WO2015000123A1 - Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate - Google Patents

Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate Download PDF

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Publication number
WO2015000123A1
WO2015000123A1 PCT/CN2013/078625 CN2013078625W WO2015000123A1 WO 2015000123 A1 WO2015000123 A1 WO 2015000123A1 CN 2013078625 W CN2013078625 W CN 2013078625W WO 2015000123 A1 WO2015000123 A1 WO 2015000123A1
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Prior art keywords
compound
meth
acrylate
polyol compound
manufacturing
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PCT/CN2013/078625
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English (en)
French (fr)
Inventor
Norio Kosaka
Tsuneyuki Ohtaguro
Bingbing LIU
Jian Guo
Changjun DENG
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Dic Corporation
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Application filed by Dic Corporation filed Critical Dic Corporation
Priority to KR1020157035545A priority Critical patent/KR20160029020A/ko
Priority to JP2015524613A priority patent/JP5839249B2/ja
Priority to PCT/CN2013/078625 priority patent/WO2015000123A1/en
Priority to CN201380077733.9A priority patent/CN105408300A/zh
Priority to TW102129864A priority patent/TW201502117A/zh
Publication of WO2015000123A1 publication Critical patent/WO2015000123A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems

Definitions

  • the present invention relates to a method for manufacturing a (meth) acryloyl group-containing polyol compound produced by selectively (meth) acrylating part of hydroxyl groups of a polyol compound having at least three hydroxyl groups in the molecular structure, a (meth) acryloyl group-containing polyol compound produced by the manufacturing method, and an urethane
  • Diol compounds having two hydroxyl groups in the molecular structure are compounds useful as resin raw materials for polyester resins, polyurethane resins, and the like, and diol compounds having various structures are known nowadays.
  • (meth) acryloyl group-containing diol compounds including a plurality of (meth) acryloyl groups in the molecular structure have especially high utility values as raw materials for active energy ray-curable resins.
  • group-containing diol compound is produced by a method in which a polyol compound serves as a raw material and part of hydroxyl groups thereof are (meth) acrylated and, specifically, is produced by, for example, a method in which two hydroxyl groups of hydroxyl groups included in a polyol compound are protected through acetalyzation, the resulting polyol compound is acrylated by (meth) acrylic acid or the like, and acetal protection is removed through hydrolysis.
  • an efficient method for manufacturing the (meth) acryloyl group-containing diol compound for example, a method in which pentaerythritol is reacted with benzaldehyde to produce an acetal compound, this was reacted with (meth) acryloyl chloride, and acetal protection is removed through hydrolysis, so as to produce pentaerythritol di (meth) acrylate has been known (refer to PTL 1) .
  • a step to monoacetalize pentaerythritol proceeds efficiently and, therefore, monobenzalpentaerythritol serving as an
  • the present invention relates to a method for manufacturing a (meth) acryloyl group-containing polyol compound (x3), the method including the steps of producing a hydroxyl
  • group-containing ketal compound (xl) by reacting a polyol compound (A) having at least three hydroxyl groups in the molecular structure with a cyclic ketone compound (B) at the proportion in which the ratio [ (OH) / (CO) ] of the number of moles of hydroxyl groups (OH) included in the above-described polyol compound (A) to the number of moles of carbonyl groups (CO) included in the above-described cyclic ketone compound (B) falls within the range of 3 to 12 in an organic solvent (S) in the presence of an acid catalyst, producing a (meth) acrylate compound (x2) by (meth) acrylating hydroxyl groups included in the resulting hydroxyl group-containing ketal compound (x1), and hydrolyzing the resulting (meth) acrylate compound (x2) .
  • the present invention further relates to a (meth) acryloyl group-containing polyol compound (x3) produced by the above-described manufacturing method.
  • the present invention further relates to an urethane
  • (meth) acrylate produced by reacting the above-described (meth) acryloyl group-containing polyol compound (x3) , a polyisocyanate compound, and a monohydroxy (meth) acrylate compound.
  • the present invention relates to a curable resin composition containing the above-described urethane (meth) acrylate.
  • the present invention further relates to a cured material produced by curing the above-described curable resin
  • Fig. 1 is a GC-MS chart of a hydroxyl group-containing ketal compound (xl-1) produced in Example 1.
  • Fig. 2 is a 13 C-NMR chart of pentaerythritol diacrylate produced in Example 1.
  • the method for manufacturing a (meth) acryloyl group-containing polyol compound (x3), according to the present invention includes three steps as described below.
  • Step 1 a step to produce a hydroxyl group-containing ketal compound (xl) by reacting a polyol compound (A) having at least three hydroxyl groups in the molecular structure with a cyclic ketone compound (B) at the proportion in which the ratio
  • Step 2 a step to produce a (meth) acrylate compound (x2) by (meth) acrylating hydroxyl groups included in the resulting hydroxyl group-containing ketal compound (x1)
  • Step 3 a step to hydrolyze the resulting (meth) acrylate compound
  • (meth) acryloyl group-containing polyol compound (x3) having a (meth) acryloyl group and, in addition, at least two hydroxyl groups in the molecular structure can simply efficiently be produced at a high yield.
  • the above-described polyol compound (A) used in Step 1 according to the present invention is not specifically limited insofar as at least three hydroxyl groups are included in the molecular structure.
  • Specific examples include trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and diglycerin. They may be used alone, or at least two types may be used in combination.
  • crystalline compounds are preferable because of ease of separation from the hydroxyl group-containing ketal compound (xl) after Step 1 is finished.
  • trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol are preferable.
  • tetra- or more functional polyol compounds are preferable because a finally produced (meth) acryloyl group-containing polyol compound (x3) has a plurality of (meth) acryloyl groups and is especially useful as a material for resins, e.g., an urethane (meth) acrylate.
  • Tetrafunctional to hexafunctional polyol compounds are more preferable and, specifically,
  • pentaerythritol, ditrimethylolpropane, and dipentaerythritol are especially preferable.
  • the cyclic ketone compound (B) is used as an acetalization agent to protect hydroxyl groups included in the above-described polyol compound (A) .
  • the cyclic ketone compound (B) is characterized by exhibiting excellent reaction efficiency in both ketalization reaction and deketalization reaction through hydrolysis. Examples of the cyclic ketone compound (B) used in the present invention include
  • the reaction proportion of the polyol compound (A) having at least three hydroxyl groups in the molecular structure to the cyclic ketone compound (B) is the proportion in which the ratio [ (OH) / (CO) ] of the number of moles of hydroxyl groups (OH) included in the above-described polyol compound (A) to the number of moles of carbonyl groups (CO) included in the cyclic ketone compound (B) falls within the range of 3 to 12. In the case where the ratio is specified to be within this range, the hydroxyl
  • the ratio [ (OH) / (CO) ] is more preferably within the range of 3.5 to 8 because the
  • the polyol compound (A) used in the present invention is especially preferably a tetra- or more functional polyol compounds.
  • a preferable final product is a
  • the hydroxyl group-containing ketal compound (x1) produced in Step 1 is preferably a monoketal compound.
  • the carbonyl group in the cyclic ketone compound (B) is preferably within the range of 0.95 to 0.5 mol, and more preferably within the range of 0.85 to 0.75 mol, relative to 1 mol of the above-described polyol compound (A) because the hydroxyl group-containing monoketal compound is produced at a high yield.
  • An organic solvent used in Step 1 is selected appropriately in accordance with the pressure condition during the reaction and compounds employed as the above-described polyol compound (A) and the above-described cyclic ketone compound (B) .
  • Preferable aspects include two conditions, that is, the case where the reaction in Step 1 is induced under the pressure condition of 740 to 780 mmHg and the case where the reaction in Step 1 is induced under the pressure condition of 100 to 300 mmHg. Each of the cases will be described below.
  • Step 1 In the case where the above-described reaction in Step 1 is induced under the pressure condition of 740 to 780 mmHg, it is preferable to use a mixed solvent of an organic solvent (S1), which forms a heterogeneous azeotropic mixture with water under a pressure condition of 760 mmHg, and a polar solvent (S2) , which has a boiling point higher than or equal to the azeotropic point of the water and the above-described organic solvent (S1) under a pressure condition of 760 mmHg, because the reaction proceeds more efficiently.
  • S1 organic solvent
  • S2 polar solvent
  • the above-described organic solvent (S1) which forms a heterogeneous azeotropic mixture with water under a pressure condition of 760 mmHg refers to an organic solvent which azeotropes with water and which exhibits poor miscibility with water but forms a heterogeneous azeotropic mixture.
  • the solvent exhibiting poor miscibility with water has a solubility into water of preferably 1% or less under the condition of 25 degrees Celsius and 760 mmHg.
  • the organic solvent (S1) is used for the purpose of azeotroping the water generated by the reaction between the above-described polyol compound (A) and the above-described cyclic ketone compound (B) so as to remove the water from the reaction system. Therefore, it is preferable that an organic solvent exhibiting poor miscibility with water be selected because of reusability by being separated from the water after the water is removed through azeotropy.
  • organic solvents examples include diethyl ether, diisopropyl ether, ethyl acetate, dichloromethane, chloroform, tetrachloromethane, 1, 2-dichloroethane, pentane, hexane, heptane, cyclohexane, benzene, toluene, and xylene. They may be used alone, or at least two types may be used in combination.
  • ethyl acetate, hexane, cyclohexane, toluene, and xylene are preferable from the viewpoint of ease in industrial use, and cyclohexane is especially preferable because of low toxicity and ease of handling.
  • the reaction temperature may be higher than the azeotropic point of the water and the above-described organic solvent (S1) under the pressure condition concerned and is preferably within the range of 95 to 135 degrees Celsius because the reaction proceeds more efficiently.
  • the above-described polar solvent (S2) has a boiling point higher than or equal to the azeotropic point of the water and the above-described organic solvent (S1) under a pressure condition of 760 mmHg. That is, the polar solvent (S2) is not specifically limited insofar as the polar solvent has a boiling point higher than or equal to the reaction temperature and is inert to the reaction when the above-described polyol compound (A) and the cyclic ketone compound (B) are reacted at a temperature condition higher than or equal to the azeotropic point of the water and the organic solvent (S1) under a pressure condition of 760 mmHg.
  • a polar solvent having a boiling point of 100 degrees Celsius or higher under a pressure condition of 760 mmHg is preferable.
  • aprotic polar solvents e.g., 1,4-dioxane, ⁇ , ⁇ -dimethylformamide, and dimethylsulfoxide. They may be used alone, or at least two types may be used in combination.
  • the proportion of usage of the above-described organic solvent (S1) and the above-described polar solvent (S2) depend on the types of the respective materials employed, although the mass ratio [(S1)/(S2)] of the two is preferably within the range of 0.1/10 to 10/10, and more preferably within the range of 0.5/10 to 5/10 because an effect of increasing the reaction rate is more improved.
  • the reaction temperature is preferably within the range of 65 to 100 degrees Celsius because the reaction proceeds more efficiently.
  • the organic solvent employed here is not specifically limited insofar as the organic solvent has a boiling point higher than or equal to the reaction temperature under the above-described pressure condition and is inert to the reaction.
  • a polar solvent (S3) having a boiling point of 100 degrees Celsius or higher under a pressure condition of 760 mmHg is preferable.
  • Examples include aprotic polar solvents, e.g., 1,4-dioxane, ⁇ , ⁇ -dimethylformamide, and dimethylsulfoxide.
  • a polar solvent having a boiling point of 150 degrees Celsius or higher under a pressure condition of 760 mmHg is preferable because an effect of increasing the reaction rate is more improved.
  • Examples include ⁇ , ⁇ -dimethylformamide and dimethylsulfoxide.
  • Examples of acid catalysts used in Step 1 described above include inorganic acids, e.g., hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids, e.g., methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids, e.g., boron trifluoride, anhydrous aluminum chloride, and zinc chloride. They may be used alone, or at least two types may be used in combination. Most of all, paratoluenesulfonic acid is preferable because the catalyst activity is high.
  • the usage of the acid catalyst is preferably within the range of 0.1 to 5 percent by mole relative to the above-described polyol compound (A) because sufficient catalyst performance is delivered.
  • Step 1 the predetermined hydroxyl
  • group-containing ketal compound (x1) can be produced by removing unreacted polyol compound (A) from reaction products by filtration or recrystallization.
  • the separated and removed polyol compound (A) can be recovered and reused, as described above .
  • a monoketal polyol compound (x1) produced in Step 1 can be favorably utilized as a precursor of a reactive group-containing polyol compound, e.g., the (meth) acryloyl group-containing polyol compound (x3) , by changing hydroxyl groups in the molecular structure to other functional groups and inducing deketalization through hydrolysis.
  • a reactive group-containing polyol compound e.g., the (meth) acryloyl group-containing polyol compound (x3)
  • the (meth)acryloyl group-containing polyol compound (x3) which is a specific example of the above-described reactive group-containing polyol compound is produced by a method including Step 2 to (meth) acrylate hydroxyl groups included in the hydroxyl group-containing ketal compound (x1) produced in Step 1 described above and Step 3 to hydrolyze the (meth) acrylate compound (x2) produced in Step 2.
  • Method 1 a method in which the above-described hydroxyl group-containing ketal compound (x1) is reacted with a halogenated product of 3-chloropropionyl chloride or the like in the presence of a base catalyst, e.g., triethylamine
  • Method 2 a method in which the above-described hydroxyl group-containing ketal compound (x1) is reacted with a (meth) acrylic acid ester compound, e.g., ethyl (meth) acrylate, in the presence of a transesterification catalyst
  • the halogenated product of 3-chloropropionyl chloride or the like be used in an excessive amount within the range of 1.05 to 1.25 mol relative to 1 mol of hydroxyl group in the above-described hydroxyl group-containing ketal compound (x1) because the reaction efficiency is enhanced.
  • the usage of the base catalyst is preferably within the range of 2.0 to 2.2 mol relative to 1 mol of halogenated product of 3-chloropropionyl chloride or the like.
  • the reaction in Method 1 described above can be induced under a temperature condition of -10 to 30 degrees Celsius, for example.
  • the reaction concerned proceeds even under a condition of no solvent, although an organic solvent may be used appropriately, as necessary.
  • (meth) acrylic acid ester compound be used in an excessive amount within the range of 1.05 to 1.25 mol relative to 1 mol of hydroxyl group in the above-described hydroxyl group-containing ketal compound (xl) because the reaction efficiency is enhanced.
  • Any transesterification catalyst can be utilized in Method 2 described above.
  • a polystannoxane compound represented by the following general formula (1) can be favorably used as a recoverable, reusable catalyst.
  • each R represents individually a methyl group or an ethyl group
  • each X represents individually an
  • n represents an integer of 1 to 8.
  • polystannoxane compounds include C1 (SnMe 2 O) 2 SnMe 2 C1 (hereafter abbreviated to "trimer”) produced by trimerizing dimethyl-tin-dichloride.
  • the usage of the transesterification catalyst is preferably within the range of 0.5 to 5 percent by mass relative to the total mass of the monoketal polyol compound and the (meth) acrylic acid ester.
  • the reaction in Method 2 described above can be induced under a temperature condition of 85 to 120 degrees Celsius, for example.
  • the reaction concerned proceeds even under a condition of no solvent, although an organic solvent may be used appropriately, as necessary.
  • the acrylic acid ester compound which is a reaction raw material, may be used excessively to a great extent, so as to serve both as a substrate and a solvent.
  • Step 3 to hydrolyze the (meth) acrylate compound (x2) produced by Method 1, Method 2, or the like described above can produce the predetermined (meth) acryloyl group-containing polyol compound (x3) efficiently through hydrolysis in an alcohol solvent under a condition of the acid catalyst.
  • the resulting (meth) acryloyl group-containing polyol compound (x3) is useful as a raw material for the active energy ray-curable resin.
  • an urethane (meth) acrylate can be produced by reacting the above-described (meth) acryloyl
  • a polyester (meth) acrylate can be produced by reacting the above-described (meth) acryloyl group-containing polyol compound (x3) , a polycarboxylic acid compound, and a monohydroxy (meth) acrylate compound.
  • the (meth) acryloyl group-containing diol compound having two hydroxyl groups and a plurality of (meth) acryloyl groups in the molecular structure is a more preferable form of the
  • Amount of injection 1 microliter
  • Injection inlet temperature 300 degrees Celsius
  • Amount of injection 1 microliter
  • Injection inlet temperature 280 degrees Celsius
  • Interface temperature 300 degrees Celsius
  • GCMS-QP2010 produced by SHIMADZU CORPORATION Ion source temperature: 200 degrees Celsius
  • Pulse angle 45 degrees Celsius pulse
  • a flask provided with a thermometer, an agitator, a condenser, and a Dean-Stark apparatus was charged with 136 g (1.0 mol) of pentaerythritol, 600 ml of ⁇ , ⁇ -dimethylformamide, and 60 ml of cyclohexane and 3.7 g of paratoluenesulfonic acid serving as a catalyst was added.
  • the temperature was raised to 110 degrees Celsius while agitation was performed, so that pentaerythritol was dissolved into ⁇ , ⁇ -dimethylformamide. Thereafter, 78 g (0.8 mol) of cyclohexanone was added.
  • reaction temperature was maintained at 120 degrees Celsius, and the reaction was continued while generated water was removed by distillation. After generation of water became not observed, reflux was performed for further 1 hour. Cooling to room temperature was performed while agitation was continued, and unreacted pentaerythritol was removed by filtration under reduced pressure. ⁇ , ⁇ -dimethylformamide was removed from the filtrate under reduced pressure, ethyl acetate was added, and
  • Fig. 1 shows a GC-MS chart of the resulting solid.
  • the solid concerned was analyzed by the GC-MS and the 13 C-NMR and was identified as a ketal compound of pentaerythritol (hereafter referred to as "hydroxyl group-containing ketal compound (x1-1)”) represented by the following structural formula (I) .
  • the yield of the present reaction was 43% with reference to the number of moles of charged cyclohexanone .
  • a flask provided with a thermometer, an agitator, and a condenser was charged with 21.6 g (0.1 mol) of hydroxyl group-containing ketal compound (x1-1) produced as described above, 120 ml of dichloromethane, and 46.5 g of triethylamine, and cooling to -5 degrees Celsius was performed.
  • ⁇ solution in which 29 g of 3-chloropropionyl chloride was dissolved into 40 ml of dichloromethane was dropped little by little while the reaction system was maintained at 0 degrees Celsius or lower. After the dropping was finished, the temperature was lowered to room temperature gradually, and a reaction was induced for further 4 hours.
  • the resulting water layer was extracted with ethyl acetate, and washing was performed using sodium hydrogen carbonate saturated aqueous solution until the pH reached 7.
  • An organic layer was dehydrated with magnesium sulfate and, thereafter, was concentrated under a condition of ambient temperature and reduced pressure, so as to produce 4.1
  • Fig. 2 shows the C-NMR chart diagram of the resulting liquid.
  • the resulting liquid was analyzed by
  • hydroxyl group-containing ketal compound (x1-2) represented by the following structural formula (III) .
  • the yield of the present reaction was 34% with reference to the number of moles of charged cyclopentanone.
  • a flask provided with a thermometer, an agitator, and a condenser was charged with 136 g (1.0 mol) of pentaerythritol and 600 ml of ⁇ , ⁇ -dimethylformamide, and 3.7 g of paratoluenesulfonic acid serving as a catalyst was added.
  • the temperature was raised to 80 degrees Celsius while agitation was performed, so that pentaerythritol was dissolved into ⁇ , ⁇ -dimethylformamide. Thereafter, 78 g (0.8 mol) of cyclohexanone was added.
  • the reaction system was decompressed to 140 mmHg while the reaction temperature was maintained at 80 degrees Celsius, and the reaction was continued while generated water was removed by distillation. After generation of water became not observed, reflux was performed for further 1 hour. Cooling to room temperature and returning to normal pressure were performed while agitation was continued, and unreacted pentaerythritol was removed by filtration under reduced pressure.
  • a flask provided with a thermometer, an agitator, and a condenser was charged with 33.6 g (0.2 mol) of hexamethylene diisocyanate.
  • methyl ethyl ketone was further mixed in such a way that the solid content became 80%, and the temperature in the system was adjusted to 50 degrees Celsius.
  • Addition of 24.4 g (0.1 mol) of pentaerythritol diacrylate produced in Example 1 was performed while air was blown into the system. The temperature in the system was raised to 80 degrees Celsius, and a reaction was induced for 4 hours.
  • Active energy ray-curable resin compositions (1) and (2) having a solid content of 50% were produced by mixing 12.5 parts by weight of Urethane acrylate (1) and (2), respectively, produced as described above, 0.4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, and 7.5 parts by weight of butyl acetate.
  • Active energy ray-curable resin compositions (1) or (2) produced as described above was applied to a PET film (125 micrometers) by using a bar coater in such a way that the dry film thickness became 5 micrometers.
  • a solvent was dried at 70 degrees Celsius for 5 minutes and, thereafter, ultraviolet rays were applied by a high-pressure mercury vapor lamp (80 W/cm) in such a way that the amount of irradiation became 500 mJ/cm , so that Hard coat films (1) and (2) were produced. In this regard, ultraviolet rays were applied in an air atmosphere.
  • a pencil hardness test was performed on the basis of JIS K5600-5-4. Measurements were performed five times per hardness, and the hardness at which the number of times of getting hurt was 0 or 1 was specified to be the hardness of the Hard coat film.
  • a disc-shaped indenter having a diameter of 2.4 cm was wrapped with 0.5 g of steel wool ("BONSTAR #0000" produced by Nippon Steel Wool Co. , Ltd. ) , 1 kgf of load was applied to the indenter, and the indenter was reciprocated 200 times on the coating film surface of the hard coat film.
  • the haze values of the coating film before and after the test were measured using an automatic haze computer ("HZ-2" produced by Suga Test Instruments Co., Ltd. ) , and the amount of change (%) in haze value was calculated.
  • a mandrel test was performed on the basis of JIS K5600-5-1. Specifically, a mandrel tester ("Bending tester" produced by T.P GIKEN K.K.) was used, and the test was performed, where the hard coat film was wound around a test rod, and it was visually examined whether cracking occurred in the cured coating layer of the film or not. A minimum diameter of the test rod, at which cracking did not occur, was specified to be the evaluation result. As the minimum diameter became smaller, the coating film exhibited higher flexibility.
  • a specimen was prepared by cutting each of Hard coat films (1) and (2) into a square measuring 10 cm by 10 cm. The specimen was placed on a horizontal surface, and the height of floating of each of the four corners from the horizontal surface was measured, and evaluation was performed on the basis of the average value thereof. The results are shown in Table 2. A smaller value indicates more excellence in curling resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/CN2013/078625 2013-07-02 2013-07-02 Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate WO2015000123A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020157035545A KR20160029020A (ko) 2013-07-02 2013-07-02 (메타)아크릴로일기 함유 폴리올 화합물의 제조 방법, (메타)아크릴로일기 함유 폴리올 화합물, 및 우레탄(메타)아크릴레이트
JP2015524613A JP5839249B2 (ja) 2013-07-02 2013-07-02 （メタ）アクロイル基含有ポリオール化合物の製造方法、（メタ）アクロイル基含有ポリオール化合物、及びウレタン（メタ）アクリレート
PCT/CN2013/078625 WO2015000123A1 (en) 2013-07-02 2013-07-02 Method for manufacturing (meth)acryloyl group-containing polyol compound, (meth)acryloyl group-containing polyol compound, and urethane (meth)acrylate
CN201380077733.9A CN105408300A (zh) 2013-07-02 2013-07-02 含有(甲基)丙烯酰基的多元醇化合物的制备方法、含有(甲基)丙烯酰基的多元醇化合物以及聚氨酯(甲基)丙烯酸酯
TW102129864A TW201502117A (zh) 2013-07-02 2013-08-20 含有（甲基）丙烯醯基的多元醇化合物的製造方法、含有（甲基）丙烯醯基的多元醇化合物、胺基甲酸酯（甲基）丙烯酸酯、硬化性樹脂組成物、硬化物

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WO2016194765A1 (ja) * 2015-06-04 2016-12-08 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017002102A (ja) * 2015-06-04 2017-01-05 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム

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JP7284635B2 (ja) * 2018-05-30 2023-05-31 住友化学株式会社 樹脂、レジスト組成物及びレジストパターンの製造方法
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