Di(meth)acrylates, di(meth)acrylate mixtures, curable compositions, and cured products

Abstract

The present application relates to di(meth)acrylates, di(meth)acrylate mixtures, curable compositions, and cured products. Various properties of the resulting cured products and the like are further improved. A compound represented by formula (I). In formula (I), R 1 is an alkylene chain having a total carbon atom number of 12 to 30 with at least one substituent selected from the group consisting of an alkyl group having a carbon atom number of 1 to 4 and an alkenyl group having a carbon atom number of 2 to 4, and satisfying condition (A) or (B). (A) In the alkylene chain, (A1) at least one of the substituents is an alkyl group having a carbon atom number of 2 to 4 or an alkenyl group having a carbon atom number of 2 to 4, or (A2) the number of alkyl groups having a carbon atom number of 1 to 4 in the substituents is only one. (B) In the alkenylene chain, (B1) at least one of the substituents is bonded to a carbon atom forming a double bond, or (B2) at least one of the substituents is an alkenyl group having a carbon atom number of 2 to 4. R 2 is a hydrogen atom or a methyl group.

Description

Technical Field

[0001] This invention relates to di(meth)acrylates, mixtures of di(meth)acrylates, curable compositions, and cured products. Background Technology

[0002] Di(meth)acrylate and curable compositions containing di(meth)acrylate are used in various technical fields as raw materials for photosensitive materials such as resists, coating materials such as inks and paints, adhesives, building materials, polymers, color developers, surfactants, plasticizers, insecticides, bactericides, pharmaceuticals, and rubber-based pharmaceuticals.

[0003] For example, Patent Document 1 and Patent Document 2 disclose di(meth)acrylates that can produce cured products with excellent adhesion to various resins and low water absorption.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2003-002919 Patent Document 2: International Publication No. 2023 / 282117 Summary of the Invention

[0005] The problem that the invention aims to solve While di(meth)acrylates that can improve the physical properties of the obtained cured products have been proposed as described above, there is a need for di(meth)acrylates that can further improve the various physical properties of the obtained cured products.

[0006] Therefore, one of the main objectives of this invention is to provide di(meth)acrylates that can further improve the various physical properties of the resulting cured products.

[0007] Methods for solving problems The present invention provides an invention in the following manner.

[0008] <1> Di(meth)acrylate, which is represented by the following formula (I).

[0009] [Chemical Formula 1] (In formula (I), R) 1 It is an alkylene chain or an alkenylene chain having a total carbon number of 12 to 30, having at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms, and satisfying the following condition (A) or (B).

[0010] (A) In the aforementioned alkylene chain, (A1) At least one of the aforementioned substituents is an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, or, (A2) The number of alkyl groups with 1 to 4 carbon atoms in the aforementioned substituents is only 1.

[0011] (B) In the aforementioned alkenyl chain, (B1) At least one of the aforementioned substituents is bonded to the carbon atom forming the aforementioned double bond, or, (B2) At least one of the aforementioned substituents is an alkenyl group having 2 to 4 carbon atoms.

[0012] R 2 (This can be a hydrogen atom or a methyl group.) <2> Di(meth)acrylate mixture, which contains <1> The di(meth)acrylate, exist 1 In H-NMR spectra, the ratio of the integral value α in the range of 0.5–1.85 ppm to the integral value β in the range of 4.1–4.3 ppm is α:β = 6–15:1.

[0013] <3> Curable composition comprising <1> or <2> The di(meth)acrylate mentioned above.

[0014] <4> <3> The cured product of the curable composition.

[0015] Invention Effects According to the present invention, di(meth)acrylates that can improve various properties of the obtained cured products, etc., can be provided. Detailed Implementation

[0016] The present invention will now be described in detail, but its scope is not limited to this description. Throughout this specification, "(meth)acrylate" refers to "acrylate" or "methacrylate," "(meth)acrylate alkyl" refers to "alkyl acrylate" or "alkyl methacrylate," and "(meth)acryloyl" refers to "acryloyl" or "methacryloyl." Furthermore, unless otherwise specified, the term "alkyl" includes both straight-chain and alicyclic alkyl groups. Additionally, when using "~" to indicate a numerical range, the values ​​at both ends are included.

[0017] 1. Di(meth)acrylate The di(meth)acrylate of the present invention is a compound represented by the following formula (I).

[0018] [Chemical Formula 2] Here, in equation (I), R 1 It is an alkylene chain or an alkenylene chain having a total carbon number of 12 to 30, having at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms, and satisfying the following condition (A) or (B).

[0019] (A) In the aforementioned alkylene chain, (A1) At least one of the aforementioned substituents is an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, or, (A2) The number of alkyl groups with 1 to 4 carbon atoms in the aforementioned substituents is only 1.

[0020] (B) In the aforementioned alkenyl chain, (B1) At least one of the aforementioned substituents is bonded to the carbon atom forming the aforementioned double bond, or, (B2) At least one of the aforementioned substituents is an alkenyl group having 2 to 4 carbon atoms.

[0021] R 2 It can be a hydrogen atom or a methyl group.

[0022] Regarding the reasons why various properties of cured products are improved when the di(meth)acrylate of the present invention is used as a raw material, although not necessarily limited to theory, the following can be inferred. Specifically, it is believed that, with respect to the di(meth)acrylate of the present invention, since the aforementioned alkylene or alkenyl chains are chains having a certain number of carbon atoms or more, they are compounds with high hydrophobicity and low water absorption. As a result, the cured products exhibit excellent acid and alkali resistance, and shrinkage during curing is suppressed. On the other hand, if the aforementioned alkylene or alkenyl chains have a certain number of carbon atoms or more, the crystallinity increases, thus tending to result in lower impact resistance and brittleness. In this regard, it is believed that, with regard to the di(meth)acrylate of the present invention, since the aforementioned alkylene chain or alkenyl chain has the aforementioned substituents and intermolecular steric hindrance is generated, even if the aforementioned alkylene chain or alkenyl chain is a chain with a certain number of carbon atoms or more, the crosslinking density and crystallinity of the obtained cured product are easily reduced. It is possible to improve the softness and brittleness of the cured product while maintaining the reduction of shrinkage during curing and the acid and alkali resistance of the cured product.

[0023] From the viewpoint of achieving an easily operable viscosity, the aforementioned R in the di(meth)acrylate of the present invention 1 The total number of carbon atoms is preferably 14 to 28, more preferably 14 to 26, even more preferably 16 to 26, and particularly preferably 18 to 24.

[0024] The aforementioned alkylene chain or alkenylene chain may have one of the aforementioned substituents, or two or more of the same or different types of the aforementioned substituents, provided that conditions (A) or (B) are met.

[0025] <alkylene chains and alkenylene chains> From the viewpoint of improving the effect of the present invention, the number of carbon atoms (excluding substituents) of the aforementioned alkylene chain or alkenylene chain is preferably 14 to 22, more preferably 16 to 20.

[0026] The aforementioned alkylene chains do not have double or triple bonds in the chain. Examples of such alkylene chains include, for instance, n-tetradecylene, n-pentadecanylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadecanylene, n-eicosylene, n-monodecylene, n-dididecylene, n-tridecylene, n-tetradecylene, n-pentadecanylene, n-hexadecylene, n-heptadecylene, and n-octadecylene.

[0027] The aforementioned alkenyl chain has one or more double bonds, and may also have two or more double bonds. Additionally, it may have one or more triple bonds. The same applies to the alkenyl groups described later. Examples of such alkenyl chains include chains formed by double bond bonding at least a portion of the aforementioned alkylene chains. The number of double bonds in the alkenyl chain is not particularly limited, but from the viewpoint of improving the effect of the present invention, 1 to 4 are preferred, and more preferably 1 or 2. Furthermore, regarding the position of the double bonds in the alkenyl chain, from the viewpoint of improving the effect of the present invention, it is preferable that the double bonds are formed on carbon atoms other than those bonded to the oxygen atom, and more preferably on carbon atoms other than those directly bonded to the carbon atom bonded to the oxygen atom.

[0028] <Substituent> From the viewpoint of improving the effect of the present invention, the number of all substituents in the aforementioned alkylene chain is preferably 1 to 4, more preferably 1. From the viewpoint of improving the effect of the present invention, the number of all substituents in the aforementioned alkenylene chain is preferably 1 or 2. When multiple substituents are present, the substituents are preferably bonded to different atoms in different chains, and it is preferable that there is one or more carbon atoms without substituents among the carbon atoms bonded to the substituents, and more preferably that there are four or more carbon atoms.

[0029] Examples of alkyl groups having 1 to 4 carbon atoms in the aforementioned alkylene or alkenylene chains include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. From the viewpoint of improving the effect of the present invention, the alkyl groups having 1 to 4 carbon atoms in the aforementioned alkylene or alkenylene chains are preferably alkyl groups having 2 to 3 carbon atoms, and more preferably ethyl.

[0030] Examples of alkenyl groups having 2 to 4 carbon atoms in the aforementioned alkylene or alkenylene chains include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, and 3-butenyl. From the viewpoint of improving the effectiveness of the present invention, alkenyl groups having 2 to 4 carbon atoms in the aforementioned alkylene or alkenylene chains are preferably alkenyl groups having 2 to 3 carbon atoms, and more preferably vinyl.

[0031] Regarding the carbon atoms bonded to the substituents in the aforementioned alkylene chain or alkenylene chain, from the viewpoint of improving the effect of the present invention, it is preferable to use carbon atoms other than those bonded to oxygen atoms, and more preferably carbon atoms other than those directly bonded to carbon atoms bonded to oxygen atoms.

[0032] <Conditions (A) and (B)> From the viewpoint of excellent flexibility of the obtained cured product, the di(meth)acrylate of the present invention preferably satisfies condition (A). Furthermore, from the viewpoint of excellent heat resistance of the obtained cured product, condition (B) is preferably satisfied. Hereinafter, conditions (A) and (B) will be described, but points common to the above will be omitted.

[0033] "Condition (A)" The di(meth)acrylate of the present invention that satisfies condition (A1) contains an alkylene chain having a total carbon number of 12 to 30, having at least one substituent, wherein at least one of the substituents is an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. For the di(meth)acrylate of the present invention that satisfies condition (A1), it is permissible as long as at least one of the substituents is an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms (hereinafter referred to as the substituent of condition (A1)), and it may also have two or more substituents of condition (A1). The di(meth)acrylate of the present invention that satisfies condition (A1) may also have substituents other than those of condition (A1).

[0034] Specific examples of the di(meth)acrylates of the present invention that satisfy condition (A1) include 8-ethyloctadecane-1,18-diol di(meth)acrylate represented by formula (A1-1), 7-ethyltetradecane-1,14-diol di(meth)acrylate represented by formula (A1-2), and 7-vinyltetradecane-1,14-diol di(meth)acrylate represented by formula (A1-3). It should be noted that R in each formula represents a hydrogen atom or a methyl group.

[0035] [Chemical Formula 3] The di(meth)acrylate of the present invention that satisfies condition (A2) contains an alkylene chain having a total carbon number of 12 to 30 and having at least one substituent, and having only one alkyl group having a carbon number of 1 to 4. With respect to the di(meth)acrylate of the present invention that satisfies condition (A2), other substituents may also be present as long as there is only one alkyl group having a carbon number of 1 to 4.

[0036] Specific examples of the di(meth)acrylates of the present invention that satisfy condition (A2) include 8-methylhexadecane-1,16-diol di(meth)acrylate represented by the following formula (A2-1). It should be noted that R in the formula represents a hydrogen atom or a methyl group.

[0037] [Chemical Formula 4] Condition (B) The di(meth)acrylate of the present invention that satisfies condition (B) contains an alkenyl chain having a total carbon number of 12 to 30, comprising at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms; (B1) at least one of the aforementioned substituents is bonded to the carbon atom forming the aforementioned double bond; or (B2) at least one of the aforementioned substituents is an alkenyl group having 2 to 4 carbon atoms. The di(meth)acrylate of the present invention that satisfies condition (B) may satisfy only condition (B1), only condition (B2), or both conditions (B1) and (B2). Furthermore, the di(meth)acrylate of the present invention may also have other substituents as long as condition (B) is satisfied.

[0038] The di(meth)acrylate of the present invention, satisfying condition (B1), contains an alkenyl chain having a total carbon number of 12 to 30, comprising at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms, wherein at least one of the aforementioned substituents is bonded to the carbon atom forming the aforementioned double bond. The di(meth)acrylate of the present invention, satisfying condition (B1), may also have other substituents.

[0039] Specific examples of the di(meth)acrylates of the present invention that satisfy condition (B1) include 8,13-dimethyleicosano-8,12-diene-1,20-diol di(meth)acrylate represented by formula (B1-1) below, and 8-methylhexadecane-8-ene-1,16-diol di(meth)acrylate represented by formula (B1-2) below. It should be noted that R in each formula represents a hydrogen atom or a methyl group.

[0040] [Chemical Formula 5] The di(meth)acrylate of the present invention that satisfies condition (B2) contains an alkenyl chain having a total carbon number of 12 to 30, comprising at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms, wherein at least one of the aforementioned substituents is an alkenyl group having 2 to 4 carbon atoms. The di(meth)acrylate of the present invention that satisfies condition (B2) may also have other substituents.

[0041] Specific examples of the di(meth)acrylates of the present invention that satisfy condition (B2) include 11-vinyloctadecane-8-ene-1,18-diol di(meth)acrylate represented by the following formula (B2-1). It should be noted that R in the formula represents a hydrogen atom or a methyl group.

[0042] [Chemical Formula 6] 2. Di(meth)acrylate mixture The di(meth)acrylate mixture of the present invention (hereinafter, sometimes simply referred to as the mixture of the present invention) is a mixture comprising at least the di(meth)acrylate of the present invention described above, and a di(meth)acrylate derivative thereof, in 1 In the 1H-NMR spectrum, the ratio of the integral value α (0.5–1.85 ppm) to the integral value β (4.1–4.3 ppm) is α:β = 6–15:1. Generally, compounds circulating as di(meth)acrylates can be considered mixtures containing the di(meth)acrylate, its derivatives (meth)acrylates, and unavoidable impurities such as residual raw materials and metal ions. Therefore, the mixture of the present invention can also be considered a di(meth)acrylate as a commonly circulated compound. Furthermore, the mixture of the present invention may contain polymerization inhibitors or the like added as needed to maintain quality, etc.

[0043] The term "meth acrylate" refers to a meth acrylate that can be generated during the manufacturing process of the dimeth acrylate of the present invention. As described below, the dimeth acrylate of the present invention can be representatively manufactured using diols, and (meth)acrylic acid, (meth)acrylates, (meth)acrylic anhydrides, etc. (hereinafter referred to as (meth)acrylates) as raw materials. Commonly available diols, in addition to the diol corresponding to the dimeth acrylate of the present invention, also include diols that are structural isomers of the diol (isomeric diols) and diols with different total carbon numbers (isomeric diols). Therefore, when commonly available diols are used as raw materials, isomers and isomeric diols can also react with (meth)acrylates to obtain a mixture of mono(meth)acrylates and di(meth)acrylates that, in addition to the dimeth acrylate of the present invention, also contain isomers and isomeric diols. The di(meth)acrylate of the present invention can also be extracted from the mixture by purification or the like, or the content of the di(meth)acrylate of the present invention in the mixture can be increased. However, depending on the type and amount of the di(meth)acrylate and the intended use of the di(meth)acrylate of the present invention, there may be situations where no substantial problems arise even if the content of the di(meth)acrylate of the present invention is not increased to the extent necessary.

[0044] Therefore, the inventors of this application focus on the mixture of the present invention. 1 H-NMR spectroscopy revealed that if it were in a mixture... 1 A mixture with an integral value α of 0.5 to 1.85 ppm and an integral value β of 4.1 to 4.3 ppm in H-NMR spectra of α:β = 6 to 15:1 can exert the various effects brought about by the di(meth)acrylate of the present invention.

[0045] The mixture of the present invention is a mixture comprising the di(meth)acrylate of the present invention and one or more derivatives of the di(meth)acrylate, or it may be a mixture comprising two or more derivatives of the di(meth)acrylate. Furthermore, the mixture of the present invention may contain only one or more di(meth)acrylates of the present invention, or it may be a mixture comprising two or more di(meth)acrylates of the present invention and one or more derivatives of the di(meth)acrylate corresponding to them. The di(meth)acrylate mixture of the present invention may be circulated as a mixture comprising these derivatives of the di(meth)acrylate.

[0046] As described above, examples of meth acrylates include those derived from compounds contained in diols that serve as raw materials. Representative examples include isomeric mono(meth)acrylates and isomeric di(meth)acrylates generated by reacting isomeric diols with methacrylic acids, isomeric mono(meth)acrylates and isomeric di(meth)acrylates generated by reacting isomeric diols with methacrylic acids, and mono(meth)acrylates corresponding to the di(meth)acrylates of this invention.

[0047] Regarding the lower limit of the proportion of the di(meth)acrylate of the present invention in the mixture of the present invention, there is no particular limitation as long as the above integral value α:β = 6 to 15:1 is satisfied. However, from the viewpoint of fully utilizing the effect obtained by including the di(meth)acrylate of the present invention, it is preferably 5 mol% or more, more preferably 7 mol% or more, and even more preferably 10 mol% or more. The upper limit of the proportion of the di(meth)acrylate of the present invention in the mixture of the present invention is not particularly limited, but considering the proportion of generally included structural isomers, it is 90 mol% or less.

[0048] Regarding the lower limit of the total amount of di(meth)acrylate and methacrylate of the present invention in the mixture of the present invention, there is no particular limitation as long as the integral value α:β = 6 to 15:1 is satisfied. However, from the viewpoint of fully utilizing the effect of the di(meth)acrylate mixture of the present invention, it is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. The upper limit of the total amount of di(meth)acrylate and methacrylate of the present invention in the mixture of the present invention is not particularly limited, but considering the proportion of other generally included components, it is 99% by mass or less.

[0049] The integral value α is the mixture of the present invention 1 The integral values ​​of 0.5 to 1.85 ppm in the H-NMR spectrum correspond to the peaks of protons bonded to saturated carbons in the alkylene and alkenylene chains of the various (meth)acrylates contained in the mixtures of the present invention. The integral value α also includes protons bonded to saturated carbons of the aforementioned substituents contained in the alkylene or alkenylene chains. There is no particular limitation on the value of the integral value α as long as α:β = 6 to 15:1 is satisfied. As an example, 25 to 60, 30 to 55, and 35 to 50 are possible values, and combinations of these upper and lower limits are also possible.

[0050] The integral value β is the mixture's 1The integrated values ​​of 4.1 to 4.3 ppm in the 1H-NMR spectrum correspond to the peaks of the terminal methylene protons adjacent to the (meth)acryloyl groups of the various (meth)acrylates contained in the mixtures of the present invention. There are no particular limitations on the value of the integrated value β, as long as α:β = 6 to 15:1 is satisfied; as an example, it can be 3.9 to 4.2, 3.95 to 4.15, or a combination of these upper and lower limits.

[0051] Mixture 1 H-NMR spectroscopy can be performed as follows: using an NMR apparatus (Bruker, 500 MHz), a mixture of di(meth)acrylates is dissolved at a concentration of 0.2% in deuterated chloroform containing tetramethylsilane as a reference, and the reaction is carried out at 25°C. 1 H-NMR determination.

[0052] 3. Curing composition [Composition of the curable composition] The curable composition of the present invention comprises at least the di(meth)acrylate of the present invention. The curable composition of the present invention may comprise one or more di(meth)acrylates of the present invention. Additionally, it may comprise one or more similar di(meth)acrylates corresponding to these di(meth)acrylates of the present invention. Furthermore, similarly to the above, the curable composition of the present invention may also be described as a composition comprising a mixture of di(meth)acrylates of the present invention and other components described below.

[0053] The curable composition of the present invention may also contain other components besides the di(meth)acrylate of the present invention. Examples of other components include, for instance, fillers, epoxy resins, phenolic resins, polyimide resins, polyamide-imide resins, and (meth)acrylate resins, compounds containing unsaturated bonds, polymerizable monomers such as benzoxazine compounds (especially other (meth)acrylate monomers), crosslinking agents, curing agents, and polymerization initiators (thermal polymerization initiators, photopolymerization initiators, etc.).

[0054] The curable composition of the present invention can be a photocurable composition that is cured by light irradiation, or a thermocurable composition that is cured by heat.

[0055] 4. Cured product The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention. As a method for manufacturing the aforementioned cured product, examples include methods such as coating the curable composition of the present invention onto a substrate or various components to form a desired shape, followed by heating or irradiation with light (e.g., ultraviolet light) to cure the aforementioned curable composition; however, this method is not particularly limited, and known methods may be used depending on the purpose and intended use of forming the cured product. The curing conditions may be suitably adjusted according to the aforementioned curable composition used.

[0056] Cured products include not only those that are fully cured but also those that are partially cured. The shape of a fully cured product is not particularly limited and can be made into the desired shape depending on the application; examples include plates, rods, blocks, and films. A partially cured product preferably has a viscosity suitable for its application as an adhesive, varnish, grease, or similar product.

[0057] The cured product of the present invention is superior in at least one aspect of properties such as smoothness, transparency, chemical resistance, water resistance, flexibility, and dimensional stability.

[0058] 5. Method for manufacturing di(meth)acrylate The di(meth)acrylate of the present invention can be produced, for example, by reacting a diol represented by the following formula (II) with the above-mentioned (meth)acrylate.

[0059] [Chemical Formula 7] (In formula (II), R 1 It is an alkylene chain or an alkenylene chain having a total carbon number of 12 to 30, having at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms, and satisfying the following condition (A) or (B).

[0060] (A) In the aforementioned alkylene chain, (A1) At least one of the aforementioned substituents is an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, or, (A2) The number of alkyl groups with 1 to 4 carbon atoms in the aforementioned substituents is only 1.

[0061] (B) In the aforementioned alkenyl chain, (B1) At least one of the aforementioned substituents is bonded to the carbon atom forming the aforementioned double bond, or, (B2) At least one of the aforementioned substituents is an alkenyl group having 2 to 4 carbon atoms.

[0062] In the diol represented by formula (II), the above conditions (A), (B) and R 1 As with the above, the explanation is omitted.

[0063] Examples of known methods for producing di(meth)acrylates include dehydration condensation and transesterification. Additionally, catalysts, solvents, and other substances commonly used in the production of di(meth)acrylates can be used during the reaction.

[0064] Example The present invention will be described in detail below with examples, but the present invention is not limited to these examples.

[0065] (Example 1: Preparation of a mixture of di(meth)acrylates based on the dehydration condensation method) (Example 1-1) To a 300 mL three-necked flask equipped with a thermometer, stirrer, air inlet tube, water separator, and reflux tube, 50.0 g of OK Diol B (hydroxyl value 353.5, manufactured by Okamura Oil Co., Ltd.), 56.8 g of acrylic acid, 0.3 g of p-toluenesulfonic acid monohydrate as an acid catalyst, and 100 mL of toluene as a solvent were added. The mixture was heated to 110 °C, and the reaction was carried out for 5 hours while removing the water generated using a water separator. After the reaction was completed, the reaction solution was transferred to a separatory funnel, water was added, and the upper organic layer was washed five times with water. Then, the toluene was removed by distillation using an evaporator to obtain a 1-1 65.2 g mixture of diacrylates, which is the target compound.

[0066] The hydroxyl value of the diacrylate mixture 1-1 was determined according to JIS K 0070 1992, and the result was 0.4. Furthermore, infrared spectroscopy analysis (FT-IR: manufactured by Nippon Spectrophotometer Co., Ltd.) confirmed the peak originating from the hydroxyl group (3324 cm⁻¹). -1 The disappearance of ) and the peak corresponding to the acryloyl group (1724 cm⁻¹) -1 1636cm -1 1620cm -1 The formation of ) was further confirmed by gas chromatography-mass spectrometry (GC-MS, Shimadzu Corporation QP-2010). The analysis confirmed that the diacrylate mixture 1-1 mainly contained component 1 (molecular weight 422) and component 2 (molecular weight 366). Furthermore, the diacrylate mixture 1-1 was further processed according to the above method. 1 H-NMR analysis was performed to determine the integral values ​​α and β, and the α:β ratio was calculated. The results are shown in Table 1.

[0067] Next, the diacrylate mixture 1-1 obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3 / 1 (volume ratio)) to separate the first and second components. Each separated component was then subjected to... 1 ¹H-NMR analysis (Mercury-300, Varian, solvent: CDCl3) identified component 1 as 8-ethyloctadecane-1,18-diol diacrylate and component 2 as 7-ethyltetradecanediol diacrylate. The spectra of the two components are shown in Table 2. It should be noted that component 1 refers to the component with the highest content among the di(meth)acrylates of the present invention contained in diacrylate mixture 1-1. Similarly, component 2 refers to the component with the highest content among the di(meth)acrylates of the present invention contained in diacrylate mixture 1-1. These aspects are also consistent in other embodiments described later.

[0068] (Examples 1-2 to 1-5, Comparative Examples 1-1 and 1-2) Except for changing the ingredients and proportions (parts by mass) as described in Table 1, each di(meth)acrylate mixture 1-2 to 1-5, and comparative di(meth)acrylate mixtures 1-1 and 1-2, were prepared using the same method as in Example 1-1, and the components were separated from each di(meth)acrylate mixture. The results are shown in Tables 2 and 3. It should be noted that the diols shown in Table 2 refer to the following diols.

[0069] OK Diol B Hydroxyl value 353.5, manufactured by Okamura Oils Co., Ltd. OK Diol P Hydroxyl value 325.2, manufactured by Okamura Oils Co., Ltd. OK Diol PU Hydroxyl value 326.0, iodine value 136.6, manufactured by Okamura Oil Manufacturing Co., Ltd. Pripol 2033 A mixture of saturated branched diols with 36 carbon atoms and a hydroxyl value of 210.0, manufactured by Cargill. [Table 1] [Table 2] (Examples 1-2': Preparation of diacrylate mixtures based on transesterification) Diol P 360.0 g, methyl acrylate 225.9 g, tetraisopropyl titanium (catalyst) 8.95 g, and n-hexane (solvent) 150 mL were added to a 1 L five-necked flask equipped with a thermometer, stirrer, air inlet, packed column, and distributor. The mixture was heated to 110 °C, and the reaction was carried out for 18 hours while removing the generated methanol using the distributor. After the reaction was completed, water was added to the reaction solution, and the catalyst was removed by filtration. Then, the n-hexane was removed from the filtrate by distillation using an evaporator, yielding a 1-2' 452.0 g mixture of diacrylates, which is the target compound.

[0070] (Example 2: Production and evaluation of cured products made by light curing) The di(meth)acrylate mixtures obtained in Example 1 were mixed according to the compositions in Table 3 and mixed at 60°C for 1 hour to prepare the curable compositions involved in each example and comparative example. 1.5 g of each curable composition was added to a Teflon petri dish with an inner diameter of 5 cm and irradiated with UV light (365 nm) from a height of 1.5 cm for 5 minutes. Then, the surface of each cured product was cleaned with acetone and dried to obtain the cured products (test pieces) involved in each example and comparative example. It should be noted that multiple test pieces involved in each example and comparative example were prepared for various tests. In Table 3, BDMB represents 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrylbenzene, and the composition ratios are expressed as mass ratios.

[0071] The cured products obtained were evaluated as follows. Details of each evaluation are described below, and the results are shown in Table 3. It should be noted that in Comparative Examples 2-7 and 2-8, which used comparative di(meth)acrylate mixtures, cured products could not be obtained, therefore the evaluations could not be performed.

[0072] (1) Curing properties The curing rate (the percentage of the composition that has been cured relative to the input composition) is calculated using the following formula.

[0073] Curing rate (%) = (mass of cured product obtained) ÷ (mass of the composition added) × 100 Based on the calculated curing rate, the curing performance is judged according to the following criteria.

[0074] A: The curing rate is over 70%.

[0075] B: Curing rate is less than 70%.

[0076] (2) Warpage height of resin (evaluation of dimensional stability) The cured products of each embodiment and comparative example were left to stand at room temperature for 24 hours. Then, the resin was left to stand with the convex portion of the warped resin as the bottom surface, and the length of the portion with the greatest warping was measured.

[0077] (3) Smoothness (evaluation of dimensional stability) The cured products involved in each embodiment and comparative example were left to stand for approximately 24 hours. Then, the surface of each cured product was visually observed and evaluated according to the following criteria.

[0078] A: Unsightly bumps or cracks cannot be identified.

[0079] B: Localized unevenness and cracks were produced.

[0080] C: The whole contains unevenness and cracks.

[0081] (4) Transparency The cured products involved in each embodiment and comparative example were left to stand for approximately 24 hours. Then, the surface of each cured product was visually observed and evaluated according to the following criteria.

[0082] A: Transparent.

[0083] B: Turbid.

[0084] (5) Glass transition temperature (Tg) The cured products involved in each embodiment and comparative example were broken up, and the glass transition temperature (Tg) of each broken product involved in each embodiment and comparative example was determined by analyzing it using a differential scanning calorimeter (DSC, DSC-60 manufactured by Shimadzu Corporation) under the following conditions.

[0085] Temperature and time: -50℃, 10 minutes Heating rate: 10℃ / minute Heating temperature: 200℃ (6) Water absorption rate After measuring the mass of the cured products involved in each embodiment and comparative example, the cured products involved in each embodiment and comparative example were left to stand in 100 mL of water at room temperature for 24 hours. Then, the cured products involved in each embodiment and comparative example were taken out, the water adhering to the surface was removed, and the mass was measured. The water absorption rate was calculated by the following formula.

[0086] Water absorption rate (%) = ((resin mass after addition (g) - resin mass before addition (g)) / (resin mass before addition (g))) × 100 (7) Acid resistance The cured products involved in each embodiment and comparative example were immersed in a 5% by mass sulfuric acid aqueous solution for 24 hours. Then, each cured product was removed, the surface condition was observed, and evaluated according to the following criteria.

[0087] A: No change.

[0088] B: Partially cloudy.

[0089] C: The entire face is pale and cloudy.

[0090] (8) Alkali resistance The cured products involved in each embodiment and comparative example were immersed in a 5% (w / w) sodium hydroxide aqueous solution for 24 hours. Then, each cured product was removed, and its surface condition was observed and evaluated according to the following criteria.

[0091] A: Partially cloudy.

[0092] B: The entire face is pale and cloudy.

[0093] [Table 3] (Example 3: Preparation and evaluation of cured products made by thermosetting) The di(meth)acrylate mixtures obtained in Example 1 were mixed separately in Teflon petri dishes with an inner diameter of 5 cm according to the compositions in Table 4. The mixtures were then heated at 120°C for 1 hour, and further heated at 150°C for 1 hour to obtain the cured products (test pieces) involved in each example and comparative example. It should be noted that three test pieces were prepared for each example and comparative example. In Table 4, DCP represents dicumyl peroxide, and the composition ratios represent mass ratios.

[0094] The obtained cured products were evaluated as follows. The details of each evaluation are recorded below, and the results are shown in Table 4.

[0095] (1) Impact resistance test For the test pieces involved in each embodiment and comparative example, a weight (800g) was dropped freely from a height of 10cm. This operation was repeated until the thermosetting resin sample cracked or broke, and the number of times was measured. This test was performed on 3 test pieces involved in each embodiment and comparative example, and the impact resistance was evaluated based on the average value of the obtained results according to the following criteria. The results are shown in Table 4.

[0096] A: Even after dropping the heavy object more than 10 times, the sample was not damaged.

[0097] B: When the heavy object is dropped 7 to 9 times, the sample is damaged or cracked.

[0098] C: When the heavy object is dropped 4 to 6 times, the sample is damaged or cracked.

[0099] D: The sample was damaged or cracked when the weight was dropped less than 3 times.

[0100] [Table 4] Industrial availability The di(meth)acrylate of the present invention can be suitably used as a raw material for photosensitive materials such as resists, coating materials such as inks and paints, adhesives, building materials, polymers, color developers, surfactants, plasticizers, insecticides, bactericides, pharmaceuticals, and rubber-based pharmaceuticals.

Claims

1. Di(meth)acrylate, represented by the following formula (I), In equation (I), R 1 It is an alkylene chain or an alkenylene chain with a total carbon number of 12 to 30 that has at least one substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms and satisfies the following condition (A) or (B). (A) In the alkylene chain, (A1) At least one of the substituents is an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, or, (A2) The number of alkyl groups with 1 to 4 carbon atoms in the substituent is only one; (B) In the said alkenyl chain, (B1) At least one of the substituents is bonded to the carbon atom forming the double bond, or, (B2) At least one of the substituents is an alkenyl group having 2 to 4 carbon atoms; R 2 It can be a hydrogen atom or a methyl group.

2. A mixture of di(meth)acrylates comprising the di(meth)acrylate of claim 1. exist 1 In H-NMR spectra, the ratio of the integral value α in the range of 0.5–1.85 ppm to the integral value β in the range of 4.1–4.3 ppm is α:β = 6–15:

1.

3. A curable composition comprising the di(meth)acrylate of claim 1.

4. The cured product of the curable composition according to claim 3.

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