JP2010168580A - Radical-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder resin being excellent in an effect for reducing suppression of radical polymerization by oxygen and being excellent in a close-adhesion property, transparency and heat-resistance, and a radical-curable resin composition using the binder resin in the radical curable resin composition containing a radical-polymerizable monomer and the binder resin. <P>SOLUTION: In the radical-curable resin composition containing the radical-polymerizable monomer and the binder resin, a resin containing a constitution unit represented by formula (1) in a main chain is used as the binder resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a binder resin that can be used in a radical curable resin composition that can be cured by heat or irradiation with active energy rays, and a radical curable resin composition that includes the binder resin.

The curable resin composition is used in various industrial fields. Among them, the radical curable resin composition comprising a radical polymerizable monomer and a binder resin has a high curing speed and durability of a chemical bond to be formed. It is excellent in terms of economy and has a wide range of applications and is used in various applications such as coating materials, adhesives, sealing materials, adhesives, paints, inks, resists, dental materials, lenses, molding materials, etc. .

  However, since the radical curing reaction is generally inhibited by polymerization due to oxygen, there are many problems in surface curability and thin film curability. As one of the methods for reducing polymerization inhibition by oxygen, a method of introducing an oxygen scavenging functional group into a radical polymerizable monomer and / or binder resin is well known, and as such a functional group, Often, functional groups containing oxygen or nitrogen atoms are used.

  In applications using radically curable resin compositions, adhesion is often required, and from this point, functional groups containing oxygen and nitrogen atoms are often used. Examples of such functional groups include ether bondable functional groups (polyethylene oxide chain, tetrahydrofurfuryl group, etc.), amino groups, amide groups, urethane groups, etc., but functional groups containing nitrogen atoms are colored. In many applications where transparency is required, ether-bonding functional groups are often preferred. Among them, the tetrahydrofurfuryl group, which is a 5-membered cyclic ether functional group, has good adhesion. It is excellent as an ether-bonding functional group, and there are various usage examples (see, for example, Patent Document 1 and Patent Document 2).

  As a radical polymerizable monomer into which a tetrahydrofurfuryl group is introduced, tetrahydrofurfuryl (meth) acrylate described in Patent Document 1 is well known. As a method for introducing a tetrahydrofurfuryl group into a binder resin, as described in Patent Document 2, poly (meth) acrylic acid having a tetrahydrofurfuryl group in a side chain by polymerizing tetrahydrofurfuryl (meth) acrylate is used. A method of obtaining an ester resin is common. On the other hand, there is a method of obtaining a resin having a tetrahydrofuran ring which is a 5-membered ether ring in the main chain instead of a side chain by cyclopolymerizing 1,6-dienes (for example, Non-Patent Document 1, Non-Patent Document 1, Non-Patent Document 1, Patent Document 2 and Non-Patent Document 3), the application method and use of the resin are not described.

Japanese Examined Patent Publication No. 7-107140 JP 2000-292923 A

Takashi Tsuda, Lon J. et al. Mathias, POLYMER, 1994, Volume 35, pp 3317-3328 Robert D. Thompson, William L. Jarrett, Lon J. et al. Mathias, Macromolecules, 1992, 25, p. 6455-6459 Michio Urushizaki, Toshiyuki Kodaira, Takeji Furuta, Yutaka Yamada, Shoji Oshitani, Macromolecules, 1999, Vol. 32, p. 322-327

A radical curable resin composition using a radical polymerizable monomer having a tetrahydrofurfuryl group or a binder resin having a tetrahydrofurfuryl group in the side chain is excellent in air curability (oxygen scavenging), In addition, adhesion and transparency are good, but there is still room for improvement in heat resistance.

  The present invention has been made in view of the above problems, and is capable of reducing radical polymerization inhibition by oxygen, having excellent adhesion and transparency, and having excellent heat resistance, and a radical curable binder resin for compositions. And a radical curable composition using the binder resin.

The present inventor pays attention to a polymer having a structural unit represented by the formula (1) in the main chain, and is mainly curable in air (oxygen scavenging), and good adhesion and transparency. Found in a structure having a tetrahydrofuran ring in the chain and found to have excellent heat resistance, and various uses such as coating materials, adhesives, sealants, adhesives, paints, inks, resists, dental materials, lenses, molding materials, etc. The inventors have arrived at the present invention by conceiving that they can be suitably used for the radical curable resin composition used in the present invention.

  That is, the present invention provides a radical curable resin composition containing a radical polymerizable monomer and a binder resin, wherein the binder resin is a resin containing a structural unit represented by formula (1) in the main chain. It is a radical curable resin composition characterized by being. The binder resin is also a binder resin for a radical curable resin composition, wherein the binder resin is a resin containing a structural unit represented by the formula (1) in the main chain.

ADVANTAGE OF THE INVENTION According to this invention, the radical curable resin composition which is excellent not only in sclerosis | hardenability in air (oxygen scavenging property) but adhesiveness and transparency is excellent also in heat resistance is provided. Therefore, the radical curable resin composition of the present invention is used for applications that require heat resistance among the applications in which the radical curable composition is used, for example, sealing materials for electronic parts, overcoats, and coatings. It is particularly suitable for materials, adhesives, solder resists, color filter resists, lenses for electronic parts, molding materials and the like.

A ¹ H-NMR chart measured using the resin powder obtained in Example 1-1 is shown in FIG. The measured ¹ H-NMR chart using the resin powder obtained in Example 1-8 is shown in FIG.

The present invention will be described in detail below, but these are examples of embodiments of the present invention, and the present invention is not limited to these contents.

  First, each component of the radical curable resin composition of this invention is demonstrated. The essential components of the radical curable resin composition of the present invention are (A) a radical polymerizable monomer and (B) a binder resin, and (B) the binder resin is a structural unit represented by the formula (1). In the main chain. The radical curable resin composition of the present invention preferably contains (C) a radical polymerization initiator for improving curability in addition to the above essential components, and further includes types of radical polymerizable monomers and binder resins, and various uses. (D) Diluent and (E) Other components may be blended according to the purpose and required characteristics. Hereinafter, each component which comprises the radical curable resin composition of this invention is demonstrated.

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms).

(A) Radical polymerizable monomer The radical polymerizable monomer is a low molecular weight compound having a radical polymerizable unsaturated group that is polymerized by heat, irradiation of active energy rays, or the like. Gives radical curability. In particular, a liquid having a low viscosity at room temperature is also called a reactive diluent because it also has a function as a diluent for adjusting viscosity, and is particularly preferably used in applications where use of a solvent is disliked. As such radically polymerizable monomers, conventionally known monomers can be used, and one or more kinds may be appropriately selected according to the purpose and application. The radical polymerizable monomer is classified into a monofunctional radical polymerizable monomer having only one radical polymerizable unsaturated group in the same molecule and a polyfunctional radical polymerizable monomer having two or more. can do.

  Specific examples of the monofunctional radical polymerizable monomer include, for example, methyl methacrylate), ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth) acrylate. , N-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (meth) acryl T-amyl acid, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate Methyl, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ben (meth) acrylate , Phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methacrylic acid 2- Methoxyethyl, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) Β-ethylglycidyl acrylate, (meth) acrylic acid (3, (Ethoxycyclohexyl) methyl, (meth) acrylic acid esters such as N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate; N, N-dimethyl ( (Meth) acrylamides such as (meth) acrylamide and N-methylol (meth) acrylamide; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; maleic acid, fumaric acid and itacone Unsaturated polycarboxylic acids such as acid, citraconic acid and mesaconic acid; chain extension between unsaturated groups and carboxyl groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate Unsaturated monocarboxylic acids; maleic anhydride, itaconic anhydride, etc. Unsaturated acid anhydrides; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, methoxystyrene; N-substitution such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide Maleimides; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2 -Ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl Vinyl ethers such as ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N -N-vinyl compounds such as vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate;

  Specific examples of the polyfunctional radical polymerizable monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, Ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added di Pentaerythritol hexa (meth) acrylate, ε -Caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, etc. Polyfunctional (meth) acrylates; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide di Vinyl ether, trimethylolpropane tri Nyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetra Polyfunctional vinyl ethers such as vinyl ether and ethylene oxide-added dipentaerythritol hexavinyl ether; 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, ( (Meth) acrylic acid 2-vinyloxy Propyl, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, (meth) acrylic acid 4 -Vinyloxymethylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, etc. Vinyl ether group-containing (meth) acrylic acid esters; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanedi All diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glyceryl triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, Polyfunctional allyl ethers such as dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether; Meta) Allyl group-containing (meth) acrylic esters such as allyl acrylate; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri Polyfunctional (meth) acryloyl group-containing isocyanurates such as (methacryloyloxyethyl) isocyanurate; Multifunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Multifunctional such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate Reaction of isocyanate with hydroxyl-containing (meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Multifunctional urethane (meth) acrylates obtained; polyfunctional aromatic vinyl compounds such as divinylbenzene, and the like.

  Among these polyfunctional radically polymerizable monomers, polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, and (meth) acryloyl group-containing isocyanates are considered due to reactivity, economy and availability. A polyfunctional monomer having a (meth) acryloyl group, such as a nurate, is preferable, and exemplified by the trade name, KAYARAD R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), DPHA, DPHA-2C , D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-00 5 (manufactured by Nippon Kayaku); Aronix M-203S, M-208, M-211B, M-215, M-220, M-225, M-270, M-240, M-309, M-310 M-321, M-350, M-360, M-370, M-313, M-315, M-325, M-327, M-306, M-305, M-451, M-450, M -408, M-403, M-400, M-402, M-404, M-406, M-405, M-510, M-520 (above, manufactured by Toagosei); Light acrylate 3EG-A, 4EG- A, 9EG-A, DCP-A, BP-4EA, BP-4PA, HPP-A, PTMGA-250, G201PTMP-A, TMP-6EO-3A, TMP-3EO-A (manufactured by Kyoeisha Chemical), Wright Ester EG, 2 EG, 3EG, 4EG, 9EG, G101P, G201P, BP-2EM, BP-6EM, TMP (above, manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry) Etc.

  The molecular weight of the radical polymerizable monomer of the present invention may be appropriately set according to the purpose and application, but 2000 or less is preferable in terms of handling.

  The amount of the radical polymerizable monomer used may be appropriately set according to the type, purpose, and use of the radical polymerizable monomer and binder resin to be used. From the point, it is 5-1000 mass% with respect to binder resin, Preferably it is 15-700 mass%, More preferably, it is 20-500 mass%.

(B) Binder resin The binder resin is a polymer compound that mainly affects the properties of the coating film after drying and the physical properties of the coating film after curing, and is a component that contributes to radical curability. The binder resin of the present invention is a resin containing the structural unit represented by the formula (1) in the main chain, can reduce radical polymerization inhibition by oxygen, is excellent in adhesion and transparency, and is excellent in heat resistance. .

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  The expression of the above-described characteristics in the binder resin of the present invention is presumed to be caused by the tetrahydrofuran ring contained in the structural unit represented by the formula (1) and the methylene groups on both sides of the tetrahydrofuran ring. It is known that the tetrahydrofurfuryl group, which is a functional group containing a tetrahydrofuran ring, captures oxygen by the mechanism represented by the following formula (3) and reduces the inhibition of curing by oxygen in radical curing using heat and active energy rays. However, the binder resin of the present invention is considered to exhibit the effect of reducing radical curing inhibition by oxygen with the same mechanism as shown in the following formula (4). In addition, the tetrahydrofuran ring has a function as a so-called Lewis base (donor of a lone pair), and the tetrahydrofuran ring and the functional group on the surface of the base material are likely to interact with each other. .

  As one of the preferable usage modes of the radical curable resin composition of the present invention, a coloring radical curable resin composition by adding a coloring material (pigment, dye) as other components such as paint, colored ink, and colored resist. However, the binder resin of the present invention has excellent colorant dispersion stability. This is presumably because the tetrahydrofuran ring as the Lewis base interacts with the color material (pigment, dye) surface and the functional group of the color material dispersant. In addition, tetrahydrofuran is a solvent that has the ability to dissolve a very wide range of substances, and is a solvent that is often used not only for industrial use but also for analysis and research purposes. However, the binder resin of the present invention has excellent compatibility and dry re-dissolution. The reason for this is considered to be that it has a tetrahydrofuran structure.

  The binder resin of the present invention has a high heat resistance because it has a ring structure in the main chain, and has good transparency because it does not contain a nitrogen atom. Resins having a ring structure in the main chain have high heat resistance, but in most cases lack flexibility, but the repeating unit containing a tetrahydrofuran ring in the binder resin of the present invention represented by formula (1) is located on both sides of the tetrahydrofuran ring. Because of the methylene group, it has high flexibility, and each performance derived from the tetrahydrofuran ring such as curability in air (oxygen scavenging), adhesion, colorant dispersibility, compatibility, and dry re-dissolution is effective. It is thought to develop. The performance derived from these tetrahydrofuran rings can be expressed to some extent even in a (meth) acrylic copolymer having a tetrahydrofurfuryl group in the side chain such as a tetrahydrofurfuryl copolymer of (meth) acrylic acid, It is difficult to develop high heat resistance like the binder resin of the present invention. One of the preferred modes of use of the radical curable resin composition of the present invention is a sealing material or an overcoat for electronic parts. This is because the radical curable resin composition of the present invention has an oxygen scavenging property ( That is, both the antioxidant ability and high heat resistance can be achieved, and the elements and the like can be protected from oxidation and deterioration due to heat.

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms).

  R of the structural unit represented by the formula (1) in the binder resin of the present invention represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As described above, since the development of each performance of the binder resin of the present invention is caused by the tetrahydrofuran ring in the main chain and the methylene group on both sides of the tetrahydrofuran ring, R is appropriately selected according to the purpose and application. do it.

  Specific examples of R include, for example, a hydrogen atom; methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t-amyl, n- Hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, Chain saturated hydrocarbon groups such as eicosyl, ceryl, and melyl; chain saturated hydrocarbons such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl, phenoxyethyl, and phenoxyethoxyethyl A part of the hydrogen atom of the hydrogen group Alkoxy-substituted chain saturated hydrocarbon group substituted with a di group; hydroxy-substituted chain saturated hydrocarbon group in which part of the hydrogen atoms of a chain saturated hydrocarbon group such as hydroxyethyl, hydroxypropyl, hydroxybutyl, etc. is replaced with a hydroxy group A halogen-substituted chain saturated hydrocarbon group in which a part of hydrogen atoms of a chain saturated hydrocarbon group such as fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl, dibromoethyl and the like is replaced by halogen; vinyl, allyl, methallyl, Chain unsaturated hydrocarbon groups such as crotyl and propargyl, and chain unsaturated hydrocarbon groups in which part of the hydrogen atoms are replaced with alkoxy groups, hydroxy groups or halogens; cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4- t-butylcyclohexyl, tricyclodecanyl Cycloaliphatic hydrocarbon groups such as isobornyl, adamantyl and dicyclopentadienyl, and alicyclic hydrocarbon groups in which part of the hydrogen atoms are replaced by alkoxy groups, hydroxy groups or halogens; phenyl, methylphenyl, dimethylphenyl , Trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl and the like, and some of the hydrogen atoms are alkoxy groups, hydroxy groups, And aromatic hydrocarbon groups substituted with halogen. Further, a substituent may be further bonded to these organic groups. Two or more of R in formula (1) may be the same or different.

  The content of the structural unit represented by the formula (1) in the binder resin of the present invention depends on the purpose, application, the ratio of the binder resin of the present invention to the radical polymerizable monomer, and the molecular weight of the binder resin of the present invention. However, it is usually 1 to 100 mol%, preferably 2 to 100 mol%, more preferably 5 to 100 mol% in all repeating structural units. When the ratio of the binder resin of the present invention to the radical polymerizable monomer is large, the performance tends to be exhibited even if the content of the structural unit represented by the formula (1) is small. When the ratio of the binder resin of the present invention is small, the content tends to be easily developed when the content is increased.

  In particular, in applications where a color material is added (ink, paint, etc.), when the binder resin of the present invention has a high molecular weight, the performance can be achieved even if the content of the structural unit represented by the formula (1) is small. There is a tendency to develop, and when the molecular weight is low, increasing the content tends to facilitate performance. This is considered to be related to the number of structural units represented by the formula (1) contained per main chain (hereinafter referred to as the average number of functional groups), and the average number of functional groups is 0.5 or more. Preferably, it is 1.0 or more, more preferably 2.0 or more.

The average number of functional groups is represented by the following formula.
Average number of functional groups = A / P
A: Number of moles of the structural unit represented by the formula (1) included in the unit mass [mol / g]
P: Number of moles of the binder resin of the present invention contained in unit mass [mol / g]
A can be calculated as the following equation, including the case where there are two or more types of structural units represented by the equation (1).
A = ΣA _x (X = 1, 2, 3,...)
A _x = unit mass × (C _x / 100) / F _x
A _x : Number of moles of the structural unit represented by the formula (1) of the X (X = 1, 2, 3,...) Type contained in the unit mass [mol / g]
C _x : the mass ratio [% by mass] of the structural unit represented by the formula (1) of the X (X = 1, 2, 3,...) Type contained in the unit mass.
F _x : X (X = 1, 2, 3,...) Molecular weight [g / mol] of the structural unit represented by the formula (1) of the type
P can be approximated by the following formula using the number average molecular weight (Mn) of the binder resin of the present invention.
P = unit mass / Mn
Mn: Number average molecular weight of the binder resin of the present invention Therefore, the average number of functional groups is represented by the following formula using C _x , F _x , and Mn.
Average functional group number = Mn × Σ {(C _x / 100) × (1 / F _x )}
In addition, when obtaining by the manufacturing method including the process of superposing | polymerizing the monomer component containing the monomer represented by Formula (2), the binder resin of this invention is represented by Formula (2) so that it may mention later. Since the cyclization rate of the monomer (the ratio at which the structural unit represented by the formula (1) is formed from the monomer represented by the formula (2)) is high, C _x and F _x are It can be approximated as follows.
C _x : Mass ratio of the monomer represented by the formula (2) of the X (X = 1, 2, 3,.
F _x : X (X = 1, 2, 3,...) Molecular weight [g / mol] of the monomer represented by the formula (2) of the type
Further, when the reaction rate of each monomer used in the polymerization is similarly high (for example, the reaction rate of each monomer is 90 mol% or more), C _x is as follows: Can be approximated.
C _x : Mass ratio of the monomer represented by the formula (2) of the X (X = 1, 2, 3,...) Type in the monomer component [mass%]
It is preferable that the binder resin of this invention is a thing obtained by the manufacturing method including the process of superposing | polymerizing the monomer component containing the monomer represented by Formula (2). This is because the monomer represented by the formula (2) is polymerized to produce the structural unit represented by the formula (1) at a high rate, and is unlikely to cause abnormal high molecular weight or gelation. .

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  R of the monomer represented by the formula (2) represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be appropriately selected according to the purpose and application. Specific examples of R are the same as R in the formula (1).

  Moreover, when the monomer represented by formula (2) is exemplified by the compound name, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, α-allyloxymethyl ethyl acrylate, α- N-propyl allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate t -Butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate n-hexyl, α-allyl S-hexyl oxymethyl acrylate, α-allyloxymethyl acrylate n-heptyl, α-allyl N-octyl dimethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, capryl of α-allyloxymethyl acrylate, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl decyl acrylate, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl lauryl acrylate, α-allyloxymethyl acrylate tridecyl, α-allyloxymethyl Myristyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, α-allyloxymethyl acetate Nonadecyl oxalate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, methoxyethyl α-allyloxymethyl acrylate, methoxyethoxy α-allyloxymethyl acrylate Ethyl, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, ethoxyethyl α-allyloxymethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, α-allyl Phenoxyethyl oxymethyl acrylate, α-allyloxymethyl acrylate phenoxyethoxyethyl, α-allyloxymethyl acrylate hydroxyethyl, α-allyloxymethyl acrylate hydroxypropyl α-allyloxymethyl acrylate hydroxybutyl, α-allyloxymethyl acrylate fluoroethyl, α-allyloxymethyl acrylate difluoroethyl, α-allyloxymethyl acrylate acrylate, α-allyloxymethyl acrylate acrylate, α -Bromoethyl allyloxymethyl acrylate, dibromoethyl α-allyloxymethyl acrylate, vinyl α-allyloxymethyl acrylate, allyl α-allyloxymethyl acrylate, methallyl α-allyloxymethyl acrylate, α-allyloxymethyl Crotyl acrylate, propargyl α-allyloxymethyl acrylate, cyclopentyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 4 Methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyl Dicyclopentadienyl oxymethyl acrylate, phenyl α-allyloxymethyl acrylate, methyl phenyl α-allyloxymethyl acrylate, dimethyl phenyl α-allyloxymethyl acrylate, trimethyl phenyl α-allyloxymethyl acrylate, α -4-t-butylphenyl allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate, diphenylethyl α-allyloxymethyl acrylate, - allyloxymethylacrylate triphenylmethyl, alpha-allyloxymethylacrylate cinnamyl, alpha-allyloxymethylacrylate naphthyl, alpha-allyloxymethylacrylate anthranyl. These monomers represented by the formula (2) can be used alone or in combination of two or more.

  In addition to the monomer represented by the formula (2), the monomer component may contain another copolymerizable monomer, the type and amount of which are the radical curable resin of the present invention. What is necessary is just to select and adjust suitably according to the objective and use of a composition.

  Examples of such other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, ( N-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (meth) acrylic t -Amyl, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, Octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, ( T) Phenyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid glycidyl, (meth) acrylic acid β-methylglycidyl, (meth) acrylic acid β -Ethyl glycidyl, (meth) acrylic acid (3,4-epoxy (Meth) acrylic acid esters such as cyclocyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate; N, N-dimethyl (meta ) (Meth) acrylamides such as acrylamide and N-methylol (meth) acrylamide; Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid Unsaturated polyvalent carboxylic acids such as citraconic acid and mesaconic acid; chain extension between unsaturated group and carboxyl group such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate Unsaturated monocarboxylic acids, such as maleic anhydride and itaconic anhydride Anhydrides; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, methoxystyrene; N-substituted maleimides such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide; Macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam; 1,3-butadiene, isoprene Conjugated dienes such as chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; methyl vinyl ether, ethyl vinyl ether Propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxy Vinyl ethers such as butyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; isocyanatoethyl (meth) acrylate, allyl And unsaturated isocyanates such as isocyanate. These other copolymerizable monomers can be used alone or in combination of two or more.

  The content ratio of the monomer represented by the formula (2) contained in the monomer component is the purpose, the use, the ratio of the binder resin of the present invention to the radical polymerizable monomer, and the binder resin of the present invention. What is necessary is just to set suitably according to molecular weight, Usually, 1-100 mol% in all the monomer components, Preferably it is 2-100 mol%, More preferably, it is 5-100 mol%.

  As the polymerization method of the monomer component, known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and may be appropriately selected according to the purpose and application. It is advantageous, and the structure adjustment such as molecular weight is easy and preferable. As the polymerization mechanism, a polymerization method based on a known mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. However, the polymerization method based on the radical polymerization mechanism is based on the cyclization rate (formula (2 The ratio of the structural unit represented by the formula (1) produced from the monomer represented by the formula (1) is high, and is industrially advantageous.

  A known method can be used as a method for initiating polymerization, provided that energy necessary for initiating polymerization is supplied to the monomer component from an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams or the like. In addition, it is preferable to use a polymerization initiator in combination, because the energy required for the initiation of polymerization can be greatly reduced and the reaction can be easily controlled.

As a method for controlling the molecular weight, a known method can be used. For example, it can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.
When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism and the type of monomer used. May be appropriately set according to the polymerization conditions such as the amount, the polymerization temperature, and the polymerization concentration. Moreover, when using a solvent when setting it as curable resin composition later, it is efficient and preferable that the solvent used in that case is included.

  Examples of the solvent used include monoalcohols such as methanol, ethanol, isopropanol, n-butanol, and s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether , Glycol monoethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol Class: Ethylene glycol dimethyl ether Ter, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether and other glycol ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Esters of glycol monoethers such as noethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Alkyl esters such as methyl propionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl Ketones such as ruethylketone, methylisobutylketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; dimethylformamide, dimethylacetamide and N-methylpyrrolidone And amides such as water, and the like. These may be used alone or in combination of two or more.

  As a usage-amount of a solvent, 40-1000 mass% is preferable with respect to 100 mass% of all monomer components, and 100-400 mass% is more preferable.

  When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate.

  Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy-2- Ethyl hexanoate, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2- Methyl propionate), hydrogen peroxide, persulfate, and the like, and known peroxides and azo compounds may be used. These may be used alone or in combination of two or more. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

  The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.1 to 20% by mass is preferable with respect to 100% by mass of all monomer components, and 0.5 to 15% by mass is more preferable.

  When the monomer component is polymerized by a radical polymerization mechanism, a known chain transfer agent may be used as necessary, and it is more preferable to use in combination with a radical polymerization initiator. When a chain transfer agent is used at the time of polymerization, there is a tendency that increase in molecular weight distribution and gelation can be suppressed. Specific examples of such chain transfer agents include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, N-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), di Mercaptocarboxylic esters such as pentaerythritol hexakis (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane, etc. Alkyl mercaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3 -Mercaptopropionyloxy) -ethyl] mercaptoisocyanurates such as isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; simple units such as α-methylstyrene dimer Monomeric dimers; alkyl halides such as carbon tetrabromide; Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercaptoalcohols, aromatic mercaptans; mercaptoisocyanurates in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. Compounds having a mercapto group, such as catechol, are preferred. These may be used alone or in combination of two or more.

  The amount of chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of monomers used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.1 to 20% by mass is preferable with respect to 100% by mass of all monomer components, and 0.5 to 15% by mass is more preferable.

  The polymerization temperature when the monomer component is polymerized using a polymerization initiator that generates radicals by heat by a radical polymerization mechanism includes the type and amount of the monomer used, the type and amount of the polymerization initiator, etc. However, it is preferably 50 to 200 ° C, more preferably 70 to 150 ° C.

  Examples of steps other than the step of polymerizing the monomer component include steps performed by known polymer production methods, such as polymer modification treatment steps, purification steps such as reprecipitation and liquid separation, and two steps. A solvent removal / pelletizing step using a screw extruder or the like, a step of adjusting the concentration of the polymer by removing or adding the solvent, and the like can be used as necessary. The polymer modification treatment process will be described below.

  The binder resin of the present invention may be obtained by polymerizing a monomer component containing the monomer represented by the formula (2) and then performing a modification treatment. By performing the modification treatment, it is possible to obtain a structure that is difficult to obtain only by performing a normal polymerization step such as introduction of a radically polymerizable unsaturated group or introduction of a graft chain. In particular, it is preferable to use a binder resin having a radical polymerizable unsaturated group by a modification treatment because the curability of the radical curable resin composition is improved.

  Such a modification treatment method is not particularly limited as long as the constitutional unit represented by the formula (1) in the binder resin is not completely lost. For example, a monomer having a functional group X And a method of reacting a compound having a functional group Y capable of reacting with the functional group X after polymerizing the monomer component containing.

  Examples of such combinations of functional groups X and Y include, for example, carboxyl group and hydroxy group, carboxyl group and epoxy group, carboxyl group and isocyanate group, hydroxy group and isocyanate group, acid anhydride group and hydroxy group, acid anhydride Groups and amino groups. Specifically, for example, it is possible to obtain a binder resin having a radically polymerizable unsaturated group by reacting glycidyl (meth) acrylate after polymerizing a monomer component containing (meth) acrylic acid, A binder resin having polycaprolactone in the graft chain can be obtained by polymerizing a monomer component containing glycidyl (meth) acrylate and then reacting one terminal carboxyl group-based polycaprolactone.

  The weight average molecular weight of the binder resin of the present invention may be appropriately set according to the purpose and application, but is usually 2000 to 250,000, preferably 3000 to 200000, and more preferably 4000 to 150,000.

  The ratio of the binder resin of the present invention in the radical curable resin composition of the present invention may be appropriately set according to the type, purpose, and use of the radical polymerizable monomer and binder resin to be used. As shown in the radical polymerizable monomer.

(C) Radical polymerization initiator As a method of curing the radical curable resin composition of the present invention, the radical curable resin of the present invention is used from an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. What is necessary is just to supply energy required for radical polymerization start to a composition, and also using a radical polymerization initiator together can reduce significantly energy required for radical polymerization start, and can improve sclerosis | hardenability, and is preferable. The radical polymerization initiator includes a thermal radical polymerization initiator that generates a polymerization initiating radical by heating, and a photo radical polymerization initiator that generates a polymerization initiating radical by irradiation of energy rays such as electromagnetic waves and electron beams. 1 type or 2 types or more can be used. It is also preferable to add one or more conventionally known thermal radical polymerization accelerators, photosensitizers, photoradical polymerization accelerators, and the like as necessary.

  Specific examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide). Oxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1, 1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (T-Butylperoxy) butane, 2,2-bis (4 4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydro Peroxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane , T-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethyl Hexanoyl peroxide, octanoylpa Oxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butyl) (Cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3 Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxy Pivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperper Oxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t- Hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutylene , T-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2 -Ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5 -Bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilylper Oxide 3,3 ', 4,4'-teto Organo-oxide initiators such as la (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane; 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1 -[(1-cyano-1-methylethyl) azo] formamide, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2 ' -Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2-Methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2 ' Azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-Methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-Hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- 4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidine-2- Yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [1,1-bis (hydride) Roxymethyl) ethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2-methylpropionamide), 2,2′- Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4- And azo initiators such as cyanopentanoic acid) and 2,2'-azobis [2- (hydroxymethyl) propionitrile].

  Examples of the thermal radical polymerization accelerator that can be used together with the thermal radical polymerization initiator include metal soaps such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, and potassium; Quaternary ammonium salts; thiourea compounds; ketone compounds, etc., specifically, for example, cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, naphthenic acid Manganese, dimethylaniline, triethanolamine, triethylbenzylammonium chloride, di (2-hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, methyl acetoacetate and the like can be mentioned.

  Specific examples of the radical photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methyl Alkylphenone compounds such as phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone and 2-carboxybenzophenone Compound: Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4 -Thioxanthone compounds such as diethylthioxanthone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6 Bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis ( Halomethylated triazine compounds such as trichloromethyl) -s-triazine; 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- ( 2'-benzofuryl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like halomethylated oxadiazoles Compound; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 Biimidazole compounds such as 5′-tetraphenyl-1,2′-biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1 Oxime ester compounds such as [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like; p-dimethylaminobenzoic acid, p-diethylamino Benzoic acid ester compounds such as Ikiko acid; acridine compounds such as 9-phenyl acridine; and the like.

  Sensitivity and curability can be improved by using a photosensitizer and a photoradical polymerization accelerator together with the photoradical initiator. Examples of such photosensitizers and photoradical polymerization accelerators include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; ethyl 4-dimethylaminobenzoate, 4-dimethylamino Examples include dialkylaminobenzene compounds such as 2-ethylhexyl benzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole.

  The total amount of the radical polymerization initiator added may be appropriately set according to the purpose and application, and is not particularly limited. However, from the viewpoint of balance between curability, adverse effects of decomposition products, and economy, radical curable resin composition It is 0.01-30 mass% with respect to the whole thing, Preferably it is 0.05-20 mass%, More preferably, it is 0.1-15 mass%.

  The total amount of the thermal radical polymerization accelerator, photosensitizer, and photoradical polymerization accelerator added may be appropriately set according to the purpose and application, and is not particularly limited. From the point of balance of property, it is 0.001-20 mass% with respect to the whole radical curable resin composition, Preferably it is 0.05-10 mass%, More preferably, it is 0.01-10 mass%.

(D) Diluent In the radically curable resin composition of the present invention, the viscosity is lowered and the handleability is improved, the coating film is formed by drying, the dispersion medium of the coloring material, etc., as necessary. In addition to the above essential components, a low viscosity organic solvent or water capable of dissolving or dispersing each component in the radical curable resin composition may be added as a diluent.

  As such a diluent, a conventionally known one can be used, and it may be appropriately selected according to the purpose and application, and is not particularly limited. For example, methanol, ethanol, isopropanol, n-butanol, s-butanol and the like are used. Monoalcohols; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether Glycol monoethers such as ter, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, etc. Glycol ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Teracetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, etc. Esters of glycol monoethers; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypro Alkyl esters such as ethyl pionate, methyl acetoacetate and ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; hexane, cyclohexane, Aliphatic hydrocarbons such as octane; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, water and the like. These may be used alone or in combination of two or more.

  The amount of the diluent used may be appropriately set depending on the purpose and application, and is not particularly limited, but is usually 0 to 90% by mass, preferably 0 to 80% by mass with respect to the entire radical curable resin composition. %.

(E) Other components The radical curable resin composition of the present invention is a filler, a resin other than the binder resin of the present invention, a coloring material (pigment, dye), a dispersant, depending on the purpose and required characteristics of each application. Plasticizer, polymerization inhibitor, ultraviolet absorber, antioxidant, matting agent, antifoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, thixotropic agent, thixotropic agent, Components other than the above essential components such as coupling agents such as silane, aluminum and titanium, cationic polymerizable compounds and acid generators may be blended.

  For example, when using the radical curable resin composition of the present invention for adhesives or pressure-sensitive adhesives, if necessary, resins other than the binder resin of the present invention, tackifiers such as tackifiers, various fillers, A coloring material, a dispersing agent, etc. can be mix | blended. A use mode in which the adhesive or pressure-sensitive adhesive thus obtained is applied on a metal, glass, paper, resin, or other substrate and cured by heating or irradiation with active energy rays is one of the preferred embodiments of the present invention. One.

  When the radical curable resin composition of the present invention is used for inks or paints, a resin other than the binder resin of the present invention, various fillers, a coloring material, a dispersant, a drying oil, a dryer, etc. may be blended as necessary. Can do. The use mode in which the ink or paint thus obtained is applied onto a metal, glass, paper, resin, or other base material and cured by heating or irradiation with active energy rays is one of the preferred embodiments of the present invention. is there.

  When the radical curable resin composition of the present invention is used for a curable molding material, a resin other than the binder resin of the present invention, various fillers, a coloring material, a dispersant, an ultraviolet absorber, and the like are blended as necessary. Can do. The curable molding material thus obtained is used as it is or impregnated in a reinforcing fiber such as glass fiber, carbon fiber or aramid fiber, and cured by heating or irradiation with active energy rays. One.

  When the radical curable resin composition of the present invention is used for resist applications, an alkali-soluble binder resin, an epoxy resin, various fillers, a colorant, a dispersant, and the like can be blended as necessary. The use mode in which the resist material thus obtained is applied on a metal, glass, resin, or other substrate, cured by irradiation with active energy rays, developed with an alkaline developer, and image formation is suitable for the present invention. It is one of the embodiments.

  The radical curable resin composition of the present invention can be obtained by blending, mixing, dissolving, or dispersing blending components such as a radical polymerizable monomer, a binder resin, and other additives.

  The radical curable resin composition of the present invention includes an adhesive, an adhesive, a biomaterial, a dental material, an optical member, an information recording material, an optical fiber material, a color filter resist, a solder resist, a plating resist, an insulator, and a sealing material. , Inkjet ink, printing ink, paint, casting material, decorative plate, WPC, coating material, photosensitive resin plate, dry film, lining material, civil engineering and building material, putty, repair material, flooring material, paving material gel coat, overcoat It can be used in a wide range of applications such as molding materials such as hand lay-up, spray-up, pultrusion, filament winding, SMC, BMC, and polymer solid electrolytes.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Synthesis of monomer represented by formula (2)>
[Synthesis Examples 1 to 5]
As shown in Table 1, each α-allyloxymethyl acrylate ester (AMA-R), which is a monomer represented by the formula (2), is used as a catalyst according to Japanese Patent Laid-Open No. 10-226669. -Diazabicyclo [2.2.2] octane was synthesized from allyl alcohol and the corresponding α-hydroxymethyl acrylate ester (HMA-R).

<Synthesis of Resin Containing Structural Unit Represented by Formula (1) in Main Chain>
Hereinafter, the synthesis of a resin containing the structural unit represented by the formula (1) in the main chain will be described. In addition, measurement of solid content of the obtained resin solution, measurement of resin weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), and structural unit represented by formula (1) Calculation of the average number of functional groups, extraction of the resin powder, measurement of ¹ H-NMR, and the like were performed as follows.

(Mw, Mn, Mw / Mn)
What diluted the resin solution with tetrahydrofuran and filtered with the filter of the hole diameter 0.45 micrometer was measured with the following gel permeation chromatography (GPC) apparatus and conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh)
Elution solvent: Tetrahydrofuran standard: Standard polystyrene (manufactured by Tosoh)
Separation column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation).

(Average number of functional groups)
Average number of functional groups = Mn × {(weight ratio of AMA-R in monomer component [mass%] / 100) × (1 / AMA-R molecular weight)}.

(Resin removal)
A part of the resin solution was diluted with tetrahydrofuran and poured into excess hexane for reprecipitation. The precipitate was taken out by filtration and then vacuum dried at 70 ° C. (for 5 hours or more) to obtain a white resin powder.

⁽¹ H-NMR measurement)
200 mg of the white powder obtained as described above was dissolved in 3 g of heavy dimethyl sulfoxide containing tetramethylsilane and measured with a nuclear magnetic resonance apparatus (200 MHz, manufactured by Varian).

(Solid content)
About 0.3 g of the resin solution was weighed into an aluminum cup, dissolved by adding about 2 g of acetone, and then naturally dried at room temperature. After drying at 140 ° C. for 3 hours using a hot air dryer, the product was allowed to cool in a desiccator and the weight was measured. The solid content of the resin solution was calculated from the weight loss.

[Example 1-1]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 213.5 parts of propylene glycol monomethyl ether acetate (PGMEA) was charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, 200.0 parts of AMA-M obtained in Synthesis Example 1 was added to the dropping tank A, and 4.7 parts of t-butylperoxy-2-ethylhexanoate (PBO) and 42.0 parts of PGMEA were added to the dropping tank B. In a dropping tank C, 3.5 parts of methyl 3-mercaptopropionate (MPM) and 44.5 parts of PGMEA were stirred and mixed.

After confirming that the internal temperature of the reaction tank was stabilized, the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C. From the dropping tank B, the polymerization reaction was carried out by dropping over 3.5 hours and from the dropping tank C over 4 hours. After completion of the dropwise addition, the temperature was increased and the temperature was increased to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 2.
Moreover, < ¹ > H-NMR was measured using the obtained resin powder. ^{A 1} H-NMR chart is shown in FIG.

[Examples 1-2 to 1-5]
A resin solution and a white powder of resin were obtained in the same manner as in Example 1-1 except that the type of ether ring monomer prepared in the dropping tank A was changed to that shown in Table 2. The analysis results are shown in Table 2.

[Example 1-6]
A resin solution and a white resin powder were obtained in the same manner as in Example 1-1 except that 121.8 parts of AMA-M and 78.2 parts of methyl methacrylate (MMA) were prepared in the dropping tank A. The analysis results are shown in Table 2.

[Example 1-7]
A resin solution and a white resin powder were obtained in the same manner as in Example 1-1 except that 60.0 parts of AMA-M and 140.0 parts of MMA were prepared in the dropping tank A. The analysis results are shown in Table 2.

[Example 1-8]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 223.7 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, in the dropping tank A, 60.0 parts of AMA-M obtained in Synthesis Example 1, 110.0 parts of benzyl methacrylate (BZMA), 1.4 parts of MMA, and 28.6 parts of methacrylic acid (MAA) were mixed with stirring. In the dropping tank B, 4.7 parts of PBO and 37.3 parts of PGMEA are stirred and mixed. In the dropping tank C, 3.0 parts of 3-mercaptopropionic acid (MPA) and 39.0 parts of PGMEA are stirred and mixed. Prepared.

  After confirming that the internal temperature of the reaction tank was stabilized, the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C. From the dropping tanks B and C, the polymerization reaction was carried out by dropping over 3.5 hours. 30 minutes after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 2. Moreover, when the solid content of the resin solution was measured as described above, it was 40.6%.

Moreover, < ¹ > H-NMR was measured using the obtained resin powder. ^{A 1} H-NMR chart is shown in FIG.

[Example 1-9]
Example 1-8 except that the mixture prepared in the dropping tank A was changed to a well-mixed mixture of AMA-M 20.0 parts, BZMA 110.0 parts, MMA 41.4 parts, and MAA 28.6 parts. A resin solution was obtained in the same manner. The analysis results are shown in Table 2. Moreover, when the solid content of the resin solution was measured as described above, it was 40.3%.

[Comparative Example 1-1]
A resin solution and a white powder of resin were obtained in the same manner as in Example 1-1 except that 200.0 parts of tetrahydrofurfuryl methacrylate (THM) was prepared in the dropping tank A. The analysis results are shown in Table 2.

[Comparative Example 1-2]
A resin solution and a white resin powder were obtained in the same manner as in Example 1-1 except that 200.0 parts of MMA was prepared in the dropping tank A. The analysis results are shown in Table 2.

[Comparative Example 1-3]
Other than changing the mixed solution prepared in the dropping tank A to 60.0 parts of benzylmaleimide (BZMI), 110.0 parts of BZMA, 1.4 parts of MMA, 28.6 parts of MAA, 60.0 parts of PGMEA and well mixed with stirring. Produced a resin solution and a white resin powder in the same manner as in Comparative Example 1-8. The analysis results are shown in Table 2.
BZMI is a monomer capable of obtaining a resin having an imide ring structure in the main chain, which is known as a resin having high heat resistance.

[Comparative Example 1-4]
The resin solution and the resin were prepared in the same manner as in Example 1-8 except that the mixture prepared in the dropping tank A was changed to a mixture obtained by stirring and mixing 110.0 parts of BZMA, 61.4 parts of MMA, and 28.6 parts of MAA. A white powder was obtained. The analysis results are shown in Table 2. Moreover, when the solid content of the resin solution was measured as described above, it was 40.4%.

<Evaluation of the effect of reducing polymerization inhibition by oxygen (surface curability)>
As an index for evaluating the effect of reducing polymerization inhibition by oxygen, surface curability in photo radical curing was used. In order to clearly evaluate the effect of the structural unit represented by the formula (1) on the surface curability, conditions that easily cause polymerization inhibition by oxygen (radical polymerizable monomer, photoradical polymerization initiator, compounding ratio, film thickness) Etc.).

[Example 2-1]
1.2 parts of binder resin powder obtained in Example 1-1, 2.8 parts of trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur) 1173 (manufactured by Ciba Specialty Chemicals) and 6.0 parts of isopropyl acetate (IPAC) were stirred and mixed to obtain a uniform solution, which was applied to a float plate glass using a bar coater. After naturally drying at room temperature for 10 minutes, it was dried at 70 ° C. for 5 minutes using a hot air drier to obtain a photo-radical curable coating film having a thickness of 10 μm. Next, UV was irradiated using an ultra-high pressure mercury lamp capable of irradiating the coating film with a certain amount of light, and the surface was touched to confirm tackiness. UV irradiation and finger touch were repeated, and the UV integrated irradiation dose [J / cm ² ] when the surface was tackless was recorded. The smaller the UV integrated irradiation amount, the better the surface curability. The results are shown in Table 3.

[Examples 2-2 to 2-7, comparative examples 2-1 to 2-2]
Surface curability was evaluated in the same manner as in Example 2-1, except that the binder resin powder used was changed as shown in Table 3. The results are shown in Table 3.

<Evaluation of adhesion>
Adhesiveness is one of the coating film performance after curing that the binder resin greatly contributes, and in order to clearly evaluate the effect on the adhesiveness of the structural unit represented by the formula (1), it was evaluated only with the binder resin. . The resin structure is a resin structure that does not contain an acid group such as a carboxyl group or a strong base such as an amine.

[Example 3-1]
The binder resin powder obtained in Example 1-1 was dissolved in IPAC to obtain a 39% solution. This was applied to a float plate glass using a bar coater, naturally dried at room temperature for 10 minutes, and then dried at 70 ° C. for 5 minutes using a hot air dryer to obtain a binder resin coating film having a thickness of 10 μm. The adhesion of this coating film was evaluated on a scale of 0 to 5 according to JIS K 5600-5-6 (cross cut method). The results are shown in Table 3.

[Examples 3-2 to 3-6, Comparative examples 3-1 to 3-2]
Adhesion was evaluated in the same manner as in Example 3-1, except that the binder resin powder used was changed as shown in Table 3. The results are shown in Table 3.

(Effect on surface curability and adhesion of the binder resin of the present invention)
From the results of the binder resin of Examples 1-1, 1-6, and 1-7 and the result of the binder resin of Comparative Example 1-2, the surface curability and the structural unit represented by the formula (1) are included. From the result of the resin of Comparative Example 1-1, the effect is the same as that of a resin having a tetrahydrofurfuryl group in the side chain in the surface curability, and a tetrahydrofurfuryl group is added to the side chain in the adhesion. It turns out that it is higher than the resin which has. Moreover, even if it changes R in the structural unit represented by Formula (1) from the result of the binder resin of Examples 1-1 to 1-5, it turns out that the effect expresses.

<Evaluation of thermal decomposition resistance>
Thermal decomposition resistance is one of the coating film performance after curing that the binder resin greatly contributes. In order to clearly evaluate the effect of the structural unit represented by the formula (1) on the thermal decomposition resistance, only the binder resin is used. evaluated.

[Example 4-1]
The binder resin powder obtained in Example 1-1 was measured under the following measuring equipment and conditions to obtain a dynamic TG curve. A 5% weight loss temperature was obtained from the obtained TG curve. The results are shown in Table 4.
Device: Thermo Plus TG8120 (Rigaku)
Atmosphere: Nitrogen flow 100 ml / min Temperature rising condition: Step-like isothermal control (SIA mode), Temperature rising rate = 10 ° C./min, Mass change rate value = 0.005% / sec.

[Examples 4-2 to 4-5, comparative examples 4-1 to 4-2]
The 5% weight reduction temperature of each binder resin was measured in the same manner as in Example 4-1, except that the binder resin powder used was changed as shown in Table 4. The results are shown in Table 4.

<Evaluation of transparency>
Transparency is one of the coating film performances after curing that greatly contributes to the binder resin. In order to clarify the difference in transparency, evaluation was made only with the binder resin.

[Example 5-1]
The binder resin powder obtained in Example 1-1 was dissolved in PGMEA to form a 30% solution, and the transmittance [%] at a wavelength of 400 nm of this solution was measured with a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). It was set as the transmittance before heating. On the other hand, the binder resin powder is put in a glass container and heated at 230 ° C. for 1.5 hours, and then dissolved in PGMEA to form a 30% solution. The transmittance [%] at a wavelength of 400 nm is measured, and this is transmitted after heating. Rate. Moreover, the transmittance | permeability retention [%] was computed according to following Formula using the transmittance | permeability before and after a heating. The results are shown in Table 4.
Transmittance retention [%] = transmittance after heating / transmittance before heating × 100.

[Examples 5-2 to 5-5, Comparative examples 5-1 to 5-2]
Transparency was evaluated in the same manner as in Example 5-1, except that the binder resin powder used was changed as shown in Table 4. The results are shown in Table 4.

(Effects on heat decomposability and transparency of binder resin of the present invention)
From Examples 4-1 to 4-5 and Comparative Example 4-1, the binder resin of the present invention has much higher heat decomposition resistance than the binder resin having a tetrahydrofurfuryl group in the side chain, and Example 4-4 From Comparative Example 4-2, it can be seen that the level is comparable to that of known heat resistant resins (resins containing an imide ring in the main chain). From Examples 5-1 to 5-5 and Comparative Examples 5-1 to 5-2, the binder resin of the present invention contains a binder resin having a tetrahydrofurfuryl group in the side chain, and an imide ring in the main chain. It can be seen that the resin has higher transparency than the resin to be used, and has both high thermal decomposition resistance and transparency at a high level.

<Evaluation of colorant dispersibility>
[Example 6-1]
(Preparation of colorant dispersion composition)
First, SOLSPERSE24000GR (manufactured by Nippon Lubrizol) as a dispersant was dissolved in PGMEA to 20%, and a binder resin solution prepared by diluting the resin solution obtained in Example 1-8 to 20% with PGMEA was prepared. did.
Next, C.I. I. Pigment Green 36 (Monastral Green 6Y-CL, manufactured by Heubach) 3.75 parts, and C.I. I. Pigment Yellow 150 (Yellow Pigment E4GN-GT, manufactured by Lanxess) 2.5 parts and 0.2 part of SOLPERSE 12000 (manufactured by Nihon Lubrizol) as a dispersant were weighed in a 225 ml mayonnaise bottle. Further, 3.75 parts of the 20% dispersant solution prepared in advance, 14.0 parts of the 20% binder resin solution, 25.8 parts of PGMEA, and 50 parts of zirconia beads having a diameter of 1.0 mm were added to a 225 ml mayonnaise bottle. Weighed and covered. This was shaken with a paint shaker for 3 hours for dispersion treatment, and then the color material dispersion composition and zirconia beads were fractionated to obtain a color material dispersion composition.

(Confirmation of distributed status)
The median diameter of the colorant dispersion composition immediately after the dispersion treatment was measured with a dynamic light scattering type particle size distribution measuring device (LB-500, manufactured by Horiba, Ltd.), and the median system was 100 nm or less. What exceeded 100 nm was set as x. The results are shown in Table 5.

(Evaluation of dispersion stability)
The obtained colorant dispersion is stored in a temperature-controlled room (23 ° C.), and after dispersion treatment, the viscosity after 1 day, 2 weeks, and 4 weeks is measured using a cone plate type rotational viscometer (TVE22LT, manufactured by Toki Sangyo Co., Ltd.). ). The viscosity increase rate was calculated according to the following formula. The results are shown in Table 5.
Viscosity increase rate [%] = viscosity after 2 weeks (or after 4 weeks) / viscosity after 1 day × 100-100
[Example 6-2, Comparative example 6-1]
Except that the binder resin solution was changed as shown in Table 5, the color material dispersion composition was prepared and the color material dispersibility was evaluated in the same manner as in Example 6-1.

(Effect on the colorant dispersibility of the binder resin of the present invention)
It can be seen from Examples 6-1 and 6-2 and Comparative Example 6-1 that the dispersion stability is improved as compared with a general binder resin by including the structural unit represented by the formula (1).

The radical curable resin composition of the present invention is not only curable in air (oxygen scavenging property) but also excellent in adhesion and transparency, and very excellent in heat resistance. Biomaterials, dental materials, optical members, information recording materials, optical fiber materials, color filter resists, solder resists, plating resists, insulators, sealants, inkjet inks, printing inks, paints, casting materials, decorative plates, WPC, coating material, photosensitive resin plate, dry film, lining material, civil engineering and building material, putty, repair material, flooring material, paving material gel coat, overcoat, hand lay-up, spray-up, pultrusion, filament winding, SMC, It can be used in a wide range of applications such as molding materials such as BMC and polymer solid electrolytes.

Claims (4)

In the radical curable resin composition containing a radical polymerizable monomer and a binder resin, the binder resin is a resin containing a structural unit represented by the following formula (1) in the main chain. A radical curable resin composition.

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.) The radical curable resin composition according to claim 1, wherein the binder resin is obtained by a production method including a step of polymerizing a monomer component containing a monomer represented by the following formula (2).

It is a binder resin used for the radical curable resin composition of Claim 1, Comprising: The said binder resin is resin which contains the structural unit represented by following formula (1) in a principal chain, It is characterized by the above-mentioned. A binder resin for a radical curable resin composition.

A binder resin used in the radical curable resin composition according to claim 2, wherein the binder resin comprises a step of polymerizing a monomer component containing a monomer represented by the following formula (2). A binder resin for a radical curable resin composition, which is a resin obtained by the method and containing a structural unit represented by the following formula (1) in the main chain.

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.)

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