Classifications

• • 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
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/04—Acids, Metal salts or ammonium salts thereof
  • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
  • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates

Definitions

• the present invention relates to urethane (meth)acrylate and a photocurable resin composition containing the same.
• Photocurable resins are widely used in a variety of applications, such as coating materials such as hard coats, manufacturing of three-dimensional objects, and photoresists.
• urethane (meth)acrylate is one of the representative photocurable resins, and as the uses of photocurable resin compositions expand and the physical properties required for photocurable resin compositions become more sophisticated and diversified, etc. Therefore, urethane (meth)acrylate and photocurable resin compositions containing the same are required to be capable of forming films or layers with excellent various properties such as mechanical strength and flexibility.
• a resist material used for etching in the production of printed wiring boards, plating in the field of metal precision processing, etc. consists of a layer made of a photosensitive resin composition (hereinafter referred to as a "photosensitive layer"), a support film, and the like.
• a photosensitive element is used, which is composed of a protective film depending on the situation.
• Pattern formation on the printed wiring board is performed through a development process.
• development using a negative photoresist the above-mentioned photosensitive layer is irradiated with active energy rays using a mask to develop a difference in solubility between exposed and unexposed areas, and the unexposed areas are dissolved with a solvent.
• a pattern of a predetermined shape is formed.
• the photosensitive element is sometimes used in the form of a roll, but since the photosensitive layer is bent when wound into a roll, the photosensitive layer is required to have flexibility. Furthermore, bending the photosensitive layer may cause whitening of a part of the photosensitive layer, which leads to poor quality of the product, so performance that does not cause whitening is also required.
• the photocurable resin composition has the ability to form a photosensitive layer that will not be torn by the spray pressure of a developer or washing with water. required.
• improving mechanical strength deteriorates flexibility, but in order to meet all of the above requirements, it is necessary to form a photosensitive layer with excellent flexibility and mechanical strength, which are contradictory. Become.
• a photosensitive layer on a support film is generally performed by applying a photocurable resin composition in the form of a solution to the support film, but if the viscosity of the composition is too high at this time, the composition may not be uniformly coated. If the viscosity is too low, the film formed from the composition will be thin and the desired properties such as strength will not be obtained. Therefore, photocurable resin compositions are also required to have thixotropy in order to control rheology.
• Patent Document 1 a pattern with excellent resolution and flexibility is formed by combining a binder polymer with a degree of dispersion (weight average molecular weight/number average molecular weight) of 1.6 or less and a specific photopolymerizable compound.
• a photosensitive resin composition that can be used is disclosed.
• the photosensitive resin composition described in Patent Document 1 is insufficient in film retention rate and thixotropy.
• Patent Document 2 discloses a photosensitive resist liquid having thixotropic properties, but does not consider flexibility.
• Patent Document 3 discloses that a specific acrylic resin composition forms a film that does not whiten when folded, but does not consider the residual film rate or thixotropy.
• the object of the present invention is to provide a photocurable resin composition that has an excellent residual film rate after development, flexibility, and mechanical strength, can form a film that does not whiten when rolled, and has excellent thixotropy. It is to provide.
• R 1 is a hydrogen atom or a methyl group
• l, m and n each represent an average degree of polymerization
• l is a number from 1 to 20
• m is a number from 0 to 15.
• n is a number from 1 to 10.
• the three R 2 's are each independently an alkylene group having 1 to 10 carbon atoms.
• R 3 is an alkylene group having 2 to 4 carbon atoms, and p represents the average degree of polymerization and is a number of 1 or more and less than 5.
• the amounts of the components in the reaction [1] above are the sum of the polyoxyalkylene derivative (A), the polyisocyanate compound (B), and the dihydroxy compound (C) (hereinafter referred to as the "total of reactants”). ).
• the photocurable resin composition of [2] may be referred to as “photocurable resin composition (I)".
• the content of the components in the photocurable resin composition (I) is the sum of the urethane (meth)acrylate, the (meth)acrylic acid polymer, and the photopolymerization initiator (hereinafter referred to as " It is the value for the sum of components (I).
• R 1 is a hydrogen atom or a methyl group
• l, m and n each represent an average degree of polymerization
• l is a number from 1 to 20
• m is a number from 0 to 15.
• n is a number from 1 to 10.
• a photocurable resin composition containing.
• the photocurable resin composition of [3] may be referred to as "photocurable resin composition (II)".
• the content of the components in the photocurable resin composition (II) is as follows: the urethane (meth)acrylate, the polyoxyalkylene derivative (A), the (meth)acrylic acid-based polymer, and the photocurable resin composition (II). This is a value relative to the total amount of polymerization initiators (hereinafter sometimes referred to as "sum of components (II)").
• urethane (meth)acrylate of the present invention By using the urethane (meth)acrylate of the present invention, it is possible to form a film that has excellent residual film rate after development, flexibility, and mechanical strength, and does not whiten when rolled, and has excellent thixotropic properties.
• a curable resin composition can be obtained.
• (meth)acrylate means acrylate or methacrylate.
• (meth)acrylate means acrylate and/or methacrylate when two or more (meth)acrylates may be present.
• Terms such as “(meth)acrylic acid” also have the same meaning as “(meth)acrylate.”
• polyethylene glycol chain means a polyoxyethylene chain
• polypropylene glycol chain means a polyoxypropylene chain
• polybutylene glycol chain means a polyoxybutylene chain
• polytetramethylene glycol chain means a polyoxytetramethylene chain
• propylene group means a propanediyl group
• butylene group means a butanediyl group. Therefore, both the propylene group and the butylene group may be linear or branched.
• polyoxyalkylene derivative (A) The polyoxyalkylene derivative (A) used in the present invention has the formula (1):
• R 1 is a hydrogen atom or a methyl group
• l, m and n each represent an average degree of polymerization
• l is a number from 1 to 20
• m is a number from 0 to 15.
• n is a number from 1 to 10.
• It is a compound represented by Only one type of polyoxyalkylene derivative (A) may be used, or two or more types may be used in combination.
• R 1 is preferably a methyl group.
• l, m, and n are average polymerization of oxyethylene group (C 2 H 4 O), oxypropylene group (C 3 H 6 O), and oxybutylene group (C 4 H 8 O), respectively. degree. Therefore, l, m, and n may all be decimal numbers. Moreover, (C 3 H 6 O) is an arbitrary structural unit, and m may be 0.
• l is 1 to 20, preferably 4 to 17, more preferably 6 to 15, even more preferably 8 to 12.
• m is 0 to 15, preferably 0 to 10, more preferably 0 to 5, even more preferably 0 to 2, particularly preferably 0.
• n is 1-10, preferably 2-9, more preferably 3-8, even more preferably 4-6.
• the butylene group may be either linear or branched, but from the viewpoint of the flexibility of the film formed from the photocurable resin composition and the residual film rate, a linear butylene group is preferable. That is, (C 4 H 8 O) in formula (1) is preferably an oxytetramethylene group.
• C 2 H 4 O, C 3 H 6 O and C 4 H 8 O in -(C 2 H 4 O ) l - (C 3 H 6 O) m - (C 4 H 8 O) n - may exist randomly or form a block, and the arrangement order thereof is not particularly limited and may be different from the arrangement described in formula (1).
• the polyoxyalkylene derivative (A) As the polyoxyalkylene derivative (A), a commercially available one or a synthesized one may be used. In order to form a film with excellent flexibility, residual film rate, and mechanical strength, the polyoxyalkylene derivative (A) has R 1 a methyl group, m is 0, and C 4 H 8 O. Polyethylene glycol-tetramethylene glycol monomethacrylate in which is an oxytetramethylene group is preferred. In addition, as mentioned above, C 2 H 4 O and C 4 H 8 O in polyethylene glycol-tetramethylene glycol monomethacrylate may be present randomly or may form blocks, and The arrangement order of these is not particularly limited.
• polyisocyanate compound (B) The polyisocyanate compound (B) used in the present invention has the formula (2):
• the three R 2 's are each independently an alkylene group having 1 to 10 carbon atoms.
• It is a compound represented by Only one type of polyisocyanate compound (B) may be used, or two or more types may be used in combination.
• the three R 2 's in formula (2) may be the same or different, but from the viewpoint of availability, it is preferable that the three R 2 's are the same.
• the alkylene group for R 2 may be linear or branched, but is preferably linear.
• the number of carbon atoms in R 2 is preferably 3 to 9, more preferably 4 to 8, and still more preferably 5 to 7.
• the polyisocyanate compound (B) in which the number of carbon atoms in R2 is within the above range the mechanical strength and residual film rate can be improved while maintaining the flexibility of the film formed from the photocurable resin composition. can be improved.
• polyisocyanate compound (B) a commercially available one or a synthesized one may be used.
• examples of the polyisocyanate compound (B) include isocyanurates of diisocyanates (that is, trimers of diisocyanates) (eg, Duranate TPA-100 and Duranate TKA-100 manufactured by Asahi Kasei Chemicals).
• isocyanurate of hexamethylene diisocyanate that is, trimer of hexamethylene diisocyanate
• the dihydroxy compound (C) used in the present invention has the formula (3): HO-(R 3 O) p -H (3) (In the formula, R 3 is an alkylene group having 2 to 4 carbon atoms, and p represents the average degree of polymerization and is a number of 1 or more and less than 5.) It is a compound represented by The dihydroxy compound (C) may be used alone or in combination of two or more. Note that the dihydroxy compound (C) is an optional component, and it may be used without using the dihydroxy compound (C). , the urethane (meth)acrylate of the present invention can be produced.
• the alkylene group for R 3 may be linear or branched.
• the number of carbon atoms in R 3 is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.
• p is the average degree of polymerization, it may be a decimal number. p is preferably 1 to 4, more preferably 1 to 3, even more preferably 2.
• diethylene glycol is particularly preferable from the viewpoint of the residual film ratio of the film.
• the urethane (meth)acrylate of the present invention is produced by a urethanization reaction of 75 to 90% by mass of a polyoxyalkylene derivative (A), 10 to 25% by mass of a polyisocyanate compound (B), and 0 to 5% by mass of a dihydroxy compound (C). obtained by.
• the amount of polyoxyalkylene derivative (A) in the urethanization reaction is preferably 78 to 89% by mass, more preferably 79 to 88% by mass, even more preferably 81 to 86% by mass, particularly Preferably it is 83 to 85% by mass.
• the amount of the polyisocyanate compound (B) in the urethanization reaction is preferably 11 to 22% by mass, more preferably 12 to 21% by mass, even more preferably 14 to 19% by mass, particularly preferably is 15 to 17% by mass.
• the amount of the dihydroxy compound (C) in the urethanization reaction is preferably 0 to 4% by mass, more preferably 0 to 3% by mass, even more preferably 0.01 to 2% by mass, based on the total amount of reactants.
• the urethane (meth)acrylate of the present invention can be produced with good productivity and without residual raw materials or gelation, and furthermore, it can be photocured. It is possible to improve the mechanical strength and residual film rate while maintaining the flexibility of the film formed from the flexible resin composition.
• the urethanization reaction is preferably carried out in the presence of a catalyst and a polymerization inhibitor.
• a catalyst and a polymerization inhibitor examples include cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, and trimethyltin.
• Examples include hydroxide, dimethyltin dichloride, dibutyltin acetate, dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfite, tin octenoate, and the like. Only one type of catalyst may be used, or two or more types may be used in combination. If a catalyst is used, its amount is preferably from 10 to 1,000 ppm (by weight), based on the total reactants.
• polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, catechol, p-tert-butylcatechol, 2,6-di-tert-butyl-m-cresol, and 2,6-di- Phenols such as tert-butyl-4-methylphenol, pyrogallol, ⁇ -naphthol, quinones such as benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyquinone; nitrobenzene, m-dinitrobenzene, Nitro or nitroso compounds such as 2-methyl-2-nitrosopropane, ⁇ -phenyl-tert-butylnitrone, 5,5-dimethyl-1-pyrroline-1-oxide; chloranyl-amine, diphenylamine, diphenylpicrylhydrazine, Examples include amines
• a polymerization inhibitor When a polymerization inhibitor is used, its amount is preferably 10 to 10,000 ppm (based on mass), more preferably 100 to 1,000 ppm, based on the total amount of reactants. If the amount of the polymerization inhibitor is less than 10 ppm, a sufficient polymerization inhibiting effect may not be obtained, and if it exceeds 10,000 ppm, there is a risk of adversely affecting the physical properties of the urethane (meth)acrylate obtained.
• the reaction temperature in the urethanization reaction is preferably 20 to 90°C, and the reaction time is preferably 1 to 30 hours.
• the reaction temperature is lower than 20° C. or when the reaction time is shorter than 1 hour, the yield of the desired urethane (meth)acrylate tends to decrease.
• the reaction temperature exceeds 90° C. or the reaction time exceeds 30 hours, coloring of the urethane (meth)acrylate and side reactions tend to occur more easily.
• organic solvent may be used in the urethanization reaction.
• organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. etc.
• the end point of the urethanization reaction can be confirmed by the disappearance of the infrared absorption spectrum at 2270 cm ⁇ 1 indicating isocyanate groups or by determining the content of isocyanate groups by the method described in JIS K 7301. In the latter method, the content of isocyanate groups is calculated, and the process is terminated when the content of isocyanate groups becomes 0.5% by mass or less, preferably 0.1% by mass or less of the urethane (meth)acrylate.
• the present invention Urethane (meth)acrylate of the present invention, (meth)acrylic acid-based polymer having an acid value of 50 to 300 mgKOH/g, and a photopolymerization initiator, Provided is a photocurable resin composition (I) containing the following.
• the present invention also provides the urethane (meth)acrylate of the present invention, A polyoxyalkylene derivative (A) represented by the above formula (1), (meth)acrylic acid-based polymer having an acid value of 50 to 300 mgKOH/g, and a photopolymerization initiator, Provided is a photocurable resin composition (II) containing the following.
• photocurable resin compositions (I) and (II) each component in the photocurable resin compositions (I) and (II) will be explained in order. Each component may be used alone or in combination of two or more. Note that hereinafter, "photocurable resin compositions (I) and (II)" may be collectively referred to as “photocurable resin composition of the present invention”.
• the description of the urethane (meth)acrylate of the present invention is as described above.
• the content of the urethane (meth)acrylate of the present invention in the photocurable resin composition (I) is 35 to 60% by mass, preferably 43 to 57% by mass, more preferably is 47 to 53% by mass.
• the content of the urethane (meth)acrylate of the present invention in the photocurable resin composition (II) is 30 to 50% by mass, preferably 40 to 50% by mass, more preferably is 44 to 50% by mass.
• the description of the polyoxyalkylene derivative (A) in the photocurable resin composition (II) is the same as that described for [Polyoxyalkylene derivative (A)].
• the content of the polyoxyalkylene derivative (A) in the photocurable resin composition (II) imparts flexibility to the film without impairing the thixotropic properties of the composition and the mechanical strength of the resulting film. From this point of view, it is 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 1 to 6% by weight, based on the total of components (II). If this content is less than 0.01% by mass, no improvement in the flexibility of the film will be observed, and if it is more than 10% by mass, the mechanical strength of the film will decrease.
• the photocurable resin composition of the present invention contains a (meth)acrylic acid-based polymer having an acid value of 50 to 300 mgKOH/g.
• a (meth)acrylic acid-based polymer having an acid value of 50 to 300 mgKOH/g.
• (meth)acrylic acid-based polymer means a polymer having a structural unit derived from (meth)acrylic acid.
• the acid value of the (meth)acrylic acid-based polymer is preferably 80 to 180 mgKOH/g, preferably 100 to 150 mgKOH/g from the viewpoint of developability.
• the (meth)acrylic acid-based polymer is preferably a copolymer of (meth)acrylic acid and an alkyl (meth)acrylate.
• alkyl in this specification also includes cycloalkyl.
• (Meth)acrylic acid and alkyl (meth)acrylate may be used alone or in combination of two or more. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and (meth)acrylate.
• Examples include hexyl acid, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
• the (meth)acrylic acid-based polymer is more preferably a copolymer of (meth)acrylic acid, cyclohexyl (meth)acrylate, and methyl (meth)acrylate, and even more preferably a copolymer of methacrylic acid, cyclohexyl methacrylate, and methacrylate. It is a copolymer of acid methyl.
• the weight average molecular weight of the (meth)acrylic acid-based polymer is preferably from 10,000 to 100,000, more preferably from 15 to 15, from the viewpoint of mechanical strength and flexibility of the film formed from the photocurable resin composition. ,000 to 80,000, more preferably 20,000 to 60,000.
• the weight average molecular weight is a value measured by gel permeation chromatography (GPC).
• the content of the (meth)acrylic acid-based polymer in the photocurable resin composition (I) is 35 to 60% by mass, preferably 39 to 56.5% by mass, based on the total of the components (I). More preferably, it is 44 to 52% by mass.
• the content of the (meth)acrylic acid-based polymer in the photocurable resin composition (II) is 40 to 60% by mass, preferably 43 to 57% by mass, more preferably is 46 to 54% by mass.
• the photocurable resin composition of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, o-benzoylmethylbenzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, p-dimethylaminobenzoic acid. Isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexylphenyl ketone (e.g.
• Irgacure 184 manufactured by BASF 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g. BASF) Darocure 1173), 2,2-dimethoxy-1,2-diphenylethan-1-one (for example, Irgacure 651, manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2 -morpholino-propanone-1 (for example, Irgacure 907 manufactured by BASF), 2-benzyl-2-dimethylamino-1(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl) -Phenylphosphine oxide, methylbenzyl formate, etc.
• Irgacure 651, manufactured by BASF 2-methyl-1-[4-(methylthio)phenyl]-2 -morpholino-propanone-1
• Irgacure 907 manufactured by BASF 2-benzyl-2-dimethylamino-1(4
• the content of the photopolymerization initiator in the photocurable resin composition (I) is 0.1 to 5% by mass, preferably 0.5 to 4% by mass, more preferably is 1 to 3% by mass.
• the content of the photopolymerization initiator in the photocurable resin composition (II) is 0.1 to 5% by mass, preferably 0.5 to 4% by mass, more preferably is 1 to 3% by mass.
• a solvent and other components can be added to the photocurable resin composition of the present invention as long as they do not impair the effects of the present invention.
• any known solvent can be used, such as methyl alcohol, ethyl alcohol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, N,N-dimethylformamide, tetrahydrofuran, benzene, toluene, diethylene glycol monomethyl ether, diethylene glycol.
• examples include monoethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl acetate, and propylene glycol monomethyl acetate. Only one type of solvent may be used, or two or more types may be used in combination.
• its content in the photocurable resin composition (I) is preferably 35 to 60% by mass, more preferably 40 to 60% by mass based on the entire photocurable resin composition (I). % by mass, more preferably 45 to 55% by mass.
• its content in the photocurable resin composition (II) is preferably 35 to 65% by mass, more preferably 40 to 60% by mass based on the entire photocurable resin composition (II). % by mass, more preferably 45 to 55% by mass.
• Other components include, for example, heat resistance improvers, leveling agents, development aids, inorganic fine particles, coupling agents, fillers, thermosetting resins such as epoxy resins, phenolic resins, and polyvinylphenols, curing agents, plasticizers, and polymerization agents. Examples include inhibitors, antioxidants, antifoaming agents, viscosity modifiers, pigments, and the like. As for the other components, only one type may be used, or two or more types may be used in combination.
• the photocurable resin composition of the present invention can be applied to a substrate by a known method, such as dipping coating, spray coating, flow coating, shower coating, roll coating, etc. Examples include coating, spin coating, and brush coating.
• a cured film can be formed by irradiating the photocurable resin composition of the present invention with active energy rays such as ultraviolet rays, visible rays, radiation, and electron beams.
• active energy rays such as ultraviolet rays, visible rays, radiation, and electron beams.
• a high pressure mercury lamp, a metal halide lamp, etc. can be used for photocuring.
• the atmosphere in which the light is irradiated may be air or an inert gas such as nitrogen or argon.
• Polyoxyalkylene derivative (A):polyisocyanate compound (B) mass ratio was 84:16, polyisocyanate compound (B) (isocyanurate of hexamethylene diisocyanate manufactured by Asahi Kasei Chemicals, trade name: Duranate TPA- 100, isocyanate group content: 23.1% by mass) was charged into the flask and held at 70° C. for 5 hours to perform a reaction. Then, the reaction is carried out in accordance with JIS K 7301 until the content of isocyanate groups becomes 0.1% by mass or less, and then 0.1 g of hydroquinone monomethyl ether as a polymerization inhibitor is charged into the flask to obtain the desired urethane. (Meth)acrylate was obtained.
• Amount of methacrylic 20% by mass, amount of cyclohexyl methacrylate: 50% by mass, based on the monomer components forming Polymer 1 (i.e., the total of methacrylic acid, cyclohexyl methacrylate, and methyl methacrylate).
• a photocurable resin composition was prepared by mixing 100 g of methyl methacrylate (30% by mass), the acid value of Polymer 1: 130 mgKOH/g, and the weight average molecular weight of Polymer 1: 30,000.
• Example 2 A photocurable resin composition was obtained by performing the same operation as in Example 1 except that 100 g of urethane (meth)acrylate of Synthesis Example 2 was used instead of 100 g of urethane (meth)acrylate of Synthesis Example 1. .
• Example 3 Instead of 100 g of urethane (meth)acrylate in Synthesis Example 1, 99 g of urethane (meth)acrylate in Synthesis Example 1 and polyethylene glycol-tetramethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name: A photocurable resin composition was obtained in the same manner as in Example 1 except that 1 g of Bremmer 55PET-800) was used.
• Example 4 Instead of 100 g of urethane (meth)acrylate in Synthesis Example 1, 95 g of urethane (meth)acrylate in Synthesis Example 1 and polyethylene glycol-tetramethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name: A photocurable resin composition was obtained in the same manner as in Example 1 except that 5 g of Bremmer 55PET-800) was used.
• Example 5 Instead of 100 g of urethane (meth)acrylate in Synthesis Example 1, 97.5 g of urethane (meth)acrylate in Synthesis Example 2 and polyethylene glycol-tetramethylene glycol monomethacrylate (manufactured by NOF Corporation, product) as the polyoxyalkylene derivative (A) were used.
• a photocurable resin composition was obtained by carrying out the same operation as in Example 1 except that 2.5 g of Bremmer 55PET-800) was used.
• Comparative example 2 A photocurable resin composition was obtained by performing the same operation as in Example 1 except that 100 g of urethane (meth)acrylate of Comparative Synthesis Example 1 was used instead of 100 g of urethane (meth)acrylate of Synthesis Example 1. Ta.
• TI value viscosity of the photocurable resin composition at a temperature of 25 °C and a shear rate of 1 s -1 /
• the TI value is calculated from the viscosity of the photocurable resin composition at a temperature of 25 ° C and a shear rate of 10 s -1 , and the following: Thixotropy was evaluated based on the following criteria. The results are shown in Tables 1 and 2. ⁇ : TI value is 1.5 or more ⁇ : TI value is 1.1 or more and less than 1.5 ⁇ : TI value is 1.0 or more and less than 1.1
• the photocurable resin composition was applied to a polyethylene terephthalate (PET) film (“A4100” manufactured by Toyobo Co., Ltd., film thickness 50 ⁇ m) and dried on a hot plate at 120° C. for 5 minutes to obtain a film of the photocurable resin composition.
• PET polyethylene terephthalate
• Ta Using a cylindrical mandrel bending tester (manufactured by BEVS), the operation of winding the obtained film around a cylinder having a diameter of 8 mm was repeated 10 times. After this test, the appearance of the film was visually confirmed, and whitening was evaluated based on the following criteria. The results are shown in Tables 1 and 2.
• ⁇ There is no change in the appearance of the film after the test.
• ⁇ The film slightly whitens after the test.
• ⁇ The film turns white after the test.
• the photocurable resin composition was applied to a glass substrate, dried at 120°C, and the film thickness (initial film thickness) of the resulting coating film was measured. Next, the obtained coating film was irradiated with ultraviolet rays to prepare a cured film. The resulting cured film was immersed in a 0.4% by mass tetramethylammonium hydroxide aqueous solution for 60 seconds, washed with water, and dried, after which the thickness of the cured film (film thickness after immersion) was measured.
• Remaining film rate (%) Film thickness after immersion ( ⁇ m) / Initial film thickness ( ⁇ m) ⁇ 100
• the residual film rate was calculated from the following and evaluated based on the following criteria. The results are shown in Tables 1 and 2. ⁇ : Remaining film rate is 85% or more ⁇ : Remaining film rate is 80% or more and less than 85% ⁇ : Remaining film rate is less than 80%
• the photocurable resin compositions of Examples 1 to 5 had excellent thixotropy, and the cured films obtained from them had excellent film retention and tensile strength. It can be seen that it has good strength, elongation at break, and does not whiten when bent.
• Comparative Example 1 has insufficient tensile strength due to the large amount of polyoxyalkylene derivative (A) used.
• Comparative Example 2 has insufficient elongation at break because the urethane (meth)acrylate of Comparative Synthesis Example 1, which does not meet the requirements of the present invention, is used instead of the urethane (meth)acrylate of the present invention.
• Comparative Example 3 uses trimethylolpropane triacrylate instead of the urethane (meth)acrylate of the present invention, and therefore has insufficient elongation at break.
• the photocurable resin composition containing the urethane (meth)acrylate of the present invention is useful as a coating material, a photoresist, etc., and for manufacturing three-dimensional objects.

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