JP2012201730A - Method for producing vinyl polymer and method for producing polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a vinyl polymer having two or more hydroxy groups at one terminal; to provide a method for producing a polyurethane obtained by reacting the vinyl polymer, a polyol and a polyisocyanate; and to provide a method for producing a binder for an inkjet printing ink comprising the dispersion of the polyurethane.SOLUTION: The method for producing the binder for the inkjet printing ink includes mixing a vinyl monomer (B) with a chain transfer agent (C) having a mercapto group and two or more hydroxy groups at one terminal in the presence of an active hydrogen-containing compound (A) regulated so as to have a viscosity within the range of 5-10,000 mPa s by being heated to a radical polymerization temperature within the range of 50-200°C to carry out a radical polymerization to afford the vinyl polymer (D) having the two or more hydroxy groups at one terminal, and reacting the resultant vinyl polymer (D) with the polyisocyanate (F) to produce the polyurethane (G), and mixing the polyurethane (G) with an aqueous medium (H) to cause phase inversion emulsification.

Description

  The present invention relates to a method for producing a vinyl polymer having two or more hydroxyl groups at one end. The present invention also relates to a method for producing polyurethane using the vinyl polymer.

  Vinyl polymers are used in various applications including coating agents and adhesives. It is known that the vinyl polymer can be generally produced by a radical polymerization reaction of a vinyl group of a vinyl monomer.

  However, since the radical polymerization reaction is likely to cause a stop reaction due to the influence of oxygen or the like, for example, the reaction is performed in the presence of an inert gas such as nitrogen, or dissolved oxygen is removed by a method such as bubbling. It was necessary to minimize the influence of the oxygen by using raw materials and solvents.

  As a method for producing the vinyl polymer, specifically, the inside of the reaction vessel is replaced with nitrogen gas, and the vinyl monomer is radically polymerized under the condition that the amount of dissolved oxygen in the reaction system is adjusted to 20 ppm. A method is known (for example, refer to Patent Document 1).

  However, the above method requires a step of replacing the reaction vessel with an inert gas in addition to the polymerization reaction step, and a step of removing dissolved oxygen contained in the raw materials, etc. In some cases, the production process is complicated, and the production efficiency is reduced.

  Further, in the method of radical polymerization of a vinyl monomer in the presence of an organic solvent such as benzene or methyl ethyl ketone as described in the above-mentioned document 1, a polymerization time of about 10 hours is required to complete the radical polymerization reaction. There was a case. In the above method, it may be difficult to increase the yield of the target compound to a practically sufficient level due to the influence of side reactions and the like.

  From the above, it is difficult to cause a stop reaction even in the presence of oxygen, and the production efficiency of the target vinyl polymer can be improved in each stage by shortening the polymerization time and improving the yield. The invention of the manufacturing method has been sought by the industry.

  By the way, as the vinyl polymer, for example, a vinyl polymer having two hydroxyl groups at one end is known, and such a vinyl polymer is used as a polyol raw material when used for production of polyurethane or the like. There is a case.

  However, even if an attempt is made to produce a vinyl polymer having two hydroxyl groups at one end by a conventional method using a solvent such as benzene or methyl ethyl ketone, as described above, the polymerization time can be shortened and the vinyl weight can be reduced. In some cases, the yield of the coalescence cannot be increased, and the production efficiency of the vinyl polymer cannot be improved.

  In addition, the vinyl polymer having two hydroxyl groups at one end obtained by the conventional method often includes a chain transfer agent remaining unreacted, a side reaction product, and the like. In some cases, the production reaction was delayed and the production efficiency of the target polyurethane was lowered.

JP 2003-226702 A

  The problem to be solved by the present invention is that it is difficult to cause a side reaction such as a termination reaction even in the presence of oxygen, and realizes shortening of the polymerization time and improvement of the yield of the main product. Another object of the present invention is to provide a method for producing a vinyl polymer having two or more hydroxyl groups at one end capable of remarkably improving the production efficiency of the vinyl polymer.

  In addition, the problem to be solved by the present invention is to reduce the production time and increase the yield of the vinyl polymer having two or more hydroxyl groups at one end, and to produce polyurethane using the same. It is an object of the present invention to provide a method for producing a polyurethane which can prevent a delay in the urethanization reaction of the polyurethane, and can reduce the production time and increase the yield of the polyurethane.

  The inventors have studied to solve the above problems, and used a relatively high viscosity active hydrogen atom-containing compound instead of the organic solvent such as methyl ethyl ketone as a solvent for performing the radical polymerization reaction. It has been found that when a radical polymerization reaction of a vinyl monomer is carried out in an active hydrogen atom-containing compound, the production efficiency of the desired vinyl polymer obtained can be improved.

  Further, it has been found that the production efficiency of polyurethane can be improved by using a vinyl monomer having two or more hydroxyl groups at one end obtained by the above method and using a mixture containing the vinyl polymer and polyol. It was.

  That is, in the present invention, in the presence of the active hydrogen atom-containing compound (A) adjusted to a viscosity in the range of 5 mPa · s to 10000 mPa · s by heating to a radical polymerization temperature in the range of 50 ° C. to 200 ° C. , A vinyl monomer (B), a mercapto group and a chain transfer agent (C) having two or more hydroxyl groups at one end, and radical polymerization, and two or more hydroxyl groups at one end The present invention relates to a method for producing a vinyl polymer (D) having

  Moreover, this invention is 500- which is the active hydrogen atom containing compound (A) adjusted to the viscosity of the range of 5mPa * s-10000mPa * s by heating to the radical polymerization temperature of the range of 50 to 200 degreeC. In the presence of a polyol (A-1) having a number average molecular weight of 10,000, a vinyl monomer (B) and a chain transfer agent (C) having a mercapto group and two or more hydroxyl groups at one end are mixed. A polyol (E) containing a mixture of a vinyl polymer (D) having two or more hydroxyl groups at one end obtained by radical polymerization and the polyol (A-1), and a polyisocyanate (F) It is related with the manufacturing method of the polyurethane (G) characterized by making these react.

  The method for producing a vinyl polymer of the present invention prevents side reactions such as termination reaction of the vinyl polymer even in the presence of oxygen, shortens the polymerization time, and improves the yield of the desired vinyl polymer. Therefore, the production efficiency can be remarkably improved.

  Moreover, if it is the manufacturing method of the said polyurethane, when manufacturing the vinyl polymer (D) which has a 2 or more hydroxyl group in the one end as said vinyl polymer, urethane which may arise by using a chain transfer agent It is possible to improve the production efficiency of polyurethane since the delay of the polymerization reaction can be prevented.

  In the presence of the active hydrogen atom-containing compound (A) adjusted to a viscosity in the range of 5 mPa · s to 10000 mPa · s by heating to a radical polymerization temperature in the range of 50 ° C. to 200 ° C., the present invention By mixing the monomer (B), a mercapto group, a chain transfer agent (C) having two or more hydroxyl groups at one end, and other components as necessary, the chain transfer agent (C) The present invention relates to a method for producing a vinyl polymer (D) having two or more hydroxyl groups at one terminal end by proceeding radical polymerization of the vinyl monomer (B) starting from a mercapto group possessed by .

  In the present invention, as a solvent for polymerizing the vinyl monomer (B) or the like, for example, a conventional ketone solvent such as methyl ethyl ketone or acetone, benzene or the like is not substantially used, and the viscosity is higher than those. It is important to use the active hydrogen atom-containing compound (A) in order to shorten the polymerization time and to improve the yield of the target vinyl polymer.

  As the active hydrogen atom-containing compound (A), it is essential to use a compound having a viscosity in the range of 5 mPa · s to 10000 mPa · s at the temperature at which the vinyl monomer (B) is radically polymerized. Since radical polymerization of the vinyl monomer (B) is usually carried out in a temperature range of 50 ° C. to 200 ° C., the active hydrogen atom-containing compound (A) is heated and adjusted to a predetermined temperature within the range. It is essential to use one having a viscosity in the range of 5 mPa · s to 10000 mPa · s. For example, if radical polymerization of the vinyl monomer (B) is performed at 80 ° C., the viscosity when the active hydrogen atom-containing compound (A) is adjusted to 80 ° C. is in the range of 5 mPa · s to 10000 mPa · s. Use what is inside.

  Here, since the above-mentioned methyl ethyl ketone and acetone are about 0.3 mPa · s and about 0.2 mPa · s at 50 ° C., respectively, they both have a viscosity of 5 mPa · s or less. Even if these are used as a solvent in the radical polymerization and the solvent, the vinyl monomer (B), the chain transfer agent (C), etc. are mixed and radical polymerization is attempted, the radical polymerization time is sufficient. It cannot be shortened, and the yield of the target vinyl polymer (D) may not be improved.

  Further, instead of the active hydrogen atom-containing compound (A), the viscosity when adjusted to a radical polymerization temperature in the range of 50 ° C. to 200 ° C., for example, can be outside the above range, for example, the aromatic ring concentration is 5000 mmol / kg or more When the polyester polyol or the like is used, the vinyl monomer (B) is difficult to uniformly dissolve in the active hydrogen atom-containing compound (A) and the polymerization reaction may not proceed sufficiently.

  Therefore, it is preferable to use the active hydrogen atom-containing compound (A) adjusted to a viscosity of 10 mPa · s to 7500 mPa · s at a predetermined radical polymerization temperature in the range of 50 ° C. to 200 ° C. It is more preferable to use one adjusted to a viscosity of 10 mPa · s to 5000 mPa · s.

  The present invention does not exclude the use of other solvents other than the active hydrogen atom-containing compound (A) as a solvent for producing the vinyl polymer (D). An active hydrogen atom-containing compound other than the atom-containing compound (A) or a conventionally known solvent such as methyl ethyl ketone may be used. However, in the case of using such a solvent, it is preferable to use it within a range that does not impair the good production efficiency of the vinyl polymer (D), and they are used as solvents for producing the vinyl polymer (D). It is preferably used in the range of 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 0% by mass with respect to the total amount.

  As described above, the radical polymerization temperature is usually in the range of 50 ° C to 200 ° C, preferably in the range of 50 ° C to 150 ° C, and more preferably in the range of 60 ° C to 120 ° C. The specific radical polymerization temperature is determined by the polymerization initiator used, the type of the active hydrogen atom-containing compound (A), the type of viscosity, and the like.

  The active hydrogen atom-containing compound (A) adjusted to the predetermined viscosity by heating to a predetermined radical polymerization temperature within the range of 50 ° C. to 200 ° C. has a vinyl monomer (B) or a mercapto group. It is mixed with the chain transfer agent (C) and other components as required.

  At the time of mixing, from the viewpoint of suppressing radical polymerization termination reaction and the like, the amount of dissolved oxygen contained in the raw material such as the active hydrogen atom-containing compound (A) is reduced by bubbling with an inert gas or the like. Also good. Further, the mixing may be performed in a reaction vessel substituted with an inert gas.

  In the mixing, for example, the vinyl monomer (B), the chain transfer agent (C) and other components are supplied separately or a mixture thereof in the presence of the active hydrogen atom-containing compound (A). Can be done. The supply may be batch supply or sequential supply such as dropping.

  After mixing the active hydrogen atom-containing compound (A), the vinyl monomer (B), the chain transfer agent (C) having a mercapto group, and other components as necessary, radical polymerization is performed under the above conditions. By proceeding, a vinyl polymer (D) in which the vinyl monomer (B) is radically polymerized starting from the mercapto group of the chain transfer agent (C) can be obtained.

  The radical polymerization time varies depending on the radical polymerization temperature, the molecular weight of the target vinyl polymer (D), etc., but is approximately half the time compared to the case where a conventional solvent such as methyl ethyl ketone is used. be able to. Specifically, when polymerizing methacrylic acid to produce a methacrylic resin, when methyl ethyl ketone is used as a solvent, a polymerization time of about 10 hours is required. However, if the active hydrogen atom-containing compound (A) is used in place of the methyl ethyl ketone, it is possible to produce a substantially similar vinyl polymer (D) in about 5 hours of polymerization time.

  In addition, the vinyl polymer (D) obtained by the production method of the present invention includes a vinyl monomer (B) remaining as an unreacted substance, a chain transfer agent (C), and a by-product due to a side reaction. There is. However, their content can be remarkably reduced as compared with the conventional production method using methyl ethyl ketone or the like as a solvent, and the content of such by-products is usually 1% by mass or less. It is possible to suppress it.

  Moreover, the yield of the target vinyl polymer (D) can be remarkably improved by suppressing the content of the unreacted products and by-products.

The production method of the present invention can be applied to the production of a vinyl polymer (D) having a number average molecular weight in the range of about 500 to 10,000, although it varies depending on the purpose of use. Among them, it is preferable to apply to the production of the vinyl polymer (D) having a number average molecular weight of 1000 to 3000 when used as a raw material for producing polyurethane (G) having good durability and flexibility. More preferably, it is applied to the production of the vinyl polymer (D) having a number average molecular weight in the range of 1000 to 2500.
As the vinyl polymer (D-1) having two hydroxyl groups at one end to be described later, those having a number average molecular weight within the above range can be used.

  Further, the vinyl polymer (D) obtained by the production method of the present invention can take a relatively sharp molecular weight distribution as compared with the vinyl polymer obtained by the conventional method.

  As the active hydrogen atom-containing compound (A) that can be used in the method for producing the vinyl polymer (D) of the present invention as described above, when adjusted to a predetermined radical polymerization temperature in the range of 50 ° C to 200 ° C, Any of those having a viscosity in the range of 5 mPa · s to 10000 mPa · s can be used.

  As the active hydrogen atom-containing compound (A), for example, a compound having a hydroxyl group or an amino group can be used, and specifically, polyol (A-1), polyamine (A-2) or the like can be used. It is possible to use polyol (A-1).

  As said polyol (A-1), polyether polyol, polyester polyol, polyester ether polyol, polycarbonate polyol etc. can be used, for example. Among these, polyether polyol is used from the viewpoint of reducing the viscosity of the mixture of the active hydrogen atom-containing compound (A) and the vinyl polymer (D) and improving the production efficiency of the polyurethane (G) described later. It is preferable.

  The polyol (A-1) can be used as long as it can be adjusted to a predetermined viscosity at the radical polymerization temperature, even if it is solid at room temperature of 25 ° C., for example.

  As the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Specifically, it is preferable to use polyoxytetramethylene glycol, polypropylene glycol, or polyethylene glycol as the polyether polyol because the viscosity at the time of radical polymerization of the vinyl monomer (B) can be easily adjusted. .

  Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyesters obtained by the above, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.

  Examples of the polycarboxylic acid that can be used include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.

  Moreover, as said polyester ether polyol, what reacted the polyether polyol which the said alkylene oxide added to the said initiator and polycarboxylic acid can be used, for example. As the initiator and the alkylene oxide, the same ones exemplified as those usable when the polyether polyol is produced can be used. Moreover, as said polycarboxylic acid, the thing similar to what was illustrated as what can be used when manufacturing the said polyester polyol can be used.

  Moreover, as said polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, what is obtained by making phosgene, bisphenol A, etc. react can be used.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone Relatively low molecular weight dihydroxy compounds such as resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene adipate, Polyester polyols such as polyhexamethylene succinate and polycaprolactone can be used.

  Moreover, as said polyol (A-1), a comparatively low molecular weight polyol can be used besides the above-mentioned thing. Examples of relatively low molecular weight polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and triglyceride. Methylolethane, trimethylolpropane and the like can be used.

  As said polyol (A-1), when adjusting to the predetermined radical polymerization temperature in the range of 50 degreeC-200 degreeC, the viscosity of the range of 5 mPa * s-10000 mPa * s can be provided, As a result, oxygen exists. Even so, in order to realize suppression of by-products and improvement in the yield of the desired product, those having a number average molecular weight of 500 to 10,000 are preferable, and have a number average molecular weight in the range of 1000 to 3000. It is more preferable to use one. The polyol (A-1) having the predetermined viscosity is preferably an aliphatic polyol.

  Examples of the polyamine (A-2) usable for the active hydrogen atom-containing compound (A) include polyoxyalkylene diamines such as polyoxyethylene diamine, polyoxyalkylene triamines such as polyoxyethylene triamine, and ethylenediamine. Diethylenetriamine or the like can be used.

  Moreover, as said polyamine (A-2), the ether type polyamine etc. which were obtained by making the said polyamine react with the molecular both ends of polyols, such as polyoxyethylene glycol and polyoxypropylene glycol, can also be used.

  Examples of the vinyl monomer (B) used in the method for producing the vinyl polymer (D) of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) (Meth) acrylic acid esters such as acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate; (meth) acrylic acid, ( (Meth) acrylic acid -Acid groups or acid anhydride groups such as carboxyethyl, 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride Containing vinyl monomer; (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N- Butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide; 2-aziridinylethyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N, N-die Ruaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meta ) Acryloyloxyethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine; N -Methylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate; aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine , Vinyl fe Nitrogen-containing vinyl monomers such as ruamine and p-aminostyrene; nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3 Fluorine-containing vinyl monomers such as 3-pentafluoropropyl (meth) acrylate and perfluorocyclohexyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether Vinyl ethers such as butyl vinyl ether; vinyl compounds having an aromatic ring such as styrene, α-methylstyrene, divinylstyrene; isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinyl Pyrrolidone: Polyoxyethylene group-containing vinyl polymers such as polyoxyethylene monomethyl ether (meth) acrylate and polyoxyethylene monoethyl ether (meth) acrylate can be used.

  As the vinyl monomer (B), it is possible to use one containing at least one selected from the group consisting of the (meth) acrylic acid and the (meth) acrylic ester, and the chain transfer agent (C). This is preferable because it is easy to control the reaction and the production efficiency of the vinyl polymer (D) can be further improved.

  The vinyl monomer (B) is preferably used in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the active hydrogen atom-containing compound (A), and in the range of 10 to 350 parts by mass. Is preferably used in order to allow radical polymerization to proceed efficiently.

  Examples of the chain transfer agent (C) include 3-mercapto-1,2-propanediol (thioglycerin), 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 2- Mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,3-propanediol, Chain transfer agent (C) having a mercapto group and two or more hydroxyl groups such as 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol Can be used. Especially, it is preferable to use the chain transfer agent (C-1) which has a mercapto group and two hydroxyl groups from a viewpoint of manufacturing chain | strand-shaped polyurethane as polyurethane (G) mentioned later, specifically ,. It is preferable to use 3-mercapto-1,2-propanediol because it has little odor, is excellent in terms of workability and safety, and is versatile.

  The chain transfer agent (C) is used in the range of 1 to 10 parts by mass with respect to the total amount of the vinyl monomer (B), and only the vinyl monomer (B) and the like are reduced in the reaction product. And it is more preferable when improving production efficiency, such as a vinyl polymer (D) and a polyurethane (G).

  When manufacturing the said vinyl polymer (D), a polymerization initiator etc. can be used as needed other than the said chain transfer agent (C).

  Examples of the polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyoctoate, and t-butyl peroxide. Organic peroxides such as oxybenzoate, lauroyl peroxide, trade name “Niper BMT-K40” (manufactured by NOF Corporation; mixture of m-toluoyl peroxide and benzoyl peroxide), azobisisobutyronitrile Azo-based compounds such as trade name “ABN-E” [Nippon Hydrazine Kogyo Co., Ltd .; 2,2′-azobis (2-methylbutyronitrile)] can be used. Among them, those that generate radicals at about 70 ° C. to 120 ° C. are preferable. Specifically, azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), or the like is preferably used.

  When using the said polymerization initiator, you may mix with the said active hydrogen atom containing compound (A) previously, and you may mix beforehand with either of other components.

  When using the said polymerization initiator, it is preferable to use the said polymerization initiator in 0.01 mass part-10 mass parts with respect to 100 mass parts of vinyl monomers (B).

  The vinyl polymer (D) having two or more hydroxyl groups at one end obtained by the above method can be used, for example, as a polyol raw material when producing polyurethane, polyester or the like. Specifically, the polyurethane (G) is a vinyl polymer (D) having two or more hydroxyl groups at one end obtained by the above method, preferably a vinyl polymer having two hydroxyl groups at one end ( A polyol (E) containing a mixture of D-1) and a polyol (A-1) having a number average molecular weight of 500 to 10,000 which is the active hydrogen atom-containing compound (A), and a polyisocyanate (F), and If necessary, it can be produced by reacting a chain extender. The hydroxyl group of the vinyl polymer (D) can react with the isocyanate group of the polyisocyanate (F) to form a urethane bond.

  The active hydrogen atom-containing compound (A) used as a solvent when producing the vinyl polymer (D) is consumed as a part of the polyol (E) that is a raw material for producing the polyurethane (G).

  In the reaction of the polyol (E) and the polyisocyanate (F), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (F) to the hydroxyl group of the polyol (E) is 0.8-2. It is preferable to carry out in the range of 5, more preferably in the range of 0.9 to 1.5.

  The reaction is preferably performed in the range of 20 ° C. to 120 ° C. for about 30 minutes to 24 hours.

  The reaction of the polyol (E) and the polyisocyanate (F) may be performed in an organic solvent or without a solvent.

  Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. Can be used alone or in combination of two or more.

  The polyol (E) used in producing the polyurethane (G) is a total of 50% by mass to 100% of the vinyl polymer (D) and the polyol (A) with respect to the total amount of the polyol (E). It is preferable to carry out at a mass ratio of mass% in order to impart good flexibility and toughness to the polyurethane (G) obtained.

  In addition to the vinyl polymer (D) and the active hydrogen atom-containing compound (A), the polyol (E) may be used in combination with other polyols as necessary.

  As said other polyol, polyol similar to the polyol (A-1) illustrated as what can be used for the said active hydrogen atom containing compound (A), and polyols other than the said polyol (A-1) should be used. Can do.

  As said other polyol, the thing similar to what was illustrated as what can be used for the said polyol (A-1), such as polyether polyol, polyester polyol, polyester ether polyol, polycarbonate polyol, can be used, for example. .

  When producing an aqueous polyurethane which can be dissolved or dispersed in the aqueous medium (H) as the polyurethane (G), a hydrophilic group-containing polyol (e-1) can be used as the other polyol.

  As said hydrophilic group containing polyol (e-1), what has a hydrophilic group can be used, for example, an anionic group containing polyol, a cationic group containing polyol, and a nonionic group containing polyol are used. Among them, it is preferable to use an anionic group-containing polyol or a cationic group-containing polyol.

  As the anionic group-containing polyol, for example, a carboxyl group-containing polyol or a sulfonic acid group-containing polyol can be used.

  Examples of the carboxyl group-containing polyol include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and the like. Among them, it is preferable to use 2,2′-dimethylolpropionic acid. Moreover, the carboxyl group-containing polyester polyol obtained by making the said carboxyl group-containing polyol and various polycarboxylic acids react can also be used.

  Examples of the sulfonic acid group-containing polyol include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the low molecular weight polyol. Polyester polyol obtained by reacting can be used.

  The carboxyl group-containing polyol or sulfonic acid group-containing polyol is preferably used in the range where the acid value of the polyurethane (G) is 10 to 70, and more preferably 10 to 60. In addition, the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said polyurethane (G).

  The anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to exhibit good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, NaOH, KOH, and LiOH. A metal hydroxide containing etc. can be used. The basic compound is preferably used in the range of basic compound / anionic group = 0.5 to 3.0 (molar ratio) from the viewpoint of improving the water dispersion stability of the resulting coating agent. It is more preferable to use in the range which becomes 0.9-2.0 (molar ratio).

  Further, as the cationic group-containing polyol, for example, a tertiary amino group-containing polyol can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in one molecule, and a secondary amine. A polyol obtained by reacting with can be used.

  It is preferable that a part or all of the cationic group is neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.

  Further, the tertiary amino group as the cationic group is preferably partly or entirely quaternized. As the quaternizing agent, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and dimethyl sulfate is preferably used.

  Further, as the nonionic group-containing polyol, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

  The hydrophilic group-containing polyol (e-1) is preferably used in the range of 1% by mass to 45% by mass with respect to the total mass of raw materials used for the production of the polyurethane (G).

  Examples of the polyisocyanate (F) used in the production of the polyurethane (G) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, Aromatic polyisocyanates such as diisocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and alicyclic structures Having polyiso It is possible to use the Aneto. Among them, it is preferable to use an aliphatic polyisocyanate from the viewpoint of preventing yellow discoloration, and from the viewpoint of further improving the scratch resistance and alkali resistance in addition to the above-mentioned discoloration prevention, an aliphatic cyclic structure-containing polyisocyanate. Is preferably used.

  When manufacturing the said polyurethane (G), a chain extender can also be used as needed. Since the chain extender forms a urea bond by reacting with an isocyanate group or the like of the polyurethane, it is preferably used in a scene where high hardness or the like is required. On the other hand, when improvement in flexibility and adhesion was required, the polyurethane (G) was obtained by using a polyurethane obtained without using a chain extender, and by limiting the amount of use to a minimum. It is preferable to use polyurethane, specifically, one having a urea bond ratio contained in the polyurethane of 10% by mass or less.

  As the chain extender, polyamine, other active hydrogen atom-containing compounds and the like can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Razide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, and ethylenediamine is preferably used.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose. , Glycols such as methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used alone or in combination of two or more thereof within a range in which the storage stability of the coating agent of the present invention is not lowered.

  The chain extender is preferably used, for example, in a range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), 0.3 to 1.0 (equivalent It is more preferable to use it in the range of the ratio.

  Examples of the polyurethane (G) obtained by reacting the polyol (E), the polyisocyanate (F), and the chain extender as necessary include, for example, the vinyl polymer (C) at one end. If a vinyl polymer (C-2) having two hydroxyl groups is used, the vinyl polymer structure is derived from the vinyl polymer (C-2) as a side chain with respect to the polyurethane structure as the main chain structure. Examples include grafted polyurethane. Further, when a vinyl polymer having one hydroxyl group at one end is used as the vinyl polymer (C), a vinyl polymer structure derived from the vinyl polymer is provided at one end or both ends of a polyurethane molecule. Polyurethane can be obtained.

  When the vinyl polymer structure derived from the vinyl polymer (D) is present in the side chain of the polyurethane (G), it has other hydroxyl groups other than the two or more hydroxyl groups at one end. It is preferable to use those not present. Specifically, it is preferable not to use a hydroxyl group-containing vinyl monomer together with those exemplified as vinyl monomers that can be used in the production of the vinyl polymer (D). When the polyurethane (G) or the like is produced, if the vinyl polymer structure derived from the vinyl polymer (D) does not need to be present in the side chain, the hydroxyl group-containing vinyl monomer is used. Also good.

  As said polyurethane (G), it is preferable to use what contains 1 mass%-70 mass% of vinyl polymer structures derived from said vinyl polymer (C) with respect to the said polyurethane (G) whole quantity. It is preferable to use those containing from 50% by mass to 50% by mass in order to form a cured product having excellent durability and weather resistance.

  Moreover, as said polyurethane (G), it is preferable to use what has a weight average molecular weight of the range of 10,000-150,000, and it is more preferable to use the thing of 15000-50000.

  The polyurethane (G) obtained by the above method may be, for example, a solvent-free one generally referred to as hot melt, or one dissolved in various organic solvents. The polyurethane (G-1) having a hydrophilic group obtained by using the hydrophilic group-containing polyol (e-1) when producing the polyurethane (G) is dissolved in the aqueous medium (H) or It is preferable that it is dispersed.

  The aqueous polyurethane composition in which the polyurethane (G-1) is dissolved or dispersed in the aqueous medium (H) is mixed with the polyurethane (G-1) or an organic solvent solution thereof and the aqueous medium (H), so-called conversion. It can be produced by phase emulsification. Specifically, it can be produced by the following method.

  [Method 1] A part of the hydrophilic group of the polyurethane (G-1) obtained by reacting the polyol (E) containing the hydrophilic group-containing polyol (e-1) and the like with the polyisocyanate (F) or A method in which, after neutralizing or quaternizing all, the aqueous medium (H) is added to disperse the polyurethane (G-1) in water.

  [Method 2] A part of the hydrophilic group of the polyurethane (G-1) obtained by reacting the polyol (E) containing the hydrophilic group-containing polyol (e-1) and the like with the polyisocyanate (F) or A method in which, after neutralizing or quaternizing all, the aqueous medium (H) is added, and the polyurethane (G-1) is dispersed in water by chain extension using the chain extender as necessary.

  [Method 3] Polyurethane obtained by reacting the polyol (E) containing the hydrophilic group-containing polyol (e-1) and the like with the polyisocyanate (F), and, if necessary, the same chain extender as described above In a reaction vessel in a batch or divided, and a chain extension reaction is carried out to produce polyurethane (G-1), and then part or all of the hydrophilic groups in the obtained polyurethane (G-1) are produced. A method in which after neutralization or quaternization, an aqueous medium (H) is added and dispersed in water.

  The aqueous medium (H) is a solvent in which the polyurethane (G-1) can be dispersed. Examples of the aqueous medium (H) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  In the [Method 1] to [Method 3], an emulsifier may be used as necessary. In addition, when water is dissolved or dispersed, a machine such as a homogenizer may be used as necessary.

  Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers; Cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. It is. Among these, from the viewpoint of maintaining excellent storage stability such as polyurethane (G), it is basically preferable to use an anionic or nonionic emulsifier. Moreover, as long as the mixing stability of the polyurethane (G) can be maintained, for example, a cationic emulsifier and an amphoteric emulsifier may be used in combination.

  The vinyl polymer (D) obtained by the above-mentioned method and the polyurethane (G) obtained by using the same, for example, with an organic solvent or an aqueous medium as a solvent, for example, a coating agent, an adhesive, a molding material, It can be used in pigment dispersants and binders for gravure inks, inkjet inks and functional inks, or acceptors, hot melt adhesives, urethane foams, and the like.

  The composition containing the vinyl polymer (D) or polyurethane (G) may be used in combination with a curing agent or a curing catalyst depending on the application to be used.

Examples of the curing agent include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, a polyisocyanate, and the like. Examples of the curing catalyst include lithium hydroxide. Sodium hydroxide, potassium hydroxide and the like can be used.
The

  As described above, among the vinyl polymers (D) obtained by the above method, a hydroxyl group-containing vinyl polymer, preferably a vinyl polymer (D-1) having two or more hydroxyl groups at one end, more preferably a piece. Polyurethane using a vinyl polymer having a hydroxyl group obtained in the presence of conventional methyl ethyl ketone, etc. by producing a polyurethane (G) using a vinyl polymer (D-2) having two hydroxyl groups at the terminal Compared with the case of producing the polyurethane (G), the production time of the polyurethane (G) can be reduced to about 2/3.

  The polyurethane (G) obtained by the above method has a small amount of residual unreacted vinyl monomer (B), is not gelled, and has excellent dispersion stability. Can be suitably used.

  The ink jet printing ink binder is polyurethane (G) with respect to the total amount of the ink jet printing ink binder from the viewpoint of achieving both the storage stability of the ink, excellent scratch resistance, and durability such as alkali resistance. It is preferable that 10-50 mass% is contained, and it is more preferable that 15-35 mass% is contained. Further, the ink jet printing ink binder preferably contains 50% by mass to 90% by mass of the aqueous medium (H), and 65% by mass to 85% by mass with respect to the total amount of the binder for ink jet printing ink. It is more preferable.

  The ink jet printing ink binder can be used for ink jet printing inks, for example, in combination with pigments, dyes, and other various additives as required. In addition, when using water-based inkjet printing ink, it is preferable to use a polyurethane (G-1) as said polyurethane (G).

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.
As the inorganic pigment, for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite and the like can be used.

  Examples of the organic pigment include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, Organic pigments such as diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used.

  Examples of the dye include azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, Naphthoquinone dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane, and the like can be used.

  Examples of the additives include polymer dispersants, viscosity modifiers, wetting agents, antifoaming agents, surfactants, preservatives, pH adjusting agents, chelating agents, plasticizers, ultraviolet absorbers, and antioxidants. In addition, acrylic resins and the like that have been used as binders for conventional ink jet printing inks can be used.

  As the polymer dispersant, for example, an acrylic resin, a styrene-acrylic resin, or the like can be used, and any of a random type, a block type, and a graft type can be used. When using the polymer dispersant, an acid or a base may be used in combination to neutralize the polymer dispersant.

  Of the ink jet printing inks, water-based ink jet printing inks can be prepared, for example, by the following manufacturing method.

  (1) The pigment or dye, the aqueous medium (H), the binder for ink jet printing ink containing the polyurethane (G-1), and if necessary, the additive are collectively used using various dispersing devices. To prepare ink by mixing.

  (2) An ink precursor composed of an aqueous dispersion of pigment or dye is prepared by mixing the pigment or dye, the aqueous medium (H) and, if necessary, the additive using various dispersing devices. Then, an ink precursor composed of an aqueous dispersion of the pigment or dye, an ink-jet printing ink binder containing the polyurethane (G-1), and an aqueous medium and additives as necessary are dispersed in various ways. A method of preparing ink by mixing using an apparatus.

  The ink precursor containing the pigment used in the ink production method described in (2) above can be prepared, for example, by the following method.

  (I) A pigment obtained by mixing a kneaded product obtained by pre-kneading additives such as a pigment and a polymer dispersing agent using a two-roll or a mixer with an aqueous medium using various dispersing devices. A method for preparing an ink precursor comprising an aqueous dispersion containing

  (Ii) After the pigment and the polymer dispersant are mixed using various dispersing devices, the polymer dispersant is deposited on the surface of the pigment by controlling the solubility of the polymer dispersant, and further dispersed. A method of preparing an ink precursor comprising an aqueous dispersion containing a pigment by mixing them using an apparatus.

  (Iii) The pigment and the additive are mixed using various dispersing devices, and then the mixture and the resin emulsion are mixed using the dispersing device to prepare an ink precursor composed of an aqueous dispersion containing the pigment. how to.

  The ink for ink jet printing obtained above preferably has a volume average particle diameter of 200 nm or less, particularly in the case of forming a higher gloss image such as photographic image quality, the range of 80 to 120 nm. It is more preferable that

  The inkjet printing ink is 0.2 to 10% by mass of the polyurethane (C), 50 to 95% by mass of an aqueous medium, and 0.5 to 15% of a pigment or dye based on the entire inkjet printing ink. It is preferable to contain the mass%.

  The ink for ink jet printing of the present invention obtained by the above method can be used exclusively for ink jet printing using an ink jet printer, for example, ink jet printing on a substrate such as paper, plastic film, metal film or sheet. be able to. The ink jet method is not particularly limited, but a known method such as a continuous jet type (charge control type, spray type, etc.) or an on-demand type (piezo type, thermal type, electrostatic suction type, etc.) should be applied. Can do.

  Since the printed matter printed using the ink for ink jet printing of the present invention has excellent scratch resistance, it is difficult to cause deterioration of a printed image due to lack of pigments and the like, and has excellent alkali resistance. Since it has a high color density image, it can be prevented by bleed or the like due to adhesion of alkaline detergent to the printed image surface, and can be obtained, for example, by photographic printing by inkjet printing or high-speed printing by inkjet printing. It can be used for various purposes such as printed materials.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Example 1] Preparation of vinyl polymer (a1-1) having two hydroxyl groups at one end Polypropylene glycol (several) was added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet. The average molecular weight is 2000, and the viscosity when heated to 80 ° C. is about 40 mPa · s.) 500 parts by mass are charged, and then 302 parts by mass of methyl methacrylate, 172 parts by mass of butyl acrylate, and 3-mercapto-1,2-propane By supplying 24 parts by mass of diol and 2 parts by mass of 2,2′-azobis (2-methylpropionitrile) and reacting them, a vinyl polymer having a number average molecular weight of 2000 and having two hydroxyl groups at one end (a1 A solution of -1) was obtained.

[Example 2] Preparation of vinyl polymer (a1-2) having two hydroxyl groups at one end Polyoxytetramethylene was added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet. 500 parts by weight of glycol (number average molecular weight 2000, viscosity when heated to 80 ° C .: about 450 mPa · s) 500 parts by weight, and then 302 parts by weight of methyl methacrylate, 172 parts by weight of butyl acrylate and 3-mercapto-1, By supplying 24 parts by mass of 2-propanediol and 2 parts by mass of 2,2′-azobis (2-methylpropionitrile) and reacting them, a vinyl polymer having two hydroxyl groups at one end with a number average molecular weight of 2000 is obtained. A solution of the union (a1-2) was obtained.

[Example 3] Preparation of vinyl polymer (a1-3) having two hydroxyl groups at one end. A 4-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen introduction tube was charged with 1,4- Polyester polyol obtained by reacting butanediol and adipic acid (number average molecular weight 2000, viscosity when heated to 80 ° C., about 750 mPa · s) 500 parts by mass were charged into the reaction vessel, and then 302 mg of methyl methacrylate. Parts by weight, 172 parts by weight of butyl acrylate, 24 parts by weight of 3-mercapto-1,2-propanediol and 2 parts by weight of 2,2′-azobis (2-methylpropionitrile) and reacting them, the number average A solution of a vinyl polymer (a1-3) having a molecular weight of 2000 and having two hydroxyl groups at one end was obtained.

[Example 4] Preparation of vinyl polymer (a1-4) having two hydroxyl groups at one end Into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, 500 parts by mass of polycarbonate diol having a number average molecular weight of 2000 obtained by reacting hexanediol and carbonate ester (viscosity of about 2600 mPa · s when heated to 80 ° C.) is charged, and then 302 parts by mass of methyl methacrylate in the reaction vessel. And 172 parts by weight of butyl acrylate, 24 parts by weight of 3-mercapto-1,2-propanediol, and 2 parts by weight of 2,2′-azobis (2-methylpropionitrile) are allowed to react, whereby the number average molecular weight is obtained. A solution of a vinyl polymer (a1-4) having two hydroxyl groups at one end of 2000 was obtained.

[Comparative Example 1] Preparation of vinyl polymer (a1'-1) having two hydroxyl groups at one end Into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, methyl ethyl ketone (80 500 parts by mass of viscosity when heated to 0 ° C., and then 302 parts by mass of methyl methacrylate, 172 parts by mass of butyl acrylate and 24 parts by mass of 3-mercapto-1,2-propanediol. And 2 parts by mass of 2,2′-azobis (2-methylpropionitrile) are reacted by being reacted to give a vinyl polymer (a1′-1) having two hydroxyl groups at one end with a number average molecular weight of 2000 ) Was obtained.

[Comparative Example 2] Preparation of vinyl polymer having two hydroxyl groups at one end (a2'-1) To a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube was added ethylene glycol ( Viscosity when heated to 80 ° C .: about 3 mPa · s) 500 parts by mass, and then 302 parts by mass of methyl methacrylate, 172 parts by mass of butyl acrylate and 24 parts by mass of 3-mercapto-1,2-propanediol in the reaction vessel And 2,2′-azobis (2-methylpropionitrile) 2 parts by mass and reacting to give a vinyl polymer (a2′-1) having two hydroxyl groups at one end with a number average molecular weight of 2000 Solution was obtained.

[Comparative Example 3] Preparation of vinyl polymer having two hydroxyl groups at one end (a3'-1) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, Polyester polyol obtained by reacting '-[isopropylidenebis [(p-phenylene) (oxy)]] diethanol (ethylene oxide adduct of bisphenol A) and isophthalic acid (number average molecular weight 2000, heated to 80 ° C) 500 mass parts), and then 302 parts by mass of methyl methacrylate and 172 parts by mass of butyl acrylate in the reaction vessel, and a viscosity of about 30000 mPa · s at the time, the concentration of the aromatic structure present in the polyester polyol is about 6700 mmol / kg) 24 parts by mass of 3-mercapto-1,2-propanediol and 2,2′-azobis (2-methylpropyl) Pionitoriru) 2 parts by supplying, by reacting, to obtain a solution of a vinyl polymer having two hydroxyl groups at one end of the number average molecular weight 2000 (a3'-1).

[Measurement of number average molecular weight of vinyl polymer]
The number average molecular weight of the vinyl polymer was measured by gel permeation chromatograph (GPC method). Specifically, the vinyl polymer was coated on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to prepare a semi-dry coating film. The obtained coating film was peeled off from the glass plate, and 0.4 g was dissolved in 100 g of tetrahydrofuran to obtain a measurement sample.

  As a measuring apparatus, Tosoh Corporation high performance liquid chromatograph HLC-8220 type was used. As a column, Tosoh Corporation column TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) was used in combination.

  Standard polystyrenes (manufactured by Showa Denko KK and Toyo Soda Co., Ltd.) as standard samples (molecular weights: 44.48 million, 4250,000, 288,000, 2750,000, 1.85 million, 860,000, 450,000, 411,000, 35. Calibration curves were created using 50,000, 190,000, 160,000, 96,000, 50,000, 37,000, 198,000, 196,000, 5570, 4000, 2980, 2030, 500). .

  Tetrahydrofuran was used as the eluent and sample solution, and the number average molecular weight was measured using a RI detector with a flow rate of 1 mL / min, a sample injection amount of 500 μL, and a sample concentration of 0.4%.

Abbreviations in Table 1 will be described below.
"PPG"; polypropylene glycol (number average molecular weight 2000)
“PTMG”: polyoxytetramethylene glycol (number average molecular weight 2000)
“PES1”: polyester polyol obtained by reacting 1,4-butanediol and adipic acid (number average molecular weight 2000)
“PC1”; polycarbonate diol obtained by reacting 1,6-hexanediol and carbonate (number average molecular weight 2000)
“EG”; ethylene glycol “MEK”; methyl ethyl ketone “PES2”; 2,2 ′-[isopropylidenebis [(p-phenylene) (oxy)]] diethanol (ethylene oxide adduct of bisphenol A) and isophthalic acid Polyester polyol (number average molecular weight 2000)

[Evaluation method for improvement in production efficiency of vinyl polymer]
[Evaluation based on reaction time]
First, the evaluation was made based on the time required for the radical polymerization reaction of 98% by mass or more of the total amount of the vinyl monomers from the time when the radical polymerization reaction of the vinyl monomer mixture was started.
Specifically, the vinyl having two hydroxyl groups at one end when all the vinyl monomer mixtures described in the examples and comparative examples are radically polymerized to form a vinyl polymer. The non-volatile content [V] (theoretical value) of the polymer solution was calculated.
Subsequently, the radical polymerization reaction of the vinyl monomer mixture was carried out under the conditions of 80 ° C. according to the description of the examples and comparative examples. In the course of the reaction, a part of the reaction mixture was collected and dried at 108 ° C. for 1 hour to measure the nonvolatile content [W] in the reaction mixture.
Based on the values of the non-volatile content [V] and [W] and the formula [non-volatile content [W] / non-volatile content [V]] × 100, radical polymerization is actually performed on the total amount of the vinyl monomer mixture. The mass ratio of the reacted vinyl monomer was calculated.
The time required from the start of the radical polymerization reaction of the vinyl monomer mixture to the mass ratio being 98% by mass or more was measured. It was evaluated that it contributed to the improvement of the production efficiency of the polymer. In addition, “−” in the table indicates that radical polymerization reaction hardly proceeded.

[Evaluation based on gel fraction]
Second, it was evaluated based on the gel fraction. Specifically, a solution of a vinyl polymer having two hydroxyl groups at one end obtained in Examples 1 to 4 and Comparative Examples 1 to 3, and “Coronate HXR” (manufactured by Nippon Polyurethane Industry Co., Ltd .: average isocyanate) An equivalent ratio of the hydroxyl group of the vinyl polymer and the active hydrogen atom-containing compound and the isocyanate group of the crosslinking agent. Were mixed in the range of [hydroxyl group / isocyanate group] = 1/1 to obtain a composition.

The composition obtained above was applied to the surface of a polypropylene film whose mass was measured in advance so that the dry film thickness was 10 μm, then dried at 100 ° C. for 5 hours, and further at room temperature for 24 hours. By leaving it for a period of time, each laminate in which a dry film was laminated on the film surface was obtained.
The mass [X] of each dry film obtained by removing the polypropylene film from the laminate was measured.

  Next, each of the dry films described above was left for 1 hour in a state of being immersed in toluene at 25 ° C., and then dried at 100 ° C. for 1 hour. The mass [Y] of each dried film after the drying was measured.

  Based on the values of the mass [X] and mass [Y] and the formula [[Y] / [X]] × 100, the gel fraction of each dry film based on the mass before and after immersion in toluene was measured. .

  Those having a gel fraction value of approximately 90% by mass or more were evaluated as having low molecular weight side reaction products and the like, and being able to improve the yield of the intended vinyl polymer.

[Evaluation method for improving polyurethane production efficiency]
[Evaluation based on reaction time]
In a nitrogen-substituted 80 ° C. vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, the vinyl weight having two hydroxyl groups at one end obtained in Examples 1-4 and Comparative Examples 1-3 One of the solutions of the coalescence, 4,4′-diphenylmethane diisocyanate (methylenediphenyl diisocyanate), the hydroxyl group of the vinyl polymer and the active hydrogen atom-containing compound contained in the solution, and the 4,4 ′ -Each polyurethane was manufactured by mixing and reacting within a range where the equivalent ratio [hydroxyl group / isocyanate group] with the isocyanate group of diphenylmethane diisocyanate is 1/2.
At that time, from the time when the vinyl polymer solution having two hydroxyl groups at one end and 4,4′-diphenylmethane diisocyanate were mixed in the equivalent ratio, they were reacted at 80 ° C., and 4,4′- The time required for the mass ratio of 4,4′-diphenylmethane diisocyanate that had undergone urethanation to the total amount of diphenylmethane diisocyanate to exceed 95 mass% was measured, and the production efficiency of such time-consuming polyurethane was evaluated. When the time was approximately within 5 hours, it was evaluated that it contributed to the improvement of polyurethane production efficiency. Moreover, the thing in which the urethanation reaction hardly progressed was made into "-" in the table | surface. The mass ratio of 4,4′-diphenylmethane diisocyanate subjected to the urethanization reaction was calculated based on the mass of unreacted 4,4′-diphenylmethane diisocyanate obtained by the back titration method and the charged amount.

[Example 5] Preparation of polyurethane and binder for inkjet printing ink containing the same In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, the vinyl polymer (a1-1) obtained above 292 parts by mass of the solution and 127 parts by mass of isophorone diisocyanate were reacted at 100 ° C. for 5 hours, 57 parts by mass of 2,2-dimethylolpropionic acid and 471 parts by mass of methyl ethyl ketone were added, and further reacted at 80 ° C. for 10 hours. Then, 5 parts by mass of methanol was added and reacted to obtain an organic solvent solution (a2-1) of polyurethane (acid value 50) having a weight average molecular weight of 50000.

  49 parts by mass of 48 mass% potassium hydroxide aqueous solution is added to the organic solvent solution (a2-1) of the polyurethane to neutralize part or all of the carboxyl groups of the polyurethane, and 1500 parts by mass of water is further added. By sufficiently stirring, an aqueous dispersion of polyurethane (a3-1) was obtained.

  Subsequently, the aqueous dispersion (a3-1) of the polyurethane is desolvated, and further adjusted by adding water so that the nonvolatile content is 25% by mass, whereby the binder (a4-1) for inkjet printing ink of the present invention is obtained. Obtained.

Comparative Example 4 Preparation of Polyurethane and Inkjet Printing Ink Binder Containing Polyurethane The vinyl polymer (a1) obtained in Comparative Example 1 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer '-1) solution 292 parts by mass and polypropylene glycol (number average molecular weight 2000) 146 parts by mass, and after reacting isophorone diisocyanate 127 parts by mass at 80 ° C for 10 hours, 2,2-dimethylolpropionic acid 57 parts by mass And 325 parts by weight of methyl ethyl ketone were added, and further reacted at 80 ° C. for 10 hours. Then, 5 parts by weight of methanol was added and reacted to give an organic solvent solution (a2) of polyurethane (acid value 50) having a weight average molecular weight of 50,000. '-1) was obtained.

  Subsequently, 49 mass parts of 48 mass% potassium hydroxide aqueous solution is added to the organic solvent solution (a2′-1) of the polyurethane to neutralize part or all of the carboxyl groups of the polyurethane, and further 1500 mass of water. An aqueous dispersion of polyurethane (a3′-1) was obtained by adding parts and stirring sufficiently.

  Subsequently, the aqueous dispersion (a3′-1) of the polyurethane is desolvated and further adjusted by adding water so that the non-volatile content becomes 25% by mass. )

[Measurement of weight average molecular weight]
The weight average molecular weight of the polyurethane (G) was measured by gel permeation chromatograph (GPC method). Specifically, polyurethane (C) was coated on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to prepare a semi-dry coating film. The obtained coating film was peeled off from the glass plate, and 0.4 g was dissolved in 100 g of tetrahydrofuran to obtain a measurement sample.

  As a measuring apparatus, Tosoh Corporation high performance liquid chromatograph HLC-8220 type was used. As a column, Tosoh Corporation column TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) was used in combination.

  Standard polystyrenes (manufactured by Showa Denko KK and Toyo Soda Co., Ltd.) as standard samples (molecular weights: 44.48 million, 4250,000, 288,000, 2750,000, 1.85 million, 860,000, 450,000, 411,000, 35. Calibration curves were created using 50,000, 190,000, 160,000, 96,000, 50,000, 37,000, 198,000, 196,000, 5570, 4000, 2980, 2030, 500). .

  Tetrahydrofuran was used as the eluent and sample solution, and the weight average molecular weight was measured using a RI detector with a flow rate of 1 mL / min, a sample injection amount of 500 μL, and a sample concentration of 0.4%.

Preparation Example 1 (Aqueous dispersion of quinacridone pigment)
1500 g of vinyl polymer (styrene / acrylic acid / methacrylic acid = 77/10/13 (mass ratio), weight average molecular weight, acid value 156 mgKOH / g), quinacridone pigment (chromoftal jet magenta DMQ, 4630 g of Ciba Specialty Chemicals), 380 g of phthalimidomethylated 3,10-dichloroquinacridone (average number of phthalimidomethyl groups per molecule is 1.4), 2600 g of diethylene glycol, and 688 g of 34% by weight potassium hydroxide aqueous solution Was charged into a planetary mixer PLM-V-50V (manufactured by Inoue Seisakusho Co., Ltd.) having a capacity of 50 L, and kneading was continued for 4 hours.

  A total amount of 8000 g of ion-exchanged water heated to 60 ° C. was added in 2 hours to obtain a colored resin composition having a nonvolatile content of 37.9% by mass.

  While adding 744 g of diethylene glycol and 7380 g of ion-exchanged water little by little to 12 kg of the colored resin composition obtained by the above method, the mixture was stirred with a dispersion stirrer, and a precursor of an aqueous dispersion of quinacridone pigment (before dispersion treatment). An aqueous dispersion) was obtained.

  Next, 18 kg of this aqueous dispersion precursor was added to a bead mill (Nanomill NM-G2L manufactured by Asada Tekko Co., Ltd., beads φ: 0.3 mm zirconia beads, bead filling amount: 85%, cooling water temperature: 10 ° C., rotation The aqueous dispersion of the quinacridone pigment was obtained by subjecting the solution passed through the bead mill to a centrifugal treatment of 13000 G × 10 minutes, followed by filtration through a filter having an effective pore size of 0.5 μm. Got. The concentration of the quinacridone pigment in this aqueous dispersion was 14.9% by mass.

[Preparation of ink for inkjet printing]
Binders (a4-1) and (a4′-) for the inkjet printing inks obtained in Example 5 and Comparative Example 4 so that the concentration of the quinacridone pigment is 4% by mass and the concentration of the polyurethane is 1% by mass. 1), an aqueous pigment dispersion of the quinacridone pigment obtained in Preparation Example 1, 2-pyrrolidinone, triethylene glycol monobutyl ether, glycerin, a surfactant (Surfinol 440, manufactured by Air Products) and ions Ink for inkjet printing was prepared by mixing and stirring the exchange water according to the following blending ratio.

(Mixing ratio of ink for inkjet printing)
-Aqueous dispersion of quinacridone pigment obtained in Preparation Example 1 (pigment concentration 14.9%); 26.8 g
・ 2-Pyrrolidinone; 8.0g
・ Triethylene glycol monobutyl ether; 8.0 g
・ Glycerin; 3.0g
・ Surfactant (Surfinol 440, manufactured by Air Products); 0.5 g
・ Ion exchange water: 48.7 g
-Binder for ink jet printing ink obtained in Example 5 and Comparative Example 4 (nonvolatile content: 25% by mass); 4.0 g

[Evaluation of ink ejection stability]
A diagnostic page was printed and the state of the nozzle was confirmed with a Photomart D5360 (manufactured by Hewlett-Packard Company) in which a black ink cartridge was filled with the inkjet pigment ink. After continuously printing 20 pages of solid print with a print density setting of 100% in an area of 18 cm × 25 cm per page, a diagnostic page was printed again to check the state of the nozzles. The change in the state of the nozzles before and after continuous solid printing was evaluated as the ink ejection property. The evaluation criteria are described below.

[Criteria]
◎: No change in nozzle state and no discharge abnormality occurred ○: Although slight ink adhesion to the nozzle was confirmed, no abnormality in ink discharge direction occurred △: Solid Abnormal ink ejection direction or non-ejection of ink occurred after printing 20 pages continuously ×: Abnormal ink ejection direction or non-ejection of ink occurred during printing. What could not be printed

Claims (11)

In the presence of the active hydrogen atom-containing compound (A) adjusted to a viscosity in the range of 5 mPa · s to 10000 mPa · s by heating to a radical polymerization temperature in the range of 50 ° C. to 200 ° C., a vinyl monomer ( B) is mixed with a mercapto group and a chain transfer agent (C) having two or more hydroxyl groups at one end, and radical polymerization is performed, and a vinyl polymer having two or more hydroxyl groups at one end ( D) Production method. The vinyl polymer (D) having two or more hydroxyl groups at one end according to claim 1, wherein the active hydrogen atom-containing compound (A) is a polyol (A-1) having a number average molecular weight of 500 to 10,000. Manufacturing method. 2. One end of claim 1, wherein the vinyl monomer (B) contains at least one vinyl monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester. A method for producing a vinyl polymer (D) having at least one hydroxyl group. The amount of the mercapto group and the chain transfer agent (C) having two or more hydroxyl groups at one end is in the range of 1 to 10 parts by mass with respect to the total amount of the vinyl monomer (B). The manufacturing method of the vinyl polymer (D) which has a 2 or more hydroxyl group in the one end of Claim 1. The piece according to claim 1, wherein the mercapto group and the chain transfer agent (C) having two or more hydroxyl groups at one end are a chain transfer agent (C-1) having a mercapto group and two hydroxyl groups. The manufacturing method of the vinyl polymer (D) which has a 2 or more hydroxyl group at the terminal. The vinyl polymer having two or more hydroxyl groups at one end according to claim 1, wherein the vinyl polymer (D) having two or more hydroxyl groups at one end has a number average molecular weight of 500 to 10,000. Manufacturing method of union (D). The number average molecular weight of 500 to 10,000, which is the active hydrogen atom-containing compound (A) adjusted to a viscosity in the range of 5 mPa · s to 10000 mPa · s by heating to a radical polymerization temperature in the range of 50 ° C. to 200 ° C. By mixing a vinyl monomer (B) with a mercapto group and a chain transfer agent (C) having two or more hydroxyl groups at one end in the presence of the polyol (A-1), and radical polymerization. A polyol (E) containing a mixture of the obtained vinyl polymer (D) having two or more hydroxyl groups at one end and the polyol (A-1), and a polyisocyanate (F) are reacted. A method for producing polyurethane (G). The amount of the mercapto group and the chain transfer agent (C) having two or more hydroxyl groups at one end is in the range of 1 to 10 parts by mass with respect to the total amount of the vinyl monomer (B). The manufacturing method of the polyurethane (G) of Claim 7. The method for producing a polyurethane (G) according to claim 7, wherein the vinyl polymer (D) having two or more hydroxyl groups at one end has a number average molecular weight of 500 to 10,000. The number average molecular weight of 500 to 10,000, which is the active hydrogen atom-containing compound (A) adjusted to a viscosity in the range of 5 mPa · s to 10000 mPa · s by heating to a radical polymerization temperature in the range of 50 ° C. to 200 ° C. By mixing a vinyl monomer (B) with a mercapto group and a chain transfer agent (C) having two or more hydroxyl groups at one end in the presence of the polyol (A-1), and radical polymerization. Polyol (E) containing the obtained vinyl polymer (D) having two or more hydroxyl groups at one end, the polyol (A-1) and the hydrophilic group-containing polyol (e-1), and polyisocyanate A polyurethane (G) is produced by reacting (F), and then the polyurethane (G) and an aqueous medium (H) are mixed and phase-inverted and emulsified. Method of manufacturing the aqueous polyurethane dispersion. The number average molecular weight of 500 to 10,000, which is the active hydrogen atom-containing compound (A) adjusted to a viscosity in the range of 5 mPa · s to 10000 mPa · s by heating to a radical polymerization temperature in the range of 50 ° C. to 200 ° C. By mixing a vinyl monomer (B) with a mercapto group and a chain transfer agent (C) having two or more hydroxyl groups at one end in the presence of the polyol (A-1), and radical polymerization. Polyol (E) containing the obtained vinyl polymer (D) having two or more hydroxyl groups at one end, the polyol (A-1) and the hydrophilic group-containing polyol (e-1), and polyisocyanate A polyurethane (G) is produced by reacting (F), and then the polyurethane (G) and an aqueous medium (H) are mixed and phase-inverted and emulsified. Method for manufacturing an ink jet printing ink binder comprising a polyurethane aqueous dispersion.