Photopolymerizable composition, polymer, and method for producing polymer

Abstract

To provide a novel polymerizable composition.SOLUTION: A photopolymerizable composition contains, as polymerizable components, a compound represented by Formula (1) and a compound having two or more ethylenically unsaturated groups.SELECTED DRAWING: None

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to photopolymerizable compositions, polymers, and methods for making polymers. [Background technology]

[0002] Currently, measures to combat global warming are being called for, such as reducing the use of fossil fuels and introducing renewable energy. Bio-based polymers have the characteristic of being carbon neutral, and by replacing plastics made from petroleum, they are expected to reduce the consumption of petroleum resources and greenhouse gas emissions.

[0003] As one of the bio-based polymers, phenolic vegetable oil (hereinafter referred to as "CNSL") extracted from the outer shells of cashew nuts is used industrially mainly as a raw material for paints, adhesives, and resins. Examples of industrial uses of CNSL include phenolic resins, epoxy hardeners, reactive diluents, woodworking paints, and brake lining additives (phenolic resin particles). It is also being considered as a cheap alternative additive to petroleum-based phenolic resins in elastomers for tires, etc.

[0004] The conventional technology for producing resins (for coatings and films) using cardanol as a raw material is described below.

[0005] Using cardanol, a phenolic compound, as a starting material, novolak or resol resin (phenolic resin) is produced by reacting it with formalin under acid or alkaline conditions. These resins are used, for example, in building materials and automobile parts. In addition, granulated phenolic resin particles are used as additives for automobile brake linings. The manufacturing process of the above-mentioned phenolic resin is described below. First, a raw material oil containing cardanol as a main component is reacted with formaldehyde and hexamethylenetetramine to produce cashew varnish (a cardanol prepolymer whose viscosity is appropriately adjusted by adding an organic solvent). Next, a metal dryer is added as a catalyst for oxidatively polymerizing the double bond site of the side chain of the cashew varnish to produce an oxidatively polymerized resin. However, the resin produced by such a process may generate formaldehyde, which is harmful to the human body and the environment, during the manufacturing stage or after commercialization. The above method is the simplest method for producing phenolic resin from CNSL, but formalin, heavy metal catalysts, and volatile organic compounds (VOCs) are used during the manufacturing process, and it can be said to be a manufacturing method that places a high burden on the human body and the environment.

[0006] Therefore, Non-Patent Document 1 reports an epoxy resin manufacturing method that does not use formalin, heavy metal catalysts, or VOCs as an environmentally friendly manufacturing process. In this manufacturing method, first, cardanol is epoxidized by reacting a raw material oil containing cardanol as the main component with epichlorohydrin. Next, an epoxy cardanol prepolymer is synthesized by thermal oxidative polymerization of the double bond portion of the side chain. Then, an amine compound is added to crosslink the epoxy cardanol prepolymer to obtain a cured product. Non-Patent Document 2 also discloses a method of adding a photocationic polymerization initiator to the epoxy cardanol prepolymer and irradiating it with UV light to obtain a cured product.

[0007] In Patent Document 1, a polymer of allylcardanol (A) and a thiol compound (B) is described, which has a disulfide bond and exhibits a Raman shift of 1450 cm when irradiated with a 532 nm laser beam. -1Raman shift for peak intensity [I(1450)] at 530cm -1 A polymer having a peak intensity ratio [I(530)] of 0.10 or more [I(530) / I(1450)] at 1000 nm is disclosed. Specifically, in Patent Document 1, allyl cardanol is prepared by reacting allyl bromide or allyl chloride with a raw material oil mainly composed of cardanol, and a cured material is produced by photopolymerizing the allyl cardanol and a thiol compound.

[0008] As a method of using cardanol as part of the raw materials, it has been reported that in the production of polymethyl methacrylate (PMMA), a polymer of methyl methacrylate (MMA), cardanol methacrylate is added to MMA in a molar fraction of 0.02 to 0.10 and the two are copolymerized to obtain PMMA with improved thermal stability (Non-Patent Document 3). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2021-11541 A [Non-patent literature]

[0010] [Non-Patent Document 1] S. Kanehashi, et al, J. Appl. Polym. Sci., 132, 42725(2015) [Non-Patent Document 2] S. Kanehashi,et al, J. Fiber Sci. Technol., 73, 210-221(2017) [Non-Patent Document 3] S. Agarwal, et al, Preparation and characterization of copolymers from methyl methacrylate and cardanyl methacrylate, Die Angewandte Makromolekulare Chemie, 248(1997)95-104 Summary of the Invention [Problem to be solved by the invention]

[0011] As described above, in the method described in Non-Patent Document 1 and Non-Patent Document 2, a polymer can be obtained using cardanol derived from biomass without using formalin, heavy metal catalysts, or VOCs. In addition, the resin obtained by the method described in Non-Patent Document 1 and Non-Patent Document 2 is thermally stable up to about 300°C and has antibacterial activity against Staphylococcus aureus and Escherichia coli, so it is expected to be applied to packaging materials and coating materials. However, an organic halogen compound such as epichlorohydrin is used for epoxidation. Since organic halogen compounds are harmful to the human body and the environment, a greener alternative process is desired from the viewpoint of producing environmentally friendly bioplastics. In addition, since the heat treatment process when producing epoxy cardanol prepolymer requires a lot of energy, further energy saving is desired. In addition, as a problem in terms of physical properties, the resin obtained by the method described in Non-Patent Document 1 and Non-Patent Document 2 tends to be colored brownish brown because it utilizes thermal polymerization (oxidative polymerization).

[0012] The method described in Patent Document 1, like Non-Patent Document 1 and Non-Patent Document 2, does not use formaldehyde, volatile organic compounds (VOCs), or heavy metal catalysts, and therefore places less of a burden on the human body and the environment. Furthermore, the method described in Patent Document 1 does not involve thermal oxidation polymerization, and is therefore excellent in terms of energy saving, and can also produce a transparent resin. However, like the methods described in Non-Patent Document 1 and Non-Patent Document 2, the method described in Patent Document 1 uses an organic halogen compound, and therefore, from the viewpoint of producing environmentally friendly bioplastics, a greener alternative process is desired. Furthermore, the resin obtained by the method described in Patent Document 1 tends to have an odor due to residual thiols, and there is room for improvement in terms of strength and heat resistance.

[0013] The method described in Non-Patent Document 3 is a method for obtaining a resin with excellent thermal stability using cardanol methacrylate, but it uses methyl methacrylate as the main monomer, and does not fully meet the objectives of reducing the consumption of petroleum resources and reducing greenhouse gas emissions. Furthermore, as a result of the inventors' investigations, it was found that a sufficient degree of crosslinking cannot be obtained when the mass ratio of cardanol methacrylate to methyl methacrylate is increased. For this reason, it became clear that there is a need to develop a new method for producing a resin with an excellent degree of crosslinking even when cardanol is used as the main monomer.

[0014] Therefore, an object of the present disclosure is to solve at least one of the above problems.

[0015] For example, the present disclosure aims to provide a polymerizable composition that can obtain a polymer using a biomass-derived raw material such as cardanol (A1). For example, the present disclosure aims to provide a polymerizable composition that does not use formalin, a heavy metal catalyst, and / or VOCs (A2). For example, the present disclosure aims to provide a polymerizable composition that does not use an organic halogen compound such as epichlorohydrin (A3). For example, the present disclosure aims to provide a polymerizable composition that is excellent in terms of energy saving (A4). For example, the present disclosure aims to provide a polymerizable composition that can obtain a polymer with excellent transparency (A5). For example, the present disclosure aims to provide a polymerizable composition that can obtain a polymer without an odor due to residual thiol (A6). For example, the present disclosure aims to provide a polymerizable composition that can obtain a polymer with excellent strength (e.g., high crosslinking degree) (A7). For example, the present disclosure aims to provide a polymerizable composition that can obtain a polymer with excellent flexibility (A8). For example, the present disclosure has an object to provide a polymerizable composition from which a polymer having excellent heat resistance can be obtained (A9). The present disclosure has an object to provide a polymerizable composition from which at least one of the objects A1 to A9 can be achieved.

[0016] For example, the present disclosure aims to provide a polymer that can be obtained by utilizing a biomass-derived raw material such as cardanol (B1). For example, the present disclosure aims to provide a polymer that can be obtained without using formalin, a heavy metal catalyst, and / or VOCs (B2). For example, the present disclosure aims to provide a polymer that can be obtained without using an organic halogen compound such as epichlorohydrin (B3). For example, the present disclosure aims to provide a polymer that can be obtained by a method that is excellent in terms of energy saving (B4). For example, the present disclosure aims to provide a polymer that is excellent in transparency (B5). For example, the present disclosure aims to provide a polymer that is free of odor due to residual thiols (B6). For example, the present disclosure aims to provide a polymer that is excellent in strength (e.g., high crosslinking degree) (B7). For example, the present disclosure aims to provide a polymer that is excellent in flexibility (B8). For example, the present disclosure aims to provide a polymer that is excellent in heat resistance (B9). An object of the present disclosure is to provide a polymer that can achieve at least one of the objects B1 to B9.

[0017] For example, the present disclosure aims to provide a method for producing a polymer by using a biomass-derived raw material such as cardanol (C1). For example, the present disclosure aims to provide a method for producing a polymer without using formalin, a heavy metal catalyst, and / or VOCs (C2). For example, the present disclosure aims to provide a method for producing a polymer without using an organic halogen compound such as epichlorohydrin (C3). For example, the present disclosure aims to provide a method for producing a polymer that is excellent in terms of energy saving (C4). For example, the present disclosure aims to provide a method for producing a polymer by which a polymer with excellent transparency can be obtained (C5). For example, the present disclosure aims to provide a method for producing a polymer by which a polymer without an odor due to residual thiol can be obtained (C6). For example, the present disclosure aims to provide a method for producing a polymer by which a polymer with excellent strength (e.g., high crosslinking degree) can be obtained (C7). For example, the present disclosure aims to provide a method for producing a polymer by which a polymer with excellent flexibility can be obtained (C8). For example, the present disclosure aims to provide a method for producing a polymer by which a polymer with excellent heat resistance can be obtained (C9). An object of the present disclosure is to provide a method for producing a polymer that can achieve at least one of the objects C1 to C9. [Means for solving the problem]

[0018] An example of this embodiment is as follows.

[0019] (1) A photopolymerizable composition comprising at least one compound (A) represented by formula (1) and a compound (B) having two or more ethylenically unsaturated groups as polymerizable components: [ka] [In formula (1), R 1 -C 15 H 31-2n group (n=0, 1, 2 or 3), R 2 is hydrogen or a methyl group. (2) The photopolymerizable composition according to (1), wherein the content of at least one compound (A) represented by formula (1) is 10 to 90 mass % based on the total amount of the polymerizable components, and the content of the compound (B) having two or more ethylenically unsaturated groups is 10 to 90 mass % based on the total amount of the polymerizable components. (3) The photopolymerizable composition according to (1) or (2), in which the total content of the at least one compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups is 80 mass% or more based on the total amount of the polymerizable components. (4) The photopolymerizable composition according to any one of (1) to (3), wherein the at least one compound (A) represented by formula (1) is an ester compound of cardanol and (meth)acrylic acid. (5) The photopolymerizable composition according to any one of (1) to (4), wherein the compound (B) having two or more ethylenically unsaturated groups is an ester compound of a polyhydric alcohol and (meth)acrylic acid. (6) The photopolymerizable composition according to any one of (1) to (5), wherein the compound (B) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of ethylene glycol di(meth)acrylate and glycerol tri(meth)acrylate. (7) A polymer comprising at least one compound (A) represented by formula (1) and a compound (B) having two or more ethylenically unsaturated groups as polymerizable components: [ka] [In formula (1), R 1 -C 15 H 31-2n group (n=0, 1, 2 or 3), R 2 is hydrogen or a methyl group. (8) The polymer according to (7), wherein the content of the at least one compound (A) represented by formula (1) is 10 to 90 mass % based on the total amount of the polymerizable components, and the content of the compound (B) having two or more ethylenically unsaturated groups is 10 to 90 mass % based on the total amount of the polymerizable components. (9) The polymer according to (7) or (8), wherein the total content of the at least one compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups is 80 mass% or more based on the total amount of polymerizable components. (10) The polymer according to any one of (7) to (9), wherein the at least one compound (A) represented by formula (1) is an ester compound of cardanol and (meth)acrylic acid. (11) The polymer according to any one of (7) to (10), wherein the compound (B) having two or more ethylenically unsaturated groups is an ester compound of a polyhydric alcohol and (meth)acrylic acid. (12) The polymer according to any one of (7) to (11), wherein the compound (B) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of ethylene glycol di(meth)acrylate and glycerol tri(meth)acrylate. (13) A method for producing a polymer, comprising a step of curing the photopolymerizable composition according to any one of (1) to (6) by a photopolymerization reaction. (14) The method according to (13), further comprising the step of reacting cardanol with (meth)acrylic anhydride to prepare at least one compound (A) represented by formula (1). (15) The method according to (13) or (14), further comprising the step of reacting a polyhydric alcohol with (meth)acrylic anhydride to prepare a compound (B) having two or more ethylenically unsaturated groups. (16) The method according to (15), wherein the polyhydric alcohol is at least one selected from ethylene glycol and glycerol. Effect of the Invention

[0020] The present disclosure can achieve at least one of the above objects. For example, the present disclosure can provide a polymerizable composition that can achieve at least one of the objects A1 to A9. The present disclosure can provide a polymer that can achieve at least one of the objects B1 to B9. For example, the present disclosure can provide a method for producing a polymer that can achieve at least one of the objects C1 to C9. [Brief description of the drawings]

[0021] [Figure 1] 1 shows a UV-VIS spectrum of copolymer film E4 (polymer of cardanol methacrylate and glycerol trimethacrylate (mass ratio 50:50)) of Example 4, and a UV-VIS spectrum of a copolymer film obtained by the method described in Non-Patent Document 1. [Diagram 2] 1 shows a photograph of the copolymer film E3 of Example 3 (a polymer of cardanol methacrylate and glycerol trimethacrylate (mass ratio 80:20)) in a state where both ends were pinched with tweezers and bent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The present embodiment will be described below. Note that the present disclosure is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope of the present disclosure.

[0023] <Photopolymerizable composition> The present embodiment relates to a photopolymerizable composition containing a compound represented by formula (1) and a compound having two or more ethylenically unsaturated groups as polymerizable components.

[0024] [Polymerizable component] (Compound (A) represented by formula (1)) The photopolymerizable composition according to this embodiment contains at least one compound (A) represented by formula (1) as a polymerizable component.

[0025] [ka] [In formula (1), R 1 -C 15 H 31-2n group (n=0, 1, 2 or 3), R 2 is hydrogen or a methyl group.

[0026] In formula (1), R 1 is, for example, any one of the following structures (a) to (d) or a combination thereof.

[0027] -(CH 2 ) 14 CH 3 (a) -(CH 2 ) 7 CH=CH(CH 2 ) 5 CH 3 (b) -(CH 2 ) 7 CH=CHCH 2 CH=CH(CH 2 ) 2 CH 3 (c) -(CH 2 ) 7 CH=CHCH 2 CH=CHCH 2 CH=CH 2 (d)

[0028] In the photopolymerizable composition according to the present embodiment, the compound (A) may be used alone or in combination of two or more. 1 A mixture of compounds having different R 2 A mixture of compounds having different R 1 and R 2 A mixture of compounds with different groups may also be used.

[0029] Compound (A) may be a synthesized product or a commercially available product, such as Cardolite GX-7201 manufactured by Cardolite Corporation.

[0030] Compound (A) can be prepared by (meth)acrylating cardanol with (meth)acrylic anhydride or (meth)acrylic chloride. That is, compound (A) is preferably an ester compound of cardanol and (meth)acrylic acid. From the viewpoint of not using an organic halogen compound, compound (A) is preferably a compound obtained by (meth)acrylating cardanol with (meth)acrylic anhydride.

[0031] In the present disclosure, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylation" means introducing an acrylic group (acryloyl group) or introducing a methacrylic group (methacryloyl group). In addition, in the present disclosure, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, and "(meth)acrylate" means an acrylate or methacrylate.

[0032] Cardanol is a component contained in cashew nut shells and contains a compound represented by the following formula (2).

[0033] [ka]

[0034] In the compound represented by formula (2), R 1 is a combination of the above structures (a) to (d). In general, cardanol is 1 About 3% of the compounds have structure (a), and R 1 About 34% of the compounds have structure (b), and R 1 About 22% of the compounds have structure (c), and R 1 The mixture contains about 41% of a compound having structure (d), but is not limited thereto.

[0035] Cardanol is commercially available in various grades depending on purity, color, odor, etc.

[0036] As the cardanol as a precursor of the compound (A), a mixture of naturally occurring compounds using CNSL as a raw material may be used, or one or more compounds (mixture) purified from CNSL may be used, or a mixture in which the composition ratio of each component in CNSL is adjusted may be used. When synthesizing the compound (A), the synthesis may be performed using cardanol containing impurities as a raw material.

[0037] (Compound (B) Having Two or More Ethylenically Unsaturated Groups) The photopolymerizable composition according to the present embodiment includes a compound (B) having two or more ethylenically unsaturated groups as a polymerizable component. The ethylenically unsaturated group refers to a functional group containing an ethylenically unsaturated double bond. Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and an allyl group. It is preferable that both of the two or more ethylenically unsaturated groups are (meth)acryloyl groups. It is preferable that the compound (B) having two or more ethylenically unsaturated groups does not contain a thiol group.

[0038] By using the compound (B) having two or more ethylenically unsaturated groups as a polymerizable component, the polymer can be made to have a higher molecular weight, and the molecules can be crosslinked, so that the entanglement of the polymer can be made more complex. As a result, it is presumed that the strength, flexibility, and heat resistance of the polymer are improved.

[0039] The compound having an ethylenically unsaturated group is a component that is polymerized by a photopolymerization initiator or radicals generated by electron beam irradiation, which will be described later, and may be, for example, a monomer or oligomer. In addition, various polymers having an ethylenically unsaturated group and having a higher molecular weight than oligomers are commercially available. Such polymers can also be crosslinked by the above-mentioned monomers or oligomers, or by the polymers themselves, to increase the molecular weight. Therefore, such polymers may be used as a compound having an ethylenically unsaturated group together with the above-mentioned monomers or oligomers.

[0040] The compound (B) is preferably an ester compound of a polyhydric alcohol and (meth)acrylic acid. The ester compound of a polyhydric alcohol and (meth)acrylic acid can be prepared, for example, by (meth)acrylating a polyhydric alcohol with (meth)acrylic anhydride or (meth)acrylic acid chloride. From the viewpoint of not using an organic halogen compound, the compound (B) is preferably a compound obtained by (meth)acrylating a polyhydric alcohol with (meth)acrylic anhydride.

[0041] Examples of polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, butanediol (1,4-butanediol), pentanediol (1,5-pentanediol), hexanediol (1,6-hexanediol), heptanediol, octanediol (1,8-octanediol), nonanediol (1,9-nonanediol), Examples of the polyhydric alcohol include decanediol, dodecanediol, tetradecanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, pentaerythritol, polypentaerythritol, polyethylene glycol, diglycerin, polyglycerin, sorbitol, mannitol, and alkylene oxide adducts thereof (e.g., ethylene oxide adducts), etc. One type of polyhydric alcohol may be used alone, or two or more types may be used in combination.

[0042] Examples of ester compounds of polyhydric alcohols and (meth)acrylic acid include di(meth)acrylates having two (meth)acryloyl groups, tri(meth)acrylates having three (meth)acryloyl groups, tetra(meth)acrylates having four (meth)acryloyl groups, penta(meth)acrylates having five (meth)acryloyl groups, and hexa(meth)acrylates having six (meth)acryloyl groups.

[0043] Examples of compounds having two ethylenically unsaturated groups (di(meth)acrylates) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Examples of the di(meth)acrylate include hexanediol di(meth)acrylate (e.g., 1,6-hexanediol di(meth)acrylate), heptanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, tetradecanediol di(meth)acrylate, 1,4-cyclohexane diacrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. The di(meth)acrylates may be used alone or in combination of two or more.

[0044] Examples of compounds having three ethylenically unsaturated groups (tri(meth)acrylates) include glycerol tri(meth)acrylate (glycerin tri(meth)acrylate), pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, and trimethyloloctane tri(meth)acrylate. One type of tri(meth)acrylate may be used alone, or two or more types may be used in combination.

[0045] Examples of compounds having four ethylenically unsaturated groups (tetra(meth)acrylates) include pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, and 1,2,3-cyclohexane tetramethacrylate. Tetra(meth)acrylates may be used alone or in combination of two or more.

[0046] Examples of compounds having five ethylenically unsaturated groups (penta(meth)acrylates) include dipentaerythritol penta(meth)acrylate, etc. The penta(meth)acrylates may be used alone or in combination of two or more.

[0047] Examples of compounds having six ethylenically unsaturated groups (hexa(meth)acrylates) include pentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, etc. Hexa(meth)acrylates may be used alone or in combination of two or more.

[0048] Furthermore, the ester compound of a polyhydric alcohol and (meth)acrylic acid may be an ester of an ethoxylated and / or propoxylated polyhydric alcohol and (meth)acrylic acid. Examples of such compounds include ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, and the like. These may be used alone or in combination of two or more.

[0049] In one embodiment, the polyhydric alcohol may be derived from biomass, which allows the target product to be obtained in an environmentally friendly manner. Therefore, it is preferable to use a polyhydric alcohol derived from biomass. Examples of the polyhydric alcohol derived from biomass include ethanediols, butanediols, vegetable oils, and polyphenols (lignin decomposition products).

[0050] (Other polymerizable components) The photopolymerizable composition according to this embodiment may further contain, as a polymerizable component, other polymerizable components in addition to the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups.

[0051] The other polymerizable components are not particularly limited, but may be, for example, a compound having one ethylenically unsaturated group. As a compound having one ethylenically unsaturated group, for example, a (meth)acrylate having one (meth)acryloyl group (hereinafter, referred to as "mono(meth)acrylates" can be mentioned. In addition to (meth)acrylic acid, the mono(meth)acrylates may include the following compounds. Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; Polyol mono(meth)acrylates such as trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, ditrimethylolpropane mono(meth)acrylate, and dipentaerythritol mono(meth)acrylate; Mono(meth)acrylates having an alicyclic group, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; Mono(meth)acrylates having a cyclic ether group, such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, and 3-ethyl-3-oxetanylmethyl (meth)acrylate; Aromatic mono(meth)acrylates such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxy (meth)acrylate, and p-cumylphenol ethylene (meth)acrylate; Mono(meth)acrylates having a maleimide group, such as (meth)acrylolyloxyethylhexahydrophthalimide; (Meth)acryloylmorpholine; and Mono(meth)acrylates having an alkoxyalkyl group, such as alkyl carbitol (meth)acrylates, such as ethyl carbitol (meth)acrylate and 2-ethylhexyl carbitol (meth)acrylate.

[0052] The other polymerizable components preferably do not contain a monomer having a thiol group. By not containing a monomer having a thiol group, a polymer without odor due to residual thiols can be provided. In addition, the other polymerizable components preferably do not contain an olefin monomer such as ethylene. By not containing an olefin monomer, deterioration over time due to residual olefins can be prevented.

[0053] (Content / Content ratio) In the photopolymerizable composition according to this embodiment, the total content of polymerizable components is not particularly limited, but is, for example, 70 mass% or more, preferably 75 mass% or more, preferably 80 mass% or more, preferably 85 mass% or more, preferably 90 mass% or more, preferably 95 mass% or more, and preferably 98 mass% or more, relative to the total amount of the photopolymerizable composition.

[0054] The content of the compound (A) represented by formula (1) is not particularly limited, but is, for example, 5 to 95% by mass relative to the total amount of the polymerizable components. The content of the compound (A) represented by formula (1) is preferably 10% by mass or more, preferably 15% by mass or more, preferably 20% by mass or more, preferably 25% by mass or more, preferably 30% by mass or more, preferably 35% by mass or more, and preferably 40% by mass or more relative to the total amount of the polymerizable components. The content of the compound (A) represented by formula (1) is preferably 90% by mass or less, preferably 85% by mass or less, preferably 80% by mass or less, preferably 75% by mass or less, preferably 70% by mass or less, preferably 65% ​​by mass or less, and preferably 60% by mass or less relative to the total amount of the polymerizable components.

[0055] The content of the compound (B) having two or more ethylenically unsaturated groups is not particularly limited, but is, for example, 5 to 95% by mass relative to the total amount of the polymerizable components. The content of the compound (B) having two or more ethylenically unsaturated groups is preferably 10% by mass or more, preferably 15% by mass or more, preferably 20% by mass or more, preferably 25% by mass or more, preferably 30% by mass or more, preferably 35% by mass or more, and preferably 40% by mass or more relative to the total amount of the polymerizable components. The content of the compound (B) having two or more ethylenically unsaturated groups is preferably 90% by mass or less, preferably 85% by mass or less, preferably 80% by mass or less, preferably 75% by mass or less, preferably 70% by mass or less, preferably 65% ​​by mass or less, and preferably 60% by mass or less relative to the total amount of the polymerizable components.

[0056] In the photopolymerizable composition according to the present embodiment, the content of the compound (A) represented by formula (1) is preferably 10 to 90% by mass relative to the total amount of the polymerizable components, and the content of the compound (B) having two or more ethylenically unsaturated groups is preferably 10 to 90% by mass relative to the total amount of the polymerizable components. In the photopolymerizable composition according to the present embodiment, the content of the compound (A) represented by formula (1) is preferably 30 to 80% by mass relative to the total amount of the polymerizable components, and the content of the compound (B) having two or more ethylenically unsaturated groups is preferably 20 to 70% by mass relative to the total amount of the polymerizable components. By setting the content of the compound (A) represented by formula (1) and the content of the compound (B) having two or more ethylenically unsaturated groups within these ranges, the strength, flexibility, and heat resistance of the polymer can be effectively achieved.

[0057] In the photopolymerizable composition according to the present embodiment, the total amount of the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups is preferably 80% by mass or more, preferably 85% by mass or more, preferably 90% by mass or more, preferably 95% by mass or more, preferably 98% by mass or more, preferably 99% by mass or more, and preferably 100% by mass, based on the total amount of the polymerizable components. By setting the total amount of the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups within these ranges, the strength, flexibility, and heat resistance of the polymer can be effectively improved.

[0058] The content of the other polymerizable components is not particularly limited, but is, for example, 0.1 to 20% by mass relative to the total amount of the polymerizable components. The content of the other polymerizable components is preferably 20% by mass or less, preferably 15% by mass or less, preferably 10% by mass or less, preferably less than 10% by mass, preferably 5% by mass or less, and preferably 1% by mass or less, relative to the total amount of the polymerizable components.

[0059] In the photopolymerizable composition according to the present embodiment, the molar ratio of the acryloyl group of the compound (A) to the ethylenically unsaturated group of the compound (B) is preferably 0.1:1.0 to 1.0:0.1, and more preferably 0.25:1 to 1:0.25. By setting the molar ratio of the acryloyl group of the compound (A) to the ethylenically unsaturated group of the compound (B) within these ranges, the strength and heat resistance of the polymer can be effectively improved.

[0060] (Photoinitiator (C)) The photopolymerizable composition according to this embodiment contains a photoinitiator (C).

[0061] The photoinitiator (C) is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable component by light, and can be appropriately selected depending on the purpose. The photoinitiator (C) is preferably one that is photosensitive to ultraviolet light to visible light.

[0062] The photopolymerizable composition according to this embodiment is cured by a radical polymerization reaction between the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups, which is promoted by radicals generated from the photoinitiator (C).

[0063] The photoinitiator (C) is not particularly limited, and any photoinitiator known to those skilled in the art can be used without any restrictions.

[0064] Examples of the photoinitiator (C) include benzoin compounds, benzil ketal compounds, acetophenone compounds, thioxanthone compounds, acylphosphine oxide compounds, benzophenone compounds, triazine compounds, oxime compounds, etc. The photoinitiator (C) may be used alone or in combination of two or more.

[0065] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal. Examples of benzyl ketal compounds include benzyl dimethyl ketal. Examples of acetophenone compounds include 2-hydroxy-2-methylpropiophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, pt-butyl trichloroacetophenone, pt-butyl dichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, azine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like. Examples of oxime compounds include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. These may be used alone or in combination of two or more.

[0066] Specifically, examples of the photoinitiator (C) include 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, BASF Japan Co., Ltd.), 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer (trade name: Esacure ONE, Lambarty Co., Ltd.), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, BASF Japan Co., Ltd.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (trade name: Irgacure 127, BASF Japan Co., Ltd.), 2,2-dimethoxy-2-phenylacetophenone (trade name: Irgacure 651 ... hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Darocur 1173, BASF Japan Ltd.), 2-methyl-1-[(4-methylthio)phenyl]-2-morpholinopropan-1-one (trade name: Irgacure 907, BASF Japan Ltd.), methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like.

[0067] Among these, as the photoinitiator (C), from the viewpoints of improving the strength of the polymer and suppressing yellowing of the polymer, acetophenone-based compounds are preferred, and 2-hydroxy-2-methylpropiophenone is more preferred.

[0068] In the photopolymerizable composition according to the present embodiment, the content of the photoinitiator (C) is preferably 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 7% by mass, based on the total amount of the polymerizable components. When the content of the photoinitiator (C) is 0.1% by mass or more, the photocuring of the composition can be efficiently promoted upon light irradiation, and curing defects are unlikely to occur. When the content of the photoinitiator (C) is 20% by mass or less, excessive light absorption by the photoinitiator (C) is suppressed, and curing defects are unlikely to occur. In addition, precipitation of the photoinitiator (C) over time is suppressed, and the storage properties of the polymer can be effectively improved. The upper and / or lower limits of these numerical ranges can be arbitrarily combined to define a preferred range.

[0069] (Other ingredients (D)) The photopolymerizable composition according to this embodiment may further contain, as necessary, another component (D) other than the polymerizable component containing the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups, and the photoinitiator (C), within a range that does not impair the effects of this embodiment.

[0070] The other component (D) is not particularly limited, and examples thereof include solvents, polymerization inhibitors, plasticizers, sensitizers, flame retardants, compatibilizers, release agents, light resistance agents, weather resistance agents, colorants, pigments, modifiers, drip prevention agents, antistatic agents, hydrolysis inhibitors, fillers, reinforcing agents, acid acceptors, reactive trapping agents, antioxidants, leveling agents, defoamers, and pigments. Examples of reinforcing agents include glass fibers, carbon fibers, talc, clay, mica, glass flakes, milled glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, and boron nitride. Examples of acid acceptors include oxides such as magnesium oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and hydrotalcite; calcium carbonate; and talc. Examples of reactive trapping agents include epoxy compounds, acid anhydride compounds, and carbodiimides. The other component (D) may be used alone or in combination of two or more.

[0071] The content of the other component (D) (also referred to as "component (D)") is preferably 25% by mass or less (or less than 25% by mass) relative to the total amount of the photopolymerizable composition, preferably 20% by mass or less (or less than 20% by mass), preferably 15% by mass or less (or less than 15% by mass), preferably 10% by mass or less (or less than 10% by mass), preferably 5% by mass or less (or less than 5% by mass), preferably 1% by mass or less (or less than 1% by mass), and preferably 0% by mass. Here, "0% by mass" means that no other components are included. However, only when the other component (D) is a reinforcing agent, a modifier, or a filler, the content of the other component (D) relative to the total amount of the photopolymerizable composition may be 15% by mass or more, 25% by mass or more, or 50% by mass or more, and the upper limit is not particularly limited, but is, for example, 150% by mass or less.

[0072] [Polymer and method for producing the polymer] The method for producing a polymer according to this embodiment includes a step of curing a photopolymerizable composition containing a compound represented by formula (1) and a compound having two or more ethylenically unsaturated groups as polymerizable components by a photopolymerization reaction.

[0073] The method for producing a polymer according to the present embodiment may include, for example, the following steps: (a) providing at least one compound (A) represented by formula (1); (b) providing a compound (B) having two or more ethylenically unsaturated groups; (c) providing a photopolymerizable composition comprising at least one compound (A) represented by formula (1), a compound (B) having two or more ethylenically unsaturated groups, and a photoinitiator (C); and (d) irradiating the photopolymerizable composition obtained in step (c) with light (e.g., ultraviolet or visible light).

[0074] Regarding step (a), in one embodiment, the compound (A) represented by formula (1) is synthesized by reacting cardanol derived from cashew nut shell liquid with (meth)acrylic anhydride under known conditions. Specifically, the compound (A) represented by formula (1) can be synthesized by reacting cardanol with (meth)acrylic anhydride in the presence of a catalyst. According to this method, cardanol derived from biomass cashew nut shell liquid can be used as the raw material, and since no organic halogen compounds are used, the method for producing the polymer according to this embodiment is more environmentally friendly.

[0075] In the esterification with (meth)acrylic anhydride, a solvent can be used as necessary, but since cardanol can function as a solvent, it is also possible to not use a solvent. By not using a solvent, a more environmentally friendly process can be provided. Examples of the solvent include hydrocarbon solvents. Examples of the hydrocarbon solvent include hexane, heptane, toluene, and dichloromethane. The solvent may be used alone or in combination of two or more.

[0076] The catalyst may be, for example, a base catalyst or a Lewis acid catalyst. Examples of the base catalyst include dimethylaminopyridine (specifically, 4-dimethylaminopyridine), triethylamine, diisopropylethylamine, or pyridine. Examples of the Lewis acid catalyst include bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate, or indium trifluoromethanesulfonate. The catalyst may be used alone or in combination of two or more.

[0077] The ratio (molar ratio) of the amount of cardanol used to the amount of (meth)acrylic anhydride used is, for example, 1:0.1 to 1:10, and is preferably 1:0.1 to 1:1 in terms of reducing consumption of petroleum resources and reducing greenhouse gas emissions, and is preferably 1:1 to 1:5 in terms of the degree of crosslinking of the resin.

[0078] The reaction temperature is not particularly limited, but is, for example, −20 to 60° C., preferably 0 to 40° C., and preferably room temperature (about 25° C.). The reaction time varies depending on conditions such as the reaction temperature, but is, for example, 0.2 to 48 hours.

[0079] After the reaction is completed, the excess (meth)acrylic anhydride and the like can be removed. The removal may be performed using an appropriate solvent or solution, or by filtration. The target product may be appropriately subjected to extraction treatment with a solvent or purification treatment by chromatography or the like.

[0080] Regarding step (b), the compound (B) having two or more ethylenically unsaturated groups is preferably an ester of a polyhydric alcohol and (meth)acrylic acid as described above, and the ester of a polyhydric alcohol and (meth)acrylic acid can be prepared, for example, by (meth)acrylation of a polyhydric alcohol with (meth)acrylic anhydride or (meth)acrylic chloride. In one embodiment, the compound (B) having two or more ethylenically unsaturated groups is synthesized by reacting a biomass-derived polyhydric alcohol with (meth)acrylic anhydride under known conditions. Specifically, the compound (B) having two or more ethylenically unsaturated groups can be synthesized by reacting a biomass-derived polyhydric alcohol with (meth)acrylic anhydride in the presence of a catalyst. According to this method, a biomass-derived polyhydric alcohol can be used as the raw material polyhydric alcohol, and since no organic halogen compound is used, the method for producing a polymer according to this embodiment is more environmentally friendly. The solvent, the amount used, the reaction conditions, the method, etc. are the same as those of the above-mentioned esterification of the compound (A) with (meth)acrylic anhydride. As mentioned above, cardanol can function as a solvent, allowing the desired product to be obtained without the use of a solvent, which can provide a more environmentally friendly process.

[0081] Step (c) can be carried out by mixing each component. The mixing can be carried out, for example, by a known method. The photopolymerizable composition may contain a solvent, or may not contain a solvent. Since the compound (A) represented by formula (1) and / or the compound having two or more ethylenically unsaturated groups can be substituted for a solvent, the photopolymerizable composition can be prepared without using a solvent (i.e., without a solvent). From the viewpoint of obtaining a homogeneous mixture, it is preferable that the mixture is ultrasonically treated. From the viewpoint of obtaining a homogeneous mixture, it is preferable that the ultrasonic treatment time is 1 minute or more.

[0082] In step (d), radicals are generated from the photoinitiator (C) by irradiation with light, and the generated radicals cause a radical polymerization reaction between the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups. The polymerization reaction produces a polymer containing a structural unit derived from the compound (A) represented by formula (1) and a structural unit derived from the compound (B) having two or more ethylenically unsaturated groups.

[0083] The light beam may be, for example, ultraviolet light or visible light having a wavelength of 300 nm to 450 nm. The irradiation time may be, for example, from 1 second to 10 minutes.

[0084] Regarding the obtained polymer, the contents and content ratios of the constituent components are as explained above in the section on [Polymerizable components] (particularly (content / content ratio)). The content of the compound (A) represented by formula (1) and / or the content of the compound (B) having two or more ethylenically unsaturated groups contained in the polymer can be calculated from the composition of the photopolymerizable composition and the charged amount (mass) of the polymerizable components when the polymer is produced.

[0085] The polymer according to the present embodiment can be obtained by utilizing a biomass-derived raw material such as cardanol, and can be obtained without using formalin, heavy metal catalysts and / or VOCs, and can be obtained without using organic halogen compounds such as epichlorohydrin. The polymer according to the present embodiment can have excellent transparency, excellent strength (specifically, a high degree of crosslinking), excellent flexibility, and excellent heat resistance. In the present embodiment, a complex crosslinked structure including the side chain of the compound (A) represented by formula (1) having a flexible hydrocarbon chain is formed by combining the compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups, which is a crosslinkable monomer, and therefore it is believed that excellent strength, flexibility, and heat resistance can be obtained.

[0086] The use of the polymer according to this embodiment is not particularly limited, and examples thereof include paints, adhesives, pressure sensitive adhesives, electro-optical materials (e.g., low dielectric constant materials), packaging materials (e.g., gas barrier materials), agricultural biodegradable mulch films, potting materials, heat resistant materials, chemical resistant materials, antibacterial materials, etc. Furthermore, the polymer according to this embodiment can have the property of controlling light scattering at a specific angle as described above, and therefore can be applied as a novel optical material. EXAMPLES

[0087] The present embodiment will be described below using examples. Note that the present disclosure is not limited to the following examples.

[0088] [Synthesis of Cardanol Methacrylate (CM)]

[0089] [ka]

[0090] Cardanol (5.00 g, 16.5 mmol) and 4-dimethylaminopyridine (0.150 g, 1.24 mmol) were added to a two-neck flask (200 mL) equipped with a magnetic stirrer and a dropping funnel. Methacrylic anhydride (3.67 mL, 24.8 mmol) was added dropwise over 5 minutes and the reaction was allowed to proceed at room temperature for 24 hours. After the reaction, 100 mL of saturated aqueous sodium bicarbonate (NaHCO 3 aq.) was added and stirred for another hour. After that, the mixture was extracted with diethyl ether, washed with saturated aqueous sodium chloride solution (NaCl aq.), and then washed with magnesium sulfate (MgSO 4 After dehydration, the solvent was removed using an evaporator, and the product was purified by column chromatography using a mixed solvent (hexane:ethyl acetate = 4:1 (volume ratio)) as the developing solvent to obtain the target product (cardanol methacrylate) as a slightly yellow transparent liquid (4.58 g, yield: 78.4%).

[0091] [Synthesis of glycerol trimethacrylate (GTM)]

[0092] [ka]

[0093] Glycerol (1.84 g, 20.0 mmol) and 4-dimethylaminopyridine (0.786 g, 6.48 mmol) were added to a two-neck flask (200 mL) equipped with a magnetic stirrer and a dropping funnel. Methacrylic anhydride (13.3 mL, 90.0 mmol) was added dropwise over 5 minutes and reacted at room temperature for 24 hours. After the reaction, 100 mL of saturated aqueous sodium bicarbonate (NaHCO 3 aq.) was added and stirred for another hour. After that, the mixture was extracted with diethyl ether, washed with saturated aqueous sodium chloride solution (NaCl aq.), and then washed with magnesium sulfate (MgSO 4 After dehydration, the solvent was removed using an evaporator, and the mixture was purified by column chromatography using a mixed solvent (hexane:ethyl acetate = 4:1 (volume ratio)) as the developing solvent to obtain the target product (glycerol trimethacrylate) as a slightly yellow transparent liquid (1.51 g, yield: 26.0%).

[0094] [Example 1] Cardanol methacrylate and glycerol trimethacrylate were weighed in a sample bottle so that the mass ratio was 95:5, and a mixed solution was prepared. 2-hydroxy-2-methylpropiophenone (HMPP), a photoradical initiator, was added to the mixed solution so that the amount was 3 mass%, and the mixture was thoroughly mixed and then degassed by vacuuming. This resulted in the preparation of a photopolymerizable composition E1.

[0095] The obtained photopolymerizable composition was dropped onto a glass plate, and another glass plate was placed on top of it to uniformly coat the glass plate. A spacer (polyimide tape: 55 μm thick) was placed between the two glass plates to avoid oxygen inhibition. Next, the glass plate coated with the photopolymerizable composition was placed on an exposure table at a distance of 10 cm from the ultraviolet irradiation window. Then, ultraviolet light was irradiated for 2 minutes. The cured film was peeled off from the glass plate to obtain a copolymer film E1. The appearance of the copolymer film E1 was transparent. The copolymer film E1 also had flexibility.

[0096] [Example 2] A photopolymerizable composition E2 and a copolymer film E2 were produced in the same manner as in Example 1, except that cardanol methacrylate and glycerol trimethacrylate were weighed into a sample bottle so that the mass ratio was 90:10.

[0097] [Example 3] A photopolymerizable composition E3 and a copolymer film E3 were produced in the same manner as in Example 1, except that cardanol methacrylate and glycerol trimethacrylate were weighed into a sample bottle so that the mass ratio was 80:20.

[0098] [Example 4] Photopolymerizable composition E4 and copolymer film E4 were produced in the same manner as in Example 1, except that cardanol methacrylate and glycerol trimethacrylate were weighed into a sample bottle so that the mass ratio was 50:50.

[0099] [Example 5] Photopolymerizable composition E5 and copolymer film E5 were produced in the same manner as in Example 1, except that cardanol methacrylate and glycerol trimethacrylate were weighed into a sample bottle so that the mass ratio was 20:80.

[0100] [Comparative Example 1] A photopolymerizable composition C1 and a polymer film C1 were produced in the same manner as in Example 1, except that cardanol methacrylate and glycerol trimethacrylate were weighed into a sample bottle so that the mass ratio was 100:0. That is, in Comparative Example 1, only cardanol methacrylate was polymerized alone, without using glycerol trimethacrylate.

[0101] [Comparative Example 2] A photopolymerizable composition C2 and a polymer film C2 were produced in the same manner as in Example 1, except that cardanol methacrylate and glycerol trimethacrylate were weighed into a sample bottle so that the mass ratio was 0:100. That is, in Comparative Example 2, only glycerol trimethacrylate was polymerized alone without using cardanol methacrylate.

[0102] [evaluation] (degree of crosslinking) The degree of crosslinking (gel fraction) of the prepared film was measured by the following process. First, the film was immersed in a solvent (acetone) for 24 hours. Next, the film was taken out and the solvent was removed by vacuum drying. Then, the gel fraction was calculated based on the weight of the film before and after immersion according to the following formula. The results are shown in Table 1.

[0103]

number

[0104] As shown in Table 1, when the component ratio of glycerol trimethacrylate was in the range of 0 to 20% (Comparative Example 1, Examples 1 to 3), the gel fraction increased as the component ratio of glycerol trimethacrylate increased. This indicates that while the degree of crosslinking was low when cardanol methacrylate was used alone, the degree of crosslinking was improved by adding glycerol trimethacrylate, which is a crosslinking monomer. When the component ratio of glycerol trimethacrylate was in the range of 20 to 100%, the gel fraction of the film was 95% or more, indicating a high degree of crosslinking.

[0105] [Table 1]

[0106] (transparency) To evaluate the transparency of the obtained film, the transmittance in the visible light region was measured. FIG. 1 shows the UV-VIS spectrum (solid line) of copolymer film E4 (polymer of cardanol methacrylate and glycerol trimethacrylate (mass ratio 50:50)) and the UV-VIS spectrum (dotted line) of a copolymer film obtained by the method described in Non-Patent Document 1 as a comparison. Specifically, the comparative film was produced by the following method. First, cardanol was epoxidized by reacting epichlorohydrin with a raw oil containing cardanol as the main component. Next, an epoxy cardanol prepolymer was synthesized by thermally oxidizing and polymerizing the double bond portion of the side chain. Then, an amine compound was added to prepare a photopolymerizable composition. This photopolymerizable composition was cured into a film in the same manner as described above.

[0107] 1, the copolymer film E4 exhibited high transmittance in the visible light region, had almost no light absorption in the visible light region, and was optically transparent. All of the other copolymer films E1 to E3 and E5 were optically transparent.

[0108] In addition, in the copolymer film of the example, a behavior of converging the scattering of light in a specific direction was observed. This behavior is presumed to be due to the non-uniform crosslinking structure of the two components (cardanyl methacrylate and glycerol trimethacrylate). This behavior was clearly confirmed as the component ratio of glycerol trimethacrylate increased. Therefore, it can be seen that the polymer according to this embodiment has applicability as a novel optical material capable of converging the scattering of light in a specific direction.

[0109] (flexibility) When polymer film C1 (glycerol trimethacrylate homopolymer) and polymer film C2 (cardanol methacrylate homopolymer) were tried to be peeled off from the glass plate with tweezers, the part pinched by the tweezers crumbled and it was difficult to peel them off. In other words, polymer films C1 and C2 had poor self-supporting properties and it was difficult to form a self-supporting film. On the other hand, copolymer films E1 to E5 could be easily peeled off from the glass plate with tweezers and were highly self-supporting. Furthermore, copolymer films E1 to E5 had excellent flexibility. Specifically, it was found that the film became softer and showed excellent flexibility as the cardanol methacrylate component increased.

[0110] Figure 2 shows a photograph of copolymer film E3 (mass ratio of cardanol methacrylate and glycerol trimethacrylate: 80:20) pinched by both ends with tweezers and bent. As shown in Figure 2, even when both ends of copolymer film E3 were pinched and completely bent, the film did not break.

[0111] From the above, it was confirmed that the polymer according to this embodiment has excellent flexibility. In addition, since the flexibility of the polymer according to this embodiment changes depending on the composition ratio of the compound (A) and the compound (B), it was found that the flexibility of the polymer (soft to hard) can be controlled by adjusting the composition ratio. Therefore, it can be applied to a wide range of material applications including packaging materials and coating materials.

[0112] (Heat resistance) To evaluate the heat resistance of the films, thermogravimetric analysis (TGA) was performed on the films E3-5 and C1-2 of Examples 3-5 and Comparative Examples 1-2. The thermogravimetric analysis was performed in a nitrogen atmosphere, and the heating rate was set to 10°C / min. The thermal decomposition temperature (T d The thermal decomposition temperature (T d ) results are shown below.

[0113] [Table 2]

[0114] The polymer film C1 (cardanol methacrylate homopolymer) showed the lowest thermal decomposition temperature among the cured products produced. In the copolymer films E3 to E5, as the component ratio of glycerol trimethacrylate increased, the thermal decomposition temperature increased, and excellent heat resistance was shown. Interestingly, the copolymer films E3 to E5 had a higher thermal decomposition temperature than the polymer film C2 (glycerol trimethacrylate homopolymer). It is considered that by combining the cardanol methacrylate component having a flexible hydrocarbon chain with glycerol trimethacrylate, which is a crosslinkable monomer, a complex crosslinked structure including the side chain of cardanol methacrylate is formed, improving heat resistance. From the above, it was confirmed that the polymer according to this embodiment has excellent heat resistance.

[0115] In the following Examples and Comparative Examples, in order to investigate the change in the degree of crosslinking (gel fraction) due to differences in the number of functional groups of the monomer copolymerized with cardanol methacrylate, copolymer films of cardanol methacrylate and a monomer having one or two methacryl groups were prepared and their gel fractions were measured.

[0116] [Example 6] A photopolymerizable composition E6 and a copolymer film E6 were produced in the same manner as in Example 3, except that ethylene glycol dimethacrylate (EGDM), a monomer having two methacrylic groups, was used instead of glycerol trimethacrylate.

[0117] [ka]

[0118] [Comparative Example 3] A photopolymerizable composition C3 and a copolymer film C3 were produced in the same manner as in Example 3, except that methyl methacrylate (MMA), a monomer having one methacrylic group, was used instead of glycerol trimethacrylate.

[0119] [ka]

[0120] [evaluation] The degree of crosslinking (gel fraction) of the prepared film was measured by the method described above. The measurement results of the gel fraction are shown in Table 3. Table 3 also shows the measurement results for film E3 of Example 3 and film C1 of Comparative Example 1.

[0121] [Table 3]

[0122] As shown in Table 3, a high gel fraction (about 95%) was obtained when ethylene glycol dimethacrylate, which has two methacrylic groups, was used, as was glycerol trimethacrylate, which has three methacrylic groups. On the other hand, when methyl methacrylate, which has only one methacrylic group, was used, the gel fraction was lower than when cardanol methacrylate was used alone. This is thought to be because the crosslinking reaction proceeds particularly effectively when the monomer has two or more functional groups, improving the crosslinking density.

[0123] From the above results, it was confirmed that in copolymerization with cardanol methacrylate, a compound having two or more ethylenically unsaturated groups as a functional group is effective as a crosslinking monomer. As described above, a compound having two or more ethylenically unsaturated groups can be synthesized at room temperature from a diol compound or polyol compound derived from biomass without using an organic halogen compound. Therefore, it is believed that the present disclosure will lead to the effective use of biomass-derived compounds.

[0124] The upper limit and / or lower limit of the numerical ranges described in this specification can be arbitrarily combined to define a preferred range. For example, the upper limit and lower limit of the numerical range can be arbitrarily combined to define a preferred range, the upper limit of the numerical range can be arbitrarily combined to define a preferred range, and the lower limit of the numerical range can be arbitrarily combined to define a preferred range.

[0125] The claims following this written disclosure are expressly incorporated herein into this written disclosure, with each claim standing on its own as a separate embodiment. The present disclosure includes all instances in which an independent claim is replaced by its dependent claim. Furthermore, any additional embodiments derived from the independent claim and the subsequent dependent claims are also expressly incorporated into this written specification.

[0126] Those skilled in the art can use the above description to make the most of the present disclosure. The claims and embodiments disclosed herein are merely descriptive and exemplary, and should not be construed as limiting the scope of the present disclosure in any way. With the aid of this disclosure, changes can be made to the details of the above embodiments without departing from the basic principles of the present disclosure. In other words, various modifications and improvements of the embodiments specifically disclosed in the above specification are within the scope of the present disclosure.

[0127] Although the present embodiment has been described in detail above, the specific configuration is not limited to this embodiment, and even if there are design changes within the scope that does not deviate from the gist of this disclosure, they are included in this disclosure.

Claims

1. A photopolymerizable composition comprising at least one compound (A) represented by formula (1) and a compound (B) having two or more ethylenically unsaturated groups as polymerizable components: 【Chemistry 1】 [In formula (1), R １ is -C １５ H ３１－２ｎ group (n=0, 1, 2 or 3), R ２ is hydrogen or a methyl group. the total content of the at least one compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups is 80 mass% or more based on the total amount of the polymerizable components; A photopolymerizable composition, wherein the compound (B) having two or more ethylenically unsaturated groups is at least one member selected from the group consisting of ethylene glycol di(meth)acrylate and glycerol tri(meth)acrylate.

2. The photopolymerizable composition according to claim 1, wherein the content of the at least one compound (A) represented by formula (1) is 10 to 90 mass % based on the total amount of the polymerizable components, and the content of the compound (B) having two or more ethylenically unsaturated groups is 10 to 90 mass % based on the total amount of the polymerizable components.

3. 3. The photopolymerizable composition according to claim 1, wherein the at least one compound (A) represented by formula (1) is an ester compound of cardanol and (meth)acrylic acid.

4. A polymer comprising at least one compound (A) represented by formula (1) and a compound (B) having two or more ethylenically unsaturated groups as polymerizable components: 【Chemistry 2】 [In formula (1), R １ is -C １５ H ３１－２ｎ group (n=0, 1, 2 or 3), R ２ is hydrogen or a methyl group. the total content of the at least one compound (A) represented by formula (1) and the compound (B) having two or more ethylenically unsaturated groups is 80 mass% or more based on the total amount of the polymerizable components; A polymer, wherein the compound (B) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of ethylene glycol di(meth)acrylate and glycerol tri(meth)acrylate.

5. The polymer according to claim 4, wherein the content of the at least one compound (A) represented by formula (1) is 10 to 90 mass% based on the total amount of the polymerizable components, and the content of the compound (B) having two or more ethylenically unsaturated groups is 10 to 90 mass% based on the total amount of the polymerizable components.

6. The polymer according to claim 4 or 5, wherein the at least one compound (A) represented by formula (1) is an ester compound of cardanol and (meth)acrylic acid.

7. A method for producing a polymer, comprising a step of curing the photopolymerizable composition according to any one of claims 1 to 3 by a photopolymerization reaction.

8. The method according to claim 7, further comprising the step of reacting cardanol with (meth)acrylic anhydride to prepare at least one compound (A) represented by formula (1).

9. The method according to claim 7 or 8, further comprising a step of reacting a polyhydric alcohol with (meth)acrylic anhydride to prepare a compound (B) having two or more ethylenically unsaturated groups, wherein the polyhydric alcohol is at least one selected from ethylene glycol and glycerol.

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