Polymer and Synthetic Resin

Abstract

To provide a (meth)acrylic acid ester for producing a polymer with low odor and high heat resistance.SOLUTION: The polymer is a homopolymer of a compound represented by formula (1), where R1 represents a hydrogen atom or a methyl group. Alternatively, the polymer is a copolymer comprising a constituent unit of the compound represented by formula (1) and a constituent unit of a specific monomer, and is used as a coating or adhesive for building components.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to polymers and synthetic resins.

Background Art

[0002] Acrylic resins tend to have high transparency and high weather resistance, and are thus used in various applications. Such applications include optical members, building materials, and the like. Among them, in the case of applications assumed to be used outdoors, for example, since the temperature may exceed 60°C due to direct sunlight, an acrylic resin having high heat resistance whose performance does not change even at such high temperatures is required. Generally, in order to improve the heat resistance of an acrylic resin, it is considered preferable that the acrylic resin is a polymer of an acrylic monomer having a rigid skeleton.

[0003] Examples of the rigid skeleton include an alicyclic skeleton. As an acrylic monomer having an alicyclic moiety, for example, Patent Document 1 describes a resin composition having tricyclodecenyl acrylate represented by the following formula (3) as a structural unit. Further, Patent Document 2 describes tricyclodecenyl methyl butyrate represented by the following formula (4), which has a structure similar to that of tricyclodecenyl acrylate and has a carbon-carbon double bond.

[0004]

Chemical formula

[0005]

Chemical formula

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] However, according to the studies by the present inventors, in the case of tricyclodecenyl acrylate described in Patent Document 1, it has been found that it may not be suitable for applications where a strong odor is not required. Further, as can be inferred from Patent Document 2, the odor varies for each compound, and the type and intensity of the odor perceived by humans tend to vary greatly depending on substituents and the like. Therefore, it is difficult to predict the odor of analogs having an unsaturated double bond from the odor of tricyclodecenylmethyl butyrate disclosed in Patent Document 2. Furthermore, since tricyclodecenylmethyl butyrate does not have an α,β-unsaturated carbonyl moiety, it is difficult to use it as an acrylic resin. Patent Document 2 also describes ester compounds and ether compounds having an unsaturated double bond such as tricyclodecenylmethyl acetate and methyl(tricyclodecenylmethyl) ether, but similarly, it is difficult to use them as an acrylic resin.

[0008] Therefore, an object of the present invention is to provide a (meth)acrylate for producing a polymer having low odor and high heat resistance.

MEANS FOR SOLVING THE PROBLEMS

[0009] As a result of intensive studies in view of the problems of the prior art, the present inventors have found that a (meth)acrylate represented by the following formula (1) can achieve the above object, and have completed the present invention. That is, the gist of the present invention is as follows.

[0010] [1] A compound represented by the following formula (1).

[0011]

CHEMICAL FORMULA

[0012] [Chemical formula] [Advantages of the Invention]

[0013] According to the present invention, a (meth) acrylic acid ester for producing a polymer having low odor and high heat resistance can be provided. [Modes for Carrying Out the Invention]

[0014] Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.

[0015] In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid. Further, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester. Further, (meth) acrylic anhydride means acrylic anhydride and / or methacrylic anhydride. Further, (meth) acrylic acid chloride means acrylic acid chloride and / or methacrylic acid chloride. Further, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic anhydride, and (meth) acrylic acid chloride are collectively referred to as (meth) acrylic acids. Further, polymerization means homopolymerization and / or copolymerization. Further, polymer means homopolymer and / or copolymer.

[0016] <1. Compound according to this embodiment> The (meth)acrylate according to this embodiment has a structure represented by the following formula (1).

[0017]

Chemical formula

[0018] In formula (1), R 1 represents a hydrogen atom or a methyl group. Among them, R1 is preferably a methyl group.

[0019] When the compound represented by the above formula (1) is used as a synthetic resin raw material for paints, adhesives, etc., it is possible to achieve both high heat resistance and low odor.

[0020] <2. Production method of the compound represented by formula (1)> The production method of the compound represented by formula (1) is not particularly limited, but it can be produced by reacting (meth)acrylic acids with tricyclodecenyl methanol. That is, it can be produced by reacting one or more selected from (meth)acrylic acid, (meth)acrylate, (meth)acrylic anhydride, and (meth)acrylic acid chloride with tricyclodecenyl methanol.

[0021] (Tricyclodecenyl methanol)

[0022] Tricyclodecenyl methanol is a compound represented by the following formula (2).

[0023]

Chemical formula

[0024] The purity of tricyclodecenylmethanol is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. By using tricyclodecenylmethanol having a purity of 50% by mass or more, the production amount of tricyclodecenylmethyl (meth)acrylate per reaction volume can be increased.

[0025] Tricyclodecenylmethanol may be any of the compounds represented by the following formula (5), the compounds represented by the following formula (6), or a mixture of isomers thereof, and the isomer ratio is not particularly limited.

[0026]

Chemical formula

[0027]

Chemical formula

[0028] Commercially available tricyclodecenylmethanol can be used, or those obtained by producing by a known method can also be used. For example, it can be produced from dicyclopentadiene by a known method.

[0029] ((Meth)acrylic acids) The purity of the total amount of (meth)acrylic acids used in the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. By using (meth)acrylic acids having a purity of 50% by mass or more, the production amount of tricyclodecenylmethyl (meth)acrylate per reaction volume can be increased.

[0030] As the (meth)acrylic acids, (meth)acrylic acid or (meth)acrylic acid ester is preferable in order to improve the recoverability of unreacted raw materials, by-products and solvents, and to reduce waste treatment. There are no particular restrictions on the (meth)acrylic acid ester, but in order to recover unreacted raw materials and by-products at a lower temperature, it is preferably a (meth)acrylic acid ester composed of (meth)acrylic acid and an alcohol having 4 or less carbon atoms, more preferably a (meth)acrylic acid ester composed of (meth)acrylic acid and an alcohol having 2 or less carbon atoms, and particularly preferably a (meth)acrylic acid ester composed of (meth)acrylic acid and an alcohol having 1 carbon atom. Specific examples of such (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and the like.

[0031] Among (meth)acrylic acid and (meth)acrylic acid esters, (meth)acrylic acid esters are more preferable, and methacrylic acid esters are even more preferable. As the methacrylic acid ester, methyl methacrylate is preferable from the viewpoints of the recoverability of by-produced alcohol and the availability of raw materials.

[0032] The amount of (meth)acrylic acids is not particularly limited, but is preferably 0.1 mol or more and 50.0 mol or less per 1 mol of tricyclodecenylmethanol. By setting the amount of (meth)acrylic acids used to 0.1 mol or more and 50.0 mol or less per 1 mol of tricyclodecenylmethanol, the production amount of tricyclodecenylmethyl (meth)acrylate per reaction volume can be increased. Among them, the amount of (meth)acrylic acids per 1 mol of tricyclodecenylmethanol is more preferably 0.5 mol or more, even more preferably 0.8 mol or more, and particularly preferably 1.0 mol or more. On the other hand, the amount of (meth)acrylic acids per 1 mol of tricyclodecenylmethanol is more preferably 30.0 mol or less, even more preferably 10.0 mol or less, and particularly preferably 5.0 mol or less.

[0033] When reacting tricyclodecenylmethanol with (meth)acrylic acids, a catalyst may or may not be used, but it is preferable to use it from the viewpoint of improving the reaction rate.

[0034] The catalyst only needs to be present in at least a part of the reaction steps and does not necessarily have to be present in all steps of the reaction process. For example, after adding the catalyst into the reaction system, some changes may occur to the catalyst during the reaction process.

[0035] The catalyst is not particularly limited and can be selected according to the (meth)acrylic acids used as raw materials. For example, when using (meth)acrylic acid esters as raw materials, known transesterification catalysts can be used.

[0036] Examples of the transesterification catalyst include Group 1 metal compounds, Group 2 metal compounds, titanium compounds, tin compounds, zirconium compounds, etc.

[0037] Examples of the Group 1 metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium methoxide, sodium methoxide, potassium methoxide, lithium - t - butoxide, sodium - t - butoxide, potassium - t - butoxide, etc.

[0038] Examples of the Group 2 metal compounds include magnesium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium methoxide, calcium methoxide, magnesium - t - butoxide, calcium - t - butoxide, etc.

[0039] Examples of the titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra - i - propoxytitanium, tetra - n - butoxytitanium, etc.

[0040] Examples of the tin compounds include dibutyltin oxide, dioctyltin oxide, etc.

[0041] Examples of the zirconium compound include zirconium tetraacetylacetonate.

[0042] From the viewpoints of activity and catalyst separation, a titanium compound is preferable, tetramethoxytitanium and tetra-n-butoxytitanium are more preferable, and tetramethoxytitanium is even more preferable.

[0043] As these catalysts, commercially available ones can be used, and those obtained by manufacturing by known methods or the like can also be used. Further, these catalysts may be used singly or in combination of two or more.

[0044] The amount of the catalyst used in the present invention is not particularly limited, but it is preferably 0.000001 mol or more and 4 mol or less per 1 mol of tricyclodecenylmethanol. By setting the amount of the catalyst used to 0.000001 mol or more per 1 mol of tricyclodecenylmethanol, a decrease in catalyst activity due to impurities can be effectively suppressed. By setting the amount of the catalyst used to 4 mol or less per 1 mol of tricyclodecenylmethanol, the load on the post-treatment step after the reaction can be reduced, and the economic efficiency can be improved. Among these, the amount of the catalyst used per 1 mol of tricyclodecenylmethanol is more preferably 0.00001 mol or more, even more preferably 0.00005 mol or more, particularly preferably 0.0001 mol or more, extremely preferably 0.0005 mol or more, and most preferably 0.001 mol or more. On the other hand, the amount of the catalyst used per 1 mol of tricyclodecenylmethanol is more preferably 1 mol or less, even more preferably 0.5 mol or less, particularly preferably 0.2 mol or less, extremely preferably 0.05 mol or less, and most preferably 0.01 mol or less.

[0045] Also, the catalyst may be in a dissolved state in the reaction solution or may not be dissolved, but it is preferably in a dissolved state. When the catalyst is in a dissolved state in the reaction solution, the production rate of tricyclodecenylmethyl (meth)acrylate can be improved.

[0046] When reacting tricyclodecenylmethanol with (meth)acrylic acids, a solvent may or may not be used.

[0047] When using a solvent, it is preferably a solvent that does not react with tricyclodecenylmethanol, (meth)acrylic acids, the catalyst, and the resulting compound. Also, although not particularly limited, from the viewpoint of separation, it is preferable to use a solvent having a large boiling point difference from tricyclodecenylmethyl (meth)acrylate. Specifically, it is preferably a solvent having a boiling point difference of 100 °C or more from tricyclodecenylmethyl (meth)acrylate, and more preferably a solvent having a boiling point difference of 150 °C or more.

[0048] Examples of such solvents include hydrocarbon solvents such as hexane, toluene, and xylene; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; amide solvents such as dimethylformamide and dimethylacetamide. These may be used alone or in combination of two or more. The amount of the solvent used is not limited either and can be appropriately selected.

[0049] The amount of the solvent used relative to tricyclodecenylmethanol is not particularly limited, but in order to improve the productivity of tricyclodecenylmethyl (meth)acrylate, it is preferably less. Specifically, it is preferably 50% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably not using a solvent.

[0050] The reaction temperature is not particularly limited, but is preferably -20°C or higher and 200°C or lower. By setting the reaction temperature to -20°C or higher, the reaction can proceed smoothly. By setting the reaction temperature to 200°C or lower, polymerization and side reactions can be suppressed. Among these, the reaction temperature is more preferably 0°C or higher, even more preferably 30°C or higher, and particularly preferably 60°C or higher. On the other hand, the reaction temperature is more preferably 180°C or lower, even more preferably 150°C or lower, and particularly preferably 130°C or lower. Note that the reaction temperature does not have to be constant and may be changed within a preferable range.

[0051] The reaction time is not particularly limited and can be appropriately selected according to the scale and conditions of the reaction, etc. For example, the reaction time is preferably 0.5 hours or longer and 100 hours or shorter. By setting the reaction time to 0.5 hours or longer, the reaction can proceed smoothly. By setting the reaction time to 100 hours or shorter, polymerization and side reactions can be suppressed. Among these, the reaction time is more preferably 1 hour or longer, even more preferably 3 hours or longer. On the other hand, the reaction time is more preferably 60 hours or shorter, even more preferably 30 hours or shorter. Note that when a continuous tank reactor is used, the reaction time is defined as the volume of the reaction solution divided by the flow rate at which it is withdrawn from the reactor.

[0052] The pressure during the reaction is not particularly limited and may be in a reduced-pressure state, atmospheric pressure, or a pressurized state.

[0053] Regarding the method of introducing the raw materials into the reaction vessel, there is no particular limitation. All of them may be introduced at once, introduced step by step, introduced continuously, or an introduction method combining these methods may also be used.

[0054] The form of the reaction vessel for carrying out the reaction is not particularly limited, and a batch tank reactor, a continuous tank reactor, a continuous tubular reactor, etc. can be used, and a batch tank reactor is preferred.

[0055] The reaction solution may contain compounds other than those described above. For example, a polymerization inhibitor may be added to the reaction solution and allowed to coexist in the reaction solution. The polymerization inhibitor is not particularly limited, but examples include quinone-based polymerization inhibitors such as benzoquinone; phenolic polymerization inhibitors such as phenol, 1,4-benzenediol, 4-methoxyphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; amine-based polymerization inhibitors such as alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine; N-oxyl-based polymerization inhibitors such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (HO-TEMPO), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl (BTOX), 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl (AMX); copper dithiocarbamate-based polymerization inhibitors such as metallic copper, copper sulfate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, etc. Among these, 4-methoxyphenol is preferred. These polymerization inhibitors may be used alone or in combination of two or more.

[0056] When using a polymerization inhibitor, the amount of the polymerization inhibitor relative to tricyclodecenyl methanol is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, particularly preferably 0.1% by mass or more in order to suppress the polymerization of the obtained tricyclodecenyl methyl (meth)acrylate. On the other hand, in order to suppress the coloring of the obtained tricyclodecenyl methyl (meth)acrylate, it is preferably 100% by mass or less, more preferably 50% by mass or less, particularly preferably 10% by mass or less.

[0057] During the reaction, during the purification of the product, and when storing the solution containing the product and the purified tricyclodecenyl methyl (meth)acrylate solution, in order to prevent the polymerization of raw materials and products, it is preferable to make the gas phase part in the reaction vessel an oxygen-containing gas atmosphere, and it is more preferable to blow an oxygen-containing gas such as oxygen or air into the reaction solution. The oxygen-containing gas may be introduced from two or more places in the reaction vessel, and its flow rate is not particularly limited.

[0058] The obtained tricyclodecenyl methyl (meth)acrylate can be purified if necessary. The purification method is not particularly limited, and known methods can be used. Examples of the purification method include liquid separation, distillation, crystallization, filtration, chromatography, etc. These may be carried out alone or in combination of two or more.

[0059] When removing insoluble by-products by filtration, it may be carried out under reduced pressure, atmospheric pressure, or increased pressure, but it is preferably carried out under increased pressure. Further, if necessary, a filter aid can be used, for example, diatomaceous earth, perlite, cellulose, etc. The temperature, pressure, type and amount of the filter aid for filtration can be appropriately selected according to the reaction conditions and the like.

[0060] When washing tricyclodecenyl methyl (meth)acrylate by liquid separation, it can be washed using an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. The concentration of the alkali and the number of washing times of the alkaline aqueous solution used can be appropriately selected according to the reaction conditions and the like.

[0061] The distillation method is not particularly limited, and examples include simple distillation, precision distillation, thin-film distillation, etc. Among these, thin-film distillation is preferable. The distillation may be carried out under reduced pressure, atmospheric pressure, or increased pressure, but it is preferably carried out under reduced pressure.

[0062] The storage container for tricyclodecenylmethyl (meth)acrylate is not particularly limited, and examples thereof include glass containers, resin containers, metal storage tanks, drums, lorries, etc.

[0063] <3. Uses> The compound represented by formula (1) is not particularly limited, but can be used, for example, as a food additive, a cosmetic additive, an optical member, a building member, a pharmaceutical raw material, a fragrance, a synthetic resin raw material, etc. As the synthetic resin raw material, it may be a resin additive. Further, as the use of the synthetic resin raw material, it can be used for paints, adhesives, various materials, etc., and these can be preferably used for optical members and building members. Among them, the compound represented by formula (1) is preferably used as a raw material for synthetic resins. Hereinafter, preferred forms will be described.

[0064] (Synthetic resin raw material) The compound represented by formula (1) can be polymerized and used as a polymer, and further can be used as a synthetic resin containing the polymer. As the polymer, it may be a homopolymer of the compound represented by formula (1) or a copolymer of the compound represented by formula (1) and other monomers. In the case of a copolymer, the copolymer composition is not particularly limited. However, in order to obtain a polymer having both high heat resistance and low odor, the number of structural units of the compound represented by formula (1) relative to the number of each structural unit constituting the polymer is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more.

[0065] Other monomers are not particularly limited as long as they are copolymerizable with the compound represented by the formula (1). Examples of copolymerizable monomers include monomers having a vinyl group. For example, aromatic monomers such as styrene, α-methylstyrene, t-butylstyrene, and chlorostyrene; (meth)acrylate monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, and 2-dimethylaminoethyl (meth)acrylate; (meth)acrylic acid; (meth)acrylamide; (meth)acrylonitrile; vinyl chloride; vinyl acetate; maleic anhydride, etc. Further, polyfunctional vinyl monomers such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and divinylbenzene can be used. These monomers may be used alone or in combination of two or more.

[0066] From the viewpoints of copolymerizability, compatibility, and imparting functionality, (meth)acrylate monomers and (meth)acrylic acid are preferred as copolymerizable monomers.

[0067] There is no particular limitation on the mass average molecular weight of the polymer, but it is preferably 1000 or more and 1000000 or less. If the mass average molecular weight is 1000 or more, the physical properties of the polymer will be good. Also, if the mass average molecular weight is 1000000 or less, the moldability will be good. The mass average molecular weight is the value calculated by gel permeation chromatography (GPC) described later.

[0068] The method for producing the polymer is not particularly limited, and known methods can be used. Examples of the polymerization system include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Also, from the viewpoints of productivity and imparting functionality, radical polymerization or anionic polymerization is preferred, and radical polymerization is preferred.

[0069] As the radical polymerization initiator, known compounds suitable for thermal polymerization, photopolymerization, etc. can be used. In thermal polymerization, peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), etc. can be mentioned. In photopolymerization, benzophenone, acetophenone, benzoin, etc. can be mentioned.

[0070] The usage amount of the radical polymerization initiator is not particularly limited, but it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more with respect to the monomer. Also, it is preferably 5% by mass or less, more preferably 3% by mass or less with respect to the monomer.

[0071] In order to control the molecular weight of the polymer, a known chain transfer agent such as mercaptan may be used.

[0072] In order to allow the polymerization to proceed smoothly, known polymerization accelerators such as metal salts such as cobalt naphthenate; tertiary amines such as dimethylaniline may be used.

[0073] The polymerization for producing the polymer can be carried out without a solvent or in a solvent. The solvent is not particularly limited, but examples include hydrocarbon solvents such as hexane and toluene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as methyl acetate and ethyl acetate; ether solvents such as tetrahydrofuran and anisole; water, etc. These may be used alone or in combination of two or more. The usage amount of the solvent is also not limited and can be appropriately selected.

[0074] The atmosphere during polymerization is not particularly limited as long as the polymerization is not inhibited, but an inert atmosphere such as nitrogen or argon is preferred. Oxygen reacts with radicals and inhibits polymerization.

[0075] The polymerization temperature is preferably 0 °C or higher, more preferably 25 °C or higher, in order to allow the polymerization to proceed smoothly. From the viewpoint of controlling the polymerization reaction, it is preferably 200 °C or lower, more preferably 150 °C or lower. The reaction temperature does not necessarily have to be constant and may be varied within a preferable range.

[0076] The usage amount of the compound represented by formula (1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, based on the total amount of the monomers. By using 0.1% by mass or more, heat resistance can be imparted to the polymer.

[0077] The synthetic resin may contain a compound other than the polymer, such as an additive for imparting functions.

[0078] As described above, the compound represented by formula (1) can be suitably used as a synthetic resin raw material, and in particular, it can be suitably used as a shrap composition used for floor materials and the like in building members. In this case, for example, it preferably contains component (A) composed of an acrylic monomer containing the compound represented by formula (1), component (B) containing at least one of a polymer of an acrylic monomer, an epoxy (meth) acrylate oligomer, and a urethane (meth) acrylate oligomer, and wax. It may also contain a curing accelerator. Examples include the compounds exemplified in JP-A-2009-203480 and the like.

[0079] As acrylic monomers, in addition to the compound represented by the formula (1), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate and the like can be mentioned. These monomers may be used alone or in combination of two or more of the compound represented by the formula (1).

[0080] As for the polymer of acrylic monomers, epoxy (meth)acrylate oligomers, and urethane (meth)acrylate oligomers, the compounds described in JP-A-2009-203480 can be mentioned. The mass average molecular weight of these polymers and oligomers is not particularly limited, but is preferably 30,000 or less.

[0081] As for the wax, there is no particular limitation, but it is preferably a wax in a dispersed state. Examples of such waxes include BYK-LP-S6665 manufactured by Big Chemie.

[0082] The ratio of the component (A) to the total 100 parts by mass of the component (A) and the component (B) is not particularly limited, but is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. On the other hand, it is preferably 90 parts by mass or less, and preferably 85 parts by mass or less.

[0083] The ratio of component (B) to a total of 100 parts by mass of components (A) and (B) is not particularly limited, but is preferably 10 parts by mass or more, more preferably 15 parts by mass or more. On the other hand, it is preferably 80 parts by mass or less, and preferably 70 parts by mass or less.

[0084] The ratio of the wax to a total of 100 parts by mass of components (A) and (B) is not particularly limited, but is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more. On the other hand, it is preferably 5 parts by mass or less, and more preferably 0.5 part by mass or less.

Examples

[0085] Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples only, and can be arbitrarily modified and implemented without departing from the gist of the present invention. The data in the examples and comparative examples were measured by the following methods.

[0086] (1) Yield The yield was calculated by the following formula. Yield (%) = (number of moles of target product) / (number of moles of reference raw material) × 100 (2) Purity The purity of each compound was calculated by gas chromatography (column: DB-1). Purity (%) = (peak area of target product) / (total of all peak areas) × 100 (3) Glass transition temperature Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., trade name: DSC6200), it was measured in the range of 25°C to 220°C at a heating rate of 10°C / min. The numerical value of the extrapolated glass transition start temperature of the second heating result was used as the glass transition temperature. (4) Mass average molecular weight Using a GPC (manufactured by Waters Japan Ltd., trade name: Alliance 2695 System), tetrahydrofuran was used as the solvent, polystyrene as the standard sample, and TSKgel superH3000, H4000, and H6000 were used as the columns. The weight-average molecular weight was measured at a flow rate of 0.5 mL / min and a column oven temperature of 40 °C.

[0087] In the examples, tricyclodecenylmethanol with a purity of 99% by mass synthesized by a known method was used. Methyl methacrylate with a purity of 99% by mass was used.

[0088] <Production Example 1> To a 3 L four-necked glass flask equipped with a Dimroth condenser, a Dean-Stark apparatus, and an air inlet tube, 500 g (3.04 mol) of tricyclodecenylmethanol, 1524 g (15.22 mol) of methyl methacrylate, and 1.52 g (12.3 mmol) of 4-methoxyphenol as a polymerization inhibitor were sequentially added. Air was blown into this mixture at a flow rate of 10 mL per minute, and the mixture was stirred for 1 hour while heating under reflux at a bath temperature of 125 °C. The water content of the mixture at this time was 79 ppm.

[0089] 1.09 g (6.08 mmol) of 95% by mass tetramethoxytitanium was added to this mixture, and the mixture was stirred for 14 hours while heating under reflux at a bath temperature of 125 °C. During this time, the by-produced methanol was extracted from the Dean-Stark apparatus. The internal temperature at this time was 92 to 109 °C.

[0090] 109 g of celite and 19 g of water were added to the obtained reaction solution, and the mixture was stirred at a bath temperature of 70 °C for 30 minutes. Then, pressure filtration was performed with nitrogen at 0.2 MPa to remove the solid content. Next, methyl methacrylate was distilled off and concentrated using an evaporator under the conditions of 50 °C and 4.3 to 9.3 kPa.

[0091] The obtained concentrated solution was transferred to a separatory funnel, 1000 g of n-hexane and 244 g of a 10% by mass aqueous sodium hydroxide solution were added, and after shaking vigorously to mix, it was allowed to stand and separated into an oil layer and an aqueous layer. The aqueous layer was withdrawn from the bottom, and then the same operation was performed on the oil layer without adding n-hexane. The oil layer was washed once with 224 g of a 10% by mass aqueous sodium hydroxide solution and twice with 250 g of water. After adding 128 mg of 4-methoxyphenol as a polymerization inhibitor to the obtained oil layer, n-hexane was distilled off and concentrated using an evaporator under the conditions of 40 °C and 5.2 - 12.1 kPa. Subsequently, it was concentrated using a vacuum pump under the conditions of 65 °C and 0.3 - 1.3 kPa while introducing air. As a result, 682 g (2.94 mol) of tricyclodecenyl methyl methacrylate, which is a pale yellow transparent liquid with a purity of 98.6% (a compound in which R1 is a methyl group in the above formula (1)), was obtained. The total yield based on tricyclodecenyl methanol was 97%.

[0092] <Example 1> Comparative test: The odor of 100 g of tricyclodecenyl methyl methacrylate obtained in Production Example 1 placed in a 110 mL glass container was confirmed. The results are shown in Table 1. The evaluation of the odor was based on the following criteria.

[0093] (Evaluation criteria) ○: Odorless or with only a slight non-unpleasant fragrance. △: Odor is felt to some extent. ×: It has a bad odor or a strong odor is felt even if it is not unpleasant.

[0094] Next, 15.0 g (65 mmol) of tricyclodecenyl methyl methacrylate, 30 g (278 mmol) of anisole, and 11 mg (6.5 μmol) of 2,2'-azobisisobutyronitrile (AIBN) were sequentially added to a 100 mL four-necked glass flask equipped with a nitrogen inlet tube. Thereafter, nitrogen was blown into the gas phase part at a flow rate of 10 mL per minute, and the mixture was stirred at a bath temperature of 80 °C for 4.5 hours. Thereafter, it was stirred at a bath temperature of 100 °C for 1 hour. Next, it was diluted with 30 g (278 mmol) of anisole, and the resulting diluted solution was added dropwise to acetone. The precipitated white solid was filtered off. Then, the obtained white solid was dried under vacuum at 25°C to obtain a polymer of tricyclodecenylmethyl methacrylate. By the above method, the glass transition temperature and the mass average molecular weight of the polymer were measured. The results obtained are shown in Table 1.

[0095] <Comparative Examples 2 to 4> The odor was evaluated in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of tricyclodecenylmethyl methacrylate. The results obtained are shown in Table 1. Further, polymers were produced in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of tricyclodecenylmethyl methacrylate. The glass transition temperatures and mass average molecular weights of these polymers are as shown in Table 1. For tetrahydrofurfuryl methacrylate, the trade name Acryester THF manufactured by Mitsubishi Chemical Corporation was used; for tricyclodecanyl methacrylate, the trade name FA-513M manufactured by Hitachi Chemical Co., Ltd. was used; and for tricyclodecenyl oxyethyl methacrylate, the trade name FA-512M manufactured by Hitachi Chemical Co., Ltd. was used.

[0096]

Table 1

[0097] From the results in Table 1, it can be seen that when tricyclodecenylmethyl methacrylate is polymerized, little odor is generated, and also, since the glass transition temperature is 80°C or higher, it has high heat resistance enabling outdoor use.

[0098] As described above, the present invention has been described with reference to the embodiments and examples, but the present invention is not limited to the above embodiments and examples. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

Claims

【Claim 1】 A synthetic resin containing a polymer which is a homopolymer of a compound represented by the following formula (1) and has a glass transition temperature of 80°C or higher. 【Chemical 1】 (In formula (1), R １ represents a methyl group.)

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