CN102617775B - Vinyl chloride-based resin, manufacture method and ink - Google Patents
Vinyl chloride-based resin, manufacture method and ink Download PDFInfo
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- CN102617775B CN102617775B CN201110463296.7A CN201110463296A CN102617775B CN 102617775 B CN102617775 B CN 102617775B CN 201110463296 A CN201110463296 A CN 201110463296A CN 102617775 B CN102617775 B CN 102617775B
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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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
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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
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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Abstract
The present invention relates to the method preparing vinyl chloride-based resin, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% are containing epoxy group(ing) vinyl monomer and (D) 2-30wt% hydroxyl vinyl monomer copolymerization, additionally add each separate section of vinyl chloride monomer (A) and hydroxyl vinyl monomer (D) in the course of the polymerization process with the amount amounting up to limited range.Gained chlorovinyl monomer is thermostability, and height is dissolved in organic solvent, and is applicable to using with white pigment.
Description
Technical field
The present invention relates to compatible with ink pigment and form the vinyl chloride-based resin of fully durable coating, preparing the method for this resin, and the ink containing this resin.
Background technology
In the prior art, ink is applied to the hydroxyl vinyl chloride-based resin of pigment-compatible to improve weather resistance and the colour developing of coating.Such as, use together with the resin that polyester polyurethane resin obtains with the saponification by vinyl chloride vinyl acetate copolymer resin by JP-A2001-271015 in embodiment 3.JP-A2005-120225 discloses following ink composite: said composition comprises the metallic colloid in organic solvent and the resin glue by obtaining the modification at least partially of vinyl chloride vinyl acetate copolymer with hydroxyl monomer component, specifically refers to Chlorovinyl-acetate vinyl-vinyl alcohol trimer.But these resins are colored, and thermostability is poor, and be not suitable for especially using with white pigment.Extra saponification step is attended by the defect that productivity reduces.
Meanwhile, polyester polyol resin uses by JP-A2001-271015 in embodiment 6 together with Chlorovinyl-acetate vinyl-hydroxyethylacrylate copolymer.JP-A2005-120225 discloses following ink composite: said composition comprises the metallic colloid in organic solvent and the resin glue by obtaining the modification at least partially of vinyl chloride vinyl acetate copolymer with hydroxyl monomer component, specifically refers to be Chlorovinyl-acetate vinyl-acrylic acid hydroxy alkyl ester trimer.And WO2006/095611 discloses following conductive ink composition: said composition comprises conducting material and Chlorovinyl-acetate vinyl-(methyl) acrylic acid hydroxy alkyl ester copolymer resin.But these resins are by obtaining in the polymerization starting the whole additives being polymerized front reactant, and solubleness is in organic solvent inadequate.Therefore the performance of ink is not satisfied.
Citing document is enumerated
Patent documentation 1:JP-A2001-271015
Patent documentation 2:JP-A2005-120225
Patent documentation 3:WO2006/095611
Summary of the invention
A kind of vinyl chloride-based resin, the method preparing this resin and ink is the object of this invention is to provide in order to what improve said circumstances; The thermostability of described resin and solubleness are in organic solvent improved and do not damage the excellent properties of conventional hydroxyl vinyl chloride-based resin, and are applicable to using together with white pigment.
Conduct extensive research to realize this target, contriver finds: when vinyl chloride-based resin is prepared by the copolymerization of following component: (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl (ester) monomer (i.e. fattyacidvinylmonomer), (C) 0.25-1.5wt% is containing epoxy group(ing) vinyl monomer and (D) 2-30wt% hydroxyl vinyl monomer, obtain heat-staple by additionally adding each separate section of vinyl chloride monomer (A) and hydroxyl vinyl monomer (D) with the amount amounting up to limited range in the course of the polymerization process, high dissolution is also applicable to the vinyl chloride-based resin used with white pigment in organic solvent, and this vinyl chloride-based resin is effective as binding agent in ink.
Therefore, the invention provides vinyl chloride-based resin, prepare the method for this resin, and ink.
[1] method of vinyl chloride-based resin is prepared, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, list (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% are containing epoxy group(ing) vinyl monomer and (D) 2-30wt% hydroxyl vinyl monomer copolymerization, additionally add each separate section of vinyl chloride monomer (A) and hydroxyl vinyl monomer (D) in the course of the polymerization process with the amount amounting up to limited range.
[2] method of [1], is characterized in that, additionally adds the separate section containing epoxy group(ing) vinyl monomer (C) further with the amount amounting up to limited range.
[3] method of [1], wherein, the initial interpolation of vinyl chloride monomer (A) and the weight ratio of other interpolation are 20: 80-60: 40.
[4] method of [1], wherein, the initial interpolation of hydroxyl vinyl monomer (D) and the weight ratio of other interpolation are 10: 90-40: 60.
[5] method of [1], wherein, the joining day of the other interpolation of hydroxyl vinyl monomer (D) is the 30-150% of the joining day of the other interpolation of chlorovinyl monomer (A).
[6] method of vinyl chloride-based resin is prepared, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% epoxy group(ing) vinyl monomer, (D) during the copolymerization of 2-30wt% hydroxyl vinyl monomer, each separate section of vinyl chloride monomer (A) and hydroxyl vinyl monomer (D) is additionally added in the course of the polymerization process with the amount amounting up to limited range, with the weight ratio of the initial interpolation and other interpolation that make vinyl chloride monomer (A) for 20: 80-60: 40, the initial interpolation of hydroxyl vinyl monomer (D) and the weight ratio of other interpolation are 10: 90-40: 60, the joining day of the other interpolation of hydroxyl vinyl monomer (D) is the 30-150% of the joining day of the other interpolation of chlorovinyl monomer (A).
[7] method of vinyl chloride-based resin is prepared, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% is containing epoxy group(ing) vinyl monomer, (D) during the copolymerization of 2-30wt% hydroxyl vinyl monomer, vinyl chloride monomer (A) is additionally added in the course of the polymerization process with the amount amounting up to limited range, containing each separate section of epoxy group(ing) vinyl monomer and hydroxyl vinyl monomer (D), with the weight ratio of the initial interpolation and other interpolation that make vinyl chloride monomer (A) for 20: 80-60: 40, the initial interpolation of hydroxyl vinyl monomer (D) and the weight ratio of other interpolation are 10: 90-40: 60, the joining day of the other interpolation of hydroxyl vinyl monomer (D) is the 30-150% of the joining day of the other interpolation of chlorovinyl monomer (A).
[8] method of [1], the component (A) wherein in adding in addition and (D) be added on 50-80 DEG C at carry out.
[9] method of [6], the component (A) wherein in adding in addition and (D) be added on 50-80 DEG C at carry out.
[10] method of [7], the component (A) wherein in adding in addition, (C) and (D) be added on 50-80 DEG C at carry out.
[11] method of [1], wherein uses and is selected from following material and carries out polyethylene copolymer alcohol as suspension agent by suspension polymerization, partly-hydrolysed polyvinyl acetate, methylcellulose gum, ethyl cellulose, Vltra tears, carboxymethyl cellulose, and Natvosol, polyvinylpyrrolidone, polyacrylamide, toxilic acid-styrol copolymer, and Gantrez, starch and gelatin, polyoxyethylene, ethylene oxide-propylene oxide block copolymer.
[12] method of [1], wherein vinyl chloride-based resin is used as the binding agent in ink.
[13] by vinyl chloride-based resin that the method for [1] obtains.
[14] by vinyl chloride-based resin that the method for [6] obtains.
[15] by vinyl chloride-based resin that the method for [7] obtains.
[16] vinyl chloride-based resin of [13], it has the polymerization degree of the vinyl units of 150-400.
[17] vinyl chloride-based resin of [14], it has the polymerization degree of the vinyl units of 150-400.
[18] vinyl chloride-based resin of [15], it has the polymerization degree of the vinyl units of 150-400.
[19] ink composite, the vinyl chloride-based resin that it comprises [13].
[20] ink composite, the vinyl chloride-based resin that it comprises [14].
[21] ink composite, the vinyl chloride-based resin that it comprises [15].
[22] ink composite of [19], it comprises the pigment be selected from by the following group formed further: Pigment white 4, Pigment white 6, Pigment white 21, Pigment black 7, pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 60, pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 57:1, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213, pigment orange 36, 43, 51, 55, 59, 61, 71 and 74, with the title of Colour Index,
The amount of described pigment with 0.1-10wt% in ink composite contains.
The beneficial effect of the invention
Vinyl chloride-based resin of the present invention is heat-staple, and high dissolution in organic solvent, and is applicable to using with white pigment.
Embodiment
The following detailed description of the present invention.The invention provides the method being prepared vinyl chloride-based resin by the following material of copolymerization: (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% are containing epoxy group(ing) vinyl monomer and (D) 2-30wt% hydroxyl vinyl monomer.The method is characterised in that, additionally or in turn adds component (A) and (D) in the course of the polymerization process, and recommends also additionally or in turn to add component (C).
For giving the vinyl chloride monomer (A) of toughness and high surface hardness to coating, use with the amount of 60-95wt%, preferably 70-85wt%.Component (A) is less than 60wt% and causes the intensity of printing-ink coating to reduce, and is greater than 95wt% and causes economizing the poor solubility in machine solvent, and produces the ink coating material of the dispersion with high viscosity and difference.The initial interpolation of vinyl chloride monomer and the weight ratio of other interpolation are 20: 80-60: 40, preferably 30: 70-50: 50.If the initial interpolation of vinyl chloride monomer is less than 20: 80, the concentration of vinyl acetate monomer can become high in early days in polymerization, and the resin finally obtained may have composition heterogeneous, causes the problem of such as resin dissolves degree deficiency.If the initial interpolation of vinyl chloride monomer is greater than 60: 40, vinyl chloride monomer concentration becomes high in early days in polymerization, and final gained resin may have composition heterogeneous, causes the problem of such as resin dissolves degree deficiency.
Fatty acid vinyl monomer (B) uses with the amount of 2-15wt%, preferably 5-10wt%.Component (B) is less than the poor solubility that 2wt% causes in organic solvent, produces the printing-ink coated material of the dispersion with high viscosity and difference, and be greater than 15wt% cause strength of coating and weather resistance inadequate.
The example of fatty acid vinyl monomer comprises: vinyl-acetic ester, monochloro for vinyl-acetic ester, propionate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, and vinyl benzoate, preferred vinyl-acetic ester.
Use with the amount of 0.25-1.5wt%, preferably 0.4-0.9wt% containing epoxy group(ing) vinyl monomer (C).The component (C) being less than 0.25wt% causes the problem of the thermally-stabilised reduction of such as resin, and is greater than the problem that 1.5wt% causes such as resin solubleness in a solvent to reduce.Example containing epoxy group(ing) vinyl monomer comprises methacrylic acid methyl glycidyl ester, vinylformic acid methylglycidyl esters, allyl glycidyl ether, chavicol glycidyl ether, and glycidyl methacrylate.
Hydroxyl vinyl monomer (D) uses with the amount of 2-30wt%, preferably 5-20wt%.Be less than 2wt% component (D) adversely to affect printing-ink performance and such as develop the color, weather resistance and adhesion, and be greater than 30wt% and cause second-order transition temperature to reduce, cause the problem of such as blocking.The initial interpolation of hydroxyl vinyl monomer is 10: 90-40: 60 with the weight ratio of adding in addition, preferably 20: 80-30: 70.If the initial interpolation of hydroxyl vinyl monomer is less than 10: 90, polymerization stability may reduce, and causes such as resin coalesced problem.If the initial interpolation of hydroxyl vinyl monomer is more than 40: 60, the highly water-soluble homopolymer of hydroxyl monomer may rise, and causes the problem that such as solubleness in a solvent reduces.The example of hydroxyl vinyl monomer comprises (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, polyethyleneglycol (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, glycerine list (methyl) acrylate, allylin, hydroxyethyl vinylethers, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, (methyl) allyl alcohol, and N-methylol (methyl) acrylamide.Wherein, (methyl) Hydroxyethyl acrylate and (methyl) Propylene glycol monoacrylate are preferred, most preferably (methyl) Propylene glycol monoacrylate.
When also additionally being added fashionable containing epoxy group(ing) vinyl monomer (C), this component (C) and hydroxyl vinyl monomer (D) can separate or add as a mixture.When component (C) is preferably 15: 85-60: 40 by the weight ratio additionally adding fashionable, initial interpolation and other interpolation.
Initial interpolation preferably start polymerization before or carry out before being heated to polymerization temperature.In other adding, component (A), being added in 1 hour, more preferably of (C) and (D) started, because the polymerization temperature selected is between 50 DEG C-80 DEG C in 30 minutes.If other interpolation is delayed by, may occur resin coalesced.The preferred 3-12 hour joining day of the interpolation that component (A) is other, more preferably 4-10 hour.Component (C) and (D) other interpolation joining day preferred 1-18 hour, more preferably 2-10 hour.The joining day of the other interpolation of preferred hydroxyl vinyl monomer (D) is 30%-150%, the more preferably 60%-110% of the joining day of the other interpolation of vinyl chloride monomer (A).Be less than 30% or time of being greater than 150wt% solubleness in organic solvent may be caused to reduce.
Except said components, can optionally use any copolymerisable monomer, its example comprises vinylbenzene, alpha-methyl styrene, vinyl cyanide, (methyl) alkyl acrylate such as (methyl) methyl acrylate and (methyl) ethyl propenoate, vinylformic acid, methacrylic acid, maleic anhydride, β-crotonic acid, methylene-succinic acid and vinylidene chloride.Based on all monomers, these monomers can use in the scope being no more than 10wt%, as long as it does not damage beneficial effect of the present invention.
When preparing vinyl chloride-based resin, the chain-transfer agent containing ring-type organo phosphorous compounds can be used.Chain-transfer agent preferred dihydro oxa-phospho hetero phenanthrene (dihydrooxaphosphaphenanthrene) base phosphorus compound, based on the gross weight of monomer, uses with the amount of 0.3-0.6wt%, preferably 0.4-0.5wt%.When compound is less than 0.3wt%, coated material may have too high viscosity and can not with predetermined concentration work or process.Ink coating may be caused to lose physical strength more than 0.6wt%, typically become fragile, and also lose weather resistance.
Effectively vinyl chloride-based resin can be obtained by suspension polymerization.Suspension polymerization is undertaken by following: purge aggregation container with nitrogen, in container, deionized water, suspension agent, polymerization starter, the separate section of vinyl chloride monomer, all fatty acid vinyl monomers, separate section containing all of epoxy group(ing) vinyl monomer or separate section and hydroxyl vinyl monomer is added under pressure, heat at the reaction temperatures with initiation reaction in nitrogen atmosphere, add vinyl chloride monomer and the hydroxyl vinyl monomer of remainder in the given time, and optionally add the remainder containing epoxy group(ing) vinyl monomer in the course of the polymerization process.
The example of suspension agent comprises polyvinyl alcohol, partly-hydrolysed polyvinyl acetate, derivatived cellulose is methylcellulose gum such as, ethyl cellulose, Vltra tears, carboxymethyl cellulose, and Natvosol, synthetic polymer is polyvinylpyrrolidone such as, polyacrylamide, toxilic acid-styrol copolymer, and Gantrez, natural polymer such as starch and gelatin, polyoxyethylene, and ethylene oxide-propylene oxide block copolymer, preferred Vltra tears.Suspension agent preferably uses with the amount of 0.05-0.3wt%, based on the gross weight of monomer, can use one or more suspension agents.
The example of polymerization starter comprises organo-peroxide such as benzoyl peroxide, lauroyl peroxide, 3, 3, 5-trimethyl hexanol superoxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) ester, peroxidation two carbon ethoxyethyl group ester, peroxy dicarbonate two-3-methoxy butyl acrylate, butyl peroxy neodecanoic acid ester and two-3, 5, 5-trimethyl hexanol superoxide, with azo-compound such as Diisopropyl azodicarboxylate and 2, 2-azo two (2, 4-dimethyl) valeronitrile, they can be used alone or two or more combinationally use.Based on the gross weight of monomer, polymerization starter preferably uses with the amount of 0.1-0.3wt%.
Based on the gross weight of monomer, the deionized water as polymerisation medium preferably uses with the amount of 50-200wt%.Additionally can use water-soluble alcohol such as methyl alcohol or Virahol with the scope being no more than 50wt%.
Polymerization temperature preferably 50 DEG C-80 DEG C, more preferably the scope of 55-75 DEG C.In enforcement of the present invention, the mean polymerisation degree of preferred vinyl unit is adjusted to the scope of 150-400 by the suitable selection of above-mentioned parameter.
During polymerization, above-mentioned chain-transfer agent, polymerization starter and suspension stabilizer all can join in polymerization system when being polymerized and starting, or add with the part of separating in the course of the polymerization process.
Once obtain vinyl chloride-based resin of the present invention by above-mentioned suspension polymerization, it is separated with water medium and drying.The dried powder obtained has the average particle size particle size of 50-300 μm.Vinyl chloride-based resin preferably has the polymerization degree of the vinyl units of 150-400.
The dried powder of chlorovinyl copolymer resin is dissolved in form solution in organic solvent, is mixed with ink by it or similarly forms.The example of the organic solvent used comprises ketone solvent such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), and pimelinketone, aromatic solvent such as toluene and dimethylbenzene, protonic solvent is tetrahydrofuran (THF) such as, dimethyl formamide, and dimethyl sulfoxide (DMSO), with ester solvent such as methyl acetate, ethyl acetate, and butylacetate, they can be used alone or two or more combinationally use.
The vinyl chloride-based resin prepared by above method is suitable as the binding agent in ink.When this resin is used as resin glue in the production of ink application composition, can optionally add other resin, its example comprises polymkeric substance or copolymer resin such as urethane resin, Nitrocellulose, vibrin, epoxy resin, polyamide resin, resol, Synolac and polyvinyl butyral resin.Wherein, optimization polyurethane resin.In this case, vinyl chloride-based resin of the present invention is preferably matched with in ink composite with the amount being no more than 40wt%, more preferably 1-25wt%.Organic solvent is preferably with at least 30wt%, more preferably at least the amount of 50wt% is present in ink composite.
Pigment used herein is listed below, title with Colour Index (ColorIndex): Pigment white 4, Pigment white 6, Pigment white 21, Pigment black 7, pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 60, pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 57:1, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213, pigment orange 36, 43, 51, 55, 59, 61, 71 and 74.Pigment optimization is included in ink composite with the amount of 0.1-10wt%.
Embodiment
Provide embodiment below for explanation the present invention.In an embodiment, all numbers and % are weight part and wt% respectively.
preparation example 1
Under nitrogen atmosphere after process, 100 parts of deionized waters are added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 32 parts of vinylchlorid, 5 parts of vinyl-acetic esters, 0.2 part of glycidyl methacrylate, 3.55 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature one reaches 63 DEG C, be continuously pumped into the mixture of 48 parts of vinylchlorid and 0.6 part of glycidyl methacrylate and 10.65 parts of Propylene glycol monoacrylates immediately respectively through 6 hours and 5.4 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability and particle size.Result is shown in table 1.The physicals of resin is often planted by following method evaluation.
A) mean polymerisation degree
By sample dissolution in oil of mirbane.Under the envrionment temperature of 30.0 DEG C, measure solution flow down the spent time in Ubbelohde viscometer, in second, use conversion table to calculate the polymerization degree of vinyl units by this time.
B) solubleness
Chlorovinyl copolymer resin is dissolved in the solvent mixture of 50 parts of methyl iso-butyl ketone (MIBK) and 50 parts of toluene, or to be dissolved in 100 parts of concentration be in the ethyl acetate of 20%.This solution is joined bottom to be printed with in the Glass tubing of letter.Visible numerical value is kept to determine solubleness (sharpness that higher numeric representation is higher) by reading letter below it.
Zero: 35cm or larger
△: 5cm to being less than 35cm
×: be less than 5cm
C) heat-resistant stability
Before the solvent mixture that chlorovinyl copolymer resin is dissolved in 50 parts of methyl iso-butyl ketone (MIBK) and 50 parts of toluene, it is heated 5 hours at 80 DEG C, and evaluate with Three Estate below.For chromaticity evaluation, use the K of different milligram number
2crO
4working curve is pre-determined at the solution of 1000ml water.Such as by aberration haze meter 20 chrominance representation and 20mgK
2crO
4the solution colour of the solution same levels in 1000ml water.
◎: solution colourity is no more than 10
Zero: solution colourity 11-20
△: solution colourity 21-49
×: solution colourity 50 or larger
D) particle size distribution
Measure the number of below 28 orders according to JISK-0069, and evaluate with Three Estate below.
Number 99.0% or higher below zero: 28 order
Number 90.1-98.9% below △: 28 orders
×: the number below 28 orders is not more than 90.0%
E) develop the color
With the solid content producing 20wt%, chlorovinyl copolymer resin is dissolved in ethyl acetate.Joining in solution by marking in following often kind pigment A and B with the amount of 2wt%, then stirring.Then by the coating of this solution example on a glass and 50 DEG C of dryings.Measure gained sample by colour-difference meter (SE2000, NIPPONDENSHOKUINDUSTRIESCo., Ltd.), represent color according to JISZ-8729.Numerical value L* represents brightness, the brightness that larger numeric representation is higher.Numerical value a* is on red-green axle, and the higher expression of numerical value is redder.Numerical value b* is on Huang-blue axle, and the higher expression of numerical value is more yellow.Such as, when red color is evaluated, when numerical value L* and a* is higher, colour developing better; When white colours is evaluated, when numerical value L* is higher and numerical value a* and b* is lower, color is whiter and colour developing is better.Described numerical value is expressed relative to the numerical value 1 of preparation embodiment 10.
Red pigment A: Pigment red 57:1
White pigment B: Pigment white 6
preparation example 2
Under nitrogen atmosphere after process, 100 parts of deionized waters are added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 54.5 parts of vinylchlorid, 2.5 parts of vinyl-acetic esters, 0.37 part of glycidyl methacrylate, 0.93 part of Propylene glycol monoacrylate, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature one reaches 63 DEG C, be continuously pumped into the mixture of 39.5 parts of vinylchlorid and 0.53 part of glycidyl methacrylate and 1.67 parts of Propylene glycol monoacrylates immediately respectively through 6 hours and 2.4 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 3
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 15.6 parts of vinylchlorid, 8 parts of vinyl-acetic esters, 0.09 part of glycidyl methacrylate, 3.4 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature one reaches 63 DEG C, be continuously pumped into the mixture of 49.4 parts of vinylchlorid and 0.31 part of glycidyl methacrylate and 23.2 parts of Propylene glycol monoacrylates immediately respectively through 6 hours and 8.4 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 4
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 32 parts of vinylchlorid, 5 parts of vinyl-acetic esters, 0.8 part of glycidyl methacrylate, 3.55 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature one reaches 63 DEG C, be continuously pumped into 48 parts of vinylchlorid and 10.65 parts of Propylene glycol monoacrylates through 6 hours and 5.4 hours respectively immediately, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.Evaluate the physicals of often kind of resin by the following method.
preparation example 5
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 80 parts of vinylchlorid, 5 parts of vinyl-acetic esters, 0.8 part of glycidyl methacrylate, 14.2 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is used for copolyreaction at 63 DEG C by heating.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled, accumulation of mud during this period, chlorovinyl copolymer resin could not be obtained.
preparation example 6
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 38.8 parts of vinylchlorid, 1.5 parts of vinyl-acetic esters, 0.05 part of glycidyl methacrylate, 0.33 part of Propylene glycol monoacrylate, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature reaches 63 DEG C, be continuously pumped into the mixture of 58.2 parts of vinylchlorid and 0.15 part of glycidyl methacrylate and 0.97 part of Propylene glycol monoacrylate respectively through 6 hours and 1.68 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 7
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 34.2 parts of vinylchlorid, 16 parts of vinyl-acetic esters, 0.64 part of glycidyl methacrylate, 10.2 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature reaches 63 DEG C, be continuously pumped into the mixture of 22.8 parts of vinylchlorid and 0.96 part of glycidyl methacrylate and 15.2 parts of Propylene glycol monoacrylates respectively through 6 hours and 9.3 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 8
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 12 parts of vinylchlorid, 5 parts of vinyl-acetic esters, 0.06 part of glycidyl methacrylate, 1.1 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature reaches 63 DEG C, be continuously pumped into the mixture of 68 parts of vinylchlorid and 0.74 part of glycidyl methacrylate and 13.1 parts of Propylene glycol monoacrylates respectively through 6 hours and 5.4 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.This autoclave is cooled.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the average polymerization skin of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 9
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 52 parts of vinylchlorid, 5 parts of vinyl-acetic esters, 0.36 part of glycidyl methacrylate, 6.4 parts of Propylene glycol monoacrylates, 0.1 part of Vltra tears as suspension agent, 0.026 part of peroxy dicarbonate two (2-ethylhexyl) ester and 0.25 part two-3,5,5-trimethyl hexanol superoxide is as polymerization starter.Under stirring in nitrogen atmosphere, reactor is heated at 63 DEG C.After temperature reaches 63 DEG C, be continuously pumped into the mixture of 28 parts of vinylchlorid and 0.44 part of glycidyl methacrylate and 7.8 parts of Propylene glycol monoacrylates respectively through 6 hours and 5.4 hours, during this period copolyreaction occur.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.Cool this autoclave.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.Measure the mean polymerisation degree of resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 10
Under nitrogen atmosphere after process, the deionized water of 100 parts is added in the autoclave being configured with agitator, 40 parts of methyl alcohol, 70.4 parts of vinylchlorid, 29.1 parts of vinyl-acetic esters, 0.5 part of glycidyl methacrylate, 0.035 part of Vltra tears is as suspension agent, 0.06 part of benzoyl peroxide and 0.01 part of two-3,5,5-trimethyl hexanol superoxide are as polymerization starter.Under stirring in nitrogen atmosphere, reactor is used for copolyreaction at 74 DEG C by heating.When the internal pressure of autoclave reaches 0.3MPa, discharge remaining pressure.Cool this autoclave.Take out resin slurry, filter, and dry, produce chlorovinyl copolymer resin.This resin is carried out saponification again, obtains the resin be made up of 87.6% vinylchlorid, 0.9% nytril 1.5% vinyl alcohol.Measure the mean polymerisation degree of this resin, solubleness, heat-resistant stability, particle size distribution and colour developing.Result is shown in table 1.
preparation example 11
Except adding the Propylene glycol monoacrylate of whole amount before polymerization, obtain vinyl chloride resin in the mode identical with preparation example 1.Result is shown in table 1.
table 1
Numerical value L*, a*, b*: relative to preparation example 10 1 numerical value and represent
MIBK: methyl iso-butyl ketone (MIBK)
Claims (20)
1. prepare the method for vinyl chloride-based resin for one kind, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% is containing epoxy group(ing) vinyl monomer, (D) during the copolymerization of 2-30wt% hydroxyl vinyl monomer, the each separate section additionally adding vinyl chloride monomer (A) and hydroxyl vinyl monomer (D) in the course of the polymerization process with the amount amounting up to limited range with the weight ratio of the initial interpolation and other interpolation that make hydroxyl vinyl monomer (D) for 10:90-40:60, wherein, the initial interpolation of vinyl chloride monomer (A) and the weight ratio of other interpolation are 20:80-60:40.
2. the method for claim 1, is characterized in that, additionally adds the separate section containing epoxy group(ing) vinyl monomer (C) further with the amount amounting up to limited range.
3. the process of claim 1 wherein, the joining day of the other interpolation of hydroxyl vinyl monomer (D) is the 30-150% of the joining day of the other interpolation of vinyl chloride monomer (A).
4. prepare the method for vinyl chloride-based resin for one kind, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% is containing epoxy group(ing) vinyl monomer, (D) during the copolymerization of 2-30wt% hydroxyl vinyl monomer, each separate section of each vinyl chloride monomer (A) and hydroxyl vinyl monomer (D) is additionally added in the course of the polymerization process with the amount amounting up to limited range, with the weight ratio of the initial interpolation and other interpolation that make vinyl chloride monomer (A) for 20:80-60:40, the initial interpolation of hydroxyl vinyl monomer (D) and the weight ratio of other interpolation are 10:90-40:60, the joining day of the other interpolation of hydroxyl vinyl monomer (D) is the 30-150% of the joining day of the other interpolation of vinyl chloride monomer (A).
5. prepare the method for vinyl chloride-based resin for one kind, it is characterized in that, when (A) 60-95wt% vinyl chloride monomer, (B) 2-15wt% fatty acid vinyl monomer, (C) 0.25-1.5wt% is containing epoxy group(ing) vinyl monomer, (D) during the copolymerization of 2-30wt% hydroxyl vinyl monomer, vinyl chloride monomer (A) is additionally added in the course of the polymerization process with the amount amounting up to limited range, containing each separate section of epoxy group(ing) vinyl monomer and hydroxyl vinyl monomer (D), with the weight ratio of the initial interpolation and other interpolation that make vinyl chloride monomer (A) for 20:80-60:40, the initial interpolation of hydroxyl vinyl monomer (D) and the weight ratio of other interpolation are 10:90-40:60, the joining day of the other interpolation of hydroxyl vinyl monomer (D) is the 30-150% of the joining day of the other interpolation of vinyl chloride monomer (A).
6. the process of claim 1 wherein component (A) in adding in addition and (D) be added on 50-80 DEG C at carry out.
7. the method for claim 4, the component (A) wherein in adding in addition and (D) be added on 50-80 DEG C at carry out.
8. the method for claim 5, the component (A) wherein in adding in addition, (C) and (D) be added on 50-80 DEG C at carry out.
9. the process of claim 1 wherein that use is selected from following material and carries out copolymerization as suspension agent by suspension polymerization: polyvinyl alcohol, partly-hydrolysed polyvinyl acetate, methylcellulose gum, ethyl cellulose, Vltra tears, carboxymethyl cellulose, and Natvosol, polyvinylpyrrolidone, polyacrylamide, toxilic acid-styrol copolymer, and Gantrez, starch and gelatin, polyoxyethylene, ethylene oxide-propylene oxide block copolymer.
10. the process of claim 1 wherein that vinyl chloride-based resin is used as the binding agent in ink.
11. vinyl chloride-based resins obtained by claim 1 method.
12. vinyl chloride-based resins obtained by claim 4 method.
13. vinyl chloride-based resins obtained by claim 5 method.
The vinyl chloride-based resin of 14. claims 11, it has the polymerization degree of the vinyl units of 150-400.
The vinyl chloride-based resin of 15. claims 12, it has the polymerization degree of the vinyl units of 150-400.
The vinyl chloride-based resin of 16. claims 13, it has the polymerization degree of the vinyl units of 150-400.
17. 1 kinds of ink composites, it comprises the vinyl chloride-based resin of claim 11.
18. 1 kinds of ink composites, it comprises the vinyl chloride-based resin of claim 12.
19. 1 kinds of ink composites, it comprises the vinyl chloride-based resin of claim 13.
The ink composite of 20. claims 17, it comprises the pigment be selected from by the following group formed further: Pigment white 4, Pigment white 6, Pigment white 21, Pigment black 7, pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 60, pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 57:1, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213, pigment orange 36, 43, 51, 55, 59, 61, 71 and 74, with the title of Colour Index,
Described pigment is contained with the amount of 0.1-10wt% in ink composite.
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| KR101759719B1 (en) * | 2016-12-05 | 2017-07-20 | 한화케미칼 주식회사 | Method for preparing vinylchloride based resin composition |
| JP6801429B2 (en) * | 2016-12-19 | 2020-12-16 | 東ソー株式会社 | Ultra high molecular weight polyethylene powder and its manufacturing method |
| JP6669099B2 (en) * | 2017-02-23 | 2020-03-18 | 日信化学工業株式会社 | Actinic ray-curable composition, actinic ray-curable ink composition, and methods for producing them |
| KR101887638B1 (en) * | 2017-09-27 | 2018-08-10 | 한화케미칼 주식회사 | Vinylchloride based resin composition and method for preparing the same |
| KR101956136B1 (en) * | 2018-07-30 | 2019-03-08 | 한화케미칼 주식회사 | Vinylchloride based copolymer and method for preparing the same |
| CN113717309B (en) * | 2021-08-18 | 2023-04-11 | 无锡洪汇新材料科技股份有限公司 | Processing modified additive and preparation method thereof |
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| GB899593A (en) * | 1958-09-13 | 1962-06-27 | Hoechst Ag | Process for preparing copolymers of vinyl chloride and vinyl acetate |
| CN1154972A (en) * | 1995-09-01 | 1997-07-23 | 联合碳化化学品及塑料技术公司 | Water dispersing substance for ethenyl polymer |
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| CA1278399C (en) * | 1985-10-15 | 1990-12-27 | Charles Neale Merriam | Vinyl chloride resins and compositions incorporating such resins |
| US5731368A (en) * | 1995-09-01 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Aoueous vinyl polymer dispersions |
| JP2001114839A (en) * | 1999-10-20 | 2001-04-24 | Nisshin Chem Ind Co Ltd | Vinyl chloride-based copolymer resin and method for producing the same |
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| GB899593A (en) * | 1958-09-13 | 1962-06-27 | Hoechst Ag | Process for preparing copolymers of vinyl chloride and vinyl acetate |
| CN1154972A (en) * | 1995-09-01 | 1997-07-23 | 联合碳化化学品及塑料技术公司 | Water dispersing substance for ethenyl polymer |
| CN1756778A (en) * | 2003-03-06 | 2006-04-05 | 瓦克聚合系统两合公司 | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin |
| CN1756777A (en) * | 2003-03-06 | 2006-04-05 | 瓦克聚合系统两合公司 | Thermostable vinylchloride mixed polymers |
| CN101175779A (en) * | 2005-09-01 | 2008-05-07 | 瓦克聚合系统两合公司 | Method for producing vinyl chloride-vinyl acetate copolymers in the form of their solid resins |
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| KR20120073122A (en) | 2012-07-04 |
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