in water. Another object of the present invention is to provide an aqueous reactive resin that exhibits high water resistance that does not substantially whiten, that is, provides a film with improved water whitening resistance, and a method for producing the same.
  • the present inventor has obtained an aqueous reactive resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of a specific aqueous urethane resin. Surprisingly, it has been found that a film capable of solving the above-mentioned problems is provided, and the present invention has been completed.
  • a new aqueous reactive resin which polymerizes (B) a polymerizable unsaturated monomer in the presence of (A) an aqueous urethane resin.
  • the (A) aqueous urethane resin is obtained by hydrolyzing a reactive silyl group (hydrolyzable silyl group and hydrolyzable silyl group that can form a crosslinked structure).
  • the water-based urethane resin has (al) a reactive silyl group capable of forming a crosslinked structure as “Si”, based on the solid content of the water-based urethane resin.
  • Aqueous reaction containing 0.;! To 10% by weight in the resin and containing (a2) anion groups in the aqueous urethane resin based on the solid content of the aqueous urethane resin from 0.01 to 1; 1. lmeq / g Provide functional resin.
  • the water-based urethane resin comprises an organic polyisocyanate component, a polyol component, and a compound having at least one active hydrogen and an anion group in the molecule;
  • a water-based reactive resin obtained by reacting a compound having at least one active hydrogen and a hydrolyzable silyl group in a molecule to obtain a urethane prepolymer, and subjecting the urethane prepolymer to a chain extension reaction.
  • the weight ratio (A) / (B) between (A) the water-based urethane resin and (B) the polymerizable unsaturated monomer is 2/8 to 8 in terms of solid content.
  • An aqueous reactive resin that is / 2 is provided.
  • the polymerizable unsaturated monomer (B) provides an aqueous reactive resin comprising a (meth) acrylic acid alkyl ester.
  • the polymerizable unsaturated monomer further comprises (C) polymerization.
  • An aqueous reactive resin comprising a reactive silane monomer is provided.
  • an aqueous reactive resin composition comprising the above-mentioned aqueous reactive resin is provided.
  • a method for producing the above-described aqueous reactive resin comprises (B) polymerizing a polymerizable unsaturated monomer in the presence of (A) an aqueous urethane resin.
  • the (A) water-based urethane resin comprises (al) a reactive silyl group capable of forming a cross-linked structure (a hydroxysilyl group obtained by hydrolyzing a hydrolyzable silyl group and a hydrolyzable silyl group).
  • a2 a method for producing an aqueous reactive resin having a cation group.
  • an organic polyisocyanate component in another embodiment of the present invention, an organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and a cation group in the molecule, and at least a molecule.
  • a urethane prepolymer is obtained by reacting one active hydrogen and a compound having a hydrolyzable silyl group. After mixing the urethane prepolymer and the (B) polymerizable unsaturated monomer, the urethane prepolymer is chain-lengthened.
  • a production method in which (A) an aqueous urethane resin is obtained by an extension reaction, and then (B) a polymerizable unsaturated monomer is polymerized.
  • the organic polyisocyanate component, the polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and at least one active hydrogen and a hydrolyzable in the molecule is obtained by reacting a compound having a silyl group, and the urethane prepolymer is subjected to a chain extension reaction to obtain (A) an aqueous urethane resin, and then (B) a polymerizable unsaturated monomer is mixed. And (B) a production method for polymerizing a polymerizable unsaturated monomer.
  • a coating agent comprising the above-mentioned aqueous reactive resin composition is provided.
  • an adhesive comprising the above-mentioned aqueous reactive resin composition is provided.
  • aqueous means a state where the resin is present in the aqueous medium, which means that the resin is dissolved in the aqueous medium! Re! Taste.
  • the “aqueous medium” refers to general water such as tap water, distilled water, or ion exchange water, but is a water-soluble or water-dispersible organic solvent, such as a monomer.
  • An organic solvent having poor reactivity with the raw material of the resin relating to the present invention for example, acetone, ethyl acetate and the like, and further water-soluble or water-dispersible monomer, oligomer, prepolymer and / or resin, etc.
  • emulsifier a polymerizable emulsifier, a polymerization initiator, a chain extender and / or various additives that are usually used in the production of water-based resins or water-soluble resins. But you can do it.
  • the aqueous reactive resin of the present invention is (A) an aqueous reactive resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of an aqueous urethane resin, (A) Since the water-based urethane resin has (al) a reactive silyl group capable of forming a crosslinked structure and (a2) ayuon group, gloss, transparency, solvent resistance and adhesion can be obtained from conventional water-based acrylic resins. While maintaining at least the same performance as acrylic film, it exhibits water resistance, especially high water resistance that does not substantially whiten even when immersed in water, i.e. improved water whitening resistance. It is possible to provide an aqueous reactive resin that provides
  • the aqueous urethane resin has (al) a reactive silyl group capable of forming a crosslinked structure as "Si", based on the solid content of the aqueous urethane resin. Contained in water-based urethane resin from 0.;! To 10% by weight, and contains (a2) anion group in water-based urethane resin based on solid content of water-based urethane resin, from 0.01 to; 1. lmeq / g In this case, water resistance and solvent resistance are further improved.
  • the aqueous urethane resin includes an organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an ionic group in the molecule,
  • a urethane prepolymer is obtained by reacting a compound having at least one active hydrogen and a hydrolyzable silanol group therein, and the urethane prepolymer is obtained by a chain length extension reaction, water resistance and solvent resistance are (Further) improved.
  • the weight ratio (A) / (B) between (A) the aqueous urethane resin and (B) the polymerizable unsaturated monomer is 2 in terms of solid content. / 8 to 8/2, water resistant , Solvent resistance, film transparency and water whitening resistance are further improved.
  • the (B) polymerizable unsaturated monomer comprises (meth) acrylic acid alkyl ester
  • water resistance, solvent resistance and water whitening resistance are Further improved.
  • the solvent resistance is further improved.
  • aqueous reactive resin of the present invention when a film having a change in water whitening value ( ⁇ L) force S10 or less measured with a color difference meter is formed, a denser film is formed.
  • the aqueous reactive resin composition according to the present invention comprises the above-mentioned aqueous reactive resin, gloss, transparency, solvent resistance and adhesion can be obtained from conventional aqueous acrylic resin compositions. While maintaining at least the same performance as acrylic film, water resistance, especially high water resistance that does not cause whitening even when immersed in water, ie, excellent water whitening resistance Can do.
  • the method for producing a water-based reactive resin of the present invention is (A) a method for polymerizing a polymerizable unsaturated monomer in the presence of a water-based urethane resin, and (A) a water-based urethane. Since the resin is a production method having (al) a reactive silyl group capable of forming a bridge structure and (a2) ayuon group, gloss, transparency, solvent resistance and adhesion are obtained from conventional aqueous acrylic resins. While maintaining at least equivalent performance as compared to the allyl film, water resistance, particularly high water resistance that does not substantially whiten even when immersed in water, that is, excellent water whitening resistance.
  • the manufacturing method of the water-system reactive resin shown can be provided.
  • the production method of the present invention relates to an organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and at least one active hydrogen and water in the molecule.
  • a urethane prepolymer is obtained by reacting a compound having a decomposable silyl group, and after mixing the urethane prepolymer and (B) a polymerizable unsaturated monomer, the urethane prepolymer is subjected to a chain extension reaction (A) an aqueous urethane.
  • the production method of the present invention relates to an organic polyisocyanate component, a polyol component, and a molecule.
  • a urethane prepolymer is obtained by reacting a compound having at least one active hydrogen and an anion group in the molecule with a compound having at least one active hydrogen and a hydrolyzable silyl group in the molecule.
  • a production method in which (A) a water-based urethane resin is obtained by an extension reaction and then (B) a polymerizable unsaturated monomer is mixed and (B) the polymerizable unsaturated monomer is polymerized, the water resistance, Solvent properties, film transparency and water whitening resistance are further improved.
  • the coating agent according to the present invention is a coating agent containing the above-mentioned aqueous reactive resin composition
  • the coating agent obtained from the conventional aqueous resin composition has gloss, transparency, solvent resistance and adhesion. While maintaining at least the same performance as compared to the above, it can exhibit water resistance, particularly high water resistance that does not substantially whiten even when immersed in water as a film, that is, excellent water whitening resistance. .
  • the adhesive according to the present invention is an adhesive containing the above-described aqueous reactive resin composition
  • the adhesive obtained from the conventional aqueous resin composition has high brightness, transparency, solvent resistance and adhesion. While maintaining at least the same performance as compared with the above, it is possible to exhibit water resistance, particularly high water resistance that does not substantially whiten even when the film is immersed in water, that is, excellent water whitening resistance.
  • the aqueous reactive resin according to the present invention is an aqueous reactive resin obtainable by polymerizing (B) a polymerizable unsaturated monomer in the presence of (A) an aqueous urethane resin, “(A) Aqueous urethane resin” has “(al) a reactive silyl group capable of forming a crosslinked structure” and “(a2) an anion group”.
  • the "(A) water-based urethane resin” according to the present invention has "(a 1) a reactive silyl group capable of forming a crosslinked structure” and "(a2) an anion group” There is no particular limitation as long as the aqueous reactive resin targeted by the present invention can be obtained.
  • the “reactive silyl group capable of forming a crosslinked structure” includes a hydrolyzable silyl group and a hydroxysilyl group obtained by hydrolysis of a hydrolyzable silyl group.
  • the “hydrolyzable silyl group” refers to a functional group containing silicon that gives a hydroxyl group (Si—OH) that is bonded to silicon by hydrolysis, for example, trimethoxysilyl group.
  • alkoxysilyl groups such as trimethoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, methoxysilyl group, monoethoxysilyl group, and monomethoxysilyl group.
  • An ethoxysilyl group, a dimethoxysilyl group, and a methoxysilyl group are preferred! /.
  • hydrolyzable silyl group more specifically, for example,
  • [Y is 10 CH or 10 CH or 10 (CH) — ⁇ (CH) — H (where n and p are integers from 1 to 3),
  • X is one (CH) one H (where q is an integer from 0 to 3),
  • a is an integer from 0 to 2.
  • hydroxysilyl group means Si— (OH), -Si (X)-(OH) Si (X)-
  • X is one (CH 3) — H (where q is an integer from 0 to 3) or H. It is thought that a hydroxysilyl group produced by hydrolysis of a hydrolyzable silyl group is bonded to each other to form a siloxane bond to form a crosslinked structure.
  • the hydrolyzable silyl group is preferably "Si" and contained in the aqueous urethane resin in an amount of 0.;! To 10% by weight based on the solid content of the aqueous urethane resin. ⁇ 1.0 wt% It is more preferable that it is contained 0.15 to 0.60 wt% is particularly preferable.
  • the hydrolyzable silyl group may be a single species or a combination of two or more thereof.
  • anion group refers to a functional group having a negative charge (eg, COO— and SO—), a functional group in which the negative charge is electrically neutralized by a counter cation (eg, COO—Na + and SO—K +, etc.) and functional groups that can release hydrogen ions in water to form negatively charged functional groups (for example, COOH and SOH).
  • these functional groups can be easily converted into each other by changing the state surrounding each functional group, for example, pH.
  • these functional groups are used alone or in combination of two or more thereof, depending on the characteristics of the water-based urethane resin. They can be used in combination.
  • “functional group having negative charge” and “functional group in which negative charge is electrically neutralized by a counter cation” include, for example, carboxylate groups (—COO— and —COOM 1 ), Sulfonate groups (one SO— and SO M 2 ), and phosphate groups (one PO H—, —PO 2 and
  • PO and M 4 is an alkali metal, alkaline
  • M 3 and M 4 may be either hydrogen.
  • ammonium NH + triethylenolamine may be used as the ammonium.
  • “functional groups capable of releasing a hydrogen ion in water to form a negatively charged functional group” include, for example, a carboxyl group (one COOH), a sulfonic acid group (or sulfo group) (one SO H
  • a carboxyl group neutralized with a base is preferable. More specifically, a carboxyl group (COO-M + ) in which a carboxyl group (COOH) is neutralized with a base is preferable. It may be a combination of a carboxyl group and a carboxylate base neutralized with a base.
  • the anion group is preferably contained in the aqueous urethane resin in an amount of 0.0 ;! to 1.lmeq / g based on the solid content of the aqueous urethane resin. 0.044—1. It is more preferable than S, more preferably 0.1 to 0.8 meq / g, and most preferably 0.2 to 0.6 meq / g.
  • meq / g indicates the number of millimoles contained per lg of the aqueous urethane resin solid content. If the diion group is less than 0 ⁇ Olmeq / g, the particle size of the (A) water-based urethane resin can be increased, resulting in a significantly unstable dispersion, which can be insufficient as a water-based urethane resin. 1. If it exceeds lmeq / g, the hydrophilicity of the water-based urethane resin becomes too high, which may cause problems such as a decrease in the water resistance of the formed film and an increase in the viscosity of the aqueous resin solution (dispersion).
  • the specific (A) water-based urethane resin according to the present invention includes an "organic polyisocyanate component", a “polyol component”, and a “compound having at least one active hydrogen and an anion group in the molecule”. And “having at least one active hydrogen and hydrolyzable silyl group in the molecule” Reacting the compound to obtain a urethane prepolymer,
  • the urethane prepolymer can be obtained by chain extension reaction.
  • Urethane prepolymer is a reaction between "organic polyisocyanate component", “polyol component” and “compound having at least one active hydrogen and anion group in the molecule” in an NCO-excess state. Next, it is preferable to obtain a part or all of NCO of the terminal NCO-containing urethane prepolymer obtained by reacting with “a compound having at least one active hydrogen and hydrolyzable silanol group in the molecule”. .
  • the obtained “urethane prepolymer” is preferably dissolved or dispersed in an aqueous solution containing a basic compound and subjected to a chain length extension reaction. If necessary, a chain extender made of a low molecular weight compound having at least two active hydrogens in the molecule may be used.
  • Urethane prepolymers can have a strong lpoxyl group (COOH), but the carboxyl group (COOH) is converted into anion (one COO) by a basic substance, so even if the chain length is extended, the prepolymer is converted to a high molecular weight. Even if it becomes, it can be easily dispersed in water.
  • COOH carboxyl group
  • aliphatic diisocyanates such as ethylene diisocyanate, 2,2,4 trimethylhexamethylene diisocyanate 1,6 xamethylene diisocyanate; hydrogenated 4,4'-diphenyl Cycloaliphatic diisocyanates, naphthalene diisocyanates such as enylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane xylene diisocyanate, isophorone diisocyanate Aromatic diisocyanates such as Of these, aliphatic and / or cycloaliphatic diisocyanates are preferably used alone or in combination for those that should be considered for discoloration over time.
  • polyol component used in the production of an aqueous urethane resin
  • those generally used in the production of a urethane resin can be used, and an aqueous reactive resin intended by the present invention can be obtained.
  • polyols include polyester polyols, polyether polyols, and polycarbonate polyols.
  • polyester polyol at least one kind of dicenolevonic acid such as succinic acid, dartaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, ethylene glycol, propylene glycol, 1, 4 1 of polyhydric alcohols such as butanediol, 1,3-butanediol, 1,6-hexanediol, neopentinoglycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, trimethylolpropane, etc.
  • dicenolevonic acid such as succinic acid, dartaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, ethylene glycol, propylene glycol, 1, 4 1 of polyhydric alcohols such as butanedi
  • polyether polyols water and polyhydric alcohols used for the synthesis of the above polyester polyols, bisphenols — phenols such as A, or primary and secondary amines such as ethylene oxide, propylene oxide, oxetane, A product obtained by ring-opening addition polymerization of a cyclic ether such as tetrahydrofuran can be used.
  • Examples thereof include one obtained by ring-opening addition polymerization (in the case of a copolymer, either a block copolymer or a random copolymer).
  • Examples of the polycarbonate-polynoole include polybutylene carbonate polyol, polyhexamethylene carbonate polyol, and poly (3-methyl-1,5-pentylene) carbonate polyol.
  • polybutadiene polyol polyisoprene polyol, polyolefin polyol, and polyacrylic ester polyol can be used alone or in combination as a polyol.
  • a compound having at least one active hydrogen and a cation group in a molecule used for the production of an aqueous urethane resin means a functional group having at least one active hydrogen in the molecule (for example, Hydroxyl group, amino group, thiol group, etc.) and the above-described anion group, and any compound that can obtain the water-based reactive resin intended by the present invention. It is not limited to. Examples of such compounds include dimethylolpropionic acid, dimethylolbutanoic acid, carboxyl group-containing polyprolatathone diol, sulfate-containing polyester polyol, and di (/ 3-hydroxyethyl) isophthalic acid-5-sulfur.
  • Examples thereof include phonic acid.
  • a compound having a strong lpoxyl group (COOH) as an anion group is preferred. More preferred are methylolpropionic acid, dimethylolbutanoic acid, and carboxyl group-containing poly strength prolatatone diol.
  • a compound having at least one active hydrogen and an anion group in the molecule means that the anion group is 0. Olmeq / g in the solid content of the water-based urethane resin (for example, in the case of COOH, in the solid content of the urethane resin) It is usually used so that lOOg contains 45 mg) or more as “COOH”.
  • the anion group is 0.044 meq / g in the aqueous urethane resin solid content lOOg (for example, ⁇ COOH '' in the case of a carboxyl group). 200mg) or more is preferable.
  • the particle size of the (A) aqueous urethane resin can be increased, resulting in an unstable dispersion, which may be unqualified.
  • the amount of anion groups increases with respect to the solid content of the aqueous urethane resin, (A) the particle size of the aqueous urethane resin decreases and the drying property, glossiness, and transparency are improved, but the water resistance of the resulting film is increased. Solvent resistance can be reduced. If the content of the anion group exceeds 1.
  • the hydrophilicity of the water-based urethane resin becomes too high, which may cause problems such as a decrease in water resistance of the film and an increase in the viscosity of the resin aqueous solution (dispersion).
  • (A) the particle diameter of the water-based urethane resin is measured by a dynamic light scattering method using "PARIII” (L ASER PARTICLE ANALYZER) manufactured by Otsuka Electronics Co., Ltd.
  • the average particle diameter of emulsions obtained by analysis by the method.
  • the particle diameter (ie, average particle diameter) of the (A) water-based urethane resin is 50 to 200 nm, preferably S, 50 to 150 nm, and particularly preferably 50 to 120 nm. .
  • the content of the anion group is determined in consideration of the balance with the hydrophilicity of the polyol component or the like. For example, if polyoxyethylene glycol is used as the polyol, Since it itself has hydrophilicity, the content of the functional group should be set low, but when a hydrophobic polyol is used, it should be set high.
  • the "compound having at least one active hydrogen and hydrolyzable silyl group in the molecule” means a functional group containing at least one active hydrogen and hydrolyzable silyl group in the molecule.
  • the compound is not particularly limited as long as it is a compound having a desired water-based reactive resin.
  • the “functional group containing active hydrogen” include a hydroxyl group, an amino group, and a thiol group.
  • the “hydrolyzable silyl group” include the hydrolyzable silyl groups described above.
  • the hydrolyzable silyl group is preferably an alkoxysilyl group. S Desirably, it is any of mono-, di-, and tri-alkoxysilyl groups. May be.
  • alkoxysilyl groups include methoxysilyl groups and ethoxysilyl groups.
  • Ethoxysilane ⁇ Mercaptopropylmethyljetoxysilane , ⁇ — / 3 -— (Aminoethyl) ⁇ —Aminopropyltrimethoxysilane, ⁇ — / 3— (Aminoethyl) ⁇ —Aminopropyl methyldimethoxysilane, ⁇ -Aminopropyl Examples include triethoxysilane, ⁇ phenyl- l -aminopropyltrimethoxysilane, and the like.
  • a compound having a trialkoxysilyl group is a more preferred aminotrialkoxysilane ⁇ ⁇ Aminopropyltrimethoxysilane is particularly preferred.
  • a compound having at least one active hydrogen and a hydrolyzable silyl group in the molecule has a hydrolyzable silyl group as "Si” in 10 mg of aqueous urethane resin per 100 g of aqueous urethane resin solids ( (O.01 wt%) or more is usually used, and the hydrolyzable silyl group is expressed as ⁇ Si '' in an amount of 200 mg per 100 g of aqueous urethane resin solids (0 (2wt%) or more is preferred.
  • the hydrolyzable silyl group When the hydrolyzable silyl group is “Si” and less than 10 mg per 100 g of aqueous urethane resin solid content, the crosslinking density may be low, and the normal effect may be insufficient. In addition, If the water-decomposable silyl group is “Si” and exceeds 10 wt% in the solid content of the water-based urethane resin, the crosslink density in the film becomes too high, and the coating film may become brittle.
  • These hydrolyzable silanol groups preferably alkoxysilyl groups, are contained in the (A) water-based urethane resin and generally react with water to form hydroxysilyl groups in an aqueous medium.
  • a chain extender consisting of "a low molecular weight compound having at least two active hydrogens in a molecule" optionally used in the production of a water-based urethane resin is a functional group containing active hydrogens in the molecule. It is not particularly limited as long as it is a chain extender composed of a compound having at least two and can obtain the target aqueous reactive resin of the present invention.
  • low molecular weight compounds having at least two active hydrogens in the molecule low molecular weight dallicols typified by ethylene glycolol, propylene glycolol, 1,4 butanediole, trimethylololepan pan, etc .; ethylenediamine, Propylene diamine, butylene diamine, hexamethylene diamine, 2, 2, 4 trimethyl hexamethylene diamine, isophorone diamine, dicyclohexyl methane 4, 4'-diamine, bisaminodipropylamine, bisaminoger Examples include amines such as tyramine and piperazine; and diethanolamine and hydrazine and derivatives thereof.
  • the chain extension reaction is usually carried out after the urethane prepolymer has been dispersed in water.
  • amines such as hydrazine and other isocyanates having a higher reactivity than water S are effective. It is preferable because it can be used for chain extension reaction. More specifically, for example, piperazine hexahydrate can be more suitably used.
  • the basic compound for example, triethylamine, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide and the like can be used.
  • the basic compound it is preferable to determine the amount of the basic compound so that the resulting aqueous urethane resin solution or urethane resin dispersion has a pH of 6-10. If the pH force is less than, the stability of the urethane resin aqueous solution or urethane resin dispersion may be insufficient.
  • a crosslinking agent such as a water-soluble isocyanate, a water-soluble epoxy resin, an aziridine compound, or an oxazoline compound may be used in combination.
  • the water-based urethane resin can be obtained in the form of a composition present in the aqueous medium by the above-described production method. That is, it can be obtained in the form of an aqueous urethane resin composition (for example, urethane resin aqueous solution, dispersion, suspension or emulsion).
  • an aqueous urethane resin composition for example, urethane resin aqueous solution, dispersion, suspension or emulsion.
  • water-based urethane resin is in the form of a composition contained in this aqueous medium, and is adjusted to a desired solid content, viscosity, pH, etc. as necessary. Used for body polymerization.
  • the water-based urethane resin composition according to the present invention described above preferably has a solid content of 25 to 50% by weight, more preferably 30 to 45% by weight, more preferably 30 to 40% by weight. Is particularly preferred.
  • solid content refers to the percentage of the weight of the composition after heating for 3 hours in an oven at 105 ° C., based on the weight of the composition before heating.
  • the aqueous urethane resin composition according to the present invention described above preferably has a viscosity of 10 to 500 mPa's, more preferably 10 to 200 mPa's, and more preferably 10 to 100 mPa's. Particularly preferred.
  • the viscosity means a value measured at 60 ° C. at 30 ° C. using a rotor No .;
  • the aqueous urethane resin composition according to the present invention described above preferably has a pH force of 6.5 to 8.5, more preferably 7 to 8.5, and particularly preferably 7 to 8. preferable.
  • pH refers to a value measured using a pH meter.
  • the water-based urethane resin composition according to the present invention has a particle size of 50 to 200 nm, preferably ⁇ 50, more preferably 150 nm, and more preferably 50 to 120 nm.
  • the particle diameter refers to the average particle diameter of the emulsion obtained by the measurement by the dynamic light scattering method as described above and the analysis by the curant method.
  • (B) polymerizable unsaturated monomer is a monomer having an ethylenic double bond, and can obtain an aqueous reactive resin intended by the present invention. If there is, there is no particular limitation.
  • Carboxylic acid is an acid having a carboxyl group (COOH), and carboxylic acid ester means an ester of carboxylic acid.
  • Carboxylic acids include saturated carboxylic acids and unsaturated rubonic acids. Examples of saturated carboxylic acids include alkanoic acids. Examples of unsaturated carboxylic acids include (meth) acrylic acid, phthalic acid, maleic acid, and phthalic anhydride. And maleic anhydride.
  • alkanoic acid examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and 2-pentapentanoic acid.
  • alkanoic acid ester means an ester of an alkanoic acid, and specifically includes (B) a polymerizable unsaturated monomer, and specifically includes butyl acetate, ethylene acetate butyl, propionate butyl, and butyl acetate butyl acetate. Etc. can be illustrated.
  • (Meth) acrylic acid refers to both acrylic acid and methacrylic acid, and includes acrylic acid, methatalic acid, and combinations of acrylic acid and methacrylic acid.
  • (Meth) acrylic acid ester refers to an ester of (meth) acrylic acid, ie, (meth) acrylate.
  • (Meta) attalate refers to both attalate and metatalate, and includes talate, metatalate, and combinations of attalate and metatalate.
  • (meth) acrylate examples include methyl (meth) acrylate and ethyl (meth) acrylate.
  • 2-ethyl hexyl (meth) acrylate pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) (Meth) acrylate, (meth) acrylate behenyl and docosyl (meth) acrylate alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxyhydroxyalkyl Examples include esters. These can be used alone or in combination of two or more.
  • (B) (meth) acrylic acid alkyl ester is preferred as the polymerizable unsaturated monomer, and more specifically, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) atalylate is preferred in the present invention.
  • styrene and derivatives thereof include styrene, methylstyrene, dimethylstyrene, and the like, and styrene is preferable.
  • the polymerizable unsaturated monomer at least one selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate and styrene is more preferable. preferable.
  • the water-based reactive resin according to the present invention has a weight ratio of (A) water-based urethane resin and (B) polymerizable unsaturated monomer ((A) / (B)) in terms of solid content.
  • (A) I (B) is particularly preferably 3/7 to 6/4.
  • Adhesiveness of base material which is an advantage of water-based urethane resin, is reduced.
  • the polymerizable silane monomer is a silane compound having an ethylenic double bond and having at least one alkoxy group, and obtains an aqueous reactive resin intended by the present invention. There is no particular limitation as long as it can be used.
  • Silane and the like can be exemplified. These can be used alone or in combination of two or more.
  • alkoxysilane having an ethylenic double bond a dialkoxysilane having an ethylenic double bond and a trialkoxysilane having an ethylenic double bond are preferable.
  • the (C) polymerizable silane monomer may be the same as (i) “compound having at least one active hydrogen and hydrolyzable silyl group in the molecule” for producing a water-based urethane resin. Useful! /
  • the urethane prepolymer After mixing ( ⁇ ) the urethane prepolymer of the water-based urethane resin and ( ⁇ ) the polymerizable unsaturated monomer, the urethane prepolymer is subjected to chain extension reaction ( ⁇ ) to obtain the urethane prepolymer, and then ( ⁇ Polymerizing polymerizable unsaturated monomers; and
  • the urethane prepolymer is subjected to chain extension reaction (i) to obtain an aqueous urethane resin, and then (ii) a polymerizable unsaturated monomer is mixed, and (ii) a polymerizable unsaturated monomer is polymerized.
  • the urethane prepolymer when performing the chain extension reaction of the urethane prepolymer, as described above, the urethane prepolymer is dissolved or dispersed in an aqueous solution that may contain a basic compound, and the chain is thus obtained.
  • An extended reaction can be performed.
  • the urethane prepolymer of the water-based urethane resin and (ii) the polymerizable unsaturated monomer are mixed, the obtained mixture is dissolved or dissolved in an aqueous solution that may contain a basic compound.
  • a chain extension reaction of the urethane prepolymer can be carried out in the presence of the polymerizable unsaturated monomer.
  • a polymerizable unsaturated monomer is polymerized to form a core, and at least part of the force around the core S (A) is covered with an aqueous urethane resin.
  • Core shell It is presumed that composite fine particles having a structure can be obtained.
  • the aqueous reactive resin of the present invention comprises (B) a polymerizable unsaturated monomer (in some cases, (C) a polymerizable silane monomer in the presence of the above-mentioned (A) aqueous urethane resin. It can be obtained by radical polymerization of YO! /,). Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • Emulsion polymerization is radical polymerization using an emulsifier using water as a medium, and a known method can be used.
  • the emulsion polymerization method include (B) a method in which a polymerizable unsaturated monomer and an emulsifier are charged and polymerized in an aqueous medium, and (B) a continuous or intermittent polymerization in the polymerizable unsaturated monomer and the emulsifier.
  • An emulsion is prepared by adding water to a polymerizable unsaturated monomer and an emulsifier, and this is dropped continuously or intermittently into the aqueous medium. And a method of polymerizing them.
  • the emulsifier has a monomer emulsifying power, and forms micelles in the process of emulsion polymerization to provide a place for polymerization to the monomer, and is immobilized on the surface of the polymer particles during or after the polymerization to improve the dispersion stability of the particles.
  • the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant.
  • anionic surfactants include alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; ammonium dodecyl polyglycol ether sulfate; ammonium alkyl sulfate such as ammonium dodecyl sulfate; sodium sulfosinoate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, trialtal amine oleate, and triethal amine abiate; sodium dodecylbenzene sulfonate, alkaline phenol hydroxy Alkyl aryl sulfonates such as ethylene metal sulfates; high alkyl naphthalenes Examples thereof include sulfonates; naphthalen
  • dialkylsulfosuccinate As an anionic surfactant, dialkylsulfosuccinate
  • Perex OT-P (manufactured by Kao Corporation) which is (sodium salt) is preferred.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers; sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; fatty acid monoglycerides such as monolaurate of glycerol; Examples thereof include ethyleneoxypropylene copolymers; condensation products of ethylene oxide and aliphatic amines, amides or acids.
  • Examples of the cationic surfactant include monoalkyl ammonium salts, dialkyl ammonium salts, ethylene oxide addition type alkyl ammonium salts, and the like.
  • Examples of amphoteric surfactants include amidopropyl betaine and amino acetate betaine.
  • polymer surfactant examples include polybulal alcohol; poly (meth) acrylate sodium, potassium poly (meth) acrylate, poly (meth) acrylate ammonium; poly (meth) acrylate, and the like.
  • Examples of reactive surfactants include polyoxyethylenearyl glycidyl nourenyl ether sulfates (Adekaria soap SE series, manufactured by Asahi Denka Kogyo Co., Ltd.), a-sulfo ⁇ - (1 (alkoxy) methyl-2 — (2-propenyloxy) ethoxy) Ammonium salt of poly (oxy 1,2-ethaneyl) (Adekaria soap SR series, manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene (or alkylene) alkyl (or alkenyl) ether sulfate Ammonium salt (PD series, manufactured by Kao Corporation), sulfosuccinic acid type reactive activator (Latemul 180 series, manufactured by Kao Corporation), alkylaryl sulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries), polyoxy Ethylene nonylpropenyl phenyl
  • Teruanmoniumu salt (Aqualon ⁇ series, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Poriokishechire Na Li glycidyl Roh loose phenyl ether (ADEKA Reasoap NE Series manufactured by Asahi Denka Engineering Gosha), polyoxyethylene nonyl Pro Bae vinyl ether (Aqualon RN series, manufactured by Daiichi Kogyo Seiyaku), a - hydro - omega - - ( alkoxy) methyl - 2 - (propenyl Niruo) ethoxy) poly (Okishi 1, 2- Etanjiiru) (ADEKA REASOAP ER series, may be exemplified by Asahi Denka Co., Ltd.).
  • alkylarylsulfosuccinic acid sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) and alkyl etherole sulfate ester ammonium salt (Aqualon® series, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are preferred.
  • a polymerization initiator is used to polymerize the polymerizable unsaturated monomer.
  • the polymerization initiator include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds.
  • KPS potassium persulfate
  • sodium persulfate sodium persulfate
  • ammonium persulfate diisopropylbenzenehydride peroxide
  • cumenehydride peroxide cumenehydride peroxide
  • t-butylnodide peroxide Perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.
  • T-butylenoperoxybenzoate 2,2-azobisisobutyronitrile
  • 2,2-azobis (2-diaminopropane) hydride chloride 2,2azobis (2,4 dimethylvaleronitrile
  • the agent can be further exemplified.
  • a chain transfer agent can be used as necessary to adjust the molecular weight of the resin.
  • chain transfer agent examples include n-dodecyl mercaptan, t-decyl mercaptan, n-butyl mercaptan, 2-ethylhexylthioglycolate, 2-mercaptoethanol, trichlorobromomethane and the like.
  • the aqueous reactive resin according to the present invention can be obtained in the form of a composition present in an aqueous medium in the above-described production method. That is, it can be obtained in the form of an aqueous reactive resin composition (for example, an aqueous reactive resin solution, dispersion, suspension or emulsion). it can.
  • an aqueous reactive resin composition for example, an aqueous reactive resin solution, dispersion, suspension or emulsion.
  • the water-based reactive resin is used in the form of a composition contained in the aqueous medium after adjusting to a desired solid content, viscosity, pH, etc. as necessary.
  • the solid content of the aqueous reactive resin composition according to the present invention is preferably 30 to 55% by weight, more preferably 30 to 50% by weight, and more preferably 35 to 50% by weight. Especially preferred.
  • the method for measuring the solid content is the same as the method described above.
  • the water-based reactive resin composition according to the present invention preferably has a viscosity power S of 30 ° C, 5 to 2000 mPa's, more preferably 5 to 1000 mPa's, and 5 to 500 mPa's. Particularly preferred is s.
  • the “viscosity” of the aqueous reactive resin composition refers to a value obtained by measurement by the method described above. For the rotor, No .;
  • the change in the water whitening value measured with a color difference meter can usually be 10 or less.
  • a L exceeds 10
  • the AL value of the formed film is 10 or less
  • a resin having a force AL value of 3 to 8 that can be used for the above applications is practically preferable, and ⁇ L A resin with a value of 3-4 is particularly preferred!
  • the aqueous reactive resin of the present invention having a small AL value (excellent in water whitening resistance) of the formed film is useful as a coating agent and an adhesive described later.
  • the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have "transparency".
  • transparency refers to “transparency” obtained by the method described in Examples.
  • the “transparency” of the film is more preferably “fully transparent”, more preferably “substantially transparent”.
  • the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have "gloss".
  • gloss means “gloss” obtained by the method described in Examples. More preferably, the “gloss” of the film is “very glossy”, preferably “shiny”.
  • the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have "solvent resistance”.
  • solvent resistance refers to the solvent resistance obtained by the method described in the Examples.
  • the “solvent resistance” of the membrane should be “almost unchanged” for both toluene and acetone. S is preferable, and “no change” is more preferable!
  • the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have a substrate "adhesion".
  • the base material “adhesion” refers to the base material “adhesion” obtained by the method described in the examples.
  • the base material of the film “transparency” is preferably “initially hardly peeled” and water-resistant “nearly peeled off! /,” For both PET and glass. It is more preferable than S to be water resistant “almost exfoliating! /,” And is particularly preferable to be initial “no exfoliating! /,” And water resistant “not exfoliating at all! /,”! .
  • the present invention further provides a coating agent containing the aqueous reactive resin composition. Moreover, this invention provides the adhesive agent containing the said water-system reactive resin composition in a preferable summary.
  • the water-based reactive resin composition according to the present invention requires a known facial material, antifungal agent, thickener, dispersant, antifoaming agent, antiseptic agent, film forming aid, and the like. It can be obtained by adding S accordingly.
  • the pigment is not particularly limited as long as it is usually a pigment. Pigments are usually classified into organic pigments and inorganic pigments.
  • organic pigments include, for example, insoluble azo pigments such as Fastero, Gazo Yellow, Gazo Orange, and Naphtho Red, phthalocyanine pigments such as copper phthalocyanine, dye rakes such as Juan rake, tannin lake, and katanol, and isoindolino erogrees And isoindolino pigments such as isoendolino yellow dish, quinacridone pigments, perylene pigments such as perylene cut and perylene maroon, and the like.
  • inorganic pigments include carbon black, white lead, red lead, yellow lead, silver vermilion, ultramarine blue, and oxide oxide. Examples include nonreto, titanium dioxide, titanium yellow, strontium chromate, molybden red, molybten white, iron black, ritbon, emerald green, guinea green and cobalt blue.
  • the filler refers to a substance added for the purpose of improving performance and reducing costs, and is not particularly limited as long as it is normally used as a filler. Specific examples include calcium carbonate, magnesium carbonate, silica, talc, clay, and alumina.
  • An antifungal agent is a substance added to suppress corrosion of a material, and is not particularly limited as long as it is usually used as an antifungal agent.
  • other resins can be mixed in the coating agent and the adhesive as necessary for the purpose of improving various performances.
  • the other resin include xylene resin, alkyd resin, urethane resin, epoxy resin, acrylic resin, tackifier, wax emulsion and the like.
  • the coating agent is preferably used as a top coating agent, particularly as a top coating agent, and a power that can be used as a base coating agent (including an intermediate coating agent and a so-called sealer).
  • the “top coat” is also called a top coat, which is a paint applied on the outermost side, and is applied for the purpose of improving the appearance, glossing, water resistance, weather resistance, etc. It refers to paint.
  • undercoat refers to paints other than topcoats, and is mainly used for the purpose of improving waterproofness, moisture proofing, adhesion to the substrate, etc. In some cases, it is also called a primer), and an intermediate coating agent is applied mainly for the purpose of improving waterproofness, moisture resistance, blister resistance, etc., connecting between the topcoat and the sealer.
  • the adhesive refers to both an aqueous solution type adhesive and a water dispersion type adhesive.
  • the water-based reactive resin of the present invention is used not only as a coating agent or adhesive but also as a component of ink, sealing material, cosmetics and the like.
  • the present invention has an excellent effect. It is thought that it is based on such reasons.
  • the present inventor whitens a film formed from emulsion by immersing it in water and water is formed at the interface of a plurality of particles constituting the film. I guessed it was caused by Then, if a specific urethane resin and a bull resin are combined with each other using a specific method in which a specific urethane resin and a vinyl resin (preferably an acrylic resin) are not simply mixed, then it can be obtained. We thought that it would be possible to obtain an aqueous reactive resin that does not allow water to enter the interface between the particles constituting the film.
  • the water-based urethane resin can act as a protective colloid, and (B) the polymerizable unsaturated monomer is polymerized to have a high molecular weight and the surroundings. It is considered that at least a part is covered with (A) water-based urethane resin.
  • a core-shell structure can be formed in which (A) the water-based urethane resin is the shell and (B) the bull-based resin polymerized with the polymerizable monomer is the core.
  • the water-based reactive resin having such a core-shell structure is formed by bonding (A) water-based urethane resins of the shell to each other by forming a cross-linked structure with (al) reactive silyl groups. It is considered that water enters the water and, as a result, the water whitening resistance of the film obtained from the obtained water-based reactive resin is excellent. (B) The force that the bull resin formed from the polymerizable unsaturated monomer is considered to form the core S, and the property based on this bull resin has a much undesirable effect from the urethane resin that forms the shell. It is thought that it can be maintained without receiving.
  • the water-based reactive resin of the present invention is characterized in that the water whitening value of the formed film changes (AU is usually 10 or less. AL shows a small value, that is, water whitening resistance. It is considered that the shell of the aqueous reactive resin of the present invention indirectly indicates that the shell of the water-based reactive resin is a highly water-resistant ( ⁇ ) urethane resin.
  • the (al) crosslink of silyl groups that can form a cross-linked structure forms a shell with a core chenole structure.
  • A Water hardly enters between water-based urethane resins, and as a result, the water-based resin is formed into a film. It is considered that even when immersed in water, it does not become white, that is, water whitening resistance is improved.
  • IPDI isophorone diisocyanate
  • polyester diol Nippon Polyurethane Industry Co., Ltd.
  • DMPA dimethylolpropionic acid
  • a resin dispersion having a solid content of 35% was obtained in the same manner as in V).
  • Tables 1 and 2 show the production of water-based urethane resin ( ⁇ -I) to water-based urethane resin ( ⁇ '-VII) and the properties of the obtained water-based resin (or resin dispersion).
  • ⁇ -I water-based urethane resin
  • ⁇ '-VII water-based urethane resin
  • the particle diameter is an average particle diameter.
  • anionic surfactant Perex OTP Kao Co., Ltd. 0 ⁇ 2g, water 6 ⁇ 7g, methyl methacrylate (MMA) 15g, 2-ethylhexyl acrylate (2EHA) 8g, metatalyloxypropyltrimethoxysilane 30.2 g of an emulsion composed of (SZ-6030 manufactured by Toray Dow Coung Silicone Co., Ltd.) was added dropwise over 2 hours with a dropping funnel.
  • MMA methyl methacrylate
  • 2EHA 2-ethylhexyl acrylate
  • a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 100 g of aqueous urethane resin (AI) and 17.8 g of water, and the temperature was raised to 70 ° C. Was sufficiently replaced with nitrogen.
  • AI aqueous urethane resin
  • a reactive reactive surfactant (Eleminol JS2 Sanyo Kasei Co., Ltd.) 0.3g, water 10g, styrene (St) 5g, methinoremethacrylate (MMA) 15g, 2-ethylenohexylatari 45.3 g of an emulsion consisting of 5 g of rate (2EHA), 5 g of butyl acrylate (BA), and 5 g of butyl metatalylate (BMA) was added dropwise over 2 hours using a dropping funnel, together with 69% Iodine Peroxide Aqueous Solution (Perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) Oxidizing agent prepared by dissolving 0.13 g in 4 g of water and thiourea dioxide (Techlite Asahi Denka Kogyo Co., Ltd.) 0.05 g in 7 g of water The dissolved reducing agent was dropped from the dropping funnel over 2 hours, and after completion of
  • a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 85.7 g of aqueous urethane resin (A-11) and 79. lg of water, and the temperature was raised to 70 ° C. The system was thoroughly replaced with nitrogen.
  • HMMA methyl methacrylate
  • 2EHA 2-ethylhexyl ateryl
  • SZ-6030 methacryloxyprovir trimethoxysilane
  • a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 85.7 g of water-based reactive urethane (A-II) and 61. lg of water, and the temperature was raised to 70 ° C. The system was thoroughly replaced with nitrogen.
  • A-II water-based reactive urethane
  • reactive nonionic anionic surfactant (AQUALON KH1025 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5g, water 18g, methylmetatalylate (MMA) 46.2g, 2-ethylhexyl acrylate (2EHA) 28.3 g of an emulsion composed of 23.3 g and methacryloxypropylmethyldimethoxysilane (Y-9910, manufactured by Toray Dow Coung Silicone Co., Ltd.) was added dropwise over 2 hours using a dropping funnel. In addition, 69% butyl hydride peroxide aqueous solution (Perbutyl H69, manufactured by Nippon Oil & Fats Co., Ltd.) 0.
  • anionic surfactant manufactured by PELEX OTP Kao Co., Ltd.
  • 0.2 g water 10 g
  • methyl metatalylate (MMA) 26.2 g
  • methacrylate Roxypropinoremethinoresinmethoxysilane Y-9910, Toray Dow Corning Silicone Co., Ltd.
  • 4 ⁇ 2 g of an emulsion consisting of 0 ⁇ 2 g was added dropwise over 2 hours using a dropping funnel.
  • a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 100 g of aqueous urethane resin (AV) and 17.8 g of water. Was sufficiently substituted with nitrogen.
  • AV aqueous urethane resin
  • reactive nonionic anionic surfactant (AQUALON KH1025, Daiichi Kogyo Seiyaku Co., Ltd.) 0.5g, water 10g, styrene (St) 5g, methyl methacrylate ⁇ ) 6 ⁇ lg, 2-ethylhexyl talylate (2EHA) 18.6g, Butylmethalylate (BMA) 5g, Methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Toray Dawco Ibushiri Silicone Co., Ltd.) 0.3g of emulsion 45.5g was added dropwise. It was dripped in a funnel over 2 hours.
  • a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 57. lg of aqueous urethane resin (A-1) and 63.9 g of water, and the temperature was raised to 70 ° C. The system was thoroughly replaced with nitrogen.
  • ayu-reactive surfactant (Eleminol JS2 manufactured by Sanyo Kasei Co., Ltd.) 0 ⁇ 7g, water 2 ⁇ 9g, methinoremethacrylate MMA (MMA) 50g, 2-tuccinorehexinole creire (2EHA) 29.5 g, Methacryloxyprovir trimethoxysilane (SZ-6030, Toray Dow Coung Silicone Co., Ltd.) 0 ⁇ 5 g of emulsified solution 103 ⁇ 6 g was added dropwise over 2 hours using a dropping funnel. did.
  • aqueous resin emulsion having a solid content of 39% was obtained in the same manner as in Example 1 except that the aqueous urethane resin ( ⁇ ⁇ ⁇ ⁇ '-VI) was used.
  • aqueous resin emulsion having a solid content of 39% was obtained in the same manner as in Example 2 except that the aqueous urethane resin ( ⁇ ⁇ ⁇ ⁇ '-VI) was used.
  • aqueous resin emulsion having a solid content of 40% was obtained in the same manner as in Example 8, except that the aqueous urethane resin ( ⁇ '-VII) was used.
  • anionic reactive surfactant (Eleminol JS2 manufactured by Sanyo Kasei Co., Ltd.) 2.5g, water 30g, styrene (St) 40g, methinomethacrylate (MMA) 24.3g, 2-ethylhexyl
  • An emulsion 132.5 g) consisting of 35 g of attalylate (2EHA) and 0.7 g of methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Toray Dow Cowing Silicone Co., Ltd.) was added dropwise over 2 hours using a dropping funnel.
  • aqueous acrylic resin emulsion obtained in Comparative Example 5 and the aqueous urethane resin (AI) were mixed at a ratio of 4 to 6 to obtain an aqueous resin emulsion having a solid content of 37%.
  • aqueous acrylic resin emulsion obtained in Comparative Example 5 and the aqueous urethane resin ( ⁇ ′-VI) were mixed at a ratio of 6: 4 to obtain an aqueous resin emulsion having a solid content of 37%.
  • aqueous resin emulsions obtained for the above use are summarized in Tables 3-6.
  • the methods for measuring solid content, viscosity, ⁇ and the like are as described above.
  • the glass transition temperature (Tg) of the acrylic resin part described in Tables 3 to 6 was obtained by calculation using the following Fox formula.
  • the Tg values of homopolymers of each monomer used to calculate Tg are shown in parentheses.
  • the Tg calculated excluding these is the glass transition temperature of the acrylic resin.
  • Tgn Tg of each monomer's homopolymer (absolute temperature)]
  • St Styrene (105 ° C)
  • MMA Methyl methacrylate (105 ° C)
  • the resin dispersion was applied onto a glass plate using a 5 mil (125 m) applicator and dried at 105 ° C. for 5 minutes.
  • the obtained films were left at room temperature for 1 hour, then immersed in toluene or acetone for 24 hours, and the state of each film was visually observed.
  • the resin dispersion was applied onto a glass plate using a 5 mil (125 m) applicator and dried at 105 ° C. for 5 minutes.
  • L0 color difference meter and L value
  • the obtained film is immersed in warm water of 40 ° C, and after 24 hours, the glass plate is taken out immediately, wiped off moisture, and within 1 minute after taking out the glass plate, the color difference ( L1) was measured.
  • the A L value of water whitening resistance was calculated from the following equation.
  • the resin dispersion was applied to a PET film (Diafoil O300E Mitsui Chemicals Polyester Film) and a glass plate with a 3 mil applicator and dried at 105 ° C for 5 minutes.
  • a peel test was performed with Cellotape (registered trademark) to examine the initial adhesion.
  • immerse in warm water at 40 ° C quickly remove the glass plate after 24 hours, wipe off the moisture, dry for 30 minutes at room temperature, perform a cello tape (registered trademark) test, and adhere after being immersed in warm water. Properties, that is, water-resistant adhesion was examined.
  • Comparative Examples 1 to 7 have insufficient performance balance. In Comparative Example 4, although water whitening resistance is excellent (AL is 5), solvent resistance and adhesion are insufficient. Comparative Examples 1, 2, 3, 5, 6, and 7 all have insufficient water whitening resistance (AL is considerably high).

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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)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine réactive hydrocompatible donnant un film équivalent en termes de brillant, de transparence, de résistance aux solvants et d'adhérence à des films obtenus à partir de résines acryliques hydrocompatibles classiques mais est amélioré en termes de résistance à l'eau, plus particulièrement de résistance à l'opalescence en présence d'eau ; et un procédé de production de la résine. La résine réactive hydrocompatible est obtenue en polymérisant (B) un ou plusieurs monomères insaturés polymérisables en présence (A) d'une résine d'uréthane hydrocompatible ayant (a1) un groupe silyle réactif capable de former une structure réticulée et (a2) un groupe anionique. La résine d'uréthane (A) contient de préférence le groupe silyle réactif (a1) en une quantité de 0,1 à 10 % en poids en termes de quantité de silicium et contient le groupe anionique (a2) en une quantité de 0,01 à 1,1 meq/g. Les monomères (B) comprennent de préférence un (méth)acrylate d'alkyle et un monomère silane polymérisable (C). La résine réactive hydrocompatible peut former un film ayant subi un changement inférieur ou égal à 10 en termes de valeur de la résistance à l'opalescence en présence d'eau (ΔL).
PCT/JP2007/065723 2006-08-11 2007-08-10 Résine réactive hydrocompatible et son procédé de production WO2008018589A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235257A (ja) * 2008-03-27 2009-10-15 Konishi Co Ltd 水性シリル化ウレタン系樹脂組成物
JP2009242515A (ja) * 2008-03-31 2009-10-22 Aica Kogyo Co Ltd 硬化性樹脂およびそれを用いた再はく離型粘着フィルム
JP2014065871A (ja) * 2012-09-27 2014-04-17 Dic Corp 水性樹脂組成物、水性塗料及び該水性塗料で塗装された物品
WO2014115710A1 (fr) * 2013-01-23 2014-07-31 Dic株式会社 Stratifié, réseau conducteur, circuit électrique et procédé de production de stratifié
WO2014142005A1 (fr) * 2013-03-13 2014-09-18 Dic株式会社 Stratifié, motif conducteur, et procédé de fabrication de stratifié
JP2016040360A (ja) * 2014-08-13 2016-03-24 三菱レイヨン株式会社 重合体粒子、重合体分散液、水性被覆材および塗装物

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KR101744980B1 (ko) 2010-12-10 2017-06-08 주식회사 엘지화학 백라이트 유닛용 점착제 조성물, 백라이트 유닛 및 액정표시 장치
JP5869780B2 (ja) * 2011-05-26 2016-02-24 株式会社カネカ 防水工法
JP6544612B2 (ja) * 2016-10-11 2019-07-17 Dic株式会社 水性樹脂組成物、コーティング剤及び物品
JP6754395B2 (ja) * 2018-06-29 2020-09-09 株式会社トウペ 電子基板用水性ポリウレタン塗料組成物および塗装品
WO2022102415A1 (fr) * 2020-11-10 2022-05-19 Dic株式会社 Agent de thermoscellage, stratifié et matériau d'emballage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59138211A (ja) * 1983-01-28 1984-08-08 Toho Chem Ind Co Ltd 水系ポリウレタンアクリル樹脂の製造方法
JPH0680930A (ja) * 1992-08-31 1994-03-22 Kao Corp 水性印刷インキ組成物
JPH09241349A (ja) * 1996-03-13 1997-09-16 Kanebo Nsc Ltd 水系反応性樹脂
JPH11279236A (ja) * 1998-03-30 1999-10-12 Toyo Ink Mfg Co Ltd 水性樹脂および該樹脂を用いたインキ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59138211A (ja) * 1983-01-28 1984-08-08 Toho Chem Ind Co Ltd 水系ポリウレタンアクリル樹脂の製造方法
JPH0680930A (ja) * 1992-08-31 1994-03-22 Kao Corp 水性印刷インキ組成物
JPH09241349A (ja) * 1996-03-13 1997-09-16 Kanebo Nsc Ltd 水系反応性樹脂
JPH11279236A (ja) * 1998-03-30 1999-10-12 Toyo Ink Mfg Co Ltd 水性樹脂および該樹脂を用いたインキ

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235257A (ja) * 2008-03-27 2009-10-15 Konishi Co Ltd 水性シリル化ウレタン系樹脂組成物
JP2009242515A (ja) * 2008-03-31 2009-10-22 Aica Kogyo Co Ltd 硬化性樹脂およびそれを用いた再はく離型粘着フィルム
JP2014065871A (ja) * 2012-09-27 2014-04-17 Dic Corp 水性樹脂組成物、水性塗料及び該水性塗料で塗装された物品
WO2014115710A1 (fr) * 2013-01-23 2014-07-31 Dic株式会社 Stratifié, réseau conducteur, circuit électrique et procédé de production de stratifié
JP5696825B2 (ja) * 2013-01-23 2015-04-08 Dic株式会社 積層体、導電性パターン、電気回路及び積層体の製造方法
US9374895B2 (en) 2013-01-23 2016-06-21 Dic Corporation Laminate, conductive pattern, electrical circuit, and method for producing laminate
WO2014142005A1 (fr) * 2013-03-13 2014-09-18 Dic株式会社 Stratifié, motif conducteur, et procédé de fabrication de stratifié
US9380701B2 (en) 2013-03-13 2016-06-28 Dic Corporation Laminate, conductive pattern, and method for producing laminate
JPWO2014142005A1 (ja) * 2013-03-13 2017-02-16 Dic株式会社 積層体、導電性パターン及び積層体の製造方法
JP2016040360A (ja) * 2014-08-13 2016-03-24 三菱レイヨン株式会社 重合体粒子、重合体分散液、水性被覆材および塗装物

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