JP6155079B2 - Polymer gel and method for producing the same - Google Patents

Description

  The present invention relates to a polymer gel containing a novel polymer crosslinked product in which a cyclic polymer chain is formed in a side chain by polymerization of a cyclic macromonomer having a cyclic polymer chain in one molecule, and a plasticizer, and It relates to the manufacturing method.

  Patent Document 1 discloses a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer composed of a polymer gel. In Patent Document 1, the polymer gel constituting the pressure-sensitive adhesive layer is composed of a polyrotaxane having a structure in which a linear molecule penetrates through openings of at least two cyclic molecules, and a (meth) acrylic acid ester copolymer. It contains a crosslinked polymer obtained by bonding.

  Such a crosslinked polymer disclosed in Patent Document 1 has a structure in which at least two (meth) acrylic acid ester copolymers are crosslinked with a polyrotaxane. Specifically, one (meth) acrylate copolymer is bonded to one cyclic molecule of the polyrotaxane via a crosslinking agent, and the other (meth) acrylate ester is bonded to the other cyclic molecule of the polyrotaxane. The copolymer has a structure bonded through a cross-linking agent. In such a polymer crosslinked product, the cyclic molecule can freely move on the linear molecule of the polyrotaxane, and the polymer gel containing the polymer crosslinked product has mechanical properties (flexibility, Excellent stretchability) and swelling.

  In Patent Documents 2 to 4, an adhesive layer made of an acrylic resin having a cross-linked structure obtained by polymerizing an acrylic monomer and an isocyanate compound as a cross-linking agent (that is, a polymer cross-linked product) is used. , Including a plasticizer (including liquid paraffin as a plasticizer). The pressure-sensitive adhesive containing such a polymer crosslinked body and a plasticizer is in a gel form, and appropriate flexibility is imparted by blending the plasticizer.

JP 2010-138259 A Japanese Patent Laid-Open No. 5-45517 Japanese Patent Laid-Open No. 9-137143 JP 2005-194366 A

  However, in order to produce the polymer gel disclosed in Patent Document 1, after synthesizing and isolating a pseudopolyrotaxane by reacting a cyclic molecule and a linear molecule, the pseudopolyrotaxane is dissolved again in another solvent. After capping the end with a capping agent, a polyrotaxane (blocked polyrotaxane) was obtained, and then the polyrotaxane was reacted with a (meth) acrylate copolymer and a crosslinking agent to crosslink the polyrotaxane cyclic molecule. It was necessary to bind the (meth) acrylic acid ester copolymer through an agent. In view of industrialization, such a multistage reaction is very disadvantageous from the viewpoint of production cost, and the yield of each stage has never been high.

  In addition, the acrylic resin disclosed in Patent Documents 2 to 4 containing a plasticizer (polymer gel) has a drawback that a large amount of plasticizer bleeds out over time. In some cases, the adherend may be contaminated by bleedout of a large amount of plasticizer.

  For these reasons, there has been a strong demand for a polymer gel that is excellent in mechanical properties (flexibility, stretchability), swelling property, bleed-out resistance, and can be more easily produced.

  The present invention has been made in view of such a situation, and is a polymer gel that is excellent in mechanical properties (flexibility, stretchability), swelling property, and bleed-out resistance, and can be easily manufactured. And it aims at providing the manufacturing method.

  The polymer gel of the present invention has the following general formula (I):

  (In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units in the parenthesis, and is an integer of 5 to 100. In addition, n + 1 Each M may be the same or different from each other.) And a structural unit derived from a polymerizable monomer other than the cyclic macromonomer. It contains a crosslinked polymer and a plasticizer.

  The polymer gel of the present invention has excellent mechanical properties (flexibility, stretchability), swelling property, and bleed-out resistance, and a cyclic macromonomer and a polymerizable monomer are present in the presence of a plasticizer. Below, it can manufacture easily only by making it superpose | polymerize.

  The method for producing the polymer gel of the present invention comprises the following general formula (I):

  (In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units of the structure in parentheses, and is an integer of 5 to 100. In addition, n + 1 M may be the same or different from each other.) And a polymerizable monomer other than the cyclic macromonomer is polymerized in the presence of a plasticizer. And a step of obtaining a polymer gel.

  According to this production method, a mechanical property (flexibility, stretchability), swelling property, and bleed resistance can be easily obtained by simply polymerizing a cyclic macromonomer and a polymerizable monomer in the presence of a plasticizer. A polymer gel excellent in out-out property can be produced.

Alternatively, the method for producing the polymer gel of the present invention comprises:
The following general formula (I)

  (In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units of the structure in parentheses, and is an integer of 5 to 100. In addition, n + 1 M may be the same or different from each other.) And a polymerizable monomer other than the cyclic macromonomer is polymerized to obtain a crosslinked polymer. And a step of obtaining a polymer gel by immersing the crosslinked polymer in a plasticizer and causing the polymer to swell.

  According to this production method, a mechanical property (flexible) can be obtained simply by polymerizing a cyclic macromonomer and a polymerizable monomer to obtain a crosslinked polymer, and immersing the crosslinked polymer in a plasticizer. Property, stretchability), swellability, and bleed-out resistance can be produced.

  According to the present invention, a novel polymer gel that is excellent in mechanical properties (flexibility, stretchability), swellability, and bleed-out resistance and can be easily produced, and a method for producing the same are provided. Can do.

It is the schematic diagram which represented typically the structure of the polymer crosslinked body in which the crosslinked structure was formed because the polymer principal chain penetrated the cyclic polymer chain. It is a ¹ H-NMR spectrum of the cyclic macromonomer used in the preparation of Example polymer gel of the present invention. It is a ¹³ C-NMR spectrum of the cyclic macromonomer used for manufacture of the polymer gel of the Example of this invention. It is a MALDI-TOF MS spectrum of the cyclic macromonomer used for manufacture of the polymer gel of the Example of this invention. It is IR spectrum of the cyclic | annular macromonomer used for manufacture of the polymer gel of the Example of this invention.

  The present invention is described in detail below.

  The polymer gel of the present invention has the following general formula (I):

  (In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units in the parenthesis, and is an integer of 5 to 100. In addition, n + 1 Each M may be the same or different from each other.) And a structural unit derived from a polymerizable monomer other than the cyclic macromonomer. It contains a polymer crosslinked product and a plasticizer.

  Hereinafter, the skeleton of the cyclic macromonomer represented by the general formula (I) constituting the structural unit of the crosslinked polymer contained in the polymer gel of the present invention will be described in detail.

  Since the cyclic macromonomer has a polymerizable carbon-carbon double bond inside as shown in the general formula (I), it has a function as a polymerizable monomer. Further, this cyclic macromonomer has a functional group formed in a cyclic structure (hereinafter referred to as a cyclic polymer chain) on its side chain.

  In the general formula (I), M is a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms. Specific examples thereof include an ethylene group (dimethylene group), a trimethylene group, a tetramethylene group, or these groups. And a group obtained by substituting a part of the hydrogen atoms with a halogen atom or a hydroxyl group. Among these, M is more preferably an alkylene group having 2 carbon atoms (that is, an ethylene group) from the viewpoint of the ability to form an inner pore and the ease of synthesis. Therefore, specific examples of the MO group in the general formula (I) include an oxyethylene group, an oxypropylene group, an oxybutylene group, or a part of hydrogen atoms of these groups substituted with a halogen atom or a hydroxyl group. The oxyethylene group is more preferable among these.

  Further, M (alkylene group having 2 to 4 carbon atoms) in the general formula (I) may be linear or branched as long as the desired physical properties are not affected. From this point of view, M is preferably linear.

  Moreover, n in general formula (I) means the number of repeating units of the structure in parentheses. For this reason, in the general formula (I), there are n + 1 M. The n + 1 Ms may be the same or different as long as they do not affect the desired physical properties, but are preferably the same from the viewpoint of ease of production. n is an integer of 5 to 100, preferably an integer of 5 to 50, and more preferably an integer of 10 to 35 from the viewpoint of ease of synthesis. The numerical value of n is particularly related to the molecular weight of the cyclic macromonomer.

  The molecular weight of the cyclic macromonomer of the present invention is usually preferably 500 to 50,000, more preferably 500 to 10,000 in terms of number average molecular weight Mn, and preferably 600 to 60000, more preferably 600 to 12,000 in terms of weight average molecular weight Mw. is there. In the present specification, “number average molecular weight Mn” and “weight average molecular weight (Mw)” are respectively measured using gel permeation chromatography (GPC), and are number average molecular weight and weight average in terms of polystyrene (PS). Mean molecular weight.

  In the present invention, the cyclic macromonomer represented by the general formula (I) is represented by the following formula (IV):

  A cyclic macromonomer represented by the formula (wherein n is an integer of 5 to 100), that is, 3,5-bis (cyclopolyethyleneglycolcarbamoyl) phenyl acrylate is preferred.

  Subsequently, the manufacturing method of the said cyclic macromonomer is explained in full detail. Here, although the manufacturing method of a cyclic | annular macromonomer is given as an example and is demonstrated, it is not limited to the following manufacturing methods.

  The cyclic macromonomer has the formula (II):

  A compound represented by formula (III):

  (In general formula (III), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units in the parenthesis, and is an integer of 5 to 100. Further, n + 1 Each M may be the same or different from each other.) The compound represented by formula (I) (cyclic macromonomer) is reacted with a compound represented by formula (C). It can be obtained by a method for producing a macromonomer. In addition, since M and n in the said general formula (III) are the same as M and n in general formula (I), description is abbreviate | omitted.

  Specifically, the cyclic macromonomer can be produced by a method for producing a cyclic macromonomer including the following (1) first step to (5) fifth step.

(1) First step: Production of α, ω-ditosyloxypolyalkylene glycol In the first step, polyalkylene glycol and tosyl chloride are reacted to produce α, ω-ditosyloxypolyalkylene glycol. . For example, α, ω-ditosyloxypolyalkylene glycol can be obtained by adding tosyl chloride dropwise to a reaction solution containing polyalkylene glycol in the presence of a basic substance such as sodium hydroxide.

  The polyalkylene glycol and tosyl chloride used in the first step, and the raw materials used in the second to fifth steps described below are commercially available unless otherwise specified. The polyalkylene glycol used in the first step can be produced according to a known production method, and the molecular weight can be adjusted and the molecular weight distribution can be monodispersed by a known method.

  Since the molecular weight of the polyalkylene glycol used in the first step can easily produce a cyclic macromonomer with little variation in quality, the number average molecular weight Mn is preferably 200 to 4500, more preferably 500 to 1500, On the other hand, the weight average molecular weight Mw is preferably 250 to 5500, more preferably 600 to 2000.

  Further, the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polyalkylene glycol used in the first step is preferably close to 1, specifically, the alkylene glycol in each polyalkylene glycol More preferably, the degree of polymerization is the same or substantially the same.

  In the first step, the use ratio of polyalkylene glycol and tosyl chloride is preferably 1: 2 to 8 and more preferably 1: 3 to 8 in terms of molar ratio. When the amount of tosyl chloride used is less than 2 moles per mole of polyalkylene glycol, the yield of the target compound (ie, α, ω-ditosyloxypolyalkylene glycol) may be reduced. On the other hand, when the amount of tosyl chloride used exceeds 8 moles with respect to 1 mole of polyalkylene glycol, the production cost may increase.

  The reaction conditions in the first step may be appropriately set depending on the type and amount of raw materials (that is, polyalkylene glycol and tosyl chloride). The reaction temperature is generally 0 to 40 ° C., preferably 0 to 20 ° C. When reaction temperature is less than 0 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 40 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high. Moreover, reaction time is 2-48 hours normally, Preferably it is 3-24 hours. When reaction time is less than 2 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 48 hours, there exists a possibility that manufacturing cost may become high. Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure. The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(2) Second step: Production of α, ω-diphthalimide polyalkylene glycol In the second step, α, ω-ditosyloxypolyalkylene glycol obtained in the first step is reacted with potassium phthalimide to obtain α. , Ω-diphthalimide polyalkylene glycol is produced. For example, α, ω-diphthalimide polyalkylene glycol can be obtained by heating and refluxing α, ω-ditosyloxypolyalkylene glycol and potassium phthalimide in a solvent such as acetonitrile.

  In the second step, the use ratio of α, ω-ditosyloxypolyalkylene glycol and potassium phthalimide is preferably 1: 2 to 6 and more preferably 1: 3 to 6 in terms of molar ratio. If the amount of potassium phthalimide used is less than 2 moles per mole of α, ω-ditosyloxypolyalkylene glycol, the yield of the target compound (ie, α, ω-diphthalimide polyalkylene glycol) may be reduced. There is. On the other hand, when the usage-amount of phthalimide potassium exceeds 6 mol with respect to 1 mol of (alpha), omega-ditosyloxy polyalkylene glycol, there exists a possibility that manufacturing cost may become high.

  The reaction conditions in the second step may be appropriately set depending on the type and amount of raw materials (that is, α, ω-ditosyloxypolyalkylene glycol and potassium phthalimide). The reaction temperature is usually 25 to 80 ° C, preferably 70 to 80 ° C. When reaction temperature is less than 25 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 80 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high. The reaction time is usually 2 to 48 hours, preferably 12 to 24 hours. When reaction time is less than 2 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 48 hours, there exists a possibility that manufacturing cost may become high. Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure. The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(3) Third step: Production of α, ω-diaminopolyalkylene glycol In the third step, the α, ω-diphthalimide polyalkylene glycol obtained in the second step is reacted with hydrazine monohydrate. According to general formula (III):

  (In general formula (III), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units in the parenthesis, and is an integer of 5 to 100. Further, n + 1 Each M may be the same or different.) (Α, ω-diaminopolyalkylene glycol) is produced. For example, α, ω-diaminopolyalkylene glycol can be obtained by heating and refluxing α, ω-diphthalimide polyalkylene glycol and hydrazine monohydrate in a solvent such as ethanol.

  In the third step, the use ratio of α, ω-diphthalimide polyalkylene glycol and hydrazine monohydrate is preferably 1: 5 to 20 in terms of molar ratio, more preferably 1:10 to 15. preferable. If the amount of hydrazine monohydrate used is less than 5 moles per mole of α, ω-diphthalimide polyalkylene glycol, the yield of the target compound (α, ω-diaminopolyalkylene glycol) may be reduced. is there. On the other hand, when the usage-amount of hydrazine monohydrate exceeds 20 mol with respect to 1 mol of (alpha), omega-diphthalimide polyalkylene glycol, there exists a possibility that manufacturing cost may become high.

  The reaction conditions in the third step may be appropriately set depending on the type and amount of raw materials (that is, α, ω-diphthalimide polyalkylene glycol, hydrazine monohydrate). The reaction temperature is usually 25 to 80 ° C, preferably 60 to 80 ° C. When reaction temperature is less than 25 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 80 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high. Moreover, reaction time is 1 to 5 hours normally, Preferably it is 2 to 4 hours. When reaction time is less than 1 hour, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 5 hours, there exists a possibility that manufacturing cost may become high. Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure. The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(4) Fourth step: Production of 5-acryloyloxyisophthalic acid 5-hydroxyisophthalic acid and acryloyl chloride are reacted to form the formula (II):

(5-acryloyloxyisophthalic acid) represented by the formula: For example, 5-acryloyloxyisophthalic acid can be obtained by dropping acryloyl chloride into a reaction solution containing 5-hydroxyisophthalic acid in the presence of a basic substance such as sodium hydroxide.

  In the fourth step, the use ratio of 5-hydroxyisophthalic acid and acryloyl chloride is preferably 1: 1 to 1.5, more preferably 1: 1 to 1.1 in terms of molar ratio. When the usage-amount of acryloyl chloride is less than 1 mol with respect to 5-hydroxyisophthalic acid, there exists a possibility that the yield of the target compound (5-acryloyloxyisophthalic acid) may fall. On the other hand, when the usage-amount of acryloyl chloride exceeds 1.5 mol with respect to 5-hydroxyisophthalic acid, there exists a possibility that manufacturing cost may become high.

  What is necessary is just to set reaction conditions suitably with the kind, quantity, etc. of a raw material (5-hydroxyisophthalic acid, acryloyl chloride). The reaction temperature is usually 0-30 ° C, preferably 5-20 ° C. When reaction temperature is less than 0 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 30 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high. Moreover, reaction time is 1 to 20 hours normally, Preferably it is 3 to 12 hours. When reaction time is less than 1 hour, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 20 hours, there exists a possibility that manufacturing cost may become high. Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure. The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(5) Step 5: Production of cyclic macromonomer 5-acryloyloxyisophthalic acid (compound represented by formula (II)) obtained in Step 4 and α, ω-diaminopolyalkylene glycol obtained in Step 3 ( By reacting the compound represented by the general formula (III) with the general formula (I):

  (In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units in the parenthesis, and is an integer of 5 to 100. In addition, n + 1 Each M may be the same or different from each other.) A compound represented by (cyclic macromonomer) is produced. For example, the compound (5-acryloyloxyisophthalic acid) represented by the formula (II) obtained in the fourth step and the compound (α, ω-diaminopolyalkylene glycol represented by the general formula (III) obtained in the third step ) In the presence of a condensing agent. Subsequently, the compound (cyclic macromonomer) represented by the general formula (I) can be obtained by washing, drying and purifying the obtained reaction mixture by a known method. In this reaction, for example, the compound represented by the formula (II) and the compound represented by the general formula (III) are each diluted in a solvent at a low concentration (high dilution), and these diluted solutions are dropped over time. It is preferable that the reaction is carried out gradually and then the reaction is carried out with stirring. When the above reaction is carried out at a high concentration, a linear polymer may be formed as a side reaction, and in this case, the yield of the cyclic macromonomer of formula (I) may be greatly affected.

  In the fifth step, the use ratio of 5-acryloyloxyisophthalic acid (compound represented by formula (II)) and α, ω-diaminopolyalkylene glycol (compound represented by general formula (III)) is in molar ratio. It is preferably 1: 0.9 to 1.1, and more preferably 1: 0.95 to 1.05. When the amount of α, ω-diaminopolyalkylene glycol (compound represented by general formula (III)) used is less than 0.9 mol relative to 5-acryloyloxyisophthalic acid (compound represented by formula (II)) The yield of the target compound (cyclic macromonomer (compound represented by formula (I))) may be reduced. On the other hand, when the amount of α, ω-diaminopolyalkylene glycol (compound represented by the general formula (III)) exceeds 1.1 mol relative to 5-acryloyloxyisophthalic acid, the production cost may increase. .

  It does not specifically limit as a condensing agent used at a 5th process, The thing conventionally used for amidation reaction can be used. Specifically, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- ( Dimethyldipropyl) carbodiimide, carbodiimides such as diisopropylcarbodiimide; arylsulfonyl chlorides such as 2,4,6-triisopropylbenzenesulfonyl chloride, p-toluenesulfonyl chloride; 2,4,6-triisopropylbenzenesulfonyl imidazolide, Arylsulfonamides such as 2,4,6-triisopropylbenzenesulfonyltriazolide; azodicarboxylic acid esters; halogenated organic sulfonyls; diphenylphosphoryl azide, diethoxyphosphonyl chloride, diethoxyphosphonyl azide, anhydrous Propylphosphonic acid, diphenylphosphonyl chloride; metal alkoxides such as magnesium dimethoxide, magnesium diethoxide, aluminum diisopropoxide, aluminum tri-tert-butoxide; alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide Hydroxides; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkaline earth metal oxides such as calcium oxide and magnesium oxide; alkali metal amides such as lithium amide; potassium carbonate; zinc chloride Examples include aluminum chloride, phosphorus oxychloride, tetramethylammonium chloride, concentrated sulfuric acid, diphosphorus pentoxide, polyphosphoric acid, acetic anhydride, carbonyldiimidazole, p-toluenesulfonyl chloride, basic ion exchange resin, and the like. Among these, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride is particularly preferable from the viewpoint of ease of synthesis.

  In the fifth step, the solvent used for diluting the compound represented by the formula (II) and the compound represented by the general formula (III) is a raw material compound (compound represented by the formula (II), general formula (III) Compound) and the target compound (compound represented by formula (I)) are not particularly limited as long as they do not adversely affect the compound and can be easily distilled off, and examples thereof include methanol, ethanol and the like. The dilution rate is about 500 to 1000 times the total amount of the compound represented by the formula (II) and the compound represented by the general formula (III).

  The reaction conditions may be appropriately set depending on the type and amount of the raw material (the compound represented by the formula (II), the compound represented by the general formula (III)). The reaction temperature is usually 0 to 40 ° C, preferably 10 to 25 ° C. When reaction temperature is less than 0 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 40 degreeC, there exists a possibility that the yield of the target compound (compound represented by general formula (I)) may fall, and there exists a possibility that manufacturing cost may become high. Moreover, reaction time is 12 to 72 hours normally, Preferably it is 24 to 48 hours. When reaction time is less than 12 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 72 hours, there exists a possibility that manufacturing cost may become high. Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure. The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere. The ratio of the compound represented by the formula (II) and the condensing agent is preferably 1: 2 to 4 and more preferably 1: 3.0 to 3.5 in terms of molar ratio. When the usage-amount of a condensing agent is less than 2 mol with respect to the compound represented by Formula (II), there exists a possibility that the yield of a target compound may fall. On the other hand, when the usage-amount of a condensing agent exceeds 4 mol with respect to the compound represented by Formula (II), there exists a possibility that manufacturing cost may become high.

  Next, a polymerizable monomer other than the cyclic macromonomer constituting the structural unit of the polymer crosslinked body contained in the polymer gel of the present invention (hereinafter simply referred to as a polymerizable monomer) will be described in detail.

  The polymerizable monomer used in the present invention is not particularly limited as long as it is a monomer (monomer) capable of undergoing a polymerization reaction. For example, a monomer exhibiting radical polymerization can be used. Specific examples of such a polymerizable monomer include styrene, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylamide derivatives, (meth) acrylonitrile, (meth) acrylic acid and salts thereof. In the present specification, (meth) acryl means methacryl or acryl, and (meth) acrylo means methacrylo or acrylo.

  Specific examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) N-decyl acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, (meth) acrylic Acrylic acid alkyl esters such as tridecyl oxalate, n-stearyl (meth) acrylate; alicyclic (meth) acrylic such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate Acid alkyl ester; 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, alkoxy group containing (meth) acrylic acid methoxypolyethylene glycol such as (meth) acrylic acid methoxytriethylene glycol (meth) Acrylic acid ester; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl, (meth) acrylic acid 2-hydroxybutyl ( (Meth) acrylic acid hydroxy Alkyl; mono (meth) acrylate glycerol, mono (meth) acrylate polyethylene glycol and polyethylene glycol-polypropylene glycol copolymer and other mono (meth) acrylate polyalkylene glycols; aromatic rings such as benzyl (meth) acrylate (Meth) acrylic acid ester having (meth) acrylic acid ester having a heterocyclic ring such as (meth) acrylic acid tetrahydrofurfuryl; 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane and the like ( (Meth) acryloyloxymethyl-2,2-dia Of 4- (meth) acryloyloxymethyl-2-cycloalkyl-1,3-dioxolane such as alkyl-1,3-dioxolane or 4- (meth) acryloyloxymethyl-2-cyclohexylene 1,3-dioxolane And (meth) acrylic acid ester having such a dioxolane structure. In addition, as a commercial item of the (meth) acrylic acid ester which has the said dioxolane structure, the brand name "MEDOL10" (4-acryloyloxymethyl-2-methyl-2-ethyl-1) made from Osaka Organic Chemical Industry Co., Ltd. is mentioned, for example. , 3-dioxolane), product with the trade name “MIBDOL10” (4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane), product with the trade name “CHDOL10” (4-acryloyloxymethyl) -2-cyclohexyl-1,3-dioxolane), product name “MMDOL30” (4-methacryloyloxymethyl-2,2-dimethyl-1,3-dioxolane), product name “MEDOL30” (4-methacryloyl) Oxymethyl-2-methyl-2-ethyl-1,3-dioxolane), quotient The product with the name “MIBDOL30” (4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane) and the product with the product name “CHDOL30” (4-methacryloyloxymethyl-2-methyl-2-methyl) Cyclohexyl-1,3-dioxolane) and the like. Each of the above (meth) acrylic acid esters may be used alone or in combination of two or more.

  Specific examples of the (meth) acrylamide derivative include N-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (meth) acrylamide; N-ethoxymethyl ( (Meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-hexyloxymethyl (meth) Acrylamide, N-heptoxymethyl (meth) acrylamide, N-octoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-propoxyethyl (meth) acrylamide, N-butoxyethyl (meth) acrylic Etc. de of N- alkoxyalkyl (meth) acrylamide; (meth) acryloyl morpholine, vinyl pyrrolidone; can be exemplified, and derivatives of these. These (meth) acrylamide derivatives may be used alone or in combination of two or more. In the present specification, (meth) acryloyl means methacryloyl or acryloyl.

  Among the polymerizable monomers described above, methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ( (Meth) acrylic acid, sodium (meth) acrylate, and (meth) acrylonitrile are easily copolymerized with the cyclic macromonomer to form a polymer having a crosslinked structure (that is, a polymer crosslinked product). This is because methyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, ( Polymerizable monomers such as sodium (meth) acrylate and (meth) acrylonitrile are sized so that they can easily pass through the cyclic polymer chain of the cyclic macromonomer, so that the main chain formed by these polymerizable monomers is a cyclic macromolecule. This is thought to be because a crosslinked structure can be formed by penetrating the cyclic polymer chain derived from the monomer. Also, methyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, (meth) Polymerizable monomers such as sodium acrylate and (meth) acrylonitrile have an advantage that they are excellent in polymerization reactivity and can produce a polymer (that is, a polymer crosslinked product) more efficiently.

  Therefore, it is preferable that the polymerizable monomer constituting the structural unit of the crosslinked polymer includes at least a polymerizable monomer having a size capable of passing through the cyclic polymer chain of the cyclic macromonomer.

  Further, when styrene is included in the polymerizable monomer constituting the structural unit of the crosslinked polymer, the polymer gel containing the crosslinked polymer can be made foamable.

  The polymer gel of the present invention contains a plasticizer together with the polymer crosslinked product. Specifically, in the polymer gel of the present invention, the plasticizer is held in the polymer crosslinked body.

  Specific examples of the plasticizer that can be used in the polymer gel of the present invention include water; monohydric alcohols such as isopropyl alcohol and butyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and dipropylene. Polyhydric alcohols such as glycol, butanediol, glycerin, pentaerythritol, sorbitol, polyethylene glycol, polypropylene glycol, polyglycerin, polyoxyethylene polyglyceryl ether, ethylene oxide / propylene oxide copolymer; castor oil, soybean oil, olive oil, etc. Natural oils; Fatty acids such as oleic acid and linolenic acid; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ether alcohols such as coal monobutyl ether and diethylene glycol monomethyl ether; other ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone Hydrocarbon solvents such as toluene, xylene, sorbeso; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, glyceryl triacetate; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, Bis (2-ethylhexyl) butale , Phthalates such as diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, isodecyl phthalate, diundecyl phthalate, diisoundecyl phthalate, dioctyl phthalate, dibutyl phthalate; fats such as butyl oleate Monobasic acid esters; dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (2- (2-butoxyethoxy) ethyl) adipate, bis (2-ethylhexyl) Azelate, dimethyl sebacate, dibutyl sebacate, bis (2-ethylhexyl) sebacate, diethyl succinate and bis (2- (2-butoxye) Toxi) ethyl) adipate dioctyl adipate, isodecyl succinate, dibasic acid esters such as dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate, pentaerythritol ester; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris ( Phosphate esters such as 2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate; tris (2-ethylhexyl) Trimellitic acid esters such as trimellitate; ricinoleic acid esters such as methylacetylricinoleate; Polyesters obtained by reacting dibasic acids with dihydric alcohols; Poly (meth) acrylic acid esters such as poly (meth) acrylic acid alkyl esters; Polycaprolactone triols, polycaprolactone diols, etc. Polyester polyols; Acetylated monoglycerides such as glycerin diacetomonolaurate; Epoxies such as epoxidized soybean oil, epoxidized linseed oil, and epoxy benzyl stearate; Polyethers such as polypropylene glycol and its derivatives; Polystyrenes such as methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polyisobutene, paraffin hydrocarbon, naphthene hydrocarbon, paraffin-naphthene If hydrocarbons, and chlorinated paraffins. These plasticizers may be used alone or in combination of two or more.

  The plasticizer is preferably a liquid at room temperature from the viewpoint of handling and the like, but depending on the application, a plastic that is in a liquid form at a temperature exceeding the room temperature (for example, 50 to 200 ° C.) may be used.

  Among the plasticizers described above, the polymer gel of the present invention comprises acetate esters, phthalate esters, aliphatic monobasic acid esters, aliphatic dibasic acid esters, glycol esters, phosphate esters, More preferably, it contains an ester plasticizer such as merit acid esters, ricinoleic acid esters, pyromellitic acid esters, polyesters, poly (meth) acrylic acid esters, polyester polyols, acetylated monoglycerides, It is particularly preferable to contain at least one selected from the group consisting of aliphatic dibasic acid esters and acetate esters.

  The polymer gel of the present invention is a production method of the present invention comprising a step of polymerizing the above-described cyclic macromonomer and the above-described polymerizable monomer in the presence of the above-described plasticizer to obtain a polymer gel. Can be manufactured. The polymerization reaction may be carried out by a conventional method. Usually, the cyclic macromonomer and the polymerizable monomer are reacted by a radical polymerization method in the presence of the plasticizer. For example, the polymerization reaction may be carried out by adding a known photopolymerization initiator to a mixture of the cyclic macromonomer and the polymerizable monomer and the plasticizer and irradiating with ultraviolet rays if desired, or by known heat It can be performed by adding a polymerization initiator and heating. Moreover, when performing the said polymerization reaction, you may add a solvent to the mixture of the said cyclic | annular macromonomer and the said polymerizable monomer, and the said plasticizer as needed. Of course, it is also possible to carry out the polymerization without adding a solvent to the mixture of the cyclic macromonomer and the polymerizable monomer and the plasticizer.

  Alternatively, the polymer gel of the present invention comprises a step of polymerizing the above-described cyclic macromonomer and the above-described polymerizable monomer to obtain a polymer crosslinked product, and immersing the polymer crosslinked product in a plasticizer. It can be produced also by the production method of the present invention having a step of obtaining a polymer gel by swelling. The polymerization reaction in this case can be carried out in the same manner as the polymerization reaction described above, except that the polymerization reaction is performed in the absence of a plasticizer. In this case, the polymerization reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent. In addition, when polymerized reaction is performed in the presence of a solvent to obtain a polymer crosslinked body, it is preferable that the polymer crosslinked body is immersed in the plasticizer and swollen after the solvent is distilled off.

  In the production method of the present invention, the mixing ratio of the cyclic macromonomer and the polymerizable monomer at the time of the polymerization reaction is not particularly limited, but for example, the cyclic macromonomer with respect to 1 mol of the polymerizable monomer. Is mixed with 0.001 to 0.5 mol, preferably 0.001 to 0.05 mol, more preferably 0.001 to 0.03 mol. ) Easily forms a crosslinked structure. When the amount of the cyclic macromonomer used is less than 0.001 mol with respect to 1 mol of the polymerizable monomer, a crosslinked structure is hardly formed, mechanical properties (flexibility, stretchability), swelling property, and There is a possibility that a polymer gel excellent in bleed-out resistance may not be obtained. On the other hand, if it exceeds 0.5 mol, the effect corresponding to the amount of cyclic macromonomer used is not improved, and it is uneconomical in terms of cost. There is a risk of becoming.

  In the production method of the present invention, the ratio of the amount of cyclic macromonomer and polymerizable monomer (total amount of cyclic macromonomer and polymerizable monomer) and the amount of plasticizer used is not particularly limited. For example, when the weight ratio is 90:10 to 15:85, and more preferably 80:20 to 20:80, the polymer crosslinked body that is a polymer of the cyclic macromonomer and the polymerizable monomer is plasticized. A soft feeling can be imparted.

  The photopolymerization initiator is not particularly limited, and examples thereof include α-hydroxyketone, α-aminoketone, benzylmethyl ketal, bisacylphosphine oxide, metallocene, and more specifically, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (product name: Irgacure (registered trademark) 2959, BASF Japan Ltd. (former Ciba Specialty Chemicals) 2) 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name: DAROCURE (registered trademark) 1173, manufactured by BASF Japan Ltd.), 1-hydroxy-cyclohexyl-phenyl -Ketone (Product name: Irgacure (registered trademark) 184, manufactured by BASF Japan Ltd.), 2 -Methyl-1- (4-methylthiophenyl) -2-monoforinopropan-1-one (product name: Irgacure (registered trademark) 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one (product name: Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  The thermal polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate. , Peroxide initiators such as cumene hydroperoxide, cyclohexanone peroxide, tert-butyl hydroxide, diisopropylbenzene hydroperoxide; 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ -Azobis (2,3-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2 '-Azobis (2-isopropylbutyroni Ryl), 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azo Examples include azo compounds such as bisisobutyrate. Each of these thermal polymerization initiators may be used alone or in combination of two or more.

  What is necessary is just to set the reaction conditions of the said polymerization reaction suitably with the kind, quantity, etc. of a cyclic | annular macromonomer and a polymerizable monomer. The reaction temperature is usually 40 to 100 ° C, preferably 60 to 90 ° C. When reaction temperature is less than 40 degreeC, there exists a possibility that reaction may not advance. On the other hand, when the reaction temperature exceeds 100 ° C., side reactions may occur. Moreover, reaction time is 5 to 24 hours normally, Preferably it is 8 to 12 hours. If the reaction time is less than 5 hours, the yield may decrease. On the other hand, when reaction time exceeds 24 hours, there exists a possibility that manufacturing cost may become high. Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure. The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

  As described above, the cyclic macromonomer and the polymerizable monomer are polymerized in the presence of a plasticizer, or the cyclic macromonomer and the polymerizable monomer are polymerized in the absence of a plasticizer. After obtaining the polymer crosslinked product, the polymer crosslinked product is immersed in a plasticizer and swollen to obtain a polymer in which the cyclic macromonomer and the polymerizable monomer are copolymerized, that is, the polymer. The polymer gel of this invention containing a crosslinked body and a plasticizer is obtained. The structure of the crosslinked polymer contained in the resulting polymer gel of the present invention is, for example, such that the cyclic macromonomer and the polymerizable monomer are randomly arranged in a straight chain, and the cyclic macromonomer is in the side chain. It is thought that it has a structure having a cyclic polymer chain derived from.

  Specifically, the main chain that grows by the progress of the polymerization reaction penetrates the cyclic polymer chain derived from the cyclic macromonomer, thereby producing a crosslinked polymer having a crosslinked structure. it is conceivable that. In the crosslinked polymer having such a crosslinked structure, the cyclic polymer chain can freely move on the main chain.

  FIG. 1 schematically shows a crosslinked polymer having a crosslinked structure formed by passing the polymer main chain 1 through the cyclic polymer chain 2 as described above. In the crosslinked polymer having the structure shown in FIG. 1, a three-dimensional network structure is formed by allowing the main chain 1 to penetrate the cyclic polymer chain 2 in a so-called threading manner. Here, since the crosslinked structure is formed by threading the main chain 1 into the cyclic polymer chain 2 as described above, the crosslinking point can be moved. For this reason, in the polymer gel containing the polymer crosslinked body having the structure shown in FIG. 1, the mobility of the main chain 1 (polymer chain segment) of the polymer crosslinked body is increased, and is caused by non-covalent bonding or covalent bonding. Compared to a polymer gel containing a polymer having a crosslinked structure, it has excellent mechanical properties (flexibility, stretchability), swelling property, bleed-out resistance, and a machine such as compressive stress. Excellent physical properties.

  For this reason, in the polymer gel of the present invention, the crosslinked polymer has a crosslinked structure in which a main chain 1 is formed through a cyclic polymer chain 2 derived from a cyclic macromonomer as shown in FIG. It is preferable to have.

  Whether or not the polymer contained in the polymer gel has a crosslinked structure can be determined, for example, by measuring the gel fraction or swelling rate of the polymer gel. The gel fraction of the polymer gel of the invention is preferably 50% or more. Further, in the measurement of the swelling rate described later, it is determined that the crosslinked structure is not formed when the polymer gel is dissolved. In addition, in this specification, a gel fraction means the gel fraction obtained by the measuring method shown below.

[Method for measuring gel fraction]
0.5 g of a sample (polymer) is weighed, 50 mL of tetrahydrofuran (THF) is poured and immersed for 24 hours, and then filtered using a # 200 mesh wire mesh to separate into insoluble gel resin and filtrate. The obtained insoluble gel resin is allowed to stand at room temperature for 2 days and further dried in a dryer at 100 ° C. for 2 hours. Thereafter, the insoluble gel resin is cooled in a desiccator, and the weight of the insoluble gel resin (dry weight of the insoluble gel resin) is measured. And a gel fraction is computed from the following formulas. In the calculation formula shown below, the content (%) of the crosslinked polymer in the sample represented by A is the amount (g) of the cyclic macromonomer and polymerizable monomer used for the production of the polymer gel. It is substantially the same as the ratio of the use amount (g) of the cyclic macromonomer and the polymerizable monomer to the total use amount (g) of the plasticizer.

Ｗ₀：ＴＨＦに溶かす前の乾燥した試料の重量（ｇ）
Ｗ₂：不溶ゲル樹脂の乾燥重量（ｇ）
Ａ：試料中の高分子架橋体の含有率（重量％）

W ₀ : weight of the dried sample before dissolving in THF (g)
W ₂ : dry weight of insoluble gel resin (g)
A: Content (% by weight) of crosslinked polymer in the sample

  Moreover, the polymer gel of the present invention has high swellability, and the swelling ratio of the polymer gel of the present invention is preferably 500 to 1300%. In addition, about the measuring method of swelling rate, it demonstrates in the term of the Example mentioned later.

  The polymer gel of the present invention has excellent mechanical properties (flexibility and stretchability). Specifically, the polymer gel of the present invention preferably has a 20% compressive strength of 0.002 to 0.4 MPa and a 40% compressive strength of 0.008 to 2.0 MPa. In this specification, “20% compression strength” means the compression strength at the time of 20% compression displacement, and “40% compression strength” means the compression strength at the time of 40% compression displacement. Moreover, the measuring method of 20% compressive strength and 40% compressive strength is demonstrated in the item of the Example mentioned later.

  The polymer gel of the present invention was obtained by a simple method of copolymerizing a cyclic macromonomer and a polymerizable monomer in the presence of a plasticizer, or by copolymerizing a cyclic macromonomer and a polymerizable monomer. It can be produced by a simple method in which the polymer crosslinked product is simply immersed in a plasticizer. Further, since the threading may occur as the polymerization reaction of the cyclic macromonomer and the polymerizable monomer proceeds (that is, the growing main chain may penetrate through the cyclic polymer chain during the polymerization reaction), the present invention. The polymer gel may have a mobile cross-linking structure in which the cross-linking point of the cross-linked polymer contained in the polymer gel can move freely, thereby having excellent mechanical properties (flexibility, stretchability), swelling It may be possible to have a bleed-out resistance and a bleed-out resistance.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.

  First, the manufacturing method of the cyclic monomer used for manufacture of the polymer gel of Examples 1-11 and the identification method of the cyclic monomer obtained by this manufacturing method are demonstrated.

[Production of cyclic macromonomer]
(1) First Step: Production of α, ω-ditosyloxypolyethylene glycol In a 1000 mL eggplant flask equipped with a dropping funnel and a magnetic stirrer, 40.0 g (40.0 mmol) of polyethylene glycol (Mw = 1000) and distilled water 20 mL, tetrahydrofuran (THF) 100 mL, and sodium hydroxide 20.0 g (500 mmol) were added, and the mixture was stirred at 0 ° C. in an air atmosphere. Thereto, 30.5 g (160 mmol) of tosyl chloride dissolved in 60 mL of THF was added dropwise over 2 hours using a dropping funnel. After completion of the dropwise addition, the mixture was further stirred for 1 hour. The reaction mixture was diluted with dichloromethane, washed with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained white solid was purified with a silica gel column (ethyl acetate → dichloromethane: methanol = 8: 2 v / v), and further freeze-dried with benzene to obtain α, ω-ditosyloxypolyethylene glycol as a white solid. 41.0 g (89% yield) was obtained.

(2) Second step: Production of α, ω-diphthalimide polyethylene glycol 40.0 g of α, ω-ditosyloxypolyethylene glycol obtained in the first step was added to a 1000 mL eggplant flask equipped with a Dimroth condenser and a magnetic stirrer. 30.0 mmol), 400 mL of acetonitrile, and 22.2 g (120 mmol) of potassium phthalimide were added, and the mixture was heated to reflux at 80 ° C. in an air atmosphere for 12 hours. After completion of the reaction, dichloromethane was added, washed twice with distilled water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained white oily substance was purified with a silica gel column (ethyl acetate → dichloromethane: methanol = 8: 2 v / v), and further freeze-dried with benzene to give α, ω-diphthalimide polyethylene glycol 35 as a white solid. 0.0 g (90% yield) was obtained.

(3) Third Step: Production of α, ω-diaminopolyethylene glycol 34.0 g of α, ω-diphthalimidopolyethylene glycol obtained in the second step was added to a 1000 mL eggplant flask equipped with a Dimroth cooler and a magnetic stirrer (26. 0 mmol), 300 mL of methanol, and 13.5 g (260 mmol) of hydrazine monohydrate were added, and the mixture was heated to reflux at 78 ° C. in an air atmosphere for 3 hours. After completion of the reaction, the precipitated solid was filtered off, the filtrate was concentrated, diluted with dichloromethane, and washed twice with distilled water. Subsequently, the target product was extracted from the organic layer to the aqueous layer using dilute hydrochloric acid. Finally, the aqueous layer was made basic by adding sodium hydroxide and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 17.7 g (yield 68%) of α, ω-diaminopolyethylene glycol as a white solid.

(4) Fourth step: Production of 5-acryloyloxyisophthalic acid In a 50 mL eggplant flask equipped with a magnetic stirrer, 25 mL of distilled water, 6.0 g of sodium hydroxide, 13 mL of 1,4-dioxane as a reaction solvent, 9.11 g (0.05 mol) of 5-hydroxyisophthalic acid was added. While cooling in an ice bath, 4.75 g (0.05 mol) of acryloyl chloride was slowly added dropwise over 30 minutes, and the mixture was further stirred for 12 hours. Concentrated hydrochloric acid was added dropwise until pH = 4, and the precipitated solid was suction filtered and recrystallized from distilled water to obtain 8.1 g (yield 68%) of 5-acryloyloxyisophthalic acid as a white solid. .

(5) Fifth step: Production of cyclic macromonomer (acr-c-PEG) 600 mL of methanol was placed in a 2 L three-necked eggplant flask equipped with a mechanical stirrer, and 4- (4,6-dimethoxy-1,3,5-triazine was added. 2-yl) -4-methylmorpholinium chloride (DMT-MM) 0.82 g (3.0 mmol) was added and dissolved. While stirring vigorously at 20 ° C., 1.0 g (1.0 mmol) of α, ω-diaminopolyethylene glycol obtained in the third step and 0.28 g of 5-acryloyloxyisophthalic acid obtained in the fourth step were put therein. 400 mL of methanol in which (1.0 mmol) was dissolved was slowly added dropwise over 12 hours using a metalol pump. After completion of the dropwise addition, stirring was continued for another 12 hours. The solvent in the reaction mixture was concentrated under reduced pressure, washed with diluted hydrochloric acid and saturated sodium hydrogen carbonate in this order, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow liquid was purified by a silica gel column (ethyl acetate → dichloromethane: methanol = 8: 2 v / v). The obtained viscous liquid was dissolved in a small amount of dichloromethane, and an appropriate amount of diethyl ether was added thereto to remove the high molecular weight component as a precipitate. The supernatant was filtered and the solvent was distilled off under reduced pressure to obtain 0.20 g (yield 20%) of a cyclic macromonomer (also referred to as acr-c-PEG in the present invention) as a colorless transparent viscous liquid.

[Identification of cyclic macromonomer]
The acr-c-PEG obtained by the production of the cyclic macromonomer was analyzed and identified by the following equipment and conditions.

⁽¹ H-NMR and ¹³ C-NMR)
With respect to acr-c-PEG obtained by the production of the cyclic macromonomer, ¹ H-NMR and ¹³ C-NMR were measured at room temperature (25 ° C.) using an EX-270 type superconducting nuclear magnetic resonance absorber manufactured by JEOL Ltd. ). Deuterated chloroform was used as a measurement solvent. Tetramethylsilane was used as a reference material. The measurement results of ¹ H-NMR and ¹³ C-NMR are shown below together with FIGS.

¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) = 8.26 (s), 7.99 (brs), 7.84 (s), 6.7-6.6 (m), 6. 4-6.3 (m), 6.1-6.0 (m), 3.7-3.6 (m)
¹³ C-NMR (67.5 MHz, CDCl ₃ ): δ (ppm) = 165.9, 164.2, 150.9, 136.0, 133.1, 127.6, 123.9, 122.5, 70.1-70.0, 40.0

(MALDI-TOF MS)
About the acr-c-PEG obtained by manufacture of the said cyclic | annular macromonomer, mass spectrometry (MALDI-TOF MS) was performed using Shimadzu Corporation KOMMPACT-2 type matrix-assisted laser ionization time-of-flight mass spectrometer. . In this mass spectrometry, α-cyano-4-hydroxycinnamic acid and sodium iodide were used as a matrix and an ionization aid, respectively. Specifically, 1 mg of a sample (acr-c-PEG) was dissolved in 1 mL of tetrahydrofuran (THF) to prepare a sample solution. Moreover, 17 mg of α-cyano-4-hydroxycinnamic acid was dissolved in 1 mL of THF to prepare a matrix solution. Thereafter, the matrix solution and the sample solution were mixed at a ratio of 1: 1. Spot 0.5 L of 0.1 mmol / mL sodium iodide solution on the sample plate, let dry for several minutes at room temperature, then spot 0.5-1.0 μL of sample / matrix mixture on it. After the solvent was volatilized with dry air, measurement was performed with the mass spectrometer. The measurement results are shown below together with FIG. In the measurement results of MALDI-TOF MS shown below, n means the degree of polymerization of PEG.

MALDI-TOF MS: m / z = 1033.8 (n = 17, [M + Na] ⁺ ), 989.7 (n = 16, [M + Na] ⁺ ), 945.7 (n = 15, [M + Na] ⁺ )

(IR)
About the acr-c-PEG obtained by manufacture of the said cyclic macromonomer, the infrared absorption (IR) spectrum was measured using the JASCO Corporation FT / IR4100 type Fourier-transform infrared spectrophotometer. A sample (acr-c-PEG) was mixed well with potassium bromide and measured after molding into a disk-shaped pellet having a diameter of about 5 mm and a thickness of about 0.1 to 0.2 mm with a pressurizer. The measurement results are shown below together with FIG.

IR (KBr): ν = 22871, 1743, 1660, 1108 cm ⁻¹

(Molecular weight)
About the acr-c-PEG obtained by manufacture of the said cyclic | annular macromonomer, the gel permeation chromatograph (GPC) measurement was performed and the weight average molecular weight Mw and the number average molecular weight Mn were calculated | required.

  Specifically, 40 mg of a sample (acr-c-PEG) was dissolved in 12 mL of tetrahydrofuran (THF) (permeation time: approximately 1 hour (complete dissolution)) and filtered through a non-aqueous chromatographic disk having a pore size of 0.45 μm. GPC measurement was performed. From the elution curve obtained by the GPC measurement and the standard polystyrene calibration curve prepared by performing GPC measurement of standard polystyrene in advance, the weight average molecular weight Mw and number average of the sample (acr-c-PEG) The molecular weight Mn was determined. The apparatus and measurement conditions for the GPC measurement are as follows.

GPC apparatus used: “PU-2080 pump (registered trademark)” manufactured by JASCO Corporation, “UV-8020 ultraviolet / visible detector (registered trademark)” manufactured by Tosoh Corporation, and “RI-2031 plus differential manufactured by JASCO Corporation. Refractive index detector (registered trademark) "
Guard column: “TSKgel (registered trademark) H8” (inner diameter 7.5 mm × 7.5 cm) × 1 manufactured by Tosoh Corporation Column: “TSKgel (registered trademark) G2500H” (inner diameter 7.8 mm × length) manufactured by Tosoh Corporation 60 cm) and “TSKgel (registered trademark) G3000H” (inner diameter 7.8 mm × length 60 cm)
Column temperature: 25 ° C
Mobile phase: THF
Mobile phase flow rate: 1.0 mL / min
Detector: RI detector Sample concentration: 0.33% by weight
Sample injection volume: 20 μL
Measurement period: 0 to 45 min
Runtime (measurement duration): 45 min
Sampling pitch: 200 msec

  As a standard polystyrene sample for a calibration curve, the weight average molecular weight Mw of the trade name “TSKgel (registered trademark) standard polystyrene” manufactured by Tosoh Corporation is 590 (number average molecular weight Mn: 520), 1010 (number average molecular weight Mn: 890). Those having 2500 (number average molecular weight Mn: 2380) and 6200 (number average molecular weight Mn: 6080) were used.

  The calibration curve was prepared by weighing the standard polystyrene for calibration curve (each standard polystyrene having a weight average molecular weight of 590, 1010, 2500 and 6200), 2 mg, 4 mg, 6 mg and 10 mg, respectively, and then dissolving in 30 mL of THF. 20 μL of the obtained solution was injected into the column. A calibration curve (tertiary equation) was prepared as a calibration curve from the retention times of these standard polystyrenes, and used for measurement of the weight average molecular weight Mw and the number average molecular weight Mn.

  About acr-c-PEG obtained by manufacture of the above-mentioned cyclic macromonomer, the measurement result of the weight average molecular weight Mw and the number average molecular weight Mn is shown below.

Weight average molecular weight Mw: 1286
Number average molecular weight Mn: 1090
Weight average molecular weight Mw / number average molecular weight Mn: 1.18

  Subsequently, the manufacturing method of the polymer gel of Examples 1-11 and Comparative Examples 1-10 is demonstrated.

[Example 1: Production of polymer gel]
In a 10-ml sample tube, 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer as a crosslinking agent, and butyl acrylate (molecular weight) as a polymerizable monomer 128.2) 3.2 g (25 mmol), 1.5 g of glyceryl triacetate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name “Triacetin”) as a plasticizer, and 0.13 g of benzoyl peroxide as a thermal polymerization initiator Were added and dissolved to prepare a blended solution. The compounded solution was purged with nitrogen, reacted at 60 ° C. for 7 hours in a nitrogen atmosphere, then reacted at 70 ° C. for 7 hours and further at 90 ° C. for 3 hours to obtain a polymer gel.

[Example 2: Production of polymer gel]
The amount of glyceryl triacetate (trade name “Triacetin”, manufactured by Daihachi Chemical Industry Co., Ltd.) as the plasticizer is 2.3 g, and the amount of benzoyl peroxide as the thermal polymerization initiator is 0.15 g. Obtained a polymer gel in the same manner as in Example 1.

[Example 3: Production of polymer gel]
The amount of glyceryl triacetate (trade name “Triacetin”, manufactured by Daihachi Chemical Industry Co., Ltd.) as the plasticizer is 3.5 g, and the amount of benzoyl peroxide as the thermal polymerization initiator is 0.18 g. Obtained a polymer gel in the same manner as in Example 1.

[Example 4: Production of polymer gel]
The amount of glyceryl triacetate (trade name “Triacetin” manufactured by Daihachi Chemical Industry Co., Ltd.) used as the plasticizer was 8.2 g, and the amount of benzoyl peroxide used as the thermal polymerization initiator was 0.29 g. Obtained a polymer gel in the same manner as in Example 1.

[Example 5: Production of polymer gel]
The amount of glyceryl triacetate (made by Daihachi Chemical Industry Co., Ltd., trade name “Triacetin”) as the plasticizer was 14 g, and the amount of benzoyl peroxide used as the thermal polymerization initiator was 0.44 g. A polymer gel was obtained in the same manner as in Example 1.

[Example 6: Production of polymer gel]
The amount of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer is 0.16 g (0.125 mmol), and glyceryl triacetate (made by Daihachi Chemical Industry Co., Ltd.) as the plasticizer is used. The polymer gel was obtained in the same manner as in Example 1 except that the amount of the trade name “Triacetin”) was 1.4 g and the amount of benzoyl peroxide used as the thermal polymerization initiator was 0.12 g. .

[Example 7: Production of polymer gel]
Instead of 3.2 g (25 mmol) of butyl acrylate (molecular weight 128.2) as the polymerizable monomer, 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “ CHDOL10 ”, molecular weight 154.2) 3.9 g (25 mmol), glyceryl triacetate as a plasticizer (made by Daihachi Chemical Industry Co., Ltd., trade name“ Triacetin ”) was 1.8 g, and thermal polymerization was performed. A polymer gel was obtained in the same manner as in Example 1 except that the amount of benzoyl peroxide used as the initiator was 0.15 g.

[Example 8: Production of polymer gel]
In place of 3.2 g (25 mmol) of butyl acrylate (molecular weight 128.2) as the polymerizable monomer, tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat # 150”, molecular weight 156.2) 3.9 g (25 mmol) was used, the amount of glyceryl triacetate (made by Daihachi Chemical Industry Co., Ltd., trade name “Triacetin”) used as a plasticizer was 1.8 g, and benzoyl peroxide as a thermal polymerization initiator was used. A polymer gel was obtained in the same manner as in Example 1 except that the amount used was 0.15 g.

[Example 9: Production of polymer gel]
In place of 3.2 g (25 mmol) of butyl acrylate (molecular weight 128.2) as the polymerizable monomer, 4.6 g (25 mmol) of 2-ethylhexyl acrylate (molecular weight 184.3) is used, and glyceryl triacetate as a plasticizer. The same as Example 1 except that the amount used (Daihachi Chemical Industry Co., Ltd., trade name “Triacetin”) was 2.1 g, and the amount of benzoyl peroxide used as the thermal polymerization initiator was 0.18 g. Thus, a polymer gel was obtained.

[Example 10: Production of polymer gel]
Instead of 1.5 g of glyceryl triacetate (trade name “Triacetin” manufactured by Daihachi Chemical Industry Co., Ltd.) as the plasticizer, 1.5 g of diethyl succinate (trade name “DESU” manufactured by Daihachi Chemical Industry Co., Ltd.) is used. A polymer gel was obtained in the same manner as in Example 1 except that.

[Example 11: Production of polymer gel]
The amount of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer was 0.08 g (0.0625 mmol), and glyceryl triacetate (made by Daihachi Chemical Industry Co., Ltd.) as a plasticizer. A polymer gel was obtained in the same manner as in Example 1 except that the amount used of the trade name “Triacetin” was 1.4 g and the amount of benzoyl peroxide used as the thermal polymerization initiator was 0.12 g.

[Comparative Example 1: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new Other than using Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) 0.28 g (0.25 mmol), and using benzoyl peroxide as the thermal polymerization initiator at 0.12 g. Obtained a polymer gel in the same manner as in Example 1.

[Comparative Example 2: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new Made by Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) 0.28 g (0.25 mmol), and the amount of benzoyl peroxide used as the thermal polymerization initiator was 0.14 g. In the same manner as in Example 2, a polymer gel was obtained.

[Comparative Example 3: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new Other than using Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) 0.28 g (0.25 mmol), and using benzoyl peroxide as the thermal polymerization initiator at 0.17 g. Obtained a polymer gel in the same manner as in Example 3.

[Comparative Example 4: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) 0.28 g (0.25 mmol) was used, and glyceryl triacetate as a plasticizer (manufactured by Daihachi Chemical Industry Co., Ltd., trade name “Triacetin”) ) Was used in the same manner as in Example 4 except that 8.1 g was used.

[Comparative Example 5: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new A polymer gel was obtained in the same manner as in Example 5 except that 0.28 g (0.25 mmol) manufactured by Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) was used.

[Comparative Example 6: Production of polymer gel]
As a crosslinking agent, instead of 0.16 g (0.125 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new A polymer gel was obtained in the same manner as in Example 6 except that 0.14 g (0.125 mmol) manufactured by Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) was used.

[Comparative Example 7: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new A polymer gel was obtained in the same manner as in Example 7 except that 0.28 g (0.25 mmol), manufactured by Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) was used.

[Comparative Example 8: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new A polymer gel was obtained in the same manner as in Example 8 except that 0.28 g (0.25 mmol), manufactured by Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) was used.

[Comparative Example 9: Production of polymer gel]
As a cross-linking agent, instead of 0.32 g (0.25 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new Other than using Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) 0.28 g (0.25 mmol), and using benzoyl peroxide as the thermal polymerization initiator at 0.17 g. Obtained a polymer gel in the same manner as in Example 9.

[Comparative Example 10: Production of polymer gel]
As a crosslinking agent, instead of 0.08 g (0.0625 mmol) of acr-c-PEG (weight average molecular weight 1286) obtained by the method for producing the cyclic macromonomer, polyethylene glycol # 1000 diacrylate (abbreviation “PEG1000”, new A polymer gel was obtained in the same manner as in Example 11 except that 0.07 g (0.0625 mmol) manufactured by Nakamura Chemical Co., Ltd., product name “A-1000”, molecular weight 1108) was used.

  About the polymer gel obtained in Examples 1-11 and Comparative Examples 1-10, 20% compressive strength, 40% compressive strength, swelling rate (%), and bleed out amount (%) were measured by the method shown below. did.

[Measuring method of 20% compressive strength and 40% compressive strength]
Under the measurement conditions shown below, the test piece (polymer gel) was compressed at a compression rate of 1 mm / min under an environment of 23 ° C., and the maximum stress (N) when the thickness of the test piece was displaced by 20% and the test The maximum stress (N) when the thickness of the piece was displaced by 40% was measured. Then, the measured maximum stress (N) at 20% displacement was substituted into the following calculation formula for compressive strength, and the compressive strength (MPa) at 20% displacement, that is, 20% compressive strength (MPa) was obtained. . Similarly, the measured maximum stress (N) at 40% displacement is substituted into the following calculation formula for compressive strength to obtain the compressive strength (MPa) at 40% displacement, that is, 40% compressive strength (MPa). It was. In addition, it measured about the test piece of 3 points | pieces, and employ | adopted these average values as compressive strength (MPa).

<Measurement conditions>
Universal testing machine: Tensilon universal testing machine UCT-10T (Orientec Co., Ltd.)
Data processing: UTPS-STD (Soft Brain Co., Ltd.)
Compression jig: Compression jig according to JIS K6767 Size of test piece: 12 mm long x 12 mm wide x 2 mm thick

<Calculation formula>
σ _m = F _m / A ₀
σ _m : compressive strength (MPa)
F _m : Maximum stress measured (N)
A ₀ : Area in contact with the compression jig of the test piece before compression (mm ² )

(Measurement method of swelling rate)
A sample (polymer) (0.5 g) was weighed, 50 mL of tetrahydrofuran (THF) was poured and immersed for 24 hours, and then filtered using a # 200 mesh wire mesh to separate into insoluble gel resin and filtrate. The weight of the insoluble gel resin immediately after filtration (that is, the weight of the swollen sample immediately after filtration) was measured, and the swelling ratio (%) was calculated from the following calculation formula.

Swelling rate (%) = {(W ₁ −W ₀ ) / W ₀ } × 100
W ₀ : weight of the dried sample before dissolving in THF (g)
W ₁ : Weight of the swollen sample immediately after filtration (g)

[Measurement method of bleed-out amount]
After weighing 0.5 g of the sample (polymer gel), use a qualitative filter paper (Advantech Toyo Co., Ltd., No. 5B, size 125 mm) to wipe the front and back surfaces of the weighed sample (adsorb bleed-out components on the filter paper) The weight was measured. The bleed out amount (%) was calculated from the following calculation formula.

Bleed-out amount (%) = (W ₃ / W ₀ ) × 100
W ₀ : Weight of sample before measurement (g)
W ₃ : Weight of bleed-out component adsorbed on filter paper (g)

  In Tables 1 and 2 below, the amount of the polymerizable monomer and crosslinking agent used in the production of the polymer gels of Examples 1 to 11 and Comparative Examples 1 to 10 (mmol), the amounts of thermal polymerization initiator and plasticizer used (G), the weight ratio of the total weight (g) of the polymerizable monomer and crosslinking agent to the weight used (g) of the plasticizer, and the production of the polymer gels of Examples 1-11 and Comparative Examples 1-10 The measurement results of 20% compressive strength (MPa), 40% compressive strength (MPa), swelling rate (%), and bleed-out amount (%) of the polymer gel obtained in (1) are shown. In Tables 1 and 2, “CHDOL10” is a product of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane manufactured by Osaka Organic Chemical Industries, Ltd. used in Example 7 and Comparative Example 7. “PEG1000” is an abbreviation for polyethylene glycol # 1000 diacrylate.

  From the results shown in Tables 1 and 2, the polymer gels of Examples 1 to 11 obtained using a cyclic macromonomer (acr-c-PEG) as a crosslinking agent are all 0.002 to 0.4 MPa. 20% compressive strength (specifically 0.004 to 0.33 MPa), 40% compressive strength 0.008 to 2.0 MPa (specifically 0.01 to 1.7 MPa), 500 to 1300% ( Specifically, it shows a swelling rate of 506 to 1287%) and a bleed out amount of 7% (specifically, 5.3% or less), mechanical properties (flexibility, stretchability), swelling property, In addition, it was confirmed that the bleed-out resistance was excellent.

  On the other hand, the polymer gels of Comparative Examples 1 to 10 obtained using polyethylene glycol # 1000 diacrylate as a crosslinking agent have mechanical properties (flexibility and stretchability), swelling properties, and bleed-out resistance. It was inferior to either. Specifically, the polymer gels of Comparative Examples 1, 2, 6, 7, and 8 have bleed-out resistance, but the 20% compressive strength exceeds 0.4 MPa, and the 40% compressive strength is 2.0 MPa. Therefore, the mechanical properties (flexibility and stretchability) were inferior, and the swelling rate was less than 500%, and the swelling property was also inferior. The polymer gels of Comparative Examples 3 to 5 have a 20% compressive strength in the range of 0.002 to 0.4 MPa and a 40% compressive strength in the range of 0.008 to 2.0 MPa. Although it is recognized as having excellent mechanical properties (flexibility and stretchability), the swelling rate is less than 500%, the swelling property is inferior, and the bleed-out amount exceeds 7%, and the bleed-out resistance It was also inferior. The polymer gel of Comparative Example 9 has a 20% compressive strength in the range of 0.002 to 0.4 MPa and a 40% compressive strength in the range of 0.008 to 2.0 MPa. It has excellent physical properties (flexibility and stretchability), and the bleed-out amount is less than 7%, which is recognized as having bleed-out resistance, but the swelling rate is less than 500%, and the swelling property is inferior. It was. Moreover, although the polymer gel of Comparative Example 10 had bleed-out resistance and swelling property, the 20% compressive strength exceeded 0.4 MPa, and the mechanical properties (flexibility and stretchability) were inferior.

  The same kind and amount of polymerizable monomer, crosslinking agent, and thermal polymerization initiator as in Example 1 were subjected to a polymerization reaction in the same manner as in Example 1 to obtain a crosslinked polymer, When the polymer crosslinked product was immersed in the same kind and amount of plasticizer as in Example 1, it had the same mechanical properties (flexibility, stretchability), swelling property and bleed-out resistance as in Example 1. A polymer gel was obtained.

  The polymer gel of the present invention can be applied as, for example, an adhesive and a coating material having scratch resistance. In addition, the polymer gel of the present invention can be applied to high-performance soft materials such as smart gels (intelligent gels) that exhibit responsiveness to external stimuli such as temperature and pH.

1 Main chain 2 Cyclic polymer chain

Claims (7)

The following general formula (I)

(In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units in the parenthesis, and is an integer of 5 to 100. In addition, n + 1 Each M may be the same or different from each other.) And a structural unit derived from a polymerizable monomer other than the cyclic macromonomer. Containing a crosslinked polymer and a plasticizer ,
As the structural unit derived from the polymerizable monomer, the crosslinked polymer has styrene, (meth) acrylic acid and a salt thereof, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylamide derivative, and (meta ) A polymer gel having a structural unit derived from at least one monomer selected from the group consisting of acrylonitrile . The polymer gel according to claim 1,
A polymer gel, wherein M in the general formula (I) of the cyclic macromonomer is an alkylene group having 2 carbon atoms. The polymer gel according to claim 1 or 2 ,
A polymer gel comprising an ester plasticizer as the plasticizer. A polymer gel according to any one of claims 1 to 3 ,
A polymer gel comprising at least one selected from the group consisting of acetate esters and aliphatic dibasic acid esters as the plasticizer. The following general formula (I)

(In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units of the structure in parentheses, and is an integer of 5 to 100. In addition, n + 1 M may be the same or different from each other.) And a polymerizable monomer other than the cyclic macromonomer is polymerized in the presence of a plasticizer. Te, have a step of obtaining a polymer gel,
The polymerizable monomer is at least one selected from the group consisting of styrene, (meth) acrylic acid and salts thereof, (meth) acrylic ester, (meth) acrylamide, (meth) acrylamide derivatives, and (meth) acrylonitrile. The manufacturing method of the polymer gel characterized by using the monomer of . The following general formula (I)

(In general formula (I), M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units of the structure in parentheses, and is an integer of 5 to 100. In addition, n + 1 M may be the same or different from each other.) And a polymerizable monomer other than the cyclic macromonomer is polymerized to obtain a crosslinked polymer. Process,
By swelling by immersing the crosslinked polymer to plasticizer have a obtaining a polymer gel,
The polymerizable monomer is at least one selected from the group consisting of styrene, (meth) acrylic acid and salts thereof, (meth) acrylic ester, (meth) acrylamide, (meth) acrylamide derivatives, and (meth) acrylonitrile. The manufacturing method of the polymer gel characterized by using the monomer of . A method for producing a polymer gel according to claim 5 or 6 ,
A method for producing a polymer gel, wherein a cyclic macromonomer in which M in the general formula (I) is an alkylene group having 2 carbon atoms is used as the cyclic macromonomer.

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