CN102686674A - Aqueous polyamide resin dispersion, method for producing same, and laminate - Google Patents

Aqueous polyamide resin dispersion, method for producing same, and laminate Download PDF

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Publication number
CN102686674A
CN102686674A CN2010800489465A CN201080048946A CN102686674A CN 102686674 A CN102686674 A CN 102686674A CN 2010800489465 A CN2010800489465 A CN 2010800489465A CN 201080048946 A CN201080048946 A CN 201080048946A CN 102686674 A CN102686674 A CN 102686674A
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polyamide resin
water dispersion
resin
dimeracid
water
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CN102686674B (en
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山田宗纪
矢野拓磨
石桥直人
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Unitika Ltd
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Unitika Ltd
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Priority claimed from JP2009251142A external-priority patent/JP5666800B2/en
Priority claimed from JP2010170774A external-priority patent/JP2012031261A/en
Priority claimed from JP2010226646A external-priority patent/JP2012077270A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • C09D177/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/46—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C08J2377/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids

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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)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is an aqueous polyamide resin dispersion, which is an aqueous dispersion obtained by dispersing a dimer acid polyamide resin (P) in an aqueous medium, wherein the resin (P) has a number average particle diameter of 0.5 [mu]m or less, contains a dimer acid as a dicarboxylic acid component in an amount of 50 mol% or more, and has an acid value of from 1 to 20 mgKOH/g which is higher than the amine value thereof, and the dispersion contains a basic compound (B) having a boiling point at normal pressure lower than 185 C and does not substantially contain an aqueous dispersing aid which has a boiling point at normal pressure of 185 C or higher or is nonvolatile.

Description

Polyamide resin water dispersion and method of manufacture thereof and laminate
Technical field
The present invention relates to a kind ofly to obtain having good adherence, flexibility, chemical resistant properties, heat-resisting fusible polyamide resin, show the water dispersion and the method for manufacture thereof of stable dispersiveness at alkalescence or acidic region.
Background technology
Have in the polyamide resin of amido linkage at main chain, the polyamide resin that mainly uses dicarboxylicacid compositions such as hexanodioic acid, sebacic acid and two amine components such as hexamethylene-diamine, quadrol to obtain through dehydration condensation is used to various fields such as food product pack purposes, industrial use.
In addition; Through being the resin that dimeracid class polyamide resin that the dehydration condensation of dicarboxylicacid composition and various two amine components of staple obtains is adherence, flexibility, chemical resistant properties, heat-resisting binding property is excellent with the dimeracid, the hot-melt adhesive, resin modified that is used as various uses such as being used for trolley part, cable is with additive etc.Dimeracid class polyamide resin has through changing dicarboxylicacid composition, two amine components, terminal sour component content, terminal amine component content etc. can control the characteristic of characteristics such as resin softening point, MFR, binding property, flexibility widely.
In addition, dimeracid is meant the dicarboxylicacid of carbon number 36, obtains through the unsaturated fatty acids dimerization with carbon numbers such as oleic acid, linolic acid 18, is the lipid acid of plant origin.
If can under the situation of the characteristic of not damaging dimeracid class polyamide resin, obtain the solution or the dispersion-s of this resin, just can be easily form on the surface of base materials such as for example resin molding or resin sheet, paper, metal have good adherence, the filming of flexibility, chemical resistant properties, heat-resisting fusible dimeracid class polyamide resin.
Yet, in the dimeracid class polyamide resin, especially its acid value, resin and the high resin of softening temperature that amine value is low, poorly soluble to all kinds of SOLVENTS such as alcohols, toluene is difficult to obtain stable solution.
On the other hand, there also have research to attempt that polyamide resins such as dimeracid class polyamide resin are carried out water-based to be decentralized to obtain water dispersion.
For example, in patent documentation 1, the method that the polyamide resin of acid value more than 8 is dispersed in the aqueous solution that contains the alkyl alkanolamine more than the 20 quality % is usually studied.Yet gelation at room temperature can take place in the water dispersion that obtains with this method, fails to obtain the excellent water dispersion of dispersion stabilization.
In patent documentation 2～5, also disclose polyamide resins such as dimeracid class polyamide resin are carried out the decentralized method of water-based, but all methods are essential composition with emulsifying agent, tensio-active agent all.Therefore; Film except containing the polyamide resin composition by what these water dispersions obtained; Also contain emulsifying agent, tensio-active agent, exist these compositions that characteristics such as the characteristic of filming, good adhesive property that for example polyamide resin had originally, chemical resistant properties are produced dysgenic problem.
Have such problem in addition: these water dispersions are LV under heating, but cooling back viscosity begins increase, and gelation takes place obvious tackify under the room temperature.
Also have,, adopt easy Water-borne modification, resin that acid value is high, but polyamide resin exists acid value high more, the easier problem of damaging original resin properties in order to obtain water dispersion.
In addition, even not tackify and the water dispersion that obtains under the room temperature, the median size minimum of the resin in the water dispersion also is 0.5 μ m, and not being is enough to form the small particle size that densification is filmed, and the dispersion stabilization of water dispersion is unexcellent.
In addition, the pH of water dispersion also exists in the acidic region problem of the dispersion-s shape that can condense, can not keep stable between the resin particle greater than 7 anionic water dispersion.Therefore, be difficult to the anionic water dispersion only be blended in the stable compound of acidic region, solution, dispersion-s etc., in acidic region with the anionic property water dispersion as paint.Likewise, cationic water dispersion also is difficult in the alkalescence zone as paint.
Patent documentation
Patent documentation 1: japanese kokai publication sho 64-20261 communique
Patent documentation 2: japanese kokai publication hei 2-4863 communique
Patent documentation 3: japanese kokai publication hei 2-4862 communique
Patent documentation 4: TOHKEMY 2000-7787 communique
Patent documentation 5: TOHKEMY 2001-270987 communique
Summary of the invention
The present invention is intended to address the above problem; Even provide a kind of dimeracid class polyamide resin that can obtain having good adherence, flexibility, chemical resistant properties, heat-resisting fusible resin coating film under the situation that is substantially free of emulsifying agent, tensio-active agent with the form dispersive that is enough to form the small particle size resin particle that densification films the still excellent water dispersion of dispersion stabilization at room temperature, and as technical task.
The present inventor furthers investigate for solving above-mentioned problem; The result finds; Through using dimeracid class polyamide resin and the basic cpd or the acidic cpd of specific composition, can under the situation of not adding non-volatility Water-borne modification auxiliary agent such as tensio-active agent or high boiling point hydrability auxiliary agent, have good stability and with small particle size dimeracid class polyamide resin is dispersed in the aqueous medium.Find in addition, be coated with this water dispersion and filming of obtaining shows good adherence, flexibility, chemical resistant properties, the heat-resisting binding property that dimeracid class polyamide resin had originally, accomplished the present invention thus.
That is, main points of the present invention are following.
(1) a kind of polyamide resin water dispersion is that dimeracid class polyamide resin (P) is dispersed in the water dispersion in the aqueous medium, wherein,
The number average bead diameter of resin (P) below 0.5 μ m,
Resin (P) contains the dimeracid that accounts for more than 50 moles of % of its dicarboxylicacid composition,
The acid value of resin (P) is 1～20mg KOH/g, is higher than its amine value,
The boiling point that contains under the normal pressure is lower than 185 ℃ basic cpd (B),
Be substantially free of boiling point under the normal pressure more than 185 ℃ or the decentralized auxiliary agent of the water-based of non-volatility.
(2) (1) described polyamide resin water dispersion is characterized in that, with respect to the solids component of dimeracid class polyamide resin (P), the boiling point that contains under the normal pressure is lower than 185 ℃ basic cpd (B) 0.01～100 quality %.
(3) (1) or (2) described polyamide resin water dispersion is characterized in that, pH is 7～13.
(4) a kind of polyamide resin water dispersion is that dimeracid class polyamide resin (P) is dispersed in the water dispersion in the aqueous medium, wherein,
The number average bead diameter of resin (P) below 0.5 μ m,
Resin (P) contains the dimeracid that accounts for more than 50 moles of % of its dicarboxylicacid composition,
The amine value of resin (P) is 1～50mg KOH/g, is higher than its acid value,
Contain acidic cpd (A),
Be substantially free of boiling point under the normal pressure more than 185 ℃ or the decentralized auxiliary agent of the water-based of non-volatility.
(5) (4) described polyamide resin water dispersion is characterized in that, acidic cpd (A) is an organic acid, with respect to the solids component of dimeracid class polyamide resin (P), contains acidic cpd (A) 0.01～100 quality %.
(6) (4) or (5) described polyamide resin water dispersion is characterized in that, pH is 2～6.
(7) each described polyamide resin water dispersion is characterized in that in (1)～(6), contains linking agent.
(8) each described polyamide resin water dispersion is characterized in that in (1)～(6), through the irradiation radioactive rays.
(9) a kind of method of manufacture of polyamide resin water dispersion; It is the method that is used for making each described polyamide resin water dispersion of above-mentioned (1)～(6); Wherein, In containing the aqueous medium of hydrophilic organic solvent, the boiling point under heated and stirred dimeracid class polyamide resin (P) and normal pressure under 70～280 ℃ the temperature is lower than 185 ℃ basic cpd (B) or acidic cpd (A).
(10) method of manufacture of (9) described polyamide resin water dispersion wherein, is heated up in a steamer hydrophilic organic solvent after the heated and stirred.
(11) a kind of laminate, its substrate surface are formed with filming of each described polyamide resin water dispersion in (1)～(8).
Polyamide resin water dispersion of the present invention is substantially free of emulsifying agent and tensio-active agent, is dispersed with the dimeracid class polyamide resin of small particle size, even gelation does not at room temperature take place yet, dispersion stabilization is excellent.Therefore, be coated with polyamide resin water dispersion of the present invention, the densification that can obtain dimeracid class polyamide resin is filmed, and adherence, flexibility, chemical resistant properties, heat-resisting binding property that gained is filmed are excellent.In addition, water dispersion of the present invention has anionic and cationic two kinds, therefore, can select water dispersion according to the acidity of wanting the blended material, alkalescence, enlarges as the use range of paint.
Use the method for manufacture of polyamide resin water dispersion of the present invention, though can obtain unavailable in the past, be substantially free of emulsifying agent and tensio-active agent, gelation does not at room temperature take place yet for the dimeracid class polyamide resin that is dispersed with small particle size, dispersion stabilization is excellent polyamide resin water dispersion of the present invention and can making expeditiously.
Embodiment
Be elaborated in the face of the present invention down.
Polyamide resin water dispersion of the present invention is that dimeracid class polyamide resin (P) is dispersed in the water dispersion in the aqueous medium.
Aqueous medium among the present invention is meant the solvent of being made up of the liquid that with water is staple, in aqueous medium, states hydrophilic organic solvent, basic cpd after can containing.
Gather on the main chain of diacid class polyamide resin (P) and have amido linkage, mainly obtain as the dimeracid of dicarboxylicacid composition and the dehydration condensation of two amine components through using.Dimeracid class polyamide resin (P) is compared with resins such as the nylon that is widely used as polyamide resin 6, nylon 66, nylon 12, has big hydrocarbyl group, thereby has flexibility.
In the present invention, as the dicarboxylicacid composition, dimeracid class polyamide resin (P) must contain the dimeracid that accounts for more than 50 moles of % of dicarboxylicacid composition total amount, preferably contains 60 moles more than the %, more preferably contains 70 moles more than the %.If the ratio of dimeracid then is difficult to manifest characteristic, the effect of dimeracid class polyamide resin (P) less than 50 moles of %.
Here; Dimeracid is meant the product that the unsaturated fatty acids dimerization of carbon numbers such as oleic acid, linolic acid 18 is obtained; As long as below 25 quality % of dimeracid composition; Also can contain promising monomeric monomer acids (carbon number 18), be other polymerized fatty acids of trimerical trimer acid (carbon number 54), carbon number 20～54, can also be with above-mentioned sour hydrogenation, its degree of unsaturation reduced and the product that obtains.The commercially available article of dimeracid have Haridimer series (HARIMA changes into Company products), Pripol series (Croda Japanese firm product), TSUNODYME series (building food picked from the fields article industrial product) etc., can use these dimeracids.
As the dicarboxylicacid composition of dimeracid class polyamide resin (P) and when using the composition beyond the dimeracid; Preferred hexanodioic acid, nonane diacid, sebacic acid, pimelic acid, suberic acid, undecane diacid, the fumaric acid etc. of using; Through containing these acid, control resin softening point, binding property etc. easily less than 50 moles of %.
In addition; Two amine components as dimeracid class polyamide resin (P); Can use quadrol, hexamethylene-diamine, tetramethylene-diamine, five methylene diamine, m-xylene diamine, phenylenediamine, NSC 446, piperazine etc., wherein preferred quadrol, hexamethylene-diamine, NSC 446, m-xylene diamine, piperazine.
During polymerization dimeracid class polyamide resin (P), through changing the feed molar ratio of above-mentioned dicarboxylicacid composition and two amine components, the polymerization degree, acid value or the amine value of may command resin (P).
The softening temperature of dimeracid class polyamide resin (P) is preferably 70～250 ℃, more preferably 80～240 ℃, especially is preferably 80～200 ℃.If softening temperature is lower than 70 ℃, then the gained intensity of filming has the tendency of reduction, and in addition, the sticking sense under the room temperature has the tendency of rising.On the other hand, if softening temperature surpasses 250 ℃, then exist to be difficult to the tendency of resin dispersion in aqueous medium.
In the present invention, in the dimeracid class polyamide resin (P), using acid value is that 1～20mg KOH/g, acid value resin high than amine value (PA) or amine value are 1～50mg KOH/g, the amine value resin high than acid value (PB).In the present invention, when using resin (PA), state basic cpd (B) after water dispersion contains, on the other hand, when using resin (PB), state acidic cpd (A) after water dispersion contains.
In the present invention, the acid value of resin (PA) is necessary for 1～20mg KOH/g, is preferably 1～15mg KOH/g, and more preferably 3～12mg KOH/g especially is preferably 3～7mgKOH/g.The acid value of resin (PA) is difficult to obtain stable water dispersion during less than 1mgKOH/g, and on the other hand, if surpass 20mg KOH/g, then the chemical resistant properties as the original superperformance of dimeracid class polyamide resin reduces.
In resin (PA), acid value must be higher than amine value.If acid value is lower than amine value, then the gained water dispersion declines to a great extent in the stability in alkalescence zone.
Therefore, the amine value of resin (PA) is preferably below 15mg KOH/g, more preferably below 5mg KOH/g, especially preferably below 2mg KOH/g.If amine value surpasses 15mg KOH/g, then dispersion stabilization has the tendency of decline.
The definition of acid value is, in resin 1g in the milligram number of the required Pottasium Hydroxide of contained acidic component.On the other hand, amine value then use with resin 1g in molar equivalents such as amine component Pottasium Hydroxide the milligram numerical table show.Both all measure through the method for putting down in writing among the JIS K2501.
When water dispersion of the present invention used resin (PA) as dimeracid class polyamide resin, the boiling point that must contain under the normal pressure was lower than 185 ℃ basic cpd (B).Boiling point through containing under the normal pressure is lower than 185 ℃ basic cpd (B), and the carboxyl of resin (PA) is neutralized, and the electric repulsive force between the carboxyl anion that neutralization produces can prevent the aggegation between particulate, obtains the excellent water dispersion of dispersion stabilization.
Being lower than 185 ℃ basic cpd (B) as the boiling point under the normal pressure, can be amines such as ammonia, organic amine compound etc.Object lesson as organic amine compound; Can enumerate out triethylamine, N, N-dimethylethanolamine, Isopropylamine, imino-bis-propylamine, ethamine, diethylamine, 3-ethoxy propylamine, 3 diethyl aminopropylamine, sec.-butylamine, propylamine, methylamino-propylamine, methyl-imino dipropyl amine, 3 methoxypropyl amine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine etc.Be lower than 185 ℃ basic cpd as the boiling point under the normal pressure, preferred triethylamine, N in above-claimed cpd, N-dimethylethanolamine.
If the boiling point of basic cpd (B) under normal pressure surpasses 185 ℃, then when the formation of coating water dispersion is filmed, be difficult to make especially organic amine compound volatilization of basic cpd (B) through drying, possibly produce detrimentally affect to health aspect, coating characteristic.
In water dispersion of the present invention, the content of basic cpd (B) is preferably 0.01～100 quality % with respect to the solids component of resin (PA), and more preferably 1～40 quality % especially is preferably 1～15 quality %.Under the situation of content less than 0.01 quality % of basic cpd (B), can lack the effect of adding basic cpd (B), be difficult to obtain the excellent water dispersion of dispersion stabilization.On the other hand, if the content of basic cpd (B) surpasses 100 quality %, then there are tendencies such as water dispersion easy colorizing, gelation, emulsion pH be excessive.
In the water dispersion of the present invention, the carboxyl in the resin (PA) can be kept stable morphology in the alkalescence zone by basic cpd (B) neutralization.As the pH of water dispersion, preferably in 7～13 scope.
On the other hand, in the present invention, the amine value of resin (PB) is necessary for 1～50mg KOH/g, is preferably 3～25mg KOH/g, more preferably 5～20mg KOH/g.Under the situation of amine value less than 1mg KOH/g, the stability of water dispersion declines to a great extent.On the other hand, if surpass 50mg KOH/g, then the gained chemical resistant properties of filming has the tendency of reduction.
In resin (PB), amine value must be higher than acid value.If amine value is lower than acid value, then the gained water dispersion significantly reduces in the stability of acidic region.
Therefore, the acid value of resin (PB) is preferably below 40mg KOH/g, more preferably below 10mg KOH/g, especially preferably below 2mg KOH/g.If acid value surpasses 40mg KOH/g, then the gained chemical resistant properties of filming has the tendency of reduction, and dispersion stabilization also reduces.
When water dispersion of the present invention uses resin (PB) as dimeracid class polyamide resin, must contain acidic cpd (A).Through containing acidic cpd (A), part or all of amino contained in the resin (PB) is neutralized, and generates positively charged ion, because cationic electric repulsive force, the aggegation between resin particle is removed, thereby makes water dispersion have stability.
The acid ionization constant (pKa) of acidic cpd (A) more preferably-9～7, is preferably-5～6 especially preferably below 8, especially is preferably 0～5.If pKa surpasses 8, then exist aminoly be difficult to be neutralized, the decentralized situation of difficult of resin.Lower limit to pKa does not have particular restriction, but if too small, then the corrodibility of acidic cpd strengthens, and can damage to be used for the decentralized equipment of water-based and the equipment that is used to utilize water dispersion etc.
In addition, acidic cpd (A) is preferably volatility, and particularly, preferred boiling point is 20～250 ℃, and more preferably 30～200 ℃, be preferably 50～150 ℃ especially, especially be preferably 50～120 ℃.If acidic cpd (A) is a non-volatility, promptly boiling point surpasses 250 ℃, and after then filming, in this was filmed, how many meetings of acidic cpd (A) were residual, and adherence, the water tolerance of filming produced detrimentally affect.On the other hand, if the boiling point of acidic cpd (A) is lower than 20 ℃, when then modulating water dispersion, acidic cpd (A) vapors away mostly, the result, in can reduce with efficient.
As pKa is the object lesson of the acidic cpd (A) below 8, can be mineral acids such as organic acids such as formic acid, acetate, propionic acid, butyric acid, valeric acid and hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.In these compounds, preferred corrodibility lower and neutralization amino aspect excellent organic acid, wherein especially preferable formic acid, acetate.
In water dispersion of the present invention, the content of acidic cpd (A) is preferably 0.01～100 quality % with respect to the solids component of resin (PB), and more preferably 1～40 quality % especially is preferably 1～15 quality %.Under the situation of content less than 0.01 quality % of acidic cpd (A), can lack the effect of adding acidic cpd (A), be difficult to obtain the excellent water dispersion of dispersion stabilization.On the other hand, if the content of acidic cpd (A) surpasses 100 quality %, then there are tendencies such as water dispersion easy colorizing, gelation, emulsion pH be too small.
In water dispersion of the present invention, the amino in the resin (PB) can be kept stable morphology at acidic region by acidic cpd (A) neutralization.As the pH of water dispersion, preferably in 2～6 scope.
Water dispersion of the present invention does not contain boiling point under the normal pressure more than 185 ℃ or the Water-borne modification auxiliary agent of non-volatility.Here, the boiling point under the normal pressure more than 185 ℃ or the Water-borne modification auxiliary agent of non-volatility be meant emulsifier component or have compound of protective colloid action etc.This just means, water dispersion of the present invention can become stable water dispersion not containing these emulsifier components or have under the situation of compound of protective colloid action.
As emulsifier component, can be cationic emulsifier, anionic emulsifier, non-ionic emulsifier or amphoteric emulsifier, except the emulsifying agent that is generally used for emulsion polymerization, also comprise surfactant-based.
For example; As anionic emulsifier, can be sulfuric acid, senior alkyl sulphonate, high carboxylic acid's salt, sulfonated alkylbenzene, polyxyethylated sulfuric acid, polyoxyethylene alkyl phenyl ether sulfuric acid, vinyl sulfosuccinic ester of higher alcohols etc.
As non-ionic emulsifier, can be compound with T 46155 structure such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether, cithrol, oxyethane propylene oxide block copolymer, T 46155 fatty amide, PEP-101, sorbitan verivate etc.
As amphoteric emulsifier, can be lauryl betaine, lauryl dimethyl amine oxide etc.
As compound with protective colloid, can be Z 150PH, carboxy-modified Z 150PH, CMC 99.5, Natvosol, hydroxypropylcellulose, treated starch, Vinylpyrrolidone polymer, ROHM and salt thereof, carboxylic polyethylene wax, carboxylic Poly Propylene Wax, carboxylic Vilaterm-number-average molecular weights such as propylene wax usually at carbonyl bearing polymer and salt thereof more than 10 quality % of the acid modified polyolefin wax class below 5000 and salt, vinylformic acid-copolymer-maleic anhydride and salt thereof, vinylbenzene-(methyl) PEMULEN TR2, ethene-(methyl) PEMULEN TR2, the mutual multipolymer of iso-butylene-maleic anhydride, (methyl) vinylformic acid-unsaturated carboxylic acid content such as (methyl) Yodo Sol GH 28, gather methylene-succinic acid and salt thereof, contain amino water-soluble acrylic copolymer, gelatin, gum arabic, casein etc. usually as the compound of the dispersion stabilizer of particulate.
In addition, water dispersion of the present invention does not contain boiling point under the normal pressure more than 185 ℃ or the Water-borne modification auxiliary agent of non-volatility, even that is do not contain boiling point under the normal pressure more than 185 ℃ or the Water-borne modification auxiliary agent of non-volatility, also can obtain stable water dispersion.Therefore, producing when being the paint of part constituent, can add above-mentioned Water-borne modification auxiliary agent according to purpose with water dispersion of the present invention.
Like this, in water dispersion of the present invention, dimeracid class polyamide resin (P) stably is dispersed in the aqueous medium; The number average bead diameter of dimeracid class polyamide resin (P) is below 0.5 μ m; Below the preferred 0.4 μ m, more preferably below the 0.2 μ m, below the especially preferred 0.1 μ m.In water dispersion, if the number average bead diameter of dimeracid class polyamide resin (P) particle surpasses 0.5 μ m, then dispersion stabilization, dilution stability reduce, and, be difficult to form fine and close filming during coating.
Here, the number average bead diameter of above-mentioned dimeracid class polyamide resin (P) particle is used dynamic light scattering determination.
In addition, the content (solid component concentration) of the dimeracid class polyamide resin (P) in the water dispersion of the present invention is preferably 3～40 quality %, especially is preferably 10～35 quality %.The content of the dimeracid class polyamide resin (P) in the water dispersion is during less than above-mentioned scope, possibly need the time when filming forming through drying process, and be difficult to form thick filming.On the other hand, the content of the dimeracid class polyamide resin (P) in the water dispersion is during more than above-mentioned scope, and the storage stability of dispersion-s reduces easily.
Then, the method for manufacture to water dispersion of the present invention describes.
In method of manufacture of the present invention; The resin (PA) and the boiling point under the normal pressure that in the aqueous medium that contains hydrophilic organic solvent, add specified amount are lower than 185 ℃ basic cpd (B); Perhaps add the resin (PB) and the acidic cpd (A) of specified amount, under 70～280 ℃ temperature, carry out heated and stirred.During heated and stirred, till the speed heated and stirred of preferably changeing with PM 100～1000 is dispersed in the aqueous medium to resin (PA) or resin (PB).
Temperature during heated and stirred is necessary for 70～280 ℃, is preferably 100～250 ℃.If the temperature during heated and stirred is lower than 70 ℃, resin (PA) or resin (PB) are disperseed fully, be difficult to obtain resin (PA) or the resin (PB) of number average bead diameter below 0.5 μ m.On the other hand, the temperature during as if heated and stirred surpasses 280 ℃, and then the molecular weight of resin (PA) or resin (PB) possibly reduce, and also can produce and press the excessively problem of rising in the system.
In addition, in method of manufacture of the present invention, from the water dispersion of gained, heat up in a steamer hydrophilic organic solvent after the preferred heated and stirred.But be good with temperature, the pressure of selecting basic cpd (B), acidic cpd (A) are heated up in a steamer this moment.
In the manufacturing process of water dispersion of the present invention, the content that adds the hydrophilic organic solvent in the aqueous medium to is preferably 10～60 quality % of aqueous medium, more preferably 20～50 quality %.There is the decentralized situation about can not fully carry out of water-based of resin (PA) or resin (PB) in the content of hydrophilic organic solvent during less than 10 quality %, and on the other hand, if surpass 60 quality %, then dispersion-s has the anxiety of gelation.
In addition, the boiling point of hydrophilic organic solvent is preferably 30～250 ℃, more preferably 50～180 ℃, especially is preferably 50～120 ℃.When the boiling point of hydrophilic organic solvent was lower than 30 ℃, the evaporable ratio increased during the modulation water dispersion, lack the effect of adding hydrophilic organic solvent, and operating environment worsens easily.If boiling point surpasses 250 ℃, then be difficult to from water dispersion, remove hydrophilic organic solvent, and have when filming remain in easily film in, the anxiety of solvent resistance reduction.
In addition, the solvability of preferred hydrophilic organic solvent in 20 ℃ water is more than 50g/L.The object lesson of this hydrophilic organic solvent has diol, derivatives such as ethers, ethylene glycol monomethyl ether such as methyl alcohol, ethanol, n-propyl alcohol (being designated hereinafter simply as " NPA "), Virahol alcohols such as (being designated hereinafter simply as " IPA "), THF (being designated hereinafter simply as " THF "), dioxane etc., can mix more than 2 kinds and use.In these hydrophilic organic solvents, consider that from promoting the decentralized angle of water-based preferred IPA, NPA, THF are also preferably with these hydrophilic organic solvents and with (IPA and THF, NPA and THF).
In the method for manufacture of water dispersion of the present invention, in containing the aqueous medium of hydrophilic organic solvent, from hydrocarbon organic solvents such as the toluene below the 10 quality % that promote the dispersive purpose, can add to account for the aqueous medium quality, hexanaphthenes.If the addition of hydrocarbon organic solvent is then remarkable with separating of water in manufacturing process above 10 quality %, have the situation of the water dispersion that can not get homogeneous.
In the method for manufacture of water dispersion of the present invention, any aggegation in this process of cooling, does not take place and obtains low viscous water dispersion in heated and stirred and the water dispersion that obtains is cooled to room temperature.Particularly, water dispersion of the present invention is below 500mPas, the abundant low viscous water dispersion of the viscosity under 25 ℃, processibility, excellent in stability.Wherein, the viscosity of water dispersion of the present invention is to be good below 300mPas, more preferably below 100mPas.
In water dispersion of the present invention, can add pigment or dyestuffs such as all ingredients such as levelling agent, skimmer, anti-foaming agent, pigment dispersing agent, UV light absorber, titanium oxide, zinc oxide, carbon black as required.
Water dispersion of the present invention preferably contains linking agent.In water dispersion, add linking agent and filming of obtaining also can reduce flowability under the high temperature of the above temperature of resin softening point.
In the present invention; As linking agent; Crosslinked material gets final product between the dimeracid class polyamide resin (P) so long as can make; Can use any material, for example preferred hydrazide compound, isocyanate compound, melamine compound, urea compounds, epoxy compounds, carbodiimide compound, oxazoline compound are good to use epoxy compounds, melamine compound and oxazoline compound especially wherein.These compounds can separately or mix and use.
In addition, as linking agent, if use the linking agent of the functional group of containing a plurality of and amino or carboxyl reaction in the molecule, then can make it with dimeracid class polyamide resin (P) in amino or carboxyl react expeditiously.In addition, as linking agent, also can use the compound that has self-bridging property or have the multivalence hapto.
In the present invention, consider, can use commercially available linking agent from the angle of easy acquisition.Particularly; As hydrazide compound; The APA series (APA-M950, APA-M980, APA-P250, APA-P280 etc.) of can Shi Da mound chemical company producing etc.; As isocyanate compound; Can be the Bayhydur 3100 that produces of BASONATPLR8878, BASONAT HW-100, Sumitomo Bayer urethane company (SBU) that BASF AG produces, Bayhydur VPLS2150/1 etc., as melamine compound, can be the Cymel325 that produces of Mitsui Cytec company etc.; As epoxy compounds; Can be the Nagase Chemtex company DENACOL series (EM-150, EM-101 etc.) of producing, ADEKARESIN EM-0517 that ADEKA company produces, EM-0526, EM-051R, EM-11-50B etc., as carbodiimide compound, can be to spin Carbodilite series (SV-02, V-02, V-02-L2, V-04, E-01, E-02, V-01, V-03, V-07, V-09, V-05) the Zuo of etc.ing that company produces Wei oxazoline compound day clearly, can be the Epocross serial (WS-500, WS-700, K-1010E, K-1020E, K-1030E, K-2010E, K-2020E, K-2030E) that produces of Japanese catalyst company etc.These compounds are commercially available with the form of the dispersion-s that contains linking agent or solution.
Content of crosslinking agent in the water dispersion is preferably 0.5～100 mass parts with respect to dimeracid class polyamide resin (P) 100 mass parts.If the content of linking agent is less than 0.5 mass parts; Then in filming, be difficult to obtain the low flow under the desired high temperature, on the other hand, if surpass 100 mass parts; Then reductions such as the liquid stabilising property of water dispersion, processibility, the result causes being difficult to obtain the fundamental property as filming.
In addition, water dispersion of the present invention is preferably through radiation exposure.Behind radiation exposure, the polyamide resin in the water dispersion crosslinked obtain promoting, even be heated to more than the resin softening point by filming of obtaining of this water dispersion, still demonstrates low flow (low flow under the high temperature).
During radiation exposure,, can in water dispersion, add the known compound that produces the living radical kind from promoting crosslinked purpose.This compounds for example can be the Irgacure184 that produces of Ciba Specialty Chemicals company, 907 etc., and its usage quantity is preferably 0.01～10 mass parts with respect to resin 100 mass parts.
The gamma ray source of radioactive rays can be alpha-ray, β ray (electron rays), gamma-rays, X ray, ultraviolet ray etc.; Preferably from β ray (electron rays), gamma-rays, the X ray of cobalt 60, wherein more preferably the β radiation exposure of gamma-rays, use rumbatron is handled.These radioactive rays can a kind irradiation separately, also can shine simultaneously more than 2 kinds, also can be during certain irradiation radioactive rays more than a kind.
When water dispersion irradiation radioactive rays, be configured near the radiation source being placed on water dispersion in the container.At this moment, preferably in irradiation process, change the position of gamma ray source or container or stir water dispersion, shine equably basically.Also can be in order to produce radical with the portion water dispersion-s be configured in shine near the gamma ray source after, mix with the remainder water dispersion-s.Also but the limit is with fluming water dispersion-s limits such as pump irradiation radioactive rays.
Irradiation dose to radioactive rays does not have particular restriction, is preferably 10～400kGy, and more preferably 20～300kGy especially is preferably 50～200kGy.If irradiation dose is then crosslinked insufficient less than 10kGy, then crosslinked excessive if surpass 400kGy, flexibility, mechanical characteristics reduce, and the anxiety in the crack of being easy to generate is arranged.
Environment during to the irradiation radioactive rays does not have particular restriction, but oxygen concn is low more, can reduce the irradiation dose of radioactive rays more.Rare gas elementes such as also available nitrogen, argon are replaced environment.
Laminate of the present invention is that a kind of water dispersion of the present invention is coated on forms the laminate of filming and obtaining on the substrate surface.As water dispersion of the present invention is coated on the method on the substrate surface; Can enumerate known method, like intaglio plate roller coat, reverse roll coating, the coating of Meyer rod, the coating of lip mould (lip coating), airblade coating, film flow coat method, spraying, dip-coating, spread coating etc.Can water dispersion be coated on substrate surface equably with these methods.
As the base material that will be coated with water dispersion, can be the base material that forms with resin material, glass material etc.Base material thickness is not had particular restriction, but be preferably 10～1000 μ m, more preferably 10～500 μ m especially are preferably 10～200 μ m.
As the resin material that can be used as base material, can be to gather (methyl) acrylics, gather (methyl) vinyl cyanide resin, polystyrene resins, polysulfones resin, polyether sulfone resin, polyethers resin, polymethylpentene resinoid, cellulosetri-acetate resinoid, polyethylene terephthalate resinoid, polyurethanes resin, regenerated cellulose resinoid, diacetyl cellulose resinoid, cellulose acetate butyrate, polyester resin, acrylonitrile-butadiene-styrene ternary copolymerized resinoid, polycarbonate resin, polyetherketone resinoid, polyvinyl chloride resin, polyvinylidene dichloride resinoid, polyvinyl alcohol resin, nylon-based resin, polythylene resin, polypropylene-based resin, polyamide-based resin, polyimide based resin, norbornene resin etc.Resin material can be through prolonged treatment.Resin material can contain known additive, stablizer, for example static inhibitor, softening agent, lubricant, inhibitor etc.Adherence when making resin material and other materials lamination improves, and pre-treatment such as corona treatment, plasma treatment, ozonize, chemical treatment, solvent treatment can be implemented in the surface of resin material.In addition, but also vapor deposition has silicon-dioxide, aluminum oxide etc., but lamination has the blocking layer, is prone to other layers such as adhesive linkage, antistatic layer, UV-absorbing layer, adhesive linkage, release layer, anti-reflecting layer, hard coat, antiglare layer.
As stated, be coated on water dispersion of the present invention on the base material after, dried heat is handled, and can remove aqueous medium, and fine and close dimeracid class polyamide resin close the echoing of filming is formed on the substrate surface.At this moment, preferably dried heat is handled under the condition of the basic cpd in heating up in a steamer the dispersion-s of anhydrating (B), acidic cpd (A), removes basic cpd (B), acidic cpd (A) in the water dispersion.
The thickness that the dimeracid class polyamide resin that on substrate surface, forms is filmed does not have particular restriction, but preferred scope at 0.05～20 μ m, more preferably 0.1～10 μ m.Coating thickness is during less than 0.05 μ m, and the characteristic that dimeracid class polyamide resin is filmed might can't fully manifest, and if the thickness of filming surpasses 20 μ m, and then the polyamide resin characteristic (effect) of filming is saturated, and is unfavorable on cost.
Embodiment
Through embodiment the present invention is specified below.Wherein, the mensuration of various characteristics value and evaluation are carried out as follows among the embodiment.
(1) characteristic value of polyamide resin
(acid value, amine value)
Method with record among the JIS K 2501 is measured.
(softening point temperature)
With resin 10mg is sample; (Linkam company produces with heating (cooling) device Heat Stage with having microscope; Heating-Freezing ATAGE TH-600 type) microscope is measured under the condition of 20 ℃/minute of heat-up rates, with resin fused temperature as softening temperature.
(melt viscosity)
Measure under 1.25/ second in resin temperature 200 or 230 ℃, velocity of shear with Brookfield fusion viscosimeter DV-II+PRO type.After fusion begins, rotated about 25 minutes, read in the elapsed time medium viscosity and be steady periodic melt viscosity value basically.
(2) solid component concentration of water dispersion
It is an amount of to take by weighing the gained water dispersion, till the quality that is heated to residue (solids component) under 150 ℃ reaches measurement, obtains solid component concentration.
(3) dispersion stabilization of water dispersion
The gained water dispersion was at room temperature left standstill 10 days, with the outward appearance of following 3 grade evaluation water dispersions.
Zero: the outward appearance no change
△: separate, partial gelization occurs
*: gelation fully has agglutinator to produce
(4) pH of water dispersion
(a making manufacturing that rises abruptly F-52) is measured pH with pH meter.
(5) viscosity of water dispersion
Measure the rotary viscosity (mPas) under 25 ℃ of the temperature with Brookfield viscometer (Tokimec company produce, DVL-BII type Digital Viscometer).
(6) number average bead diameter of the resin in the water dispersion
The number average bead diameter of the resin in the water dispersion uses day Microtrac size-grade distribution meter UPA150 (No.9340 type) of machine dress company production to measure through dynamic light scattering method.
(7) adherence
As base material, use the flexible vinyl chloride sheet, be coated with the water dispersion of gained with the Meyer rod in the one side of this base material; The thickness that makes dried resin layer is 3 μ m; Handled 1 minute at 120 ℃ of heat dryings, on flexible vinyl chloride plate surface, form resin coating film thus, obtain laminate.
To filming of gained laminate, according to the method for being put down in writing among the JIS K5600, with the cross cutting method through following 4 grade evaluation adherences.
◎: do not see that arbitrary quadrille peels off
Zero: cut edge along grid and slightly to see and peel off.Account for below 5% of integral body.
△: it is thus clear that account for peeling off of integral body about 5～15%.
*: it is thus clear that account for whole peeling off more than 15%.
(8) binding property (1)
As base material, use the flexible vinyl chloride sheet, at the one side of this base material water dispersion with Meyer rod coating gained, the thickness that makes dried resin layer is 3 μ m, 120 ℃ of heat dryings processing 1 minute, on flexible vinyl chloride plate surface, forms resin coating film thus.
Then, overlapping another flexible vinyl chloride sheet on the coated surface of flexible vinyl chloride sheet with 5 seconds of exert pressure thermal treatment of 0.2MPa, fits both under 90,120,150 ℃, obtains laminate.
It is wide that the gained laminate is cut into 15mm, as sample, under the speed that 200mm/ divides, measures 180 degree stripping strengths with tensile testing machine (accurate universal testing machine 2020 types that Intesco company produces).Under each pressurized heat treatment temp, measure with 5 samples, with its MV as stripping strength.
(9) heat-resisting binding property
As base material; Use the polyethylene terephthalate film, be coated with the water dispersion of gained in the one side of this base material with the Meyer rod, the thickness that makes dried resin layer is 2.5 μ m; Handled 90 seconds at 120 ℃ of heat dryings, form resin coating film at substrate surface thus.
Overlapping aluminium foil (non-shiny surface) on the coated surface that forms, pressurization (150 ℃/0.2MPa/5 second) obtains laminate.
Under room temperature, 60 ℃, 80 ℃, 100 ℃ various environment, measure the stripping strength of gained laminate by the method identical with above-mentioned (8).
(10) alkali resistance
As base material, use aluminium foil, at the one side of this base material water dispersion with Meyer rod coating gained, the thickness that makes dried resin layer is 2 μ m, handles 1 minute at 120 ℃ of heat dryings, thus at aluminium foil surface formation resin coating film.Afterwards, in 50 ℃ in the NaOH aqueous solution (being adjusted into pH12.0) at 20 ℃ the dipping 3 minutes after, through visual valuation film have or not the dissolving or peel off.
Zero: no change in appearance.
*: film dissolving takes place or peel off, albefaction.
(11) flexibility
By obtaining laminate with above-mentioned (7) identical method; With after cover Er Bofolankesi (Gelbo Flex) trier this laminate being carried out 100 processing (in 1 minute, carrying out 40 back and forth processing under 20 ℃, the stroke of about 15cm); For filming of laminate; Same with above-mentioned (7), according to the method for putting down in writing among the JIS K5600, carry out the adherence evaluation with the cross cutting method.
(12) with the mixed stability property of acid material
Following acidic resins water dispersion is blended in the polyamide resin water dispersion; Resin solid composition 100 mass parts with respect to the polyamide resin water dispersion; The resin solid composition that makes the acidic resins water dispersion is 10 mass parts; Stir, through following 3 grades to having or not estimating of agglutinator.
Cationic ester type polyurethane resin water dispersion (" the HYDRAN CP7050 " that DIC company produces, pH5.0, solid component concentration 25 quality %)
Cationic vinyl resin water dispersion (" UW-223XS " that great achievement fine chemistry industry company produces, pH4.0, solid component concentration 34 quality %)
Zero: no agglutinator
△: agglutinator slightly
*: agglutinator is arranged
(13) binding property (2)
As base material, use Copper Foil (the about 20 μ m of thickness), at the one side of this base material water dispersion with Meyer rod coating gained, the thickness that makes dried resin layer is 3 μ m, 120 ℃ of heat dryings 1 minute, thus at the surface of Copper Foil formation resin coating film.Then, same Copper Foil film coated surface is superimposed, (following 30 seconds of sealing load 0.2MPa) pushes at 160 ℃ with thermocompressor.
It is wide that the gained laminate is cut into 15mm, as sample, under the speed that 200mm/ divides, measures 180 degree stripping strengths with tensile testing machine (accurate universal testing machine 2020 types that Intesco company produces).Measure and to carry out with 5 samples, with its MV as stripping strength.
(14) be coated with the melt flow rate(MFR) (MFR) of film resin
Water dispersion is put into container, dropped in the drying machine remain on 120 ℃ 3 hours, remove aqueous medium.Then, to residual solids component, measure MFR according to the method (190 ℃, the 2160g loading) of JIS K7210:1999 record.Wherein, MFR is the index of Resin Flow, and the MFR value is low more, and the low flow that then is considered under the high temperature is remarkable more.
As polyamide resin, used following P-1～P-14.
When making P-1～P-14,, used " TSUNODYME 395 (trade(brand)name) " (the containing dimeracid 94 quality %, monomer acids 3 quality %, trimer acid 3 quality %) of building the production of food picked from the fields article industrial as the dimeracid raw material.
(polyamide resin P-1)
A kind of polyamide resin as the dicarboxylicacid composition, contains 100 moles of % of dimeracid, as two amine components; Contain 100 moles of % of quadrol, acid value is 15.0mg KOH/g, amine value 0.3mg KOH/g; 110 ℃ of softening temperatures are 1 at 200 ℃ melt viscosities, 100mPas.
(polyamide resin P-2)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 70 moles of % of piperazine, 30 moles of % of quadrol, acid value is 5.0mg KOH/g; Amine value 0.1mg KOH/g; 140 ℃ of softening temperatures are 23 at 200 ℃ melt viscosities, 000mPas.
(polyamide resin P-3)
A kind of polyamide resin as the dicarboxylicacid composition, contains 85 moles of % of dimeracid, 15 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 10.0mg KOH/g; Amine value 0.1mg KOH/g; 158 ℃ of softening temperatures are 10 at 200 ℃ melt viscosities, 000mPas.
(polyamide resin P-4)
A kind of polyamide resin as the dicarboxylicacid composition, contains 100 moles of % of dimeracid, as two amine components, contains 100 moles of % of quadrol, and acid value is 0.5mg KOH/g, amine value 0.2mg KOH/g, and 115 ℃ of softening temperatures are 960mPas at 200 ℃ melt viscosities.
(polyamide resin P-5)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 10.0mg KOH/g; Amine value 0.1mg KOH/g; 135 ℃ of softening temperatures are 4 at 230 ℃ melt viscosities, 200mPas.
(polyamide resin P-6)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 0.3mg KOH/g; Amine value 15.5mg KOH/g; 135 ℃ of softening temperatures are 4 at 230 ℃ melt viscosities, 500mPas.
(polyamide resin P-7)
A kind of polyamide resin as the dicarboxylicacid composition, contains 45 moles of % of dimeracid, 55 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 10.5mg KOH/g; Amine value 0.2mg KOH/g; 170 ℃ of softening temperatures are 3 at 230 ℃ melt viscosities, 000mPas.
(polyamide resin P-8)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 33.0mg KOH/g; Amine value 0.2mg KOH/g; 130 ℃ of softening temperatures are 5 at 230 ℃ melt viscosities, 000mPas.
(polyamide resin P-9)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 0.2mg KOH/g; Amine value 0.5mg KOH/g; 135 ℃ of softening temperatures are 4 at 230 ℃ melt viscosities, 200mPas.
(polyamide resin P-10)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 0.1mg KOH/g; Amine value 29.0mg KOH/g; 138 ℃ of softening temperatures are 3 at 230 ℃ melt viscosities, 900mPas.
(polyamide resin P-11)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 0.4mg KOH/g; Amine value 48.0mg KOH/g; 140 ℃ of softening temperatures are 3 at 230 ℃ melt viscosities, 800mPas.
(polyamide resin P-12)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 0.2mg KOH/g; Amine value 60.0mg KOH/g; 133 ℃ of softening temperatures are 4 at 230 ℃ melt viscosities, 400mPas.
(polyamide resin P-13)
A kind of polyamide resin as the dicarboxylicacid composition, contains 45 moles of % of dimeracid, 55 moles of % of nonane diacid; As two amine components, contain 50 moles of % of piperazine, 50 moles of % of quadrol, acid value is 0.2mg KOH/g; Amine value 15.2mg KOH/g; 130 ℃ of softening temperatures are 4 at 230 ℃ melt viscosities, 000mPas.
(polyamide resin P-14)
A kind of polyamide resin as the dicarboxylicacid composition, contains 90 moles of % of dimeracid, 10 moles of % of nonane diacid; As two amine components, contain 60 moles of % of piperazine, 40 moles of % of quadrol, acid value is 0.4mg KOH/g; Amine value 15.0mg KOH/g; 90 ℃ of softening temperatures are 3 at 230 ℃ melt viscosities, 300mPas.
Embodiment 1
To have stirrer and well heater, add the polyamide resin P-1 of 75.0g, the IPA (with the pure medicine Company products of light) of 37.5g, the THF (with the pure medicine Company products of light) of 37.5g, the N of 7.2g, the zero(ppm) water of N-dimethylethanolamine (with the pure medicine Company products of light) and 217.8g in sealable withstand voltage 1 liter of capacity Glass Containers.Stirred with the rotating speed of 300rpm on the limit, and the limit is to the system internal heating, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append 100g zero(ppm) water after, with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit filtration.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 100g of mixed solvent of IPA, THF, water, obtains polyamide resin water dispersion E-1 milky, homogeneous.
Embodiment 2
To have stirrer and well heater, add the polyamide resin P-2 of 75.0g, the IPA of 75.0g, the THF of 75.0g, the N of 6.0g, the zero(ppm) water of the toluene of N-dimethylethanolamine, 7.5g (with the pure medicine Company products of light) and 136.5g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 130 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append 230g zero(ppm) water after, with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit filtration.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 230g of mixed solvent of IPA, THF, toluene, water, obtains polyamide resin water dispersion E-2 milky, homogeneous.
Embodiment 3
To have stirrer and well heater, add the polyamide resin P-3 of 75.0g, the IPA of 93.8g, the N of 6.0g, the zero(ppm) water of N-dimethylethanolamine and 200.3g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append 130g zero(ppm) water after, with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit filtration.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 130g of mixed solvent of IPA, water, obtains polyamide resin water dispersion E-3 milky, homogeneous.
Embodiment 4
Except add triethylamine (with the pure medicine Company products of light) 6.8g, zero(ppm) water 135.7g replaces N, beyond the N-dimethylethanolamine 6.0g, by with embodiment 2 in the identical method heated and stirred put down in writing, obtain polyamide resin water dispersion milky, homogeneous.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, append the N of 6.0g, behind N-dimethylethanolamine and the 230g zero(ppm) water, filter with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 230g of mixed solvent of IPA, THF, toluene, water, obtains polyamide resin water dispersion E-4 milky, homogeneous.
Embodiment 5
Except adding triethylamine 6.8g, zero(ppm) water 199.5g replace N; Beyond the N-dimethylethanolamine 6.0g, by with embodiment 3 in the record identical method heated and stirred, afterwards; Be cooled near room temperature (about 30 ℃) while stirring; Filter with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit, obtain polyamide resin water dispersion E-5 milky, homogeneous.
Embodiment 6
Except N, the addition that the addition of N-dimethylethanolamine changes 22.5g, zero(ppm) water into changes into beyond the 202.5g, by with embodiment 1 in the record identical method obtain polyamide resin water dispersion E-6 beige, homogeneous.
Embodiment 7
Except N, the addition that the addition of N-dimethylethanolamine changes 20.0g, zero(ppm) water into changes into beyond the 122.5g, by with embodiment 2 in the record identical method obtain polyamide resin water dispersion E-7 milky, homogeneous.
Embodiment 8
Except N, the addition that the addition of N-dimethylethanolamine changes 71.5g, zero(ppm) water into changes into beyond the 71.0g, by with embodiment 2 in the record identical method obtain polyamide resin water dispersion E-8 milky, homogeneous.
Embodiment 9
To have stirrer and well heater, add the polyamide resin P-5 of 110.0g, the IPA of 110.0g, the THF of 110.0g, the N of 9.4g, the toluene of N-dimethylethanolamine, 11.0g and the zero(ppm) water of 199.6g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append 330g zero(ppm) water after, with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit filtration.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 330g of mixed solvent of IPA, THF, toluene, water, obtains polyamide resin water dispersion E-9 milk yellow, homogeneous.
Embodiment 10
To have stirrer and well heater, add the polyamide resin P-5 of 110.0g, the NPA (with the pure medicine Company products of light) of 110.0g, the N of 9.4g, the zero(ppm) water of N-dimethylethanolamine and 270.6g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, filter, obtain polyamide resin water dispersion E-10 milk yellow, homogeneous with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.
Embodiment 11
To have stirrer and well heater, add the polyamide resin P-2 of 100.0g, the IPA of 100.0g, the THF of 100.0g, the N of 9.7g, the zero(ppm) water of the normal heptane of N-dimethylethanolamine, 10.0g (with the pure medicine Company products of light) and 180.3g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 130 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append 315g zero(ppm) water after, with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit filtration.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 315g of mixed solvent of IPA, THF, normal heptane, water, obtains polyamide resin water dispersion E-11 milky, homogeneous.
Comparative example 1
To have stirrer and well heater, add the polyamide resin P-1 of 60.0g, the IPA of 240.0g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 80 ℃ of following heated and stirred 60 minutes.Obtain resin homogeneous dissolved pale yellow solution in the time of 80 ℃.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, under room temperature (about 20 ℃), left standstill 1 day, partial gelization appears in liquid, fails to obtain water dispersion.
Comparative example 2,3
Except using polyamide resin P-2 and the P-3, by attempting the IPA solution of modulation polyamide resin with comparative example 1 identical method, but resin do not dissolve in IPA, and resin mass is residual, fails to obtain water dispersion.
Comparative example 4
Except using the polyamide resin P-4 as polyamide resin, carry out 2 identical operations with embodiment, the result, the polyamide resin piece is residual, fails to obtain water dispersion.
Comparative example 5
Except not adding N, beyond the N-dimethylethanolamine, carry out 2 identical operations with embodiment, the result, the polyamide resin piece is residual, fails to obtain water dispersion.
Comparative example 6
Except the temperature with heated and stirred changes into 50 ℃, carry out 2 identical operations with embodiment, the result, the polyamide resin piece is residual, fails to obtain water dispersion.
Comparative example 7
To having polyolefin resin (BONDINE HX-8290, ARKEMA Company products, 81 ℃ of fusing points), the IPA of 60.0g, the triethylamine of 3.0g and the zero(ppm) water of 177.0g stirrer and well heater, that add 60.0g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, filter, obtain polyolefin resin water dispersion E-12 milky, homogeneous with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.
Comparative example 8
To have stirrer and well heater, add the polyamide resin P-7 of 110.0g, the IPA of 110.0g, the THF of 110.0g, the N of 9.2g, the toluene of N-dimethylethanolamine, 11.0g and the zero(ppm) water of 199.8g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, append after the zero(ppm) water of 330g, filter with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 330g of mixed solvent of IPA, THF, toluene, water, obtains polyamide resin water dispersion E-13 milky, homogeneous.
Comparative example 9
To have stirrer and well heater, add the polyamide resin P-8 of 110.0g, the IPA of 110.0g, the THF of 110.0g, the N of 28.9g, the toluene of N-dimethylethanolamine, 11.0g and the zero(ppm) water of 180.1g in sealable withstand voltage 1 liter of capacity Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, append after the zero(ppm) water of 330g, filter with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.The water dispersion of gained is added in the 1L eggplant type flask, and the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer the about 330g of mixed solvent of IPA, THF, toluene, water, obtains polyamide resin water dispersion E-14 milk yellow, homogeneous.
The characteristic value and the evaluation result of water dispersion that will be through embodiment 1～11, comparative example 7～9 gained are shown in table 1.
Table 1
Figure BDA0000158417560000191
Embodiment 12
To have stirrer and well heater, add 75g polyamide resin P-5, IPA 37.5g, THF 37.5g, N, N-dimethylethanolamine 7.5g, zero(ppm) water 217.8g in sealable 1 liter of withstand voltage Glass Containers.The limit was stirred to the system internal heating with the rotating speed of 300rpm in the limit, 120 ℃ of following heated and stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append after the zero(ppm) water of 150g, move into the 1L eggplant type flask, the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer (desolventizing) IPA, THF and hydration meter 150g.Then, filter, obtain polyamide resin water dispersion E-15 milk yellow, homogeneous with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.
Embodiment 13
To have stirrer and well heater, add 75g polyamide resin P-6 in sealable 1 liter of withstand voltage Glass Containers, as the formic acid of acidic cpd (with the pure medicine Company products of light; PKa=3.75) behind 1.9g, the THF 93.8g and zero(ppm) water 204.3g as hydrophilic organic solvent; Encloses container; The rotating speed of stirring rake is made as 300rpm, mixes.At this moment, through stirring, container bottom does not show the deposition of resin saccharoid, confirms as floating state.So, open the power supply of well heater, temperature in the container is adjusted to 120 ℃, further stirred 60 minutes.Afterwards, be cooled to while stirring (about 30 ℃) near the room temperature, append after the zero(ppm) water of 150g, move into the 1L eggplant type flask, the limit is immersed in the hot water bath that is heated to 80 ℃ the limit and is reduced pressure with evaporimeter, heats up in a steamer (desolventizing) THF and the about 150g of hydration meter.Afterwards, filter, obtain polyamide resin water dispersion E-16 brown, homogeneous with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.
Embodiment 14
Except (with the pure medicine Company products of light, pKa=4.76) 2.5g replaces carrying out 13 identical operations with embodiment beyond the formic acid 1.9g, obtains polyamide resin water dispersion E-17 milk yellow, homogeneous with acetate.
Embodiment 15
Carry out 13 identical operations except replacing the polyamide resin P-6, obtain polyamide resin water dispersion E-18 brown, homogeneous with embodiment with P-10.
Embodiment 16
Carry out 13 identical operations except replacing the polyamide resin P-6, obtain polyamide resin water dispersion E-19 brown, homogeneous with embodiment with P-11.
Embodiment 17
To have stirrer and well heater, add 75g polyamide resin P-6 in sealable 1 liter of withstand voltage Glass Containers, as the formic acid 1.9g of acidic cpd, NPA 75g and zero(ppm) water 223.1g as hydrophilic organic solvent after; Encloses container; The rotating speed of stirring rake is made as 300rpm, mixes.At this moment, through stirring, container bottom does not show the deposition of resin saccharoid, confirms as floating state.So, open the power supply of well heater, temperature in the container is adjusted to 120 ℃, further stirred 60 minutes.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, filter, obtain polyamide resin water dispersion E-20 brown, homogeneous with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.
Embodiment 18
Except change the formic acid addition into 19.0g, the zero(ppm) water addition changes into the 187.2g, use with embodiment 13 identical methods and obtain polyamide resin water dispersion E-21 brown, homogeneous.
Embodiment 19
Except change the formic acid addition into 38.0g, the zero(ppm) water addition changes into the 168.2g, use with embodiment 13 identical methods and obtain polyamide resin water dispersion E-22 brown, homogeneous.
Comparative example 10
Except replacing the polyamide resin P-6, by attempting modulation polyamide resin water dispersion with embodiment 13 identical methods with P-5.But resin mass is residual, fails to obtain water dispersion.
Comparative example 11
Except replacing the polyamide resin P-6, by attempting modulation polyamide resin water dispersion with embodiment 13 identical methods with P-9.But resin mass is residual, fails to obtain water dispersion.
Comparative example 12
Carry out 13 identical operations except replacing the polyamide resin P-6, obtain polyamide resin water dispersion E-23 brown, homogeneous with embodiment with P-12.
Comparative example 13
Carry out 13 identical operations except replacing the polyamide resin P-6, obtain polyamide resin water dispersion E-24 brown, homogeneous with embodiment with P-13.
The characteristic value and the evaluation result of water dispersion that will be through embodiment 12～19, comparative example 12～13 gained are shown in table 2.
Table 2
Figure BDA0000158417560000221
Embodiment 20,21
The polyamide resin water dispersion E-9 、 Han oxazolinyl polymer aqueous solution (the Epocross WS-700 that will obtain through embodiment 9; Japan's catalyst Company products; Solid component concentration 25 quality %) blending, with respect to polyamide resin 100 mass parts, the Shi Han oxazolinyl polymer aqueous solution is 10 mass parts; Mix under the room temperature and stirred 5 minutes, obtain containing the water dispersion E-9a of linking agent.Polyamide resin water dispersion E-9 and the binding property of the water dispersion E-9a that contains linking agent and the MFR that is coated with film resin are estimated.
Embodiment 22
To put into the glass sample bottle through the polyamide resin water dispersion E-9100g that embodiment 9 obtains, irradiation is radiogenic gamma-rays 100kGy with cobalt-60.Water dispersion E-9b stable existence still behind irradiating gamma-ray.The binding property of water dispersion E-9b behind the gammairradiation and the MFR that is coated with film resin are estimated.
Embodiment 23
To have stirrer and well heater, add 100g polyamide resin P-14 in sealable 1 liter of withstand voltage Glass Containers, as the formic acid 3.0g of acidic cpd, NPA 100g and zero(ppm) water 297g as hydrophilic organic solvent after; Encloses container; The rotating speed of stirring rake is made as 300rpm, mixes.At this moment, through stirring, container bottom does not show the deposition of resin saccharoid, confirms as floating state.So, open the power supply of well heater, temperature in the container is adjusted to 120 ℃, further stirred 60 minutes.Afterwards, be cooled near room temperature (about 30 ℃) while stirring, filter, obtain polyamide resin water dispersion E-25 flaxen, homogeneous with 300 purpose Stainless Steel Filters (line footpath 0.035mm, plain weave) slight pressurization limit, limit.Then, the binding property of polyamide resin water dispersion E-25 and the MFR that is coated with film resin being carried out 1 estimates.
Embodiment 24
With polyamide resin water dispersion E-25, epoxy compounds water dispersion (ADEKA Resin EM-051R; The ADEKA Company products, multivalence epoxy compounds, solid component concentration 50 quality %) blending; With respect to polyamide resin 100 mass parts; Making epoxy compounds is 1 mass parts, mixes under the room temperature and stirs 5 minutes, obtains containing the water dispersion E-25a of linking agent.Then, the binding property of the water dispersion E-25a that contains linking agent and the MFR that is coated with film resin are estimated.
Embodiment 25
Except admixing, with respect to polyamide resin 100 mass parts, making epoxy compounds is beyond 10 mass parts, by obtaining containing the water dispersion E-25b of linking agent with embodiment 24 identical methods.Then, the binding property of the water dispersion E-25b that contains linking agent and the MFR that is coated with film resin are estimated.
Embodiment 26
To put into the glass sample bottle through the polyamide resin water dispersion E-25 100g that embodiment 23 obtains, irradiation is radiogenic gamma-rays 100kGy with cobalt-60.Water dispersion E-25c stable existence still behind irradiating gamma-ray.The binding property of water dispersion E-25c behind the gammairradiation and the MFR that is coated with film resin are estimated.
The characteristic value and the evaluation result of water dispersion that will be through embodiment 20～26 gained are shown in table 3.
Table 3
Figure BDA0000158417560000241
Shown in table 1～3, in an embodiment, can be substantially free of boiling point under the normal pressure in that to obtain polyamide resin more than 185 ℃ or under the situation of the Water-borne modification auxiliary agent of non-volatility fine and stably be dispersed in the polyamide resin water dispersion in the aqueous medium.The laminate that is formed by filming of gained water dispersion has the excellent adherence of filming, flexibility, and its heat-resisting binding property, chemical resistant properties are also excellent.
In addition, the water dispersion that presents alkalescence of embodiment 12 with understand aggegation after acid material mixes, but in the present invention; As embodiment 13～19; Also can obtain appearing the tart water dispersion,, still can keep satisfactory stability property even these water dispersions mix with acid material.
In addition, in embodiment 20～26, in water dispersion, add linking agent, or water dispersion is carried out radiation exposure, even can obtain at high temperature mobile still low filming.
On the other hand, in comparative example 1～3, attempt dimeracid class polyamide resin is dissolved among the IPA, but in comparative example 1, under the room temperature gelation takes place, in comparative example 2,3, resin does not dissolve fully, all fails to obtain water dispersion.In comparative example 4, owing to used the dimeracid class polyamide resin of acid value 0.5mg KOH/g, thereby the polyamide resin piece is residual, fails to obtain water dispersion.In comparative example 5, owing to do not add basic cpd, thereby the polyamide resin piece is residual, fails to obtain water dispersion.In comparative example 6, the temperature during owing to heated and stirred is low excessively, thereby fully dispersion of polyamide resin, and the polyamide resin piece is residual, fails to obtain water dispersion.In comparative example 7, owing to be that used resin is the water dispersion of polyolefin resin, thereby the heat-resisting poor adhesion of the laminate that forms of coating gained water dispersion.In comparative example 8, owing to be the water dispersion that constitutes by the polyamide resin that in its dicarboxylicacid composition, contains less than the dimeracid of 50 moles of %, thereby the flexibility that gained is filmed is poor.In comparative example 9, owing to used the dimeracid class polyamide resin of acid value above 20mg KOH/g, thereby the alkali resistance that gained is filmed is poor.
In addition, in comparative example 10,, thereby fail to obtain water dispersion owing to the polyamide resin that acid value is high than amine value mixes with acidic cpd.In comparative example 11, owing to used the dimeracid class polyamide resin of amine value 0.5mg KOH/g, thereby the polyamide resin piece is residual, fails to obtain water dispersion.In comparative example 12, owing to used the dimeracid class polyamide resin of amine value above 50mg KOH/g, thereby the alkali resistance that gained is filmed is poor.In comparative example 13, owing to be the water dispersion that constitutes by the polyamide resin that in its dicarboxylicacid composition, contains less than the dimeracid of 50 moles of %, thereby the flexibility that gained is filmed is poor.

Claims (11)

1. the polyamide resin water dispersion is that dimeracid class polyamide resin (P) is dispersed in the water dispersion in the aqueous medium, wherein,
The number average bead diameter of resin (P) below 0.5 μ m,
Resin (P) contains the dimeracid that accounts for more than 50 moles of % of its dicarboxylicacid composition,
The acid value of resin (P) is 1～20mg KOH/g, and is higher than its amine value,
The boiling point that contains under the normal pressure is lower than 185 ℃ basic cpd (B),
Be substantially free of boiling point under the normal pressure more than 185 ℃ or the decentralized auxiliary agent of the water-based of non-volatility.
2. polyamide resin water dispersion according to claim 1 is characterized in that, with respect to the solids component of dimeracid class polyamide resin (P), the boiling point that contains under the normal pressure is lower than 185 ℃ basic cpd (B) 0.01～100 quality %.
3. polyamide resin water dispersion according to claim 1 and 2 is characterized in that, pH is 7～13.
4. the polyamide resin water dispersion is that dimeracid class polyamide resin (P) is dispersed in the water dispersion in the aqueous medium, wherein,
The number average bead diameter of resin (P) below 0.5 μ m,
Resin (P) contains the dimeracid that accounts for more than 50 moles of % of its dicarboxylicacid composition,
The amine value of resin (P) is 1～50mg KOH/g, and is higher than its acid value,
Contain acidic cpd (A),
Be substantially free of boiling point under the normal pressure more than 185 ℃ or the decentralized auxiliary agent of the water-based of non-volatility.
5. polyamide resin water dispersion according to claim 4 is characterized in that, acidic cpd (A) is an organic acid, with respect to the solids component of dimeracid class polyamide resin (P), contains acidic cpd (A) 0.01～100 quality %.
6. according to claim 4 or 5 described polyamide resin water dispersions, it is characterized in that pH is 2～6.
7. according to each described polyamide resin water dispersion in the claim 1～6, it is characterized in that, contain linking agent.
8. according to each described polyamide resin water dispersion in the claim 1～6, it is characterized in that, through radiation exposure.
9. the method for manufacture of polyamide resin water dispersion; It is the method that is used for making each described polyamide resin water dispersion of claim 1～6; Wherein, In containing the aqueous medium of hydrophilic organic solvent, the boiling point under heated and stirred dimeracid class polyamide resin (P) and normal pressure under 70～280 ℃ the temperature is lower than 185 ℃ basic cpd (B) or acidic cpd (A).
10. the method for manufacture of polyamide resin water dispersion according to claim 9 is characterized in that, heats up in a steamer hydrophilic organic solvent after the heated and stirred.
11. laminate, its substrate surface are formed with filming of each described polyamide resin water dispersion in the claim 1～8.
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CN107724085A (en) * 2017-11-03 2018-02-23 重庆众誉材工科技有限公司 A kind of fibrous material processing method and fibrous material inorganic agent
CN113430669A (en) * 2021-05-07 2021-09-24 中国石油大学胜利学院 Synthesis method and application of temperature-resistant, salt-resistant and shear-resistant fiber material for fracturing fluid
CN113430669B (en) * 2021-05-07 2022-05-20 中国石油大学胜利学院 Synthesis method and application of temperature-resistant, salt-resistant and shear-resistant fiber material for fracturing fluid

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