CN101511890A - Water-compatible reactive resin and process for producing the same - Google Patents

Water-compatible reactive resin and process for producing the same Download PDF

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Publication number
CN101511890A
CN101511890A CNA2007800331356A CN200780033135A CN101511890A CN 101511890 A CN101511890 A CN 101511890A CN A2007800331356 A CNA2007800331356 A CN A2007800331356A CN 200780033135 A CN200780033135 A CN 200780033135A CN 101511890 A CN101511890 A CN 101511890A
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water
resin
waterborne polyurethane
polyurethane resin
compatible reactive
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樱井哲生
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National Starch and Chemical Investment Holding Corp
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National Starch and Chemical Investment Holding Corp
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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

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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)
  • Paints Or Removers (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A water-compatible reactive resin giving a film which is equal in gloss, transparency, solvent resistance, and adhesion to films obtained from conventional water-compatible acrylic resins but is improved in water resistance, especially resistance to blushing with water; and a process for producing the resin. The water-compatible reactive resin is obtained by polymerizing (B) one or more polymerizable unsaturated monomers in the presence of (A) a water-compatible urethane resin having (a1) a reactive silyl group capable of forming a crosslinked structure and (a2) an anionic group. The urethane resin (A) preferably contains the reactive silyl group (a1) in an amount of 0.1-10 wt.% in terms of silicon amount and contains the anionic group (a2) in an amount of 0.01-1.1 meq/g. The monomers (B) preferably comprise an alkyl (meth)acrylate and a polymerizable silane monomer (C). The water-compatible reactive resin can form a film having a change in the value of resistance to blushing with water (deltaL) of 10 or lower.

Description

Water-compatible reactive resin and manufacture method thereof
Technical field
[0001] the present invention relates to comprise the water-compatible reactive resin and the manufacture method thereof of urethane resin and vinyl base resin (being preferably acrylic resin).Described water-compatible reactive resin preferably uses as the matrix (or base-material) of aqueous coating agent and tackiness agent.
Background technology
[0002] owing to its outstanding weathering resistance and toughness, acrylic resin is used for various coatings applications as the aqueous coating resin traditionally.The water-borne acrylic resin of various forms such as milk sap and microemulsion can easily be made, and have the advantage that forms the film (coating or skin) that shows outstanding weathering resistance, gloss, alkali resistance, the transparency, good solubility-resistence and bonding (or close adhesion) property usually.But, also there is the problem that snappiness, shock resistance and wear resistance are not enough and be very difficult to two kinds of base materials such as polyester and polyolefine are formed adhesion that demonstrates in water-borne acrylic resin.
[0003] except acrylic resin, the examples of resins that is used as coating resin comprises urethane resin.Urethane resin is to showing the well balanced resin of outstanding clinging power as polyester and polyolefinic base material, but it has costliness and demonstrates the insufficient problem of weathering resistance.
[0004] it should be noted that when when providing water-soluble or water dispersible to introduce ion and/or hydrophilic radical, compare the horizontal step-down of the water resisting property of the coating of formation and heat resistanceheat resistant water-based with solvent type polyurethane resin coating to urethane resin.Consider influence to environment, compare with solvent-borne type urethanum based adhesive (or polyurethane binder) with solvent-borne type urethane ester group coating (or polyurethane coating), water urethane base coating and water urethane based adhesive have stronger needs.
[0005] patent document 1 discloses by water-borne coatings and aqueous binder blended urethane resin and milk sap (aqueous solution or aqueous dispersions) thereof.As mentioned above, urethanum milk sap (or urethane milk sap) shows outstanding stability in storage and water resisting property, but when comparing with acrylic resin, its weathering resistance deficiency.And from cost consideration, urethane resin is disadvantageous, and therefore from cost consideration, it is not preferred that water-borne coatings comprises a large amount of urethanum milk sap.
[0006] because to the requirement of coating-forming agent, as high-quality and reduce cost, forward changes as the requirement of variation and high functionality, so thinks, only by using traditional single-material to be difficult to satisfy these requirements.Therefore, various motions are suggested, and wherein use each to have the multiple material of different qualities.
[0007] for example, patent document 2 is open by urethane resin and acrylic resin are mixed with binder composition.But, the urethane resin that obtains and the mixture of acrylic resin be not along with past time has enough stability, and can be separated when forming film.In addition, patent document 3 and patent document 4 are disclosed in the following urethanum-vinyl polymer dispersion liquid that obtains by the letex polymerization of Acrylic Acid Monomer of existence of waterborne polyurethane resin.Disclosed described urethanum-vinyl polymer dispersion liquid does not demonstrate enough water resisting property and good solubility-resistence in patent document 3 and 4, though can form the film with outstanding physical properties.The inventor's result of study discloses, when by will be in patent document 3 and 4 disclosed urethanum-vinyl polymer dispersion liquid when being applied to film that base material obtains and immersing in the water, brighten.Because the generation of brightening, the not talkative film that is obtained by the urethanum described in patent document 3 and 4-vinyl polymer dispersion liquid has enough water resisting property, and thinks that the influence owing to urethane resin reduces as the good solubility-resistence of acrylic resin advantage.
【0008】
Patent document 1: Japanese unexamined patent open (spy opens) 9-241349 number (No. 3618882, Japanese Patent);
Patent document 2: Japanese unexamined patent open (spy opens) 5-117611 number;
Patent document 3: Japanese unexamined patent open (spy opens) 5-132535 number;
Patent document 4: Japanese unexamined patent open (spy opens) 6-80930 number;
The disclosure of invention
The problem that solves
[0009] generation of the present invention is in order to address the above problem, and the purpose of this invention is to provide can the film forming water-compatible reactive resin of shape, and this film demonstrates water resisting property, and high waterproof particularly, even it prevents the generation of brightening substantially in being immersed in water the time; In other words, this film demonstrates the water-proof whitening of raising, keep simultaneously and identical at least gloss, transparency, good solubility-resistence and the tackiness of film that obtains from the traditional water based acrylic resin, and the manufacture method that this water-compatible reactive resin is provided.
Solve the means of described problem
[0010] in order to achieve the above object, the present inventor in depth studies, and unexpectedly find, the water-compatible reactive resin that obtains by polymerization polymerizable unsaturated monomer in the presence of specific waterborne polyurethane resin obtains realizing the film of above-mentioned purpose, and therefore the present invention is accomplished.
[0011] that is to say, according to an aspect of the present invention, provide novel water-compatible reactive (or aqueous) resin.This water-compatible reactive resin is to obtain by polymerization polymerizable unsaturated monomer in the presence of waterborne polyurethane resin (A), wherein, waterborne polyurethane resin (A) has the reactive silyl (a1) (the hydroxyl silyl that reactive silyl comprises hydrolysable silyl group and obtains by the hydrolysis hydrolysable silyl group) and the anionic group (a2) that can form crosslinking structure.
[0012] in an embodiment of the invention, water-compatible reactive resin is provided, wherein waterborne polyurethane resin (A) comprises: can form the reactive silyl (a1) of crosslinking structure, be by weight 0.1% to 10% as " Si " based on the amount of the solids content of waterborne polyurethane resin; And anionic group (a2), its amount based on the solids content of waterborne polyurethane resin is 0.01 to 1.1meq/g.
[0013] in yet another embodiment of the present invention, water-compatible reactive resin is provided, wherein waterborne polyurethane resin (A) is by making organic polyisocyanate component, polyol component, intramolecularly have the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group obtains urethane prepolymer, and chain extension reaction by this urethane prepolymer obtains.
[0014] in another embodiment of the present invention, provide water-compatible reactive resin, wherein waterborne polyurethane resin (A) is from 2/8 to 8/2 with regard to solids content with the weight ratio (A)/(B) of polymerizable unsaturated monomer (B).
[0015] in preferred implementation of the present invention, provide water-compatible reactive resin, wherein polymerizable unsaturated monomer (B) comprises (methyl) alkyl acrylate.
[0016] in another preferred embodiment of the present invention, water-compatible reactive resin is provided, wherein polymerizable unsaturated monomer (B) further comprises polymerizable silane monomer (C).
[0017] in another preferred implementation of the present invention, provide energy shape film forming water-compatible reactive resin, the variation (Δ L) that this film demonstrates the water-proof whitening value is 10 or littler, this value is measured with colorimeter.
In another preferred implementation of the present invention, provide the water-compatible reactive resin that comprises above water-compatible reactive resin composition.
[0018] in another aspect of this invention, provide the method that is used to make above-mentioned water-compatible reactive resin, be included in polymerization polymerizable unsaturated monomer (B) under the existence of waterborne polyurethane resin (A); Wherein, described waterborne polyurethane resin (A) has the reactive silyl (a1) (this silyl (a1) comprises hydrolysable silyl group and the hydroxyl silyl that obtains by this hydrolysable silyl group of hydrolysis) and the anionic group (a2) that can form crosslinking structure.
[0019] in an embodiment of another aspect of the present invention, method is provided, comprise by making organic polyisocyanate component, polyol component, intramolecularly has the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group obtains urethane prepolymer, and with this urethane prepolymer and polymerizable unsaturated monomer (B) mixing, this urethane prepolymer is carried out chain extension reaction then, thereby obtain waterborne polyurethane resin (A), then polymerization polymerizable unsaturated monomer (B).
[0020] in a preferred embodiment of the present invention, method is provided, comprise by making organic polyisocyanate component, polyol component, intramolecularly have the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group obtains urethane prepolymer, and this urethane prepolymer is carried out chain extension reaction, thereby obtain waterborne polyurethane resin (A), then it is mixed with polymerizable unsaturated monomer (B), and this polymerizable unsaturated monomer of polymerization (B).
[0021] of the present invention one preferred aspect, coating-forming agent is provided, it comprises above-mentioned water-compatible reactive resin composition.
In another aspect of the present invention, tackiness agent is provided, it comprises above-mentioned water-compatible reactive resin composition.
[0022] in the present invention, " water-based (water-based) " is meant that resin is present in the state in the aqueous medium, and this is meant that the state and/or the resin of resin dissolves in aqueous medium is not dissolved in state in the aqueous medium.
And, in the present invention, " aqueous medium " is meant the ortho-water as tap water, distilled water or ion exchanged water, and can comprise and starting raw material such as the reactive poor water-soluble or water dispersible organic solvent of resin monomer of the present invention, for example acetone or ethyl acetate, and also can comprise water-soluble or water dispersible monomer, oligopolymer, prepolymer and/or resin.Described aqueous medium can comprise emulsifying agent, polymerisable emulsifier, initiators for polymerization, chain extension agent and/or the multiple additive that uses in be everlasting water-base resin or water soluble resin are made.
Effect of the present invention
[0023] water-compatible reactive resin of the present invention is to obtain by polymerization polymerizable unsaturated monomer (B) in the presence of waterborne polyurethane resin (A), and this waterborne polyurethane resin (A) has the reactive silyl (a1) and the anionic group (a2) that can form crosslinking structure.Therefore, the water-compatible reactive resin that can form such film can be provided, this film demonstrates water resisting property, and high waterproof particularly, even it prevents from the generation of brightening from other words, to demonstrate the water-proof whitening of raising substantially in being immersed in water the time, keep simultaneously and identical at least gloss, transparency, good solubility-resistence and the tackiness of film that obtains from the traditional water based acrylic resin, and the manufacture method that this water-compatible reactive resin is provided.
[0024] about water-compatible reactive resin of the present invention, when waterborne polyurethane resin (A) comprises the reactive silyl (a1) that can form crosslinking structure, it is by weight 0.1% to 10% as " Si " based on the amount of the solids content of waterborne polyurethane resin; And anionic group (a2), when its amount based on the solids content of waterborne polyurethane resin was 0.01 to 1.1meq/g, water resisting property and good solubility-resistence further were enhanced.
[0025] about water-compatible reactive resin of the present invention, when by making organic polyisocyanate component, polyol component, intramolecularly have the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group, to obtain urethane prepolymer, and the chain extension reaction by this urethane prepolymer is when obtaining waterborne polyurethane resin (A), and water resisting property and good solubility-resistence further are enhanced.
[0026] about water-compatible reactive resin of the present invention, when the weight ratio (A)/(B) of waterborne polyurethane resin (A) and polymerizable unsaturated monomer (B) was from 2/8 to 8/2 with regard to solids content, the water resisting property of film, good solubility-resistence, the transparency and water-proof whitening were further improved.
[0027] about water-compatible reactive resin of the present invention, when polymerizable unsaturated monomer (B) comprised (methyl) alkyl acrylate, water resisting property, good solubility-resistence and water-proof whitening were further improved.
[0028] about water-compatible reactive resin of the present invention, when polymerizable unsaturated monomer (B) further comprised polymerizable silane monomer (C), good solubility-resistence was further improved.
[0029] about water-compatible reactive resin of the present invention, the variation (Δ L) that demonstrates the water-proof whitening value when formation is 10 or during the film of littler (this value is measured by using colorimeter), has formed finer and close film.
And because water-compatible reactive resin composition of the present invention comprises above-mentioned water-compatible reactive resin, therefore the film that obtains can demonstrate water resisting property, particularly high waterproof, prevents the generation of brightening when it is immersed in the water substantially; In other words, demonstrate the water-proof whitening of raising, keep simultaneously and identical at least gloss, transparency, good solubility-resistence and the tackiness of film that obtains from the traditional water based acrylic resin.
[0030] because the method for manufacturing water-compatible reactive resin of the present invention is such method, it is included in polymerization polymerizable unsaturated monomer (B) under the existence of waterborne polyurethane resin (A), wherein, waterborne polyurethane resin (A) has the reactive silyl (a1) and the anion-radicals (a2) that can form crosslinking structure, so can be provided for the method for such manufacturing water-compatible reactive resin, wherein the film that obtains from water-compatible reactive resin can demonstrate water resisting property, particularly high waterproof prevents the generation of brightening substantially when it is immersed in the water; In other words, demonstrate the water-proof whitening of raising, keep simultaneously and identical at least gloss, transparency, good solubility-resistence and the tackiness of film that obtains from the traditional water based acrylic resin.
[0031] about method of the present invention, when comprising, method makes organic polyisocyanate component, polyol component, intramolecularly has the compound of at least one active hydrogen and anionic group, has the compound reaction of at least one active hydrogen and hydrolysable silyl group to obtain urethane prepolymer with intramolecularly, and with this urethane prepolymer and polymerizable unsaturated monomer (B) mixing, carry out the chain extension reaction of urethane prepolymer then, thereby obtain waterborne polyurethane resin (A), and when making polymerizable unsaturated monomer (B) polymerization then, the water resisting property of film, the good solubility-resistence and the transparency and water-proof whitening are further improved.
[0032] about method of the present invention, when comprising, method makes organic polyisocyanate component, polyol component, intramolecularly has the compound of at least one active hydrogen and anionic group, has the compound reaction of at least one active hydrogen and hydrolysable silyl group to obtain urethane prepolymer with intramolecularly, and carry out the chain extension reaction of urethane prepolymer, thereby obtain waterborne polyurethane resin (A), and mix with polymerizable unsaturated monomer (B) then, and during polymerization polymerizable unsaturated monomer (B), the water resisting property of film, the good solubility-resistence and the transparency and water-proof whitening are further improved.
Therefore [0033] because coating-forming agent of the present invention comprises above-mentioned water-compatible reactive resin composition, the film that obtains can demonstrate water resisting property, particularly high waterproof, even it prevents the generation of brightening when being immersed in the water substantially; In other words, demonstrate the water-proof whitening of raising, keep simultaneously and identical at least gloss, transparency, good solubility-resistence and the tackiness of coating-forming agent that obtains from the traditional water based acrylic resin.
[0034] because tackiness agent of the present invention comprises above-mentioned water-compatible reactive resin composition, and the film of acquisition can demonstrate water resisting property, particularly high waterproof, even it prevents the generation of brightening when being immersed in the water substantially; In other words, demonstrate the water-proof whitening of raising, keep simultaneously and identical at least gloss, transparency, good solubility-resistence and the tackiness of tackiness agent that obtains from the traditional water based acrylic resin.
Embodiments of the present invention
[0035] water-compatible reactive resin of the present invention is to obtain by polymerization polymerizable unsaturated monomer (B) in the presence of waterborne polyurethane resin (A), and should " waterborne polyurethane resin (A) " have " the reactive silyl (a1) that can form crosslinking structure " and " anionic group (a2) ".
[0036] described " waterborne polyurethane resin (A) " of the present invention do not limited especially, as long as it has " the reactive silyl (a1) that can form crosslinking structure " and " anionic group (a2) ", and can obtain targeted activity water-base resin of the present invention.
Described " can form the reactive silyl of crosslinking structure " comprises hydrolysable silyl group and passes through the hydroxyl silyl of the hydrolysis acquisition of hydrolysable silyl group.
Described as used herein " hydrolysable silyl group " is meant siliceous functional group, it is hydrolyzed the hydroxyl (Si-OH) that generation links to each other with silicon, and the example comprises: alkoxysilyl, and as trimethoxysilyl, triethoxysilyl, dimethoxy-methyl silyl, diethoxymethyl silyl, diethoxy silyl, monosubstituted ethoxy silyl and mono methoxy silyl.Among these groups, trimethoxysilyl, triethoxysilyl, dimethoxy silyl and diethoxy silyl are particularly preferred.
[0037] more specifically, described " hydrolysable silyl group " is the functional group of formula (I) representative:
-Si(X) a(Y) 3-a
Y representative-OCH wherein 3Or-OC 2H 5Or-O (CH 2) n-O (CH 2) p-H (wherein, n and p represent 1 to 3 integer),
X representative-O (CH 2) q-H (wherein, q represents 0 to 3 integer), and
A represents 0 to 2 integer.
[0038] as used herein, described " hydroxyl silyl " representative-Si-(OH) 3,-Si (X)-(OH) 2Or-Si (X) 2-(OH).X is-O (CH 2) q-H (wherein q represents 0 to 3 integer) or H.
It is believed that the hydroxyl silyl that produces by the hydrolysable silyl group hydrolysis interconnects, thereby form siloxane bond, and therefore form crosslinking structure.
[0039] waterborne polyurethane resin preferably comprises hydrolysable silyl group, it is by weight 0.1% to 10% as " Si " based on the amount of the solids content of waterborne polyurethane resin, more preferably by weight 0.1% to 1.0%, be preferably by weight 0.15% to 0.60% especially.
Hydrolysable silyl group can be independent or two or more combination.
[0040] as used in this, " anionic group " be meant functional group with negative charge (for example-COO -With-SO 3 -), negative charge by the functional group of counter cation charge neutrality (for example-COO -Na +With-SO 3 -K +Thereby) and in water, can emit hydrogen ion form the functional group with negative charge functional group (for example-COOH and-SO 3H).Self-evident, by ambient state such as the pH that changes each functional group, these functional groups transform easily mutually.About " anionic group " of the present invention, according to the characteristic of waterborne polyurethane resin, these functional groups can use separately, or in them two or more can be used in combination.
[0041] example of " functional group with negative charge " and " negative charge is by the functional group of counter cation charge neutrality " comprises carboxylate groups (COO -With-COOM 1), sulfonate groups (SO 3 -With-SO 3M 2) and phosphate group (PO 4H ,-PO 4 2With-PO 4M 3M 4), [M wherein 1, M 2, M 3And M 4Represent basic metal, alkaline-earth metal or ammonium (M 3And M 4Any one can be hydrogen and ammonium, ammonium is except so-called ammonium NH 4 +Outside, also comprise ammonium such as triethylamine based on organic amine)].
And described " thereby can emit the functional group that hydrogen ion forms the functional group with negative charge in water " comprise, for example, and carboxyl (COOH), sulfonic group (or sulfo group) (SO 3H) and phosphate (PO 4H 2).
[0042] anionic group is preferably by alkali neutral carboxyl.More specifically, it is preferably carboxylate groups (COO -M +), wherein carboxyl (COOH) neutralized by alkali, maybe can be carboxyl with by the combination of alkali neutral carboxylate groups.
[0043] waterborne polyurethane resin, based on the solids content of waterborne polyurethane resin, the amount that preferably comprises anionic group is 0.01 to 1.1meq/g, and more preferably 0.044 to 1.1meq/g, be preferably 0.1 especially to 0.8meq/g, and most preferably be 0.2 to 0.6meq/g.
[0044] described " meq/g " is meant the mmole number of the waterborne polyurethane resin solids content of each gram.When the amount of anionic group was less than 0.01meq/g, the particle diameter of waterborne polyurethane resin (A) can increase, and can obtain very unsettled dispersion liquid, so the waterborne polyurethane resin of gained may be insufficient.On the contrary, when the amount of anionic group during more than 1.1meq/g, because the wetting ability of waterborne polyurethane resin excessively increases, the problem that the water resisting property that the film that for example will form may take place reduces and the viscosity of resin aqueous solution (dispersion liquid) increases.
[0045] specific waterborne polyurethane resin of the present invention (A) can be by making " organic polyisocyanate component ", " polyol component ", " intramolecularly has the compound of at least one active hydrogen and anionic group " and " intramolecularly has the compound of at least one active hydrogen and hydrolysable silyl group " reaction obtaining urethane prepolymer, and obtain by the chain extension reaction of this urethane prepolymer.
[0046] under the preferable case, by " organic polyisocyanate component ", " polyol component " and " intramolecularly has the compound of at least one active hydrogen and anionic group " are reacted under the state of excessive NCO group, and make the part or all of NCO group and " intramolecularly has the compound of at least one active hydrogen and hydrolysable silyl group " reaction of the urethane prepolymer that obtains then, obtain " urethane prepolymer " with terminal NCO group.
Under the preferable case, the chain extension reaction of " urethane prepolymer " that obtains is by dissolving in the aqueous solution that can comprise basic cpd or disperses to carry out.If desired, also can use the chain extension agent that comprises the low molecular compound that has at least two active hydrogens in the molecule.
[0047] when urethane prepolymer in the presence of residual NCO group, do not use the chain extension agent, when being dispersed or dissolved in the water, water can be used as the chain extension agent.Urethane prepolymer can have carboxyl (COOH), and this carboxyl (COOH) be converted into negatively charged ion (COO by alkaline matter -).Therefore, even be converted into when having high-molecular weight urethane by chain extension when prepolymer, the urethane that obtains is dispersed in the water easily.
[0048] will be used in described " organic polyisocyanate component " in the preparation of waterborne polyurethane resin (A), can be often to be used in the manufacturing of urethane resin those, and do not limited especially, as long as can obtain targeted activity water-base resin of the present invention.Its specific examples comprises aliphatic diisocyanate, as two isocyanic acid ethyls, 2,2,4-trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate; Alicyclic diisocyanate, as hydrogenation 4,4 '-diphenylmethanediisocyanate, 1,4-cyclohexyl diisocyanate, methyl cyclohexylidene vulcabond and isophorone diisocyanate; And aromatic diisocyanate as 4,4 '-diphenylmethanediisocyanate, xylylene diisocyanate, toluene-2,4-diisocyanate and naphthalene diisocyanate ester.When fading during the application that must be considered of being used for passing by in time, among these vulcabond, aliphatics and/or alicyclic diisocyanate preferably are used alone or in combination.Consider cost, it especially preferably uses hexamethylene diisocyanate and/or isophorone diisocyanate.
Described " polyol component " that [0049] will be used in the manufacturing of waterborne polyurethane resin (A) can be the component of often using in the manufacturing of urethane resin, and not be specially limited, as long as can obtain targeted activity water-base resin of the present invention.Examples of polyhydric alcohols comprises polyester polyol, polyether glycol and polycarbonate polyol.The example of polyester polyol comprises those that obtain by one or more dicarboxylic acid and one or more polyvalent alcohol polycondensations, dicarboxylic acid such as succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, nonane diacid, toxilic acid, fumaric acid, phthalic acid and terephthalic acid, polyvalent alcohol such as ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,6-hexylene glycol, neopentyl alcohol, 1,8-ethohexadiol, decamethylene-glycol, glycol ether and TriMethylolPropane(TMP); And the ring-opening polymerization by lactone obtain those.Except the polynary alcohol and water that will be used to synthetic above-mentioned polyester polyol, described polyether glycol comprises the material by cyclic ethers and phenol such as dihydroxyphenyl propane or primary amine or the acquisition of secondary amine ring opening polyaddition, this cyclic ethers such as oxyethylene, propylene oxide, trimethylene oxide or tetrahydrofuran (THF).The example of polyether glycol comprises, at least a ring opening polyaddition by propylene oxide or oxyethane arrives polyoxyethylene polyols, polyoxypropylene polyol, polyoxy tetramethylene polyvalent alcohol and the formed material of dihydroxyphenyl propane (in the situation of multipolymer, can use segmented copolymer or random copolymers).The example of polycarbonate polyol comprises polymerized thylene carbonate butyl ester polyvalent alcohol, the own ester polyol of polymerized thylene carbonate and poly-(3-methyl isophthalic acid, 5-pentylidene) carbonate polyol.
As polyvalent alcohol, polybutadiene polyol, polyisoprene polyvalent alcohol, polyolefin polyhydric alcohol and polyacrylic ester polylol also can be used alone or in combination.
Described " intramolecularly has the compound of at least one active hydrogen and anionic group " of [0050] using in the manufacturing of waterborne polyurethane resin (A) specifically do not limited, as long as its be intramolecularly have comprise at least one active hydrogen functional group (for example, hydroxyl, amino and sulfydryl) and the compound of above-mentioned anionic group, and can obtain targeted activity water-base resin of the present invention.This examples for compounds comprises dimethylol propionic acid, dimethylolpropionic acid, comprises the polycaprolactone glycol of carboxyl, comprises sulfonic polyester polyols pure and mild two (beta-hydroxyethyl) isophthalic acid-5-sulfonic acid.The tint permanence of the film that forms from the stability of the water-compatible reactive resin aqueous solution that obtains or dispersion liquid and from water-compatible reactive resin is considered, having carboxyl (COOH) is preferred as the compound of anionic group, and dimethylol propionic acid, dimethylolpropionic acid and the polycaprolactone glycol that comprises carboxyl are preferred.
[0051] described " compound with at least one active hydrogen and anionic group " so used usually, feasible solids content based on urethane resin, the amount of the anionic group that waterborne polyurethane resin comprises be 0.01meq/g or more (for example, under the situation of COOH, based on the solids content of 100g urethane resin, waterborne polyurethane resin comprises the COOH amount of 45mg).When traditional polyvalent alcohol based on polyester and polyethers is used as normally used polyol component, solids content based on the 100g waterborne polyurethane resin, the amount that waterborne polyurethane resin preferably comprises 0.044meq/g or more anionic group (for example, under the situation of carboxyl, the amount that waterborne polyurethane resin comprises COOH is 200mg).When the amount of the anionic group in the solids content of waterborne polyurethane resin is less than 0.01meq/g, the particle diameter of waterborne polyurethane resin (A) can increase and can obtain unstable dispersion liquid, and therefore the waterborne polyurethane resin that obtains may be not satisfied.On the contrary, when the amount of anionic group was big with respect to the solids content of waterborne polyurethane resin, the particle diameter of waterborne polyurethane resin (A) reduced, and therefore dry property, gloss and the transparency are enhanced.The water resisting property of the film that but, obtains and good solubility-resistence may reduce.When the amount of anionic group during more than 1.1meq/g, the wetting ability of waterborne polyurethane resin excessively increases, thereby causes water resisting property as film to reduce and the problem of resin aqueous solution (dispersion liquid) viscosity increase.
[0052] as used herein, the particle diameter of waterborne polyurethane resin (A) is by the dynamic light scattering method, uses by Otsuka Electronics Co., Ltd. " PARIII " of Sheng Chaning (LASER PARTICLE ANALYZER) measures, and uses semi-invariant method (cumlantmethod) to resolve and be defined as average particulate diameter.The particle diameter of described waterborne polyurethane resin (A) (in other words, average particulate diameter) is preferably from 50 to 200nm, more preferably from 50 to 150nm, and is preferably from 50 to 120nm especially.
[0053] amount of anionic group is definite by considering with the hydrophilic balance of polyol component.When polyoxyethylene glycol was used as polyvalent alcohol, the amount of functional group must be set in a small amount, because the possess hydrophilic property of polyoxyethylene glycol own.But, when using hydrophobic compound as polyvalent alcohol, the amount of functional group must be set in a large number.
[0054] described " compound that has at least one active hydrogen and hydrolysable silyl group in molecule " of the present invention is not specially limited, have at least one and comprise the functional group of active hydrogen and the compound of hydrolysable silyl group as long as it is an intramolecularly, and can obtain the targeted activity water-base resin.The example of described " functional group that comprises active hydrogen " comprises hydroxyl, amino and sulfydryl.Described " hydrolysable silyl group " comprises above-mentioned hydrolysable silyl group, and is preferably alkoxysilyl, maybe can be monoalkoxy silyl, dialkoxy silyl or trialkoxysilyl.The example of alkoxysilyl comprises methoxy methyl silylation and (ethoxymethyl) silylation.
[0055] " intramolecularly has the compound of at least one active hydrogen and hydrolysable silyl group " comprises gamma-amino propyl group trimethoxy silane, γ-sulfydryl propyl group trimethoxy silane, γ-sulfydryl propyl group methyl dimethoxysilane, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group methyldiethoxysilane, N-β-(aminoethyl) gamma-amino propyl trimethoxy silicane, N-β-(aminoethyl) gamma-amino propyl group methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan and N-phenyl-gamma-amino propyl trimethoxy silicane.
In the present invention, these compounds can be used alone, or two or more uses that can be combined in them.In these compounds, the compound with trialkoxysilyl is preferred, and gamma-amino propyl trimethoxy silicane such as amino-trialkoxy silane are particularly preferred.
[0056] " intramolecularly has the compound of at least one active hydrogen and hydrolysable silyl group " is used as such usually, so that the hydrolysable silyl group that comprises of waterborne polyurethane resin is 10mg (by weight 0.01%) or more as " Si " based on the amount of the solids content of 100g waterborne polyurethane resin.In order to give full play to the effect of crosslinking structure, this compound preferably is used as such, so that the hydrolysable silyl group that comprises of waterborne polyurethane resin is 200mg (by weight 0.2%) or more as " Si " based on the amount of the solids content of 100g waterborne polyurethane resin.When the amount of hydrolysable silyl group was less than 10mg as " Si " based on the amount of the solids content of 100g waterborne polyurethane resin, cross-linking density may reduce and may bring into play inadequate effect usually.On the contrary, when the amount of hydrolysable silyl group as " Si " based on the amount of the solids content of waterborne polyurethane resin more than by weight 10% the time, the cross-linking density in the film may excessively increase and coating may become fragile.Hydrolysable silyl group is preferably alkoxysilyl, is comprised in the waterborne polyurethane resin (A), and generates the hydroxyl silyl with the water reaction usually in aqueous medium.
[0057] in the manufacturing of waterborne polyurethane resin (A), chosen wantonly the chain extension agent of using, comprise " low molecular compound that intramolecularly has at least two active hydrogens ", be not specially limited, as long as it is to comprise the chain extension agent that intramolecularly has the compound of at least two functional groups that comprise active hydrogen, and can obtain targeted activity water-base resin of the present invention.The example of " intramolecularly has the low molecular compound of at least two active hydrogens " comprises, low-molecular-weight diol is as ethylene glycol, propylene glycol, 1,4-butyleneglycol and TriMethylolPropane(TMP); Amine such as quadrol, propylene diamine, butanediamine, hexanediamine, 2,2,4-trimethylammonium hexanediamine, isophorone diamine, dicyclohexyl methyl hydride-4,4 '-diamines, diamino dipropyl amine, diamino diethylamine and piperazine; And diethanolamine, hydrazine and derivative thereof.Because chain extension reaction normally carries out after urethane prepolymer is dispersed in the water, use to have the compound of hyperergy such as amine and hydrazine with isocyanic ester and can in these compounds, effectively carry out chain extension reaction.More specifically, Uricida can more preferably be used.
[0058] as " basic cpd ", for example, triethylamine, trolamine, ammoniacal liquor, sodium hydroxide and potassium hydroxide can be used.Under the preferable case, for the pH that adjusts the urethane resin aqueous solution that obtains or urethane resin dispersion liquid within from 6 to 10 scope, determine the amount of basic cpd.When pH less than 6 the time, the urethane resin aqueous solution or the urethane resin dispersion liquid stability that may become is not enough.On the contrary, when pH greater than 10 the time, the urethane resin aqueous solution or urethane resin dispersion stability excellence.But, this urethane resin may be hydrolyzed, and enters the side chain of urethane resin or terminal hydrolysable silyl group may react to each other in aqueous medium, and therefore problems of stability in storage may take place.
[0059] in the arbitrary steps of the method for manufacturing waterborne polyurethane resin of the present invention (A), various stablizers such as the antioxidant and the UV absorption agent of interpolation in conventional urethane resin synthetic, and be used for improving waterborne polyurethane resin and can be randomly added at the various tensio-active agents of the stability of aqueous solvent.And, when using waterborne polyurethane resin to make film, the use that can be combined of linking agent such as water-soluble isocyanic ester, water-soluble epoxy resin, '-aziridino compound He oxazoline compound.
[0060] in aforesaid method, waterborne polyurethane resin (A) can obtain with the form that is present in the composition in the aqueous medium.Just, it can obtain (for example, the urethane resin aqueous solution, dispersion liquid, suspension or milk sap etc.) with the form of aqueous urethane resin composition.Usually, described waterborne polyurethane resin (A), is used in the polymerization of following polymerizable unsaturated monomer (B) after randomly being adjusted to required solids content, viscosity, pH etc. to be included in the form of the composition in the aqueous medium.
[0061] solids content of aqueous urethane resin composition of the present invention is preferably by weight from 25% to 50%, and more preferably by weight from 30% to 45%, and be preferably by weight from 30% to 40% especially.As used herein, solids content is meant, in baking oven 105 ℃ down heating after 3 hours composition weight based on heating before the percentage ratio of composition weight.
The viscosity of aqueous urethane resin composition of the present invention is preferably from 10 to 500mPas, more preferably from 10 to 200mPas, and is preferably from 10 to 100mPas especially.As used herein, viscosity is meant the value by using the BM viscometer, using rotor to measure for 1 to No. 3 under 30 ℃ and 60rpm.
The pH of aqueous urethane resin composition of the present invention is preferably from 6.5 to 8.5, and more preferably from 7 to 8.5, and be preferably from 7 to 8 especially.As used herein, pH is meant the value of using pH meter to measure.
The particle diameter of aqueous urethane resin composition of the present invention is preferably from 50 to 200nm, more preferably from 50 to 150nm, and is preferably from 50 to 120nm especially.As used herein, as mentioned above, particle diameter is measured by the dynamic light scattering method, and by using the semi-invariant method to resolve, is determined as the average particulate diameter of milk sap.
[0062] targeted activity water-base resin of the present invention can be produced by polymerization polymerizable unsaturated monomer (B) under the existence of the waterborne polyurethane resin (A) that obtains in the above.
In the present invention, " polymerizable unsaturated monomer (B) " is not specially limited, and can obtain as long as it is monomer and the targeted activity water-base resin of the present invention with the two keys of alkene.Described " the two keys of alkene " are meant the two keys of free redical polymerization between carbon atom.Example with functional group of the two keys of such alkene comprises vinyl (CH 2=CH-), (methyl) allyl group (CH 2=CH-CH 2-and CH 2=C (CH 3)-CH 2-), (methyl) acryloxy (CH 2=CH-COO-and CH 2=C (CH 3)-COO-) and-COO-CH=CH-COO-.Its specific examples comprises vinylbenzene and its derivative, carboxylic acid and its ester.
Carboxylic acid is meant and has carboxyl (acid COOH), and carboxylicesters is meant the ester of carboxylic acid.Carboxylic acid comprises saturated carboxylic acid and unsaturated carboxylic acid.The example of saturated carboxylic acid comprises paraffinic acid, and the example of unsaturated carboxylic acid comprises (methyl) vinylformic acid, phthalic acid, toxilic acid, phthalate anhydride and maleic anhydride.
The specific examples of " paraffinic acid " comprises, formic acid, acetate, propionic acid, butyric acid, isopropylformic acid and 2-chloro pentane acid." alkanoates " is meant the ester of paraffinic acid, and the specific examples of polymerizable unsaturated monomer (B) comprises vinyl acetate, ethylene-vinyl acetate, propionate and vinyl acetate.
[0063] described " (methyl) vinylformic acid " be meant vinylformic acid and methacrylic acid the two, and comprise vinylformic acid, methacrylic acid, and the composition of vinylformic acid and methacrylic acid.
Described " (methyl) acrylate ((meth) acrylic acid)) " be meant (methyl) acrylic acid ester, in other words, (methyl) acrylate ((meth) acrylate).Described (methyl) acrylate be meant acrylate and methacrylic ester the two, and comprise acrylate, methacrylic ester, and the composition of acrylate and methacrylic ester.
[0064] specific examples of (methyl) acrylate comprises (methyl) alkyl acrylate, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) Octyl acrylate, (methyl) decyl acrylate, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid octadecane ester, (methyl) vinylformic acid Shan Yu ester and (methyl) vinylformic acid docosane ester; And (methyl) vinylformic acid hydroxyl alkane ester, as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxyl butyl ester and (methyl) vinylformic acid 2-hydroxy propyl ester.These (methyl) acrylate can be used alone or two or more the be combined uses in them.Described polymerizable unsaturated monomer (B) is preferably (methyl) alkyl acrylate.More specifically, (methyl) methyl acrylate, (methyl) butyl acrylate and (methyl) 2-EHA are particularly preferred in the present invention.
[0065] example of " vinylbenzene and its derivative " comprises vinylbenzene, vinyl toluene and dimethyl styrene.In these compounds, vinylbenzene is preferred.
Described polymerizable unsaturated monomer (B) preferably be selected from (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA and cinnamic at least one.
[0066] in water-compatible reactive resin of the present invention, the weight ratio (A)/(B) of waterborne polyurethane resin (A) and polymerizable unsaturated monomer (B) is with regard to solids content preferably from 2/8 to 8/2.Consider the balance of the performance of the water-compatible reactive resin that obtains, weight ratio (A)/(B) is preferably from 3/7 to 6/4 especially.When the weight ratio (A)/(B) of waterborne polyurethane resin (A) is greater than 8/2 the time, becoming as the gloss of the advantage of the resin part that obtains from polymerizable unsaturated monomer (B) and the transparency is difficult to keep, and neither be preferred on cost.On the contrary, when the weight ratio (A)/(B) of waterborne polyurethane resin (A) is less than 2/8 the time, may reduce as advantage and tackiness base material of waterborne polyurethane resin (A).
[0067] when polymerizable unsaturated monomer (B) in the presence of waterborne polyurethane resin (A) during polymerization, under the preferable case, polymerizable unsaturated monomer (B) further comprises polymerizable silane monomer (C).Just, water-compatible reactive resin preferably has the silyl from polymerizable silane monomer (C).By polymerization polymerizable silane monomer (C), the water-proof whitening of the film that obtains from the water-compatible reactive resin that obtains is enhanced, and the tackiness of base material is also improved.
[0068] polymerizable silane monomer (C) is not specially limited, as long as it is the compound with the two keys of alkene and at least one alkoxyl group, and can obtain targeted activity water-base resin of the present invention.The example comprises, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyl methyldiethoxysilane, vinyl methyl dipropoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl triethoxyl silane, gamma-methyl allyl acyloxypropyl tripropoxy silane, gamma-methyl allyl acyloxypropyl methyl dimethoxysilane and gamma-methyl allyl acyloxypropyl three (isopropoxy) silane.These polymerizable silane monomers can be used alone, or in them two or more can be used in combination.Organoalkoxysilane with the two keys of alkene is preferably dialkoxy silicane with the two keys of alkene or the trialkoxy silane with the two keys of alkene, more preferably have the trialkoxy silane of the two keys of alkene, and be preferably gamma-methyl allyl acyloxypropyl methyl dimethoxysilane or gamma-methyl allyl acyloxypropyl trimethoxysilane especially.This polymerizable silane monomer (C) can be identical with " intramolecularly has the compound of at least one active hydrogen and hydrolysable silyl group " that be used to make waterborne polyurethane resin (A).
[0069] polymerization of polymerizable unsaturated monomer (B) comprises following embodiment in the present invention:
The urethane prepolymer of waterborne polyurethane resin (A) and polymerizable unsaturated monomer (B) are mixed, and this urethane prepolymer is carried out chain extension reaction, thereby obtain waterborne polyurethane resin (A), and the embodiment of this polymerizable unsaturated monomer of polymerization (B) then; And
Urethane prepolymer is carried out chain extension reaction, thereby obtains waterborne polyurethane resin (A), mixes polymerizable unsaturated monomer (B) then, and the embodiment of this polymerizable unsaturated monomer of polymerization (B).
[0070] in these two kinds of embodiments, when urethane prepolymer was carried out chain extension reaction, as mentioned above, this chain extension reaction can be undertaken by urethane prepolymer is dissolved or is dispersed in the aqueous solution that can comprise basic cpd.When the urethane prepolymer of waterborne polyurethane resin (A) and polymerizable unsaturated monomer (B) mixed before chain extension reaction, the chain extension reaction of urethane prepolymer can be in the presence of polymerizable unsaturated monomer (B), by the mixture dissolving that will obtain or be dispersed in the aqueous solution that can comprise basic cpd and carry out.
[0071] in two kinds of embodiments, estimate to obtain to have the compound fine particle of so-called nucleocapsid structure, wherein polymerizable unsaturated monomer (B) polymerization forms nuclear, and circumnuclear at least a portion is covered by waterborne polyurethane resin (A).
[0072] water-compatible reactive resin of the present invention can be in the presence of waterborne polyurethane resin (A), the radical polymerization by polymerizable unsaturated monomer (B) (it can randomly comprise polymerizable silane monomer (C)) obtains.The example of polymerization process comprises mass polymerization, solution polymerization, suspension polymerization and emulsion polymerisation process.
In these polymerization processs, emulsion polymerisation process is particularly preferred.Emulsion polymerisation process is to use water as medium and use the free radical polymerisation process of emulsifying agent, and can use known method.The example of emulsion polymerisation process comprises that polymerizable unsaturated monomer (B) and emulsifying agent are placed into aqueous medium polymeric method then; Polymerizable unsaturated monomer (B) and emulsifying agent are dropped to aqueous medium and polymeric method continuously or intermittently; And Xiang Shuizhong adds polymerizable unsaturated monomer (B) and emulsifying agent with preparation milk sap, and milk sap is dropped in the aqueous medium also polymeric method continuously or intermittently then.
Described emulsifying agent has the monomer emulsifying power, and forms micella in the process of letex polymerization, thereby provides the polymeric place for monomer.Between polymerization period and after the polymerization, emulsifying agent is realized the dispersion stabilization of polymer beads by being fixed in the polymer beads surface.The example of emulsifying agent comprises anion surfactant, nonionogenic tenside, cats product, amphoterics and polymeric surfactant.
In order to improve water resisting property, alkali-resistivity and water-repellancy, preferred " active surfactant " that has the two keys of free redical polymerization at the emulsifying agent intramolecularly of using.
[0073] example of anion surfactant comprises, alkali metal alkyl sulfate is as sodium lauryl sulphate or dodecyl sulphate potassium; Dodecyl polyoxyethylene glycol ether sodium sulfate; The alkylsurfuric acid ammonium is as ammonium lauryl sulfate; Sulfo group Sodium.beta.-phenylacrylate (sodium sulfocinnoate); Alkylsulfonate is as an alkali metal salt of sulfonated alkane or the ammonium salt of sulfonated alkane; Soap is as lauroleate sodium, triethanol amine oleate or sylvic acid trolamine; Alkylaryl sulphonate is as the alkali metal sulfates of Sodium dodecylbenzene sulfonate or alkali phenol hydroxyalkyl vinyl (alkali phenolhydroxyethylene); High sulfonated alkyl naphathalene; Naphthene sulfonic acid formalin polycondensate; Dialkyl sulfosuccinic salt (dialkyl sulfosuccinate); Laureth sulfate; With polyxyethylated aryl-sulfate.
In the present invention, described anion surfactant is preferably PELEX OT-P (being made by KaoCorporation), and it is dialkyl sulfosuccinic salt (sodium salt).
[0074] example of nonionogenic tenside comprises Voranol EP 2001; Polyoxyethylene alkylaryl ether; Sorbitan fatty(acid)ester; The polyoxyethylene sorbitan fatty acid ester; The lipid acid monoglyceride is as the mono-laurate of glycerine; Polyoxyethylene-oxypropylene multipolymer; And the polycondensation products of oxyethane, aliphatic amide, acid amides or acid.
[0075] example of cats product comprises monoalkyl ammonium salt, dialkyl ammonium salt and oxyethane add-on type alkylammonium salt.
Examples of amphoteric surfactants comprises amido propyl betaine and trimethyl-glycine Glycinates.
The example of polymeric surfactant comprises polyvinyl alcohol; Poly-(methyl) sodium acrylate, poly-(methyl) potassium acrylate and poly-(methyl) ammonium acrylate; And poly-(methyl) acrylate.
[0076] example of active surfactant comprises the sulfuric acid (ADEKA REASOAP SE series is made by ADEKACorporation) of polyoxyethylene allyl glycidyl nonylplenyl ether; The ammonium salt of alpha-sulfo-ω-(1-(alkoxyl group) methyl-2-(2-propenyloxy group) oxyethyl group)-poly-(oxygen-1,2-second two bases) (ADEKA REASOAP SR series is made by ADEKACorporation); Polyoxyethylene (or alkylidene group) alkyl (or thiazolinyl) ether ammonium sulfate salt (PD series is made by Kao Corporation); Sulfosuccinic acid type active initiator (LATEMUL180 series is made by Kao Corporation); Alkyl allyl group sodium sulfosuccinate (ELEMINOL JS-2, by Sanyo Chemical Industries, Ltd. makes); Polyoxyethylene nonyl allyl phenyl ether sulfuric ester ammonium salt (Akuaron HS series, by Dai-IchiKogyo Seiyaku Co., Ltd. makes); Polyoxyethylene-1-(allyloxy methyl) alkyl ether sulphate ammonium salt (Akuaron KH series, by Dai-Ichi Kogyo Seiyaku Co., Ltd. makes); Polyoxyethylene allyl glycidyl nonylplenyl ether (ADEKA REASOAP NE series is made by ADEKA Corporation); Polyoxyethylene nonyl propenyl ether (Akuaron RN series, by Dai-Ichi Kogyo Seiyaku Co., Ltd. makes); And α-hydrogenation-ω-(1-(alkoxyl group) methyl-2-(propenyloxy group) oxyethyl group)-poly-(oxygen-1,2-second two bases) (ADEKA REASOAPER series is made by ADEKA Corporation).
These active surfactant can be used alone, or in them two or more can be used in combination.In these active surfactant, alkyl allyl group sodium sulfosuccinate (ELEMINOL JS-2, by Sanyo Chemical Industries, Ltd. make) and alkyl ether sulphate ammonium salt (Akuaron KH series, by Dai-Ichi Kogyo Seiyaku Co., Ltd. makes) be preferred.
[0077] under the polymeric situation, for polymerization polymerizable unsaturated monomer (B), polymerization starter is used.The example of polymerization starter comprises water-soluble or oil soluble persulphate, superoxide and azo two compounds.Polymerization starter further comprises oxygenant, as Potassium Persulphate (KPS), Sodium Persulfate, ammonium persulphate, diisopropyl benzene hydrogen peroxide, cumene hydroperoxide, tertbutyl peroxide (Perbutyl H69, make by NOF Corporation), tert butyl peroxy benzoate, 2,2-Diisopropyl azodicarboxylate, 2,2-azo two (2-diaminopropanes) hydrochloric acid and 2,2-azo two (2, the 4-methyl pentane nitrile).Also may use redox initiator, be used in combination with reductive agent, this reductive agent such as sodium bisulfite, sodium formaldehyde sulphoxylate (Superlite C, by Mitsubishi Gas Chemical Company, Inc. production), L-xitix, thiourea peroxide (TEC LIGHT, by Asahi Chemical Co., Ltd. produces), iron protochloride and organic amine.
[0078] under the situation of letex polymerization, in order to regulate the molecular weight of resin, chain-transfer agent can randomly be used.
The example of chain-transfer agent just comprising-dodecyl mercaptans, uncle-dodecyl mercaptans, just-butyl sulfhydryl, thioglycol acid 2-ethylhexyl, 2 mercapto ethanol and trichlorobromomethane.
[0079] in aforesaid method, water-compatible reactive resin of the present invention can obtain with the form that is present in the composition in the aqueous medium.Just, it can obtain with the form of water-compatible reactive resin composition (for example, the reactive resin aqueous solution, dispersion liquid, suspension or milk sap).Usually, form, randomly be adjusted to required solids content, viscosity, pH etc. after the use of water-compatible reactive resin to be included in the composition in the aqueous medium.
[0080] solids content of water-compatible reactive resin composition of the present invention is preferably, and by weight from 30% to 55%, more preferably by weight from 30% to 50%, and be preferably by weight from 35% to 50% especially.The method that is used to measure solids content is same as described above.
And the viscosity of water-compatible reactive resin composition of the present invention under 30 ℃ is preferably from 5 to 2000mPas, more preferably from 5 to 1000mPas, and is preferably from 5 to 500mPas especially." viscosity " of described water-compatible reactive resin composition is meant by using aforesaid method to measure the value that obtains.For rotor, use rotor the 1st to No. 4.
[0081] film that forms of the water-compatible reactive resin that obtains from the present invention can show that usually the variation (Δ L) of water-proof whitening value is 10 or littler, uses colorimeter to measure this value.
As used herein, " variation of water-proof whitening value (Δ L) " is meant " variation of water-proof whitening value " that the described in an embodiment method of use obtains.
When this Δ L value surpassed 10, it became not enough for the use in the various application, as was used for the coating of material of construction and is used to build the coating of exterior material.When this Δ L value of the film that forms is 10 or more hour, water-compatible reactive resin can be used to above-mentioned application.Resin with Δ L value of 3 to 8 is suitable for actual use and is preferred, and particularly preferably is the resin with Δ L value of 3 to 4.
Water-compatible reactive resin of the present invention---wherein the film that will form has little Δ L value (it is outstanding) on water-proof whitening---is used as hereinafter described coating-forming agent and tackiness agent.
[0082] film that forms from the water-compatible reactive resin of the present invention that obtains is very outstanding in " transparency ".
As used herein, " transparency " is meant " transparency " that obtains by described method in an embodiment.
" transparency " of described film is preferably " almost transparent ", and more preferably " transparent fully ".
[0083] film that forms from the water-compatible reactive resin of the present invention that obtains can be outstanding on " gloss ".
As used herein, " gloss " is meant " gloss " that obtains by described method in an embodiment.
" gloss " of film is preferably " general gloss ", and more preferably " outstanding gloss ".
[0084] film that forms from the water-compatible reactive resin of the present invention that obtains can be outstanding on " good solubility-resistence ".
As used herein, " good solubility-resistence " is meant " good solubility-resistence " that obtains by described method in an embodiment.
In the time of in being immersed in toluene and acetone, " good solubility-resistence " of this film is preferably " the slight variation ", and more preferably " do not change ".
[0085] film that forms from the water-compatible reactive resin of the present invention that obtains can have outstanding " with the tackiness of base material ".
As used herein, " with the tackiness of base material " is meant " with the tackiness of base material " that obtains by described method in an embodiment.
When using PET and glass, " with the tackiness of base material " of this film is preferably " very slight peeling off (at first) and very slight peeling off (water resisting property) ", more preferably " do not peel off (at first) and very slight peeling off (water resisting property) ", and be preferably " do not peel off (at first) and do not peel off (water resisting property) " especially.
[0086], provides the coating-forming agent that comprises above water-compatible reactive resin composition in another aspect of the present invention.Of the present invention preferred aspect, the tackiness agent that comprises above water-compatible reactive resin composition is provided.
This coating-forming agent and tackiness agent can obtain by randomly water-compatible reactive resin composition of the present invention being mixed with known pigment, rust-preventive agent, thickening material, dispersion agent, defoamer, sanitas and secondary film formers.
[0087] this pigment is not limited especially, as long as it is as pigment.This pigment is divided into pigment dyestuff and amyl group pigment usually.
The example of pigment dyestuff comprises insoluble azo pigment, as permanent yellow, diazonium Huang, diazonium orange and naphthol red; Phthalocyanine base pigment such as copper phthalocyanine; Pigment lake such as fanal color lake, tannin color lake and catanol; Isoindoline base pigment such as isoindoline are yellowish green and the isoindoline Huang is red; Quinacridine ketone group pigment; He perylene base pigment such as perylene are with perylene maroon.
The example of mineral dye comprises carbon black, white lead, red lead powder, yellow lead, zunsober, ultramarine blue, cobalt oxide, titanium dioxide, titan yellow, strontium yellow, molybdate orange, strontium molybdate, iron oxide black, lithopone, emerald green, Guignet's green and cobalt blue.
[0088] filler is meant the material that adds for the purpose of improving performance and reducing cost, and is not specially limited, as long as they are often used as filler.The specific examples of filler comprises lime carbonate, magnesiumcarbonate, silica, talcum, clay and aluminum oxide.
Rust-preventive agent is meant the material that adds in order to suppress material corrosion, and is not specially limited, as long as they are usually as rust-preventive agent.The example comprises that red lead powder, Bai Hong (white red), zincic acid lead, basic sulfatase are red in vain, basic lead chromate, calcium plumbate, zinc chromate, cyanamide lead, zinc powder, dichromate (dichloromate), baryta yellow, Sodium Nitrite, two hexamethylene ammonium nitriles, cyclohexylamine carbonate and slushing oil.
[0089] and, in order to improve the purpose of performance, described coating-forming agent and tackiness agent can randomly mix with other resin.The example of other resin comprises xylene resin, Synolac, urethane resin, Resins, epoxy, acrylic resin, tackifier and wax emulsion.
[0090] in the present invention, described coating-forming agent also can be used as coating-forming agent and following coating-forming agent (comprising inter coat agent and so-called sealing agent), and especially preferably is used as coating-forming agent.As used herein, described " going up coating-forming agent " is meant such coating, and it also is known as coating, and is applied to outermost, and its application aims is to improve appearance, increase gloss, improve water resisting property and improve weathering resistance.On the contrary, described " following coating-forming agent " is meant the coating except that last coating-forming agent, and comprises: sealing agent (being also referred to as substrate conditioning agent or priming paint), and it directly applies to base material, and purpose mainly is to improve water-repellancy, moistureproofness and to the tackiness of base material; And the inter coat agent, its application purpose is to connect coating-forming agent and sealing agent and improves water-repellancy, moistureproofness and resistance to blistering.
[0091] in the present invention, tackiness agent is meant aqueous solution type tackiness agent and aqueous dispersion type tackiness agent.Water-compatible reactive resin of the present invention not only is included in coating-forming agent or the tackiness agent, but also is used as the component of printing ink, sealing material and make-up composition.
[0092] as mentioned above, the present invention has brought into play outstanding effect, and thinks that this outstanding effect brings into play by following reason.
In order to obtain above-mentioned target, the present inventor has carried out deep research, and judges: the reason that causes brightening from the film immersion water that milk sap forms is that water penetrates into the interface between the film forming a plurality of particles of structure.The inventor also thinks, if use ad hoc approach to form the composition (only be not to use and pass through) of particular polyurethane resin and vinyl base resin with particular polyurethane resin and vinyl base resin (preferred acrylic resins) blended method, can obtain water-compatible reactive resin, it does not cause water to infiltrate into constituting the interface between the particle of the film obtain.
[0093] in the presence of waterborne polyurethane resin (A) with the active silyl (a1) that can form crosslinking structure and anionic group (a2), it is possible that radical polymerization by polymerizable unsaturated monomer (B) obtains resin, and wherein the above-mentioned specific waterborne polyurethane resin and the vinyl base resin (being preferably acrylic resin) of the radical polymerization acquisition by polymerizable unsaturated monomer (B) are not to mix simply but compound.It is believed that when radical polymerization is combined in when carrying out in the aqueous medium, waterborne polyurethane resin (A) can be as the protectiveness colloid, and polymerizable unsaturated monomer (B) is aggregated, thereby increases molecular weight, and covered by waterborne polyurethane resin (A) part around it.The result is, it is possible forming nucleocapsid structure, and this nucleocapsid structure comprises the shell that is made of waterborne polyurethane resin (A) and the nuclear that is made of the vinyl base resin of polymeric polymerisable monomer (B).In having the water-compatible reactive resin of nucleocapsid structure like this, when the waterborne polyurethane resin (A) of shell by because active silyl (a1) forms crosslinking structure when interconnection, water is difficult for infiltrating into the space between the urethane resin of shell.The result is that the film that obtains from the water-compatible reactive resin that obtains demonstrates outstanding water-proof whitening.Think,, the urethane resin that constitutes shell is formed adverse influence though the vinyl base resin-shaped nucleation that forms from polymerizable unsaturated monomer (B) can be kept based on the character of vinyl base resin.
[0094] water-compatible reactive resin of the present invention feature is, the variation of the water-proof whitening value of the film of formation (Δ L) can be shown as 10 or littler.Think that Δ L value is little, just high water-proof whitening shows indirectly, and the shell of water-compatible reactive resin of the present invention is made of the urethane resin with high waterproof (A).Think, can form silyl (a1) crosslinked of the crosslinking structure of shell (urethane resin (A)), make it between the waterborne polyurethane resin (A) of the shell that constitutes nucleocapsid structure, be difficult to infiltration water.The result is, water-base resin forms film, and even brighten hardly in being immersed in water the time, therefore improved water-proof whitening.
By following examples and comparative example, the present invention is further specified.It should be understood that the present invention is not implemented example and limits, these are examples of the present invention, and are not considered to restriction.
Embodiment
[0095] manufacturing of waterborne polyurethane resin (A)
The manufacturing of waterborne polyurethane resin (A-I)
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the isophorone diisocyanate (IPDI of 66.6g, by Sumitomo Bayer Co., Ltd. manufacturing), polyester glycol (Nipporan 4073 MW2000 of 150g, by NipponPolyurethane Industry Co., Ltd. make) and the dimethylol propionic acid (DMPA) of 12.1g, and the N-N-methyl-2-2-pyrrolidone N-of the ethyl acetate of 150g and 25g adds as solvent.By using oil bath with this mixture heating up to 80 ℃ reaction 4 hours.Be cooled to after 60 ℃, the gamma-amino propyl trimethoxy silicane of 9.9g (SILQUEST A1100, by GE ToshibaSilicones Co., Ltd. makes) is added into, and reaction was carried out 20 minutes then.Be cooled to after 50 ℃, add the triethylamine of 8.3g, then stirred 10 minutes.This prepolymer with residual NCO group is scattered in the 343g water, and dissolves the Uricida (Pz6H of 11.6g in 70g water 2O) Zhi Bei the aqueous solution is immediately added, and carries out chain extension reaction 3 hours under 50 ℃ then, thereby causes the increase of molecular weight.Use Rotary Evaporators, from the solution that so obtains, remove ethyl acetate, obtain resin dispersion liquid with solids content 35%.
[0096] manufacturing of waterborne polyurethane resin (A-II)
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the isophorone diisocyanate (IPDI of 66.6g, by Sumitomo Bayer Co., Ltd. manufacturing), polyhexamethylene carbonic ether glycol (the Nipporan 980N MW2000 of 150g, by Nippon Polyurethane Industry Co., Ltd. make) and the dimethylolpropionic acid (DMBA) of 13.3g, and the N-N-methyl-2-2-pyrrolidone N-of the ethyl acetate of 150g and 25g adds as solvent.By using oil bath with this mixture heating up to 80 ℃ reaction 4 hours.Be cooled to after 60 ℃, the gamma-amino propyl trimethoxy silicane of 9.9g (SILQUEST A1100, by GEToshiba Silicones Co., Ltd. makes) is added into, and reaction was carried out 20 minutes then.Be cooled to after 50 ℃, add the triethylamine of 8.3g, then stirred 10 minutes.This prepolymer with residual NCO group is scattered in the 345g water, and dissolves the Uricida (Pz6H of 11.6g in 70g water 2O) Zhi Bei the aqueous solution is immediately added, and carries out chain extension reaction 3 hours under 50 ℃ then, thereby causes the increase of molecular weight.Use Rotary Evaporators, from the solution that so obtains, remove ethyl acetate, obtain resin dispersion liquid with solids content 35%.
[0097] manufacturing of waterborne polyurethane resin (A-III)
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the isophorone diisocyanate (IPDI of 66.6g, by Sumitomo Bayer Co., Ltd. manufacturing), polytetramethylene ethylene glycol (the PTMG2000 MW2000 of 150g, make by MitsubishiChemical Corporation) and the dimethylolpropionic acid (DMBA) of 13.3g, and the N-N-methyl-2-2-pyrrolidone N-of 25g adds as solvent.By using oil bath with this mixture heating up to 80 ℃ reaction 4 hours.Be cooled to after 60 ℃, the gamma-amino propyl trimethoxy silicane of 9.9g (SILQUEST A1100, by GE Toshiba Silicones Co., Ltd. makes) is added into, and reaction was carried out 20 minutes then.Be cooled to after 50 ℃, add the triethylamine of 8.3g and the methyl methacrylate (MMA is corresponding to polymerizable unsaturated monomer (B)) of 163g, then stirred 10 minutes.This prepolymer with residual NCO group is scattered in the 464g water, and dissolves the Uricida (Pz6H of 11.6g in 70g water 2O) Zhi Bei the aqueous solution is immediately added, and carries out chain extension reaction 3 hours under 50 ℃ then, thereby causes the increase of molecular weight.Use Rotary Evaporators, from solution, remove ethyl acetate, obtain resin dispersion liquid with solids content 25%.
[0098] manufacturing of waterborne polyurethane resin (A-IV)
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the isophorone diisocyanate (IPDI of 66.6g, by Sumitomo Bayer Co., Ltd. manufacturing), polyester glycol (Nipporan 4073 MW2000 of 150g, by NipponPolyurethane Industry Co., and the N-N-methyl-2-2-pyrrolidone N-of the ethyl acetate of 150g and 25g adds as solvent Ltd.) and the dimethylolpropionic acid of 8.9g (DMBA).By using oil bath with this mixture heating up to 80 ℃ reaction 4 hours.Be cooled to after 60 ℃, the gamma-amino propyl trimethoxy silicane of 3.3g (SILQUEST A1100, by GE Toshiba SiliconesCo., Ltd. makes) is added into, and reaction was carried out 20 minutes then.Be cooled to after 50 ℃, add the triethylamine of 6.1g, then stirred 10 minutes.This prepolymer with residual NCO group is scattered in the aqueous solution of the PELEX OTP emulsifying agent that is dissolved with 6.7g in 334g water, and dissolves the Uricida (Pz6H of 11.6g in 70g water 2O) Zhi Bei the aqueous solution is immediately added, and carries out chain extension reaction 3 hours under 50 ℃ then, thereby causes the increase of molecular weight.Use Rotary Evaporators, from solution, remove ethyl acetate, obtain resin dispersion liquid with solids content 35%.
[0099] manufacturing of waterborne polyurethane resin (A-V)
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the isophorone diisocyanate (IPDI of 66.6g, by Sumitomo Bayer Co., Ltd. manufacturing), polyester glycol (Nipporan 4073 MW2000 of 150g, by NipponPolyurethane Industry Co., and the N-N-methyl-2-2-pyrrolidone N-of the ethyl acetate of 150g and 25g adds as solvent Ltd.) and the dimethylolpropionic acid of 8.9g (DMBA).By using oil bath with this mixture heating up to 80 ℃ reaction 4 hours.Be cooled to after 60 ℃, the gamma-amino propyl trimethoxy silicane of 3.3g (SILQUEST A1100, by GE Toshiba SiliconesCo., Ltd. makes) is added into, and reaction was carried out 20 minutes then.Be cooled to after 50 ℃, add the triethylamine of 6.1g, then stirred 10 minutes.This prepolymer with residual NCO group be scattered in 322g water, be dissolved with 18.7g as the KH1025 of emulsifying agent (by Dai-IchiKogyo Seiyaku Co., Ltd. make) the aqueous solution in, and in 70g water the Uricida (Pz6H of dissolving 11.6g 2O) Zhi Bei the aqueous solution is immediately added, and carries out chain extension reaction 3 hours under 50 ℃ then, thereby causes the increase of molecular weight.Use Rotary Evaporators, from solution, remove ethyl acetate, obtain resin dispersion liquid with solids content 35%.
[0100] waterborne polyurethane resin (A '-VI) manufacturing
With with the identical mode of waterborne polyurethane resin (A-I), except not reacting the gamma-amino propyl trimethoxy silicane, obtain resin dispersion liquid with solids content 35%.
[0101] waterborne polyurethane resin (A '-VII) manufacturing
With with the identical mode of waterborne polyurethane resin (A-V), except not reacting the gamma-amino propyl trimethoxy silicane, obtain resin dispersion liquid with solids content 35%.
[0102] waterborne polyurethane resin (A-I) to (A '-character of manufacturing VII) and the water-base resin that obtains (or resin dispersion liquid) is shown in table 1 and 2.The method of solids content, viscosity and pH in the mensuration table as mentioned above.Particle diameter is meant average particulate diameter.
Table 1
Figure A200780033135D00291
Figure A200780033135D00301
[0103]
Table 2
Figure A200780033135D00302
【0104】
Embodiment 1
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-I) of 100g, be heated to 70 ℃ after, use nitrogen fully to replace air in the system.Then, use dropping funnel, will be by anion active tensio-active agent (the ELEMINOL JS2 of 0.2g, by Sanyo Chemical Industries, Ltd. makes), the 30.2g milk sap dropping formed of the 2-EHA (2EHA) of the methyl methacrylate (MMA) of the water of 6.7g, 15.3g and 8g is more than 2 hours.Equally, use dropping funnel, will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.09g, make by NOFCorporation) be dissolved in the oxygenant for preparing in the water of 2.7g and by sodium formaldehyde sulfoxylate (Superlite C with 0.03g, by Mitsubishi Gas Chemical Company, Inc. make) be dissolved in the reductive agent for preparing in the water of 4.7g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 39% solids content by maintaining 70 ℃.
【0105】
Embodiment 2
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-I) of 100g, be heated to 70 ℃ after, use nitrogen fully to replace air in the system.Then, the use dropping funnel will be by anion surfactant (the PELEX OTP of 0.2g, make by Kao Corporation), the water of 6.7g, the methyl methacrylate (MMA) of 15g, 2-EHA (2EHA) and the methyl allyl acyloxypropyl trimethoxysilane (SZ-6030 of 8g, by Dow Corning Toray Silicone Co., Ltd. makes) the 30.2g milk sap formed drips more than 2 hours.Equally, use dropping funnel, will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.09g, make by NOF Corporation) be dissolved in the oxygenant for preparing in the water of 2.7g and by thiourea peroxide (TEC LIGHT with 0.03g, make by ADEKA Corporation) be dissolved in the reductive agent for preparing in the water of 4.7g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 39% solids content by keeping 70 ℃.
【0106】
Embodiment 3
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-I) of 100g and the water of 17.8g, be heated to 70 ℃ after, use nitrogen fully to replace air in the system.Then, the use dropping funnel will be by the anion active tensio-active agent ELEMINOL JS2 of 0.3g, by Sanyo Chemical Industries, Ltd. make), the 45.3g milk sap formed of the butyl methacrylate (BMA) of the butyl acrylate (BA) of the 2-EHA (2EHA) of the methyl methacrylate (MMA) of the vinylbenzene (St) of the water of 10g, 5g, 15g, 5g, 5g and 5g, dropping is more than 2 hours.Equally, use dropping funnel, will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.13g, make by NOF Corporation) be dissolved in the oxygenant for preparing in the water of 4g and by thiourea peroxide (TEC LIGHT with 0.05g, make by ADEKA Corporation) be dissolved in the reductive agent for preparing in the water of 4g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 70 ℃.
【0107】
Embodiment 4
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-II) of 85.7g and the water of 79.1g, and after being heated to 70 ℃, use nitrogen fully to replace air in the system.Then, use dropping funnel, with the methyl methacrylate (MMA) of 6.5g, the 2-EHA (2EHA) of 63g and the methyl allyl acyloxypropyl trimethoxysilane (SZ-6030 of 0.5g, by Dow Corning Toray SiliconeCo., Ltd. makes) the 70g mixing solutions drip more than 2 hours.Equally, use dropping funnel, will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.15g, make by NOFCorporation) be dissolved in the oxygenant for preparing in the water of 5g and by thiourea peroxide (TEC LIGHT with 0.06g, make by ADEKA Corporation) be dissolved in the reductive agent for preparing in the water of 10g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 70 ℃.
【0108】
Embodiment 5
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-II) of 85.7g and the water of 61.1g, and after being heated to 70 ℃, use nitrogen fully to replace air in the system.Then, use dropping funnel, will be by active nonionic/anion surfactant (Akuaron KH1025 of 0.5g, by Dai-Ichi KogyoSeiyaku Co., Ltd. manufacturing), the water of 18g, the methyl methacrylate (MMA) of 46.2g, 2-EHA (2EHA) and the methacryloxypropyl methyl dimethoxysilane (Y-9910 of 23.3g, by Dow Corning Toray Silicone Co., Ltd. makes) the 88.5g milk sap formed, drip more than 2 hours.Equally, use dropping funnel, will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.15g, make by NOF Corporation) be dissolved in the oxygenant for preparing in the water of 5g and by thiourea peroxide (TEC LIGHT with 0.06g, make by ADEKA Corporation) be dissolved in the reductive agent for preparing in the water of 10g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 70 ℃.
【0109】
Embodiment 6
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-III) of 200g, and after being heated to 75 ℃, use nitrogen fully to replace air in the system.Then, the aqueous solution for preparing by the Potassium Persulphate (KPS) that dissolves 0.2g in 10g water is added into, and the methyl methacrylate (MMA) that is included in the waterborne polyurethane resin (A-III) is reacted.After MMA reaction is finished, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 80 ℃.
【0110】
Embodiment 7
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-IV) of 100g and the water of 17.8g, be heated to 70 ℃ after, use nitrogen fully to replace air in the system.Then, the use dropping funnel will be by 0.2g anion surfactant (PELEX OTP, make by Kao Corporation), the water of 10g, the methyl methacrylate (MMA) of 26.2g, the 2-EHA (2EHA) of 8.6g, 0.2g methacryloxypropyl methyl dimethoxysilane (Y-9910, by Dow Corning ToraySilicone Co., Ltd. manufacturing) the 45.2g milk sap of forming drips more than 2 hours.Equally, the use dropping funnel will be by the 69% butylhydroperoxide aqueous solution (PerbutylH69 with 0.13g, make by NOF Corporation) be dissolved in the oxygenant for preparing in the water of 4g and by thiourea peroxide (TEC LIGHT with 0.05g, make by ADEKA Corporation) be dissolved in the reductive agent for preparing in the water of 7g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 70 ℃.
【0111】
Embodiment 8
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-V) of 100g and the water of 17.8g, be heated to 70 ℃ after, use nitrogen fully to replace air in the system.Then, the use dropping funnel will be by active nonionic/anion surfactant (the Akuaron KH1025 of 0.5g, by Dai-Ichi Kogyo Seiyaku Co., Ltd. manufacturing), the water of 10g, the vinylbenzene (St) of 5g, the methyl methacrylate (MMA) of 6.1g, the 2-EHA (2EHA) of 18.6g, the butyl methacrylate (BMA) of 5g and the methyl allyl acyloxypropyl trimethoxysilane (SZ-6030 of 0.3g, by DowCorning Toray Silicone Co., Ltd. manufacturing) the 45.5g milk sap of forming drips more than 2 hours.Equally, the use dropping funnel will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.13g, make by NOF Corporation) be dissolved in the oxygenant for preparing in the water of 4g and by thiourea peroxide (TEC LIGHT with 0.05g, make by ADEKACorporation) be dissolved in the reductive agent for preparing in the water of 7g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 70 ℃.
【0112】
Embodiment 9
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert the waterborne polyurethane resin (A-I) of 57.1g and the water of 63.9g, be heated to 70 ℃ after, use nitrogen fully to replace air in the system.Then, the use dropping funnel will be by 0.7g anion surfactant (ELEMINOL JS2, by Sanyo Chemical Industries, Ltd. manufacturing), the water of 22.9g, the methyl methacrylate (MMA) of 50g, the 2-EHA (2EHA) of 29.5g, 0.5 methyl allyl acyloxypropyl trimethoxysilane (SZ-6030, by DowCorning Toray Silicone Co., Ltd. manufacturing) the 103.6g milk sap of forming drips more than 2 hours.Equally, the use dropping funnel will be by the 69% butylhydroperoxide aqueous solution (Perbutyl H69 with 0.3g, make by NOF Corporation) be dissolved in the oxygenant for preparing in the water of 9g and by thiourea peroxide (TEC LIGHT with 0.1g, make by ADEKA Corporation) be dissolved in the reductive agent for preparing in the water of 16g, drip more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-compatible reactive resin milk sap with 40% solids content by keeping 70 ℃.
【0113】
The comparative example 1
Use the mode identical with embodiment 1, except the use water-base resin (A '-VI), obtain having the water-base resin milk sap of 39% solids content.
The comparative example 2
Use the mode identical with embodiment 2, except the use water-base resin (A '-VI), obtain having the water-base resin milk sap of 39% solids content.
The comparative example 3
Use the mode identical with embodiment 8, except use water-base resin (A '-VII) and methyl allyl acyloxypropyl trimethoxysilane (SZ-6030, by Dow Corning Toray Silicone Co., Ltd. makes) not reaction, the water-base resin milk sap that obtains having 39% solids content.
The comparative example 4
Use the mode identical with embodiment 8, except the use water-base resin (A '-VII), obtain having the water-base resin milk sap of 40% solids content.
【0114】
The comparative example 5
In four neck flasks of agitator, thermometer, nitrogen conduit and reflux exchanger are housed, insert 0.5g the anion active tensio-active agent (ELEMINOL JS2 by, SanyoChemical Industries, Ltd. make) and the water of 104.5g, after being heated to 80 ℃, use nitrogen fully to replace air in the system.Then, the use dropping funnel will be by 2.5g anion active tensio-active agent (ELEMINOL JS2, by Sanyo Chemical Industries, Ltd. manufacturing), the water of 30g, the vinylbenzene (St) of 40g, the methyl methacrylate (MMA) of 24.3g, the 2-EHA (2EHA) of 35g and 0.7 methyl allyl acyloxypropyl trimethoxysilane (SZ-6030, by Dow Corning Toray Silicone Co., Ltd. manufacturing) the 132.5g milk sap of forming drips more than 2 hours.Equally, use dropping funnel, the Potassium peroxide of 0.5g is dissolved in the aqueous solution for preparing in the water of 15g drips more than 2 hours.After milk sap drips fully, finished polyreaction in 1 hour, obtain water-borne acrylic resin milk sap with 40% solids content by keeping 80 ℃.
The comparative example 6
Water-borne acrylic resin milk sap that obtains in comparative example 5 and waterborne polyurethane resin (A-I) are mixed by the ratio of mixture with 4:6, obtain the water-base resin milk sap with solids content 37%.
The comparative example 7
Water-borne acrylic resin milk sap that in comparative example 5, obtains and waterborne polyurethane resin (A '-VI) mixed by ratio of mixture with 6:4, obtain water-base resin milk sap with solids content 37%.
[0115] the water-base resin milk sap that so obtains is as mentioned above summed up in to 6 at table 3.The method of mensuration solids content, viscosity and pH etc. as mentioned above.
Table 3
Figure A200780033135D00361
Figure A200780033135D00371
【0116】
Table 4
【0117】
Table 5
Figure A200780033135D00391
【0118】
Table 6
Figure A200780033135D00392
Figure A200780033135D00401
[0119], use following Fox ' s equation to measure at the second-order transition temperature (Tg) of table 3 to the part of the acrylic resin shown in 6.The Tg value of every kind of monomeric homopolymer (using in order to measure Tg) is illustrated in the bracket.About comprising the acrylic resin of methyl allyl acyloxypropyl trimethoxysilane (SZ-6030) and methacryloxypropyl methyl dimethoxysilane (Y-9910), by getting rid of Tg that these components calculate second-order transition temperature (Tg) as acrylic resin.
Fox ' s equation: 1/Tg=Σ (Wn/Tgn)/100
Wherein
Wn: the amount of the monomer n that comprises in the acrylic resin (% by weight)
Tgn: the Tg of every kind of monomeric homopolymer (absolute temperature)
St: vinylbenzene (105 ℃), MMA: methyl methacrylate (105 ℃)
2EHA: 2-EHA (70 ℃)
BMA: n-BMA (20 ℃)
BA: n-butyl acrylate (56 ℃)
[0120] about embodiment 1 to 9 and comparative example's 1 to 7 water-base resin milk sap, the transparency, gloss, good solubility-resistence and tackiness are evaluated.Appraisal procedure has been described.
The transparency of＜film 〉
On sheet glass, use 5 mils (125 μ m) spreader coating resin dispersion liquid, and following dry 5 minutes at 105 ℃.The film that obtains placed room temperature following 1 hour, passed through the transparency of visual observations film then.
A: transparent fully
B: almost transparent
C: slightly transparent
D: opaque fully
【0121】
＜gloss 〉
On sheet glass, use 5 mils (125 μ m) spreader coating resin dispersion liquid, and following dry 5 minutes at 105 ℃.The film that obtains placed room temperature following 1 hour, and passed through the gloss of visual observations film then.
A: outstanding gloss
B: common gloss
C: slight gloss
D: tarnish
【0122】
＜good solubility-resistence 〉
On sheet glass, use 5 mils (125 μ m) spreader coating resin dispersion liquid, and following dry 5 minutes at 105 ℃.The film that obtains placed room temperature following 1 hour, was immersed in toluene or the acetone 24 hours then, and the state by the visual observations film then.
A: no change
B: the slight variation
C: observe and brighten
D: brighten and expand
【0123】
＜water-proof whitening 〉
On sheet glass, use 5 mils (125 μ m) spreader coating resin dispersion liquid, and following dry 5 minutes at 105 ℃.The film that obtains placed room temperature following 1 hour, was adhered to black acrylic panel (by Nippon Testpanel Co., Ltd. makes, L=1.89, a=-0.06, b=-0.10) then, used colorimeter to measure L value (L0) then.The film that obtains is soaked in 40 ℃ the hot water.After 24 hours, sheet glass is taken out and is wiped water immediately.In 1 minute after sheet glass takes out, measure aberration (L1) by aforesaid same procedure.The value of water-proof whitening (Δ L) is calculated by following equation:
The Δ L=L1-L0 of water-proof whitening
【0124】
＜tackiness 〉
On PET film (DIAFOIL O300E, by Mitsui Chemicals, the polyester film that Inc. makes) and sheet glass, use 3 mil spreader coating resin dispersion liquids, and 105 ℃ of dryings 5 minutes down.Use
Figure A200780033135D00421
Peel off test, and detect initial tack.After 24 hours, sheet glass is taken out and is wiped water immediately in being immersed in 40 ℃ hot water.Carry out after dry 30 minutes under the room temperature
Figure A200780033135D00422
Test.Be immersed in the tackiness behind the hot water, in other words, anti-water tackiness is detected.
A: do not peel off
B: very slight peels off
C: slightly peel off
D: seriously peel off
[0125] assessment result as shown in the following Table 7.
Table 7
The transparency Gloss Good solubility-resistence toluene Good solubility-resistence acetone Water-proof whitening Tackiness (PET) is initial/water resisting property Tackiness (glass) is initial/water resisting property
Embodiment 1 A A B B 4 A/B A/A
Embodiment 2 A A A A 3 A/B A/A
Embodiment 3 A A B B 4 A/B A/A
Embodiment 4 A A A A 3 A/B A/A
Embodiment 5 A A B B 3 A/B A/A
Embodiment 6 A A A A 4 A/B A/A
Embodiment 7 A A B B 7 A/A A/B
Embodiment 8 A A A A 8 A/A A/B
Embodiment 9 A A B B 9 A/B A/B
The comparative example 1 A A D D 31 A/D A/D
The comparative example 2 A A C C 25 A/C A/D
The comparative example 3 A A D D 25 A/D A/D
The comparative example 4 A A C C 5 A/C A/D
The comparative example 5 A A B B 17 A/D A/A
The comparative example 6 B B C C 15 A/C A/A
The comparative example 7 B B D D 25 A/D A/C
[0126] obviously as seen from the result shown in the table 7, the water-compatible reactive resin of embodiment 1 to 9 shows outstanding water-proof whitening (Δ L is 10 or littler), and other character (transparency, gloss, good solubility-resistence, tackiness) is outstanding, and also outstanding on performance balance.On the contrary, comparative example 1 to 7 water-base resin is not enough on performance balance.Comparative example 4 water-base resin is water-proof whitening outstanding (Δ L is 5), and is still not enough on good solubility-resistence and tackiness.Comparative example 1,2,3,5,6 and all water-base resins of 7 show water-proof whitening deficiencies (Δ L shows quite high value).

Claims (13)

1. water-compatible reactive resin, it is to obtain by polymerization polymerizable unsaturated monomer (B) in the presence of waterborne polyurethane resin (A), wherein, described waterborne polyurethane resin (A) has the active silyl (a1) and the anionic group (a2) that can form crosslinking structure.
2. water-compatible reactive resin according to claim 1, wherein, described waterborne polyurethane resin (A) comprises that the described active silyl (a1) that can form crosslinking structure is by weight 0.1% to 10% as " Si " based on the amount of the solids content of described waterborne polyurethane resin; And described anionic group (a2) is 0.01 to 1.1meq/g based on the amount of the solids content of described waterborne polyurethane resin.
3. water-compatible reactive resin according to claim 1 and 2, wherein, described waterborne polyurethane resin (A) is by making organic polyisocyanate component, polyol component, intramolecularly have the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group obtaining urethane prepolymer, and chain extension reaction by described urethane prepolymer obtains.
4. according to each described water-compatible reactive resin among the claim 1-3, wherein, described waterborne polyurethane resin (A) is from 2/8 to 8/2 with regard to solids content with the weight ratio (A)/(B) of described polymerizable unsaturated monomer (B).
5. according to each described water-compatible reactive resin among the claim 1-4, wherein, described polymerizable unsaturated monomer (B) comprises (methyl) alkyl acrylate.
6. according to each described water-compatible reactive resin among the claim 1-5, wherein, described polymerizable unsaturated monomer (B) further comprises polymerizable silane monomer (C).
7. according to each described water-compatible reactive resin among the claim 1-6, wherein, described water-compatible reactive resin can form film, and described film shows that the variation (Δ L) of water-proof whitening value is 10 or littler, and this value uses colorimeter to measure.
8. water-compatible reactive resin composition, it comprises according to each described water-compatible reactive resin among the claim 1-7.
9. according to the manufacture method of each described water-compatible reactive resin among the claim 1-7, be included in polymerization polymerizable unsaturated monomer (B) under the existence of waterborne polyurethane resin (A), wherein, described waterborne polyurethane resin (A) has the active silyl (a1) and the anionic group (a2) that can form crosslinking structure.
10. method according to claim 9 comprises:
Make organic polyisocyanate component, polyol component, intramolecularly have the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group, to obtain urethane prepolymer
Described urethane prepolymer is mixed with polymerizable unsaturated monomer (B), carry out the chain extension reaction of described urethane prepolymer, to obtain waterborne polyurethane resin (A), the described polymerizable unsaturated monomer of polymerization (B) then.
11. method according to claim 9 comprises:
Make organic polyisocyanate component, polyol component, intramolecularly have the compound of at least one active hydrogen and anionic group and the reaction of compound that intramolecularly has at least one active hydrogen and hydrolysable silyl group, to obtain urethane prepolymer
Carry out the chain extension reaction of described urethane prepolymer,, mix with polymerizable unsaturated monomer (B) then to obtain waterborne polyurethane resin (A), and the described polymerizable unsaturated monomer of polymerization (B).
12. coating-forming agent, it comprises water-compatible reactive resin composition according to claim 8.
13. tackiness agent, it comprises water-compatible reactive resin composition according to claim 8.
CNA2007800331356A 2006-08-11 2007-08-10 Water-compatible reactive resin and process for producing the same Pending CN101511890A (en)

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