WO2017110845A1 - Composition de résine durcissable par un rayonnement d'énergie active et son procédé de production - Google Patents

Composition de résine durcissable par un rayonnement d'énergie active et son procédé de production Download PDF

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Publication number
WO2017110845A1
WO2017110845A1 PCT/JP2016/088044 JP2016088044W WO2017110845A1 WO 2017110845 A1 WO2017110845 A1 WO 2017110845A1 JP 2016088044 W JP2016088044 W JP 2016088044W WO 2017110845 A1 WO2017110845 A1 WO 2017110845A1
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meth
acrylate
compound
urethane
resin composition
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PCT/JP2016/088044
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English (en)
Japanese (ja)
Inventor
亮輔 谷口
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日本合成化学工業株式会社
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Priority to CN201680060847.6A priority Critical patent/CN108137762A/zh
Priority to JP2016574470A priority patent/JPWO2017110845A1/ja
Priority to KR1020187010833A priority patent/KR20180093878A/ko
Publication of WO2017110845A1 publication Critical patent/WO2017110845A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates to an active energy ray-curable resin composition, and more specifically, the viscosity change with time is very small, the storage stability is excellent, and it is suitably used for an adhesive composition and a coating composition.
  • the present invention relates to an active energy ray-curable resin composition.
  • active energy ray-curable resin compositions have been widely used as coating agents, adhesives, adhesives, or anchor coating agents for various substrates because curing is completed by irradiation of active energy rays for a very short time. It has been.
  • Such an active energy ray-curable resin composition is often blended with urethane (meth) acrylate and a photopolymerizable monomer, and preferably further with a photopolymerization initiator.
  • urethane (meth) acrylate is flexible. It is very often used because it has properties such as tough coatings.
  • urethane (meth) acrylate having a linear main chain application to a pressure-sensitive adhesive composition or a coating agent composition is greatly expected.
  • a transparent pressure-sensitive adhesive sheet is used for bonding the optical member.
  • the pressure-sensitive adhesive sheet is required to have excellent step following performance in addition to the adhesive strength.
  • a urethane (meth) acrylate having a relatively high molecular weight. Is used.
  • urethane (meth) acrylates various catalysts are generally used for the purpose of promoting the reaction.
  • an organotin compound is generally used because of its high activity as a urethanization reaction catalyst. in use.
  • the present inventor as a method for suppressing the increase in viscosity over time, first, in order to reduce the residual amount of unreacted isocyanate groups as much as possible, the active energy ray-curable resin composition containing a large amount of hydroxyl group-containing monomer I found something.
  • the active energy ray-curable resin composition containing a large amount of the above hydroxyl group-containing monomer has suppressed the increase in viscosity over time, but this time the viscosity of the composition will decrease over time. A new problem has arisen.
  • the present invention is an active energy ray-curable resin composition that is excellent in storage stability without causing a change in viscosity over time and is suitably used for a pressure-sensitive adhesive composition or a coating agent composition, and its The object is to provide a manufacturing method.
  • a urethane (meth) acrylate compound in an active energy ray-curable resin composition in which a urethane (meth) acrylate compound and a hydroxyl group-containing monomer are used in combination.
  • Active energy ray curing with excellent storage stability over time by using a urethane (meth) acrylate compound that uses a metal salt that is not normally used for the production of a urethane (meth) acrylate compound as a catalyst.
  • the present invention was completed by finding that a functional resin composition was obtained.
  • the present invention is an active energy ray-curable resin composition containing a urethane (meth) acrylate compound (A), an ethylenically unsaturated monomer (B) excluding the above (A), and a metal salt (X).
  • the active energy ray-curable resin composition is characterized by containing a hydroxyl group-containing monomer (b1) as the ethylenically unsaturated monomer (B). This is the second gist.
  • the active energy ray-curable resin composition obtained in the present invention is an active energy ray-curable resin composition containing the following (A), (B), and (X), and a hydroxyl group-containing monomer as the following (B):
  • (B) By containing (b1), the viscosity change with time is very small and the storage stability is excellent, so that it is suitably used for a pressure-sensitive adhesive composition or a coating agent composition.
  • (A) Urethane (meth) acrylate-based compound.
  • B An ethylenically unsaturated monomer excluding (A) above.
  • (X) Metal salt Metal salt.
  • the content of the metal salt (X) is 1 ⁇ 10 ⁇ 3 to 1 ⁇ based on 100 parts by weight of the total of the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomer (B). When it is 10 ⁇ 1 parts by weight, the viscosity change with time is further reduced.
  • the urethane (meth) acrylate compound (A) is a urethane (meth) acrylate compound having at least one of an ester bond and a carbonate bond other than the ester bond in the (meth) acryloyloxy group.
  • the effect of the present invention can be obtained with a high change in viscosity with time and excellent storage stability.
  • the urethane (meth) acrylate compound (A) has a (meth) acryloyl equivalent of 5,000 to 100,000, a flexible cured coating film can be obtained, and a more appropriate viscosity range can be obtained. Easy handling.
  • the content of the hydroxyl group-containing monomer (b1) is 20 to 70 parts by weight with respect to a total of 100 parts by weight of the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomer (B).
  • the viscosity stability over time is further improved.
  • the urethane (meth) acrylate compound (A) is a reaction product of a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a polyol compound (a3).
  • the polyol compound (a3) is at least one of a polyester polyol and a polycarbonate polyol, the effects of the present invention can be easily obtained and the versatility becomes excellent.
  • the metal salt (X) is a fatty acid metal salt having 8 to 10 carbon atoms, it exhibits a suitable catalytic ability and is excellent in reactivity.
  • an active energy ray-curable resin composition containing the following (A), (B) and (X), and containing the hydroxyl group-containing monomer (b1) as the following (B):
  • the acrylate compound (A) is reacted with the polyvalent isocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound (a2), and the polyol compound (a3) in the presence of the metal salt (X).
  • an active energy ray-curable resin composition having very little change in viscosity with time and excellent storage stability can be obtained.
  • (X) Metal salt Metal salt.
  • (meth) acrylic acid is acrylic acid or methacrylic acid
  • (meth) acryl is acrylic or methacrylic
  • (meth) acryloyl is acryloyl or methacryloyl
  • (meth) acrylate is acrylate or Each means methacrylate.
  • the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one (meth) acrylate monomer.
  • the active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate compound (A), an ethylenically unsaturated monomer (B) and a metal salt (X). In the present invention, It is characterized by containing the metal salt (X).
  • A urethane (meth) acrylate compound
  • B ethylenically unsaturated monomer
  • X metal salt
  • each component which comprises the active energy ray curable resin composition of this invention is demonstrated.
  • the metal salt (X) is preferably a fatty acid salt of a metal such as tin, bismuth, zinc or titanium, for example, tin octylate, tin decanoate, tin neodecanoate, tin laurate, tin myristate, or stearate.
  • fatty acid metal salts having 8 to 10 carbon atoms particularly preferred are tin or bismuth fatty acid salts of 8 to 10 carbon atoms because of excellent reactivity, and particularly preferred are tin octylate and tin decanoate.
  • the content of the metal salt (X) is described below of the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomers 1 ⁇ 100 parts by weight of the total of (B) 10 -3 ⁇ 1 ⁇ 10 -
  • the amount is preferably 1 part by weight, particularly preferably 2 ⁇ 10 ⁇ 3 to 8 ⁇ 10 ⁇ 2 part by weight, and further preferably 3 ⁇ 10 ⁇ 3 to 6 ⁇ 10 ⁇ 2 part by weight.
  • the content is too large, the viscosity tends to proceed, and when the content is too small, the molecular weight of the urethane (meth) acrylate compound (A) tends to decrease.
  • the metal salt (X) may be blended as a catalyst during the production of the urethane (meth) acrylate compound (A), or the urethane (meth) acrylate compound (A), an ethylenically unsaturated monomer. In addition to (B), it may be blended as a single blending component, or may be a combination of both. However, a urethane (meth) acrylate compound ( It is preferable to be blended as a catalyst during the production of A).
  • the urethane (meth) acrylate compound (A) used in the present invention is obtained by reacting a polyvalent isocyanate compound (a1) and a hydroxyl group-containing (meth) acrylate compound (a2), or a polyvalent isocyanate compound. (A1), a hydroxyl group-containing (meth) acrylate compound (a2) and a polyol compound (a3) are reacted.
  • a polyvalent isocyanate compound (a1), a hydroxyl group-containing compound (A urethane (meth) acrylate compound obtained by reacting a (meth) acrylate compound (a2) and a polyol compound (a3) is preferable.
  • the urethane (meth) acrylate compound (A) used in the present invention is a urethane (meth) acrylate compound having at least one of an ester bond (excluding an ester bond in a (meth) acryloyl group) and a carbonate bond. It is preferable that it is easy to obtain the effects of the present invention.
  • polyvalent isocyanate compound (a1) examples include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
  • Polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; alicyclic diisocyanates (for example, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 3-bis (isocyanato) Hexane, 1,4-bis (isocyanato) cyclohexane, norbornene diisocyanate, etc.), or trimer compounds or multimeric compounds of these polyisocyanates; allophanate type polyisocyanates, burette type polyisocyanates, etc. Can be mentioned. These can be used alone or in combination of two or more.
  • aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate; hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanato) cyclohexane, 1 , 4-bis (isocyanato) cyclohexane, isophorone diisocyanate, norbornene diisocyanate and the like are preferably used, and particularly preferably alicyclic diisocyanate (especially isophorone diisocyanate, hydrogenated) from the viewpoint of low curing shrinkage.
  • Diphenylmethane diisocyanate 1,3-bis (isocyanato) cyclohexane, 1,4-bis (isocyanato) cyclohexane) are used, Preferably, from the viewpoint of excellent reactivity and versatility, 1,3-bis (isocyanato) cyclohexane, isophorone diisocyanate is used.
  • Examples of the hydroxyl group-containing (meth) acrylate compound (a2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylates, hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate; 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl ( (Meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Acrylate), 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerol mono (
  • a hydroxyl group-containing (meth) acrylate compound having one ethylenically unsaturated group is preferable in terms of excellent flexibility of the pressure-sensitive adhesive layer, more preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxy Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, and glycerin mono (meth) acrylate
  • 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin mono (meth) acrylate are preferably used in terms of excellent reactivity and versatility.
  • polyol compound (a3) examples include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, (meth) acrylic polyols, polysiloxane polyols, and the like. These can be used alone or in combination of two or more.
  • polyether polyols examples include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Etc.
  • polyester polyol examples include three kinds of components such as a condensation polymer of polyhydric alcohol and polycarboxylic acid, a ring-opening polymer of cyclic ester (lactone), polyhydric alcohol, polycarboxylic acid and cyclic ester. Examples include reactants.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl.
  • Methylene diol 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), and the like.
  • cyclohexanediols such as 1,4-cyclohexanediol
  • bisphenols such as bisphenol A
  • sugar alcohols such as xylitol and sorbitol
  • polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.
  • aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid
  • -Alicyclic dicarboxylic acids such as
  • cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene, a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.
  • polyhydric alcohol examples include polyhydric alcohols exemplified in the description of the polyester-based polyol.
  • alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. It is done.
  • the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.
  • polyolefin-based polyol examples include those having a saturated hydrocarbon skeleton having a homopolymer or copolymer such as ethylene, propylene and butene, and having a hydroxyl group at the molecular end.
  • polyisoprene polyol, polybutadiene polyol, nitrile butadiene polyol, styrene butadiene polyol, and the like can be given.
  • the polyolefin-based polyol may be a hydrogenated polyolefin-based polyol in which all or part of the ethylenically unsaturated groups contained in the structure is hydrogenated.
  • Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the polymer or copolymer molecule of (meth) acrylic acid ester.
  • (meth) acrylic acid ester , For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid And (meth) acrylic acid alkyl esters such as 2-ethylhexyl, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate.
  • polysiloxane polyol examples include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.
  • polyester-based polyols, polyether-based polyols, and polycarbonate-based polyols are preferable, and polyester-based polyols and polycarbonate-based polyols are particularly preferable in that the effects of the present invention can be easily obtained and the versatility is excellent.
  • the number of hydroxyl groups contained in the polyol compound (a3) is preferably 2 to 5, particularly preferably 2 to 3, and more preferably 2. If the number of hydroxyl groups is too large, gelation tends to occur during the reaction.
  • the polyol compound (a3) preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 2,000 to 18,000, more preferably 3,000 to 16,000. is there. If the weight average molecular weight is too small, the adhesive strength of the pressure-sensitive adhesive layer tends to be reduced, and if it is too large, the reactivity with the polyvalent isocyanate compound (a1) tends to be reduced.
  • the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (excluded) was subjected to high performance liquid chromatography (manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”).
  • Shodex GPC KF-806L excludeded
  • high performance liquid chromatography manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”.
  • the hydroxyl value of the polyol compound (a3) is preferably 10 to 300 mgKOH / g, particularly preferably 15 to 150 mgKOH / g, and more preferably 20 to 120 mgKOH / g. If the hydroxyl value is too high, the urethane (meth) acrylate compound (A) tends to have a low molecular weight and the adhesive strength tends to decrease, and if it is too low, the viscosity tends to increase and the workability tends to decrease.
  • Examples of the urethane (meth) acrylate compound (A) used in the present invention include (1) the polyvalent isocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound (a2), and the polyol compound (a3). ) In a reactor in a batch or separately, and (2) a reaction product obtained by reacting a polyvalent isocyanate compound (a1) and a polyol compound (a3) in advance with a hydroxyl group-containing (meta ) A method of reacting the acrylate compound (a2) and the like can be mentioned, and the method (2) is preferable from the viewpoints of reaction stability and reduction of by-products.
  • the reaction between the polyvalent isocyanate compound (a1) and the polyol compound (a3) known reaction means can be used.
  • the molar ratio of the isocyanate group in the polyvalent isocyanate compound (a1) to the hydroxyl group in the polyol compound (a3) is usually about 2n: (2n-2) (n is an integer of 2 or more).
  • n is an integer of 2 or more.
  • the addition reaction of the reaction product obtained by reacting the polyvalent isocyanate compound (a1) and the polyol compound (a3) in advance with the hydroxyl group-containing (meth) acrylate compound (a2) is also a known reaction. Means can be used.
  • the reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2) is, for example, that the polyisocyanate compound (a1) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (a2).
  • ) Has one hydroxyl group
  • the reaction product: hydroxyl group-containing (meth) acrylate compound (a2) is about 1: 2
  • the polyisocyanate compound (a1) has three isocyanate groups.
  • the reaction product: hydroxyl group-containing (meth) acrylate compound (a2) is about 1: 3.
  • reaction In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.1% by weight or less. A (meth) acrylate compound (A) is obtained.
  • the reaction temperature during the above reaction is usually 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is usually 2 to 30 hours, preferably 3 to 20 hours.
  • the metal salt (X) is used as a catalyst, the polyvalent isocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound ( It is preferable that a urethane (meth) acrylate compound (A) is obtained by reacting a2) and the polyol compound (a3) in the presence of the metal salt (X).
  • the amount of the metal salt (X) used as a catalyst during the production of the urethane (meth) acrylate compound (A) is 5 ⁇ with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). It is preferable to add 10 ⁇ 3 to 1 ⁇ 10 ⁇ 1 parts by weight, particularly preferably 6 ⁇ 10 ⁇ 3 to 9 ⁇ 10 ⁇ 2 parts by weight, and more preferably 7 ⁇ 10 ⁇ 3 to 8 ⁇ 10. -2 parts by weight. If the blending amount is too small, the molecular weight of the urethane (meth) acrylate compound (A) tends to decrease, and if it is too large, the viscosity tends to decrease.
  • the urethane (meth) acrylate compound (A) obtained by reacting the polyvalent isocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound (a2) and the polyol compound (a3), as necessary.
  • Organic solvents having no functional group that reacts with isocyanate groups for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene May be used.
  • an ethylenically unsaturated monomer (B) described later can be used as a diluent.
  • the urethane (meth) acrylate compound (A) has a high molecular weight, the viscosity increases and handling becomes worse. Therefore, it is preferable to use an ethylenically unsaturated monomer (B) described later as a diluent.
  • the urethane (meth) acrylate compound (A) used in the present invention is produced.
  • the (meth) acryloyl equivalent of the urethane (meth) acrylate compound (A) is preferably 5,000 to 100,000, particularly preferably 6,000 to 90,000, and more preferably 7,000 to 80. 1,000, particularly preferably 8,000 to 70,000. If the (meth) acryloyl equivalent is too low, the adhesive strength of the pressure-sensitive adhesive layer tends to decrease when used as a pressure-sensitive adhesive. If it is too high, the viscosity of the urethane (meth) acrylate compound (A) becomes too high. It tends to be difficult to handle.
  • the weight average molecular weight of the urethane (meth) acrylate compound (A) is preferably 5,000 to 200,000, particularly preferably 6,000 to 150,000, and more preferably 7,000 to 120,000. Particularly preferred is 8,000 to 100,000. If the weight average molecular weight is too low, the adhesive strength of the pressure-sensitive adhesive layer tends to decrease, and if it is too high, the viscosity of the urethane (meth) acrylate compound (A) tends to be too high and handling tends to be difficult.
  • the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (excluded) was subjected to high performance liquid chromatography (manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”).
  • Shodex GPC KF-806L excludeded
  • high performance liquid chromatography manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”.
  • the viscosity of the urethane (meth) acrylate compound (A) is preferably 1,000 to 10,000,000 mPa ⁇ s, particularly preferably 2,000 to 8,000,000 at 60 ° C. 000 mPa ⁇ s, more preferably 3,000 to 6,000,000 mPa ⁇ s. If the viscosity is too high, handling tends to be difficult, and if it is too low, control of the film thickness tends to be difficult during coating. The viscosity is measured with an E-type viscometer.
  • Examples of the hydroxyl group-containing monomer (b1) include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy C1-C16 (preferably 1-12) (meth) of alkyl groups such as octyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, etc.
  • Hydroxyalkyl acrylate caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-acrylic Primary hydroxyl group-containing ethylenically unsaturated compounds such as yloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; 2-hydroxypropyl (meth) acrylate, 2- Secondary hydroxyl groups such as hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.
  • caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (me
  • ethylenically unsaturated compounds such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate are excellent in viscosity and compatibility with acrylic resins and easily available.
  • 2-hydroxybutyl (meth) acrylate, more preferably 4-hydroxybutyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.
  • the content of the hydroxyl group-containing monomer (b1) is preferably 40% by weight or more, particularly preferably 45% by weight or more, more preferably 50% by weight or more, based on the entire ethylenically unsaturated monomer (B). is there. If the content is too small, the viscosity tends to increase.
  • the content of the hydroxyl group-containing monomer (b1) is 20 to 70 parts by weight with respect to 100 parts by weight as a total of the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomer (B).
  • the amount is preferably 20 to 65 parts by weight, more preferably 25 to 60 parts by weight.
  • the hydroxyl group-containing monomer (b1) may be separately added to the urethane (meth) acrylate compound (A), or as a diluent during the production of the urethane (meth) acrylate compound (A). It may be blended.
  • an ethylenically unsaturated monomer (b2) other than the hydroxyl group-containing monomer (b1) (hereinafter sometimes referred to as “ethylenically unsaturated monomer (b2)”).
  • the ethylenically unsaturated monomer (b2) may be any of a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher monomer.
  • the monofunctional monomer may be any monomer containing one ethylenically unsaturated group.
  • Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester examples include acrylic acid dimer, methacrylic acid dimer, acrylic acid Examples include acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer.
  • 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl.
  • Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.
  • the bifunctional monomer may be any monomer containing two ethylenically unsaturated groups.
  • the tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups.
  • ethylenically unsaturated monomers (b2) it is preferable to use a monofunctional monomer in terms of excellent flexibility of the coating film, and methyl (meth) acrylate and ethyl in terms of excellent yellowness and good flexibility.
  • the ethylenically unsaturated monomer (b2) is preferably used as a diluent during the production of the urethane (meth) acrylate compound (A).
  • the active energy ray-curable resin composition of the present invention is obtained using the urethane (meth) acrylate compound (A), the ethylenically unsaturated monomer (B), and the metal salt (X).
  • the active energy ray-curable resin composition of the present invention preferably further contains a photopolymerization initiator (C) in order to efficiently perform curing with active energy rays.
  • the photopolymerization initiator (C) is not particularly limited as long as it generates radicals by the action of light.
  • diethoxyacetophenone 2-hydroxy-2-methyl-1-phenylpropan-1-one Benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 Acetophenones such as ON, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one; benzoin, benzoinmethyl Benzoins such as ON,
  • auxiliary agents for these photopolymerization initiators (C) include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethyl.
  • Benzoic acid ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone 2,4-diisopropylthioxanthone can also be used in combination.
  • These auxiliaries can be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (C) is 1 to 10 parts by weight with respect to a total of 100 parts by weight of the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomer (B). It is preferably 2 to 5 parts by weight. If the content is too small, the curing rate tends to decrease. If the content is too large, the curability does not improve and the economy tends to decrease.
  • the active energy ray-curable resin composition of the present invention includes urethane (meth) acrylate compound (A), ethylenically unsaturated monomer (B), and metal salt (X), if necessary, photopolymerization start
  • agent (C) other than the above, the antioxidant, flame retardant, antistatic agent, filler, leveling agent, stabilizer, reinforcing agent, matting agent, and other than (X), as long as the effects of the present invention are not impaired. It is also possible to contain a reaction catalyst or the like.
  • crosslinking agent a compound having an action of causing crosslinking by heat, specifically, an epoxy compound, an aziricin compound, a melamine compound, an isocyanate compound, a chelate compound, and the like can be used.
  • the active energy ray-curable resin composition of the present invention can contain a polythiol compound from the viewpoint of suppressing unreacted components and improving adhesive strength.
  • the polythiol compound is not particularly limited, but a compound having 2 to 6 mercapto groups in the molecule is preferable.
  • aliphatic polythiols such as alkanedithiol having about 2 to 20 carbon atoms, aromatics such as xylylenedithiol, etc.
  • Polythiols polythiols obtained by replacing halogen atoms of halohydrin adducts of alcohols with mercapto groups, polythiols consisting of hydrogen sulfide reaction products of polyepoxide compounds, polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule And polythiols composed of esterified products with thioglycolic acid, ⁇ -mercaptopropionic acid, or ⁇ -mercaptobutanoic acid, etc., and these can be used alone or in combination of two or more. .
  • the content of the polythiol compound is preferably 0.01 to 10 parts by weight or less with respect to 100 parts by weight in total of the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomer (B). It is particularly preferably 1 to 5 parts by weight or less.
  • the active energy ray-curable resin composition of the present invention includes alcohols such as methanol, ethanol, propanol, n-butanol, i-butanol, and the like in order to adjust the viscosity at the time of coating, if necessary; acetone Ketones such as methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetic acid such as methyl acetate, ethyl acetate and butyl acetate Esters; dilute solvents such as diacetone alcohol may be used, but the solvent may remain in the coating film and the curing component may volatilize during drying. preferable.
  • solvents such as methanol, ethanol, propanol, n-butanol, i-
  • the active energy ray-curable resin composition obtained in the present invention is cured by irradiating active energy rays after being applied on various substrates and dried.
  • the application method of the active energy ray-curable resin composition is not particularly limited, and for example, spray, shower, dipping, roll, spin, curtain, flow, slit, die, gravure, comma, dispenser, Examples include wet coating methods such as screen printing and ink jet printing.
  • a coating method when the active energy ray-curable resin composition is a solid or a high-viscosity liquid the active energy ray-curable resin composition is heated to reduce the viscosity, and then applied by the above method.
  • the melt method is mentioned.
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc.
  • Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price.
  • electron beam irradiation it can harden
  • a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm
  • an ultrahigh pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc.
  • Irradiation of about 30 to 3,000 mJ / cm 2 may be performed.
  • heating can be performed as necessary to complete the curing.
  • Examples of the base material to which the active energy ray-curable resin composition obtained in the present invention is applied include polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS), and polystyrene resin. , Polyamide resins, etc. and their molded products (films, sheets, cups, etc.), metal substrates (metal vapor deposition layers, metal plates (copper, stainless steel (SUS304, SUSBA, etc.), aluminum, zinc, magnesium, etc.)), These composite base materials, such as glass, are mentioned.
  • the thickness of the cured coating film is usually preferably 1 to 300 ⁇ m, particularly preferably 2 to 250 ⁇ m, and more preferably 5 to 200 ⁇ m.
  • the active energy ray-curable resin composition obtained in the present invention is very useful as an adhesive composition or a coating composition.
  • the present inventor has found that the catalyst used in the production of the urethane (meth) acrylate compound remains in the urethane (meth) acrylate compound, the urethane bond in the urethane (meth) acrylate, the hydroxyl group-containing monomer, However, it was speculated that a transesterification reaction was caused by the catalyst, thereby reducing the molecular weight of the urethane (meth) acrylate compound, and as a result, the viscosity was lowered with time.
  • the urethane (meth) acrylate compound has at least one of an ester bond and a carbonate bond, at least one of the ester bond and the carbonate bond in the urethane (meth) acrylate compound and a hydroxyl group-containing monomer
  • ester bond and the carbonate bond in the urethane (meth) acrylate compound and a hydroxyl group-containing monomer it was presumed that a transesterification reaction occurred and the viscosity decreased with time. Under these presumed mechanisms, intensive studies were made to arrive at the present invention.
  • Urethane (meth) acrylate compound (A) > Urethane (meth) acrylate compounds (A-1) to (A-6) were produced as urethane (meth) acrylate compounds (A) as follows.
  • the active energy ray-curable resin compositions of Examples 1 to 5 obtained using a urethane (meth) acrylate compound produced using a metal salt have a small viscosity change over time, It was excellent in storage stability.
  • the conventionally used active energy ray-curable resin compositions of Comparative Examples 1 and 3 containing urethane (meth) acrylate produced using dibutyltin dilaurate cause a decrease in viscosity over time. When it is put into practical use, problems such as unstable product state occur.
  • the active energy ray-curable resin composition of Comparative Example 2 which does not contain a hydroxyl group-containing monomer has an increase in viscosity over time, causing problems such as unstable product state when used for practical use. Met.
  • the active energy ray-curable resin composition obtained by the production method of the present invention is very useful as a pressure-sensitive adhesive composition or a coating composition, particularly as a pressure-sensitive adhesive composition or a coating composition for optical members or optical films. It is.
  • a high molecular weight urethane (meth) acrylate compound can be made stably, it can be suitably used as an adhesive for bonding optical members excellent in durability, impact resistance and step following ability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition durcissable par un rayonnement d'énergie active contenant (A), (B) et (X), la composition de résine durcissable par un rayonnement d'énergie active caractérisée en ce qu'elle contient en tant que composant (B) un monomère (b1) contenant un groupe hydroxyle, se présente sous la forme d'une composition de résine durcissable par un rayonnement d'énergie active présentant une excellente stabilité au stockage, sans aucun changement de viscosité au cours du temps, qui peut être utilisée de façon appropriée dans des compositions adhésives et des compositions de revêtement. (A) Composé de (méth)acrylate d'uréthane (B) Monomère éthylénique insaturé, excluant (A) ci-dessus. (X) Sel métallique.
PCT/JP2016/088044 2015-12-22 2016-12-21 Composition de résine durcissable par un rayonnement d'énergie active et son procédé de production WO2017110845A1 (fr)

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