JP2020012030A - Ultraviolet absorber, ultraviolet absorbing resin, ultraviolet absorbing resin composition, varnish, ultraviolet absorbing film and method for producing the same - Google Patents

Abstract

To provide an ultraviolet absorber, an ultraviolet absorbing resin, an ultraviolet absorbing resin composition, an ultraviolet absorbing film which are excellent in ultraviolet absorbing property at a wavelength of 300 nm to 400 nm and a method for producing the same; and a varnish useful in production of the ultraviolet absorbing film, and the like.SOLUTION: An ultraviolet absorber is formed of a compound represented by formula (1). An ultraviolet absorbing resin is formed of a polymer of a monomer component containing a compound represented by formula (1). An ultraviolet absorbing resin composition contains a resin and the ultraviolet absorber. In formula (1), R, Rand Reach independently represents a hydrogen atom, an aryl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; and X represents a group represented by formula (2) and a group represented by formula (3).SELECTED DRAWING: None

Description

  The present invention relates to an ultraviolet absorbent, an ultraviolet absorbent resin, an ultraviolet absorbent resin composition, a varnish, an ultraviolet absorbent film, and a method for producing the same.

  As methods for preventing deterioration of the resin due to ultraviolet rays, there are a method of adding an ultraviolet absorber to the resin and a method of reacting and bonding the ultraviolet absorber to the resin (Patent Documents 1 to 4).

JP-A-7-276831 JP-A-8-039946 JP-A-10-17557 JP-A-11-71356

  However, conventional ultraviolet absorbers have insufficient ultraviolet absorptivity in the wavelength region of 300 nm to 400 nm.

  The present invention relates to an ultraviolet absorber excellent in ultraviolet absorption at a wavelength of 300 nm to 400 nm, an ultraviolet absorption resin, an ultraviolet absorption resin composition, an ultraviolet absorption film and a method for producing the same, and the production of the ultraviolet absorption film and the like. The purpose is to provide a useful varnish.

The present invention has the following aspects.
[1] An ultraviolet absorber comprising a compound represented by the following formula (1).

(Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and X represents the following formula: A group represented by (2) or a group represented by the following formula (3) is shown.)

[2] The ultraviolet absorbent according to the above [1], which comprises an isomer mixture of the compound represented by the formula (1).
[3] An ultraviolet absorbing resin comprising a polymer of a monomer component containing the compound represented by the formula (1).
[4] The ultraviolet absorbing resin according to [3], wherein the monomer component contains a mixture of isomers of the compound represented by the formula (1).
[5] An ultraviolet absorbent resin composition comprising the resin and the ultraviolet absorbent of the above [1] or [2].
[6] A varnish comprising the ultraviolet absorbent resin of the above [3] or [4] or the ultraviolet absorbent resin composition of the above [5], and a solvent.
[7] An ultraviolet absorbing film containing the ultraviolet absorbing resin of [3] or [4] or the ultraviolet absorbing resin composition of [5].
[8] A method for producing an ultraviolet absorbing film, comprising forming a film comprising the varnish of the above [6], and drying the film.

  According to the present invention, an ultraviolet absorber excellent in ultraviolet absorption at a wavelength of 300 nm to 400 nm, an ultraviolet absorption resin, an ultraviolet absorption resin composition, an ultraviolet absorption film and a method for producing the same, and the ultraviolet absorption film and the like A varnish useful for production can be provided.

It is a graph which shows the UV absorption evaluation result of an ultraviolet absorber (monomer). It is a graph which shows the UV absorption evaluation result at the time of adding an ultraviolet absorber to resin. It is a graph which shows the UV absorptivity evaluation result of the polycarbonate resin which copolymerized the ultraviolet absorber. It is a graph which shows the UV absorption evaluation result of the phenoxy resin which copolymerized the ultraviolet absorber.

(UV absorber)
The ultraviolet absorber of the present invention comprises a compound represented by the following formula (1) (hereinafter, also referred to as “compound 1”). The compound 1 constituting the ultraviolet absorbent of the present invention may be one type or two or more types.

In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Each of the alkyl group and the alkoxy group may be linear or branched.
X represents a group represented by the following formula (2) or a group represented by the following formula (3).

Since Compound 1 has a benzene ring to which a hydroxyl group and a formyl group are bonded, it has excellent ultraviolet absorption at a wavelength of 300 nm to 400 nm. Further, it can absorb ultraviolet rays in a wide wavelength range including a wavelength of 300 nm to 400 nm.
It is considered that the reason why the compound 1 is excellent in absorbing ultraviolet light in a wavelength region of 300 nm to 400 nm is that a formyl group is further contained in a benzene ring containing a hydroxyl group.
In addition, since compound 1 has a functional group such as a hydroxyl group and a formyl group, a structure derived from compound 1 can be introduced into the resin using the functional group. For example, a monomer component containing the compound 1 can be polymerized into a polymer, or the resin can be modified with the compound 1.

The ultraviolet absorbent of the present invention preferably comprises a mixture of isomers of compound 1.
Since the isomer mixture of compound 1 contains compound 1 as a mixture of a plurality of isomers, it has lower crystallinity and better solvent solubility than a single compound 1. Therefore, operations such as polymerization and modification can be easily performed as a solution, and the workability is excellent.
The isomer mixture of the compound 1 constituting the ultraviolet absorbent of the present invention may be one kind, or two or more kinds different in at least one of R ¹ , R ² , R ³ and X.

The isomer mixture of the compound 1 typically includes two or more isomers in which the bonding positions of X in two benzene rings (a benzene ring to which OH and CHO are bonded) in the formula (1) are different. As such isomers, compounds in which the bonding position of X on one benzene ring and the bonding position of X on the other benzene ring are each at the p-position with respect to the bonding position of OH (hereinafter, “p, p′- A compound in which the bonding position of X on one benzene ring is at the o-position with respect to the bonding position of OH, and the bonding position of X on the other benzene ring is at the p-position with respect to the bonding position of OH. (Hereinafter, also referred to as “о, p-form”); a compound in which the bonding position of X on one benzene ring and the bonding position of X on the other benzene ring are each in the о position with respect to the bonding position of OH (hereinafter referred to as о, , "О, о'- body").
For example, when X is a group (methylene group) represented by the above formula (2), p, p'-form, о, p-form, о, о'-form are represented by the following formula (1a), It is represented by the following formula (1b) and the following formula (1c).

The isomer mixture contains 50 to 90% of p, p'-isomer, 10 to 50% of о, p-isomer, and 0 to 20% of о, о'-isomer based on the total mass of the isomer mixture. Is preferred. When the ratio of each of the p, p'-form, о, p-form and о, о'-form is within the above range, the workability and the solvent solubility of the polymer using the isomer mixture of compound 1 are more improved. Excellent.
The ratio (composition ratio) of the isomers constituting the isomer mixture is measured by ¹³ C-NMR (nuclear magnetic resonance analysis). Further,% of the composition is mol%.

  When X is a group represented by the formula (2), the isomer mixture has a p, p'-form of 50 to 80% and an о, p-form of 15 to 80% based on the total mass of the isomer mixture. More preferably, it contains 40%, 1 to 10% of о, о'-form, 55 to 75% of p, p'-form, 20 to 35% of о, p-form, and о, о'-form. More preferably, the content is 2 to 8%.

  When X is a group represented by the above formula (3), the isomer mixture has a p, p'-form of 50 to 85% and an о, p-form of 15 to 85% based on the total mass of the isomer mixture. More preferably, it contains 35%, more preferably 55 to 80% of p, p'-form and 20 to 30% of o, p-form.

The isomer mixture of compound 1 can be produced, for example, by the following method.
A group consisting of a compound represented by the following formula (11) (hereinafter also referred to as “salicylaldehydes”), formaldehyde and a compound represented by the following formula (13) (hereinafter also referred to as “xylylenes”). A method comprising reacting a cross-linking agent selected from the group consisting of: orthophosphoric acid in the presence of orthophosphoric acid and removing the orthophosphoric acid from the obtained reaction product.

In the formula (11), R ¹ , R ² and R ³ are as defined above.
In the formula (13), Y ¹ and Y ² each independently represent an alkoxy group having 1 to 4 carbon atoms or a halogen atom. The alkoxy group may be linear or branched. Examples of the halogen atom include a chlorine atom and a bromine atom.

  As salicylaldehydes, salicylaldehyde (also known as 2-hydroxybenzaldehyde) is preferable because the raw materials remaining after the reaction can be easily removed and recovered.

  Examples of xylylenes include bis (alkoxymethyl) xylene 4,4′-form, 2,2′-form, 2,4-form, bis (methyl halide) xylene 4,4′-form, 2,2 '-Body, 2,4-body and the like. Among these, the 4,4'-form of bis (alkoxymethyl) xylene is preferred because it is relatively inexpensive and has good reactivity with salicylaldehydes.

  When salicylaldehydes and a cross-linking agent are reacted in the presence of orthophosphoric acid, two molecules of salicylaldehydes are cross-linked by the cross-linking agent, and an isomer mixture of compound 1 is generated. When formaldehyde is used as a cross-linking agent, X of compound 1 is a group represented by the above formula (2). When xylylenes are used as the cross-linking agent, X of the compound 1 is a group represented by the formula (3).

  Orthophosphoric acid functions as a catalyst in the reaction between salicylaldehydes and a crosslinking agent. When orthophosphoric acid is used as a catalyst, the compound 1 produced and the crosslinking agent can be prevented from reacting with each other to produce a high molecular weight by-product, as compared with the case where another acid catalyst is used. Since salicylaldehydes can be selectively reacted, the yield is improved.

The reaction between the salicylaldehydes and the crosslinking agent may be performed in the presence of water.
Water may be added alone to the reaction system, or may be mixed with a crosslinking agent or orthophosphoric acid in advance and added to the reaction system in the form of an aqueous solution of a crosslinking agent or an aqueous solution of orthophosphoric acid.

  Formaldehyde may be either an aqueous solution or a solid. The concentration of formaldehyde in the aqueous solution may be, for example, 30 to 50% by mass (50% by mass, 37% by mass, etc.). The solid formaldehyde concentration may be, for example, 70-92% by mass (86% by mass, 92% by mass, etc.). The smaller the amount of water, the faster the reaction rate and the higher the yield. Therefore, 92% by mass formaldehyde is preferred.

The molar ratio of the crosslinking agent to the salicylaldehyde (crosslinking agent / salicylaldehyde) is preferably from 0.05 to 0.80, more preferably from 0.20 to 0.60.
Therefore, the amount of the crosslinking agent is preferably from 0.10 to 1.60 mol, more preferably from 0.40 to 1.20 mol, per 2 mol of salicylaldehydes.
If the ratio of the crosslinking agent to salicylaldehydes is too low, the remaining salicylaldehydes will increase and the yield will decrease. If the ratio of the cross-linking agent is too high, a large amount of high molecular weight products will be by-produced, and the yield of the isomer mixture of compound 1 will decrease.

  The amount of orthophosphoric acid is preferably from 1.0 to 30.0% by mass, more preferably from 5.0 to 15.0% by mass, based on salicylaldehydes. If the amount of orthophosphoric acid is larger than the upper limit of this range, the formyl group of salicylaldehyde will react, and the desired product may not be obtained. If the amount of orthophosphoric acid is less than the lower limit of this range, the reaction rate will be slow and unreacted crosslinking agent may remain.

The temperature at which the salicylaldehyde is reacted with the crosslinking agent (reaction temperature) is preferably from 50 to 200 ° C, more preferably from 90 to 180 ° C. If the reaction temperature is too low, the reaction may not proceed. If the reaction temperature is too high, the formyl groups of salicylaldehydes will react, and the desired product may not be obtained.
The time (reaction time) for reacting the salicylaldehyde with the crosslinking agent may be, for example, 1 to 30 hours.

  The reaction product obtained by reacting the salicylaldehyde with the crosslinking agent typically contains other components other than the mixture of isomers of compound 1. Other components include unreacted products of salicylaldehydes and cross-linking agents, and high-molecular-weight by-products. Examples of the high molecular weight compound include those in which three or more salicylaldehydes are bonded via X.

By removing orthophosphoric acid from the obtained reaction product after reacting the salicylaldehydes with the crosslinking agent, the generated compounds 1 can further react with each other, and a decrease in the purity of the compound 1 can be suppressed.
Examples of the method for removing orthophosphoric acid include a method in which a base is added to the reaction product to neutralize orthophosphoric acid, and then the reaction product is washed with water (to remove orthophosphate). The base only needs to be capable of neutralizing orthophosphoric acid, and examples thereof include triethylamine, sodium hydroxide, and potassium hydroxide.

After the orthophosphoric acid is removed, at least a part of unreacted substances is removed from the reaction product, if necessary. Thereby, the content of the isomer mixture of compound 1 can be increased.
As a method of removing at least a part of the unreacted substance, for example, a method of concentrating a reaction product can be mentioned. Salicylaldehydes, formaldehyde, and xylylenes are volatilized when the reaction product is concentrated and are removed from the reaction product. Concentration can be performed by a conventional method.
When the reaction product contains water, at least a portion of water can also be removed (dehydrated) from the reaction product by concentration.

  After removing at least a part of the unreacted substances as described above, it is preferable to further distill the reaction product to recover the evaporated components. When the reaction product is distilled, the mixture of isomers of compound 1 evaporates and distills out of the evaporator, while the high molecular weight product does not evaporate and becomes a bottom component. Therefore, the isomer mixture of compound 1 and the high molecular weight compound can be separated by distillation, and the content (purity) of the isomer mixture of compound 1 can be increased.

  Distillation methods include vacuum distillation, molecular distillation, steam distillation and the like. Among them, vacuum distillation is preferable in that compound 1 can be obtained with high purity, and thin film distillation is preferable in that compound 1 can be obtained in high yield.

  The distillation temperature (heating medium temperature) of the thin film distillation is preferably from 200 to 300 ° C, more preferably from 210 to 270 ° C. If the distillation temperature is too low, the isomer mixture of compound 1 will not evaporate, and the yield will decrease. If it is too high, impurities will evaporate, and the content of the isomer mixture of compound 1 in the evaporating component will decrease. descend.

  The degree of vacuum in the thin film distillation is preferably 20 mmHg or less, more preferably 10 mmHg or less. If the vacuum is too low, the isomer mixture of compound 1 will not be distilled. The degree of vacuum may be 0 mmHg, but if the degree of vacuum is too high, impurities are distilled off, and the content of the isomer mixture of compound 1 in the evaporating component may be reduced. Is preferred.

  The purity of the isomer mixture of compound 1 is preferably 80 area% or more, more preferably 85 area% or more, as the ratio of the peak area of the isomer mixture of compound 1 to the total peak area measured by gel permeation chromatography (GPC). Preferably, 90 area% or more is more preferable, 95 area% is particularly preferable, and 99 area% or more is most preferable. The upper limit of the content of the isomer mixture of compound 1 is not particularly limited, and may be 100 area%.

Since the ultraviolet absorbent of the present invention described above is made of Compound 1, it has excellent ultraviolet absorption at a wavelength of 300 nm to 400 nm. Further, it can absorb ultraviolet rays in a wide wavelength range including a wavelength of 300 nm to 400 nm.
In particular, when the ultraviolet absorber of the present invention comprises a mixture of isomers of Compound 1, the ultraviolet absorber of the present invention has excellent solvent solubility. Therefore, it is excellent in workability such as mixing with resin.

(Ultraviolet absorbing resin composition)
The ultraviolet absorbing resin composition of the present invention contains a resin and the above-mentioned ultraviolet absorbing agent of the present invention.

The resin is not particularly limited as long as it can be mixed with the ultraviolet absorbent of the present invention, and examples thereof include a polycarbonate resin, a phenoxy resin, a polyester resin (such as polyethylene terephthalate), a polyamide resin, an acrylic resin, and a urethane resin.
As the resin, an ultraviolet absorbing resin of the present invention described later may be used.
One type of resin may be used alone, or two or more types may be used in combination.

  The content of the ultraviolet absorbent of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the resin. If the content of the ultraviolet absorber is too small, a sufficient ultraviolet absorbing effect may not be exhibited, and if the content of the ultraviolet absorber is too large, elution or bleed-out of the ultraviolet absorber may be caused.

The ultraviolet absorbent resin composition of the present invention may further contain, if necessary, other components other than the resin and the ultraviolet absorbent of the present invention.
Other components include, for example, ultraviolet absorbers other than the ultraviolet absorber of the present invention, antioxidants, light stabilizers and the like.

The ultraviolet absorbent resin composition of the present invention can be molded into a molded article by a known molding method.
Examples of the molded body include a film and a resin plate.
Examples of the molding method include a method in which the ultraviolet absorbent resin composition of the present invention is dissolved in a solvent, the obtained varnish is formed into a film, and the film is dried.

Since the ultraviolet absorbent resin composition of the present invention described above contains the ultraviolet absorbent of the present invention, it has excellent ultraviolet absorbance at a wavelength of 300 nm to 400 nm. Further, it can absorb ultraviolet rays in a wide wavelength range including a wavelength of 300 nm to 400 nm.
In particular, when the ultraviolet absorbent of the present invention comprises a mixture of isomers of compound 1, the ultraviolet absorbent of the present invention has excellent solvent solubility, and therefore, the ultraviolet absorbent resin composition of the present invention is easily dissolved in a solvent. Can be varnished.

(UV absorbing resin)
The ultraviolet absorbing resin of the present invention comprises a polymer of a monomer component containing Compound 1 described above (hereinafter, also referred to as “polymer I”). Polymer I contains a structure derived from Compound 1. The polymer I constituting the ultraviolet absorbing resin of the present invention may be one type or two or more types.

The monomer component may consist of only the compound 1 or may further contain another monomer copolymerizable with the compound 1.
The compound 1 constituting the monomer component may be one kind or two or more kinds.

Preferably, the monomer component comprises a mixture of isomers of compound 1. As described above, the isomer mixture of Compound 1 contains Compound 1 as a mixture of a plurality of isomers, and therefore has lower crystallinity and excellent solvent solubility than a single Compound 1. Therefore, operations such as polymerization and modification can be easily performed as a solution, and the workability is excellent. Further, the polymer of the monomer component containing the isomer mixture of compound 1 is also excellent in solvent solubility, and it is easy to increase the molecular weight of the polymer and to form a varnish.
The isomer mixture of compound 1 may be used alone or in combination of two or more different in any one or more of R ¹ , R ² , R ³ and X.

The other monomer may be any as long as it can be copolymerized with the compound 1, and can be appropriately selected according to the type of the polymer I.
Examples of the type of the polymer I include a polycarbonate resin, a phenoxy resin, and a urethane resin.
When the polymer I is a polycarbonate resin, other monomers include other diol compounds other than the compound 1. Examples of other diol compounds include bisphenol compounds such as bisphenol A and bisphenol F.
When the polymer I is a phenoxy resin, examples of the other monomer include a bifunctional epoxy compound such as a bisphenol A epoxy resin and a bisphenol F epoxy resin. If necessary, another diol compound may be copolymerized.

  The ratio of compound 1 to the total molar amount of compound 1 and another monomer is preferably 0.01 to 100 mol%, more preferably 0.5 to 10 mol%, and even more preferably 0.2 to 5 mol%. If the ratio of the compound 1 is too low, the effect of absorbing ultraviolet light may be insufficient, and if the ratio is too high, there is a concern that the coloring or the strength derived from the compound 1 may be reduced.

The polymer I can be produced by polymerizing a monomer component containing the compound 1. As the polymerization method, a known polymerization method can be adopted.
Hereinafter, a method for producing the polymer I will be described by taking as an example a case where the polymer I is a polycarbonate resin and a case where the polymer I is a phenoxy resin.

<Polycarbonate resin>
The polycarbonate resin can be produced by an ordinary method, for example, by a method of reacting a diester carbonate or phosgene with a diol component containing the compound 1.

  Examples of the diester carbonate include dialkyl carbonates (preferably having an alkyl group having 1 to 4 carbon atoms) such as dimethyl carbonate and diethyl carbonate, alkylene carbonates having 1 to 4 carbon atoms (for example, ethylene carbonate), diphenyl carbonate and the like. Can be As the carbonic acid diester, one type may be used alone, or two or more types may be used in combination. Diphenyl carbonate is preferred from the viewpoint of good reactivity with the diol component, relatively low cost, and easy handling.

The diol component contains the compound 1 and may further contain another diol compound as necessary.
The other diol compound is not particularly limited as long as the reaction proceeds, and bisphenol A and bisphenol F are preferable because they are relatively inexpensive and easy to handle. Other diol compounds may be used alone or in combination of two or more.
The ratio of the compound 1 to the total molar amount of all diol components is preferably from 0.01 to 100 mol%, more preferably from 0.5 to 10.0 mol%, even more preferably from 0.2 to 5 mol%.

  The molar ratio between the carbonic acid diester or phosgene and the diol component (carbonic acid diester or phosgene / diol component) is preferably 0.80 to 1.20, and more preferably 0.95 to 1.05. If the molar ratio is too low or too high, the amount of residual monomer increases, and the performance as a polycarbonate resin may be impaired.

  The reaction temperature at the time of reacting the carbonic acid diester or phosgene with the diol component is preferably from 130 to 300 ° C, more preferably from 200 to 260 ° C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction.

The diester carbonate or phosgene is usually reacted with the diol component in the presence of a catalyst.
The catalyst is not particularly limited as long as the reaction proceeds. For example, sodium hydroxide, potassium hydroxide, magnesium metal, an alkyl zinc compound (such as di-n-butyl zinc), lithium hydroxide, lithium acetate, and titanium ester (tetraester) -N-butyl titanate, etc.), zinc oxide, lead oxide, manganese dioxide, tetraalkyl orthotitanate, zinc acetate, antimony oxide, germanium oxide, alkoxide (potassium-t-butoxide, sodium methoxide, etc.), alkali metal (lithium, Sodium), alkali metal hydrides (such as lithium hydride and sodium hydride), alkali metal hydroxides (such as lithium hydroxide and sodium hydroxide), and metal halides. One type of catalyst may be used alone, or two or more types may be used in combination.

  The amount of the catalyst to be used is preferably 0.00001 to 1.0% by mass, more preferably 0.0001 to 0.1% by mass, based on all the raw material compounds (total of the diester carbonate or phosgene and the diol component). If the amount used is higher than the upper limit of this range, the resulting polycarbonate resin may be turbid.If the amount is lower than the lower limit of this range, the polymerization rate will be low, and the polycarbonate having a high degree of polymerization will have a low polymerization rate. Resin may not be obtained.

<Phenoxy resin>
The phenoxy resin can be produced by an ordinary method, for example, by a method of reacting a bifunctional epoxy compound with a diol component containing compound 1.

  The bifunctional epoxy compound is not particularly limited as long as the reaction proceeds, and bisphenol A-type epoxy resin and bisphenol F-type epoxy resin are preferable in that they are relatively inexpensive and easy to handle. One of the bifunctional epoxy compounds may be used alone, or two or more of them may be used in combination.

The diol component contains the compound 1 and may further contain another diol compound as necessary.
The other diol compound is not particularly limited as long as the reaction proceeds, and bisphenol A and bisphenol F are preferable because they are relatively inexpensive and easy to handle. Other diol compounds may be used alone or in combination of two or more.
The ratio of compound 1 to the total molar amount of all diol components is preferably 0.01 to 100 mol%, more preferably 0.2 to 50 mol%.

  The molar ratio between the bifunctional epoxy compound and the diol component (bifunctional epoxy compound / diol component) is preferably from 0.80 to 1.20, and more preferably from 0.95 to 1.05. If the molar ratio is too low or too high, the amount of residual monomer increases, and the performance as a phenoxy resin may be impaired.

  The reaction temperature when reacting the bifunctional epoxy compound with the diol component is preferably from 60 to 200C, more preferably from 80 to 180C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction.

The bifunctional epoxy compound and the diol component are usually reacted in the presence of a catalyst.
The catalyst is not particularly limited as long as the reaction proceeds. For example, triphenylphosphine, diazabicycloundecene, sodium hydroxide, potassium hydroxide, magnesium metal, an alkyl zinc compound (such as di-n-butyl zinc), water Lithium oxide, lithium acetate, titanium ester (tetra-n-butyl titanate, etc.), zinc oxide, lead oxide, manganese dioxide, tetraalkyl orthotitanate, zinc acetate, antimony oxide, germanium oxide, alkoxide (potassium-t-butoxide, sodium) Methoxide), alkali metals (such as lithium and sodium), alkali metal hydrides (such as lithium hydride and sodium hydride), alkali metal hydroxides (such as lithium hydroxide and sodium hydroxide), and metal halides. No. One type of catalyst may be used alone, or two or more types may be used in combination.

  The amount of the catalyst to be used is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass, based on all the raw material compounds (the total of the bifunctional epoxy compound and the diol component). If the amount used is larger than the upper limit of this range, turbidity may occur in the produced phenoxy resin, and if it is smaller than the lower limit of this range, the polymerization rate is slowed down and the phenoxy resin having a high degree of polymerization is obtained. Resin may not be obtained.

The ultraviolet absorbing resin of the present invention can be molded into a molded article by a known molding method.
Examples of the molded body include a film and a resin plate.
Examples of the molding method include a method in which the ultraviolet absorbing resin of the present invention is dissolved in a solvent, the obtained varnish is formed into a film, and the film is dried.

The ultraviolet absorbing resin of the present invention described above comprises a polymer I which is a polymer of a monomer component containing compound 1, and has a structure derived from compound 1, so that the ultraviolet absorbing resin having a wavelength of 300 nm to 400 nm is used. Excellent. Ultraviolet light in a wide wavelength range including a wavelength of 300 nm to 400 nm can be absorbed.
Further, in the ultraviolet absorbing resin of the present invention, since Compound 1 is incorporated in the molecule of polymer I, there is no concern about elution or bleed-out of Compound 1, and the ultraviolet absorbing property is hardly deteriorated.
In particular, when the monomer component contains a mixture of isomers of compound 1, the ultraviolet absorbing resin of the present invention has excellent solvent solubility, and is easily converted to a high molecular weight or varnished. The varnish containing the high molecular weight polymer I has excellent film-forming properties.
In addition, many of the conventional ultraviolet absorbers are of a mixed type used by being added to a resin, and there is a concern of elution from the resin and bleed-out. There is also a copolymer type that is used by copolymerizing with other monomers, but the conventional copolymer type ultraviolet absorber is an acrylate type, which is a copolymer type ultraviolet absorber that utilizes hydroxyl groups such as polycarbonate resin and phenoxy resin. No agents have been reported.

〔varnish〕
The varnish of the present invention includes the above-described ultraviolet absorbing resin or the ultraviolet absorbing resin composition of the present invention, and a solvent.

  As the solvent, any solvent may be used as long as it can dissolve the ultraviolet absorbing resin or the ultraviolet absorbing resin composition of the present invention, for example, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methanol, ethanol, butanol, isopropyl alcohol and the like. Alcohols, toluene, xylene and the like. One kind of the solvent may be used alone, or two or more kinds may be used in combination.

The content of the solvent is appropriately set according to the solid content concentration of the varnish.
The solid content concentration of the varnish varies depending on the use, but is preferably 5 to 50% by mass, more preferably 20 to 35% by mass.
In addition, the solid content concentration of the varnish is a ratio of the mass of the varnish excluding the solvent to the total mass of the varnish.

The varnish of the present invention can further include other components as needed, as long as the effects of the present invention are not impaired.
Other components include, for example, inorganic fillers, flame retardants, waxes, light stabilizers, antioxidants, and the like.

[UV absorbing film]
The ultraviolet absorbing film of the present invention contains the above-mentioned ultraviolet absorbing resin or ultraviolet absorbing resin composition of the present invention.

  The ultraviolet-absorbing film of the present invention may further contain other components, if necessary, as long as the effects of the present invention are not impaired. As the other components, those similar to the above can be mentioned.

  The thickness of the ultraviolet absorbing film of the present invention is not particularly limited, but is, for example, 10 to 50 μm.

The ultraviolet absorbing film of the present invention can be produced, for example, by forming a film composed of the varnish of the present invention and drying the film.
Examples of the film forming method include a method of applying the varnish of the present invention on a substrate. As an application method, for example, a casting method and the like can be mentioned.
By drying the film made of varnish, the solvent is removed and an ultraviolet absorbing film is formed. The temperature during drying of the film is preferably from 40 to 200 ° C, more preferably from 100 to 150 ° C.
When the varnish of the present invention is applied on a substrate to form a film, an ultraviolet absorbing film is formed on the substrate, and after drying, the formed ultraviolet absorbing film is peeled off from the substrate to absorb ultraviolet light. To obtain a functional film.

The ultraviolet-absorbing film of the present invention contains the ultraviolet-absorbing resin or the ultraviolet-absorbing resin composition of the present invention, and thus is excellent in ultraviolet absorption at a wavelength of 300 nm to 400 nm. Ultraviolet light in a wide wavelength range including a wavelength of 300 nm to 400 nm can be absorbed.
In particular, when the ultraviolet absorbent resin of the present invention is contained, since Compound 1 is incorporated in the molecule of polymer I, there is no fear of elution or bleed out of Compound 1, and the ultraviolet absorbability is hardly deteriorated.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In each of the following examples, “parts” means “parts by mass” unless otherwise specified. "Purity" indicates the ratio (area%) of the peak area of the isomer mixture of compound 1 to the total peak area measured by GPC.

(Measuring method)
The measuring method in each example is as follows.
<Purity, monomer consumption rate>
The measurement was performed using the following GPC apparatus and column.
GPC measuring device: HLC8120GPC manufactured by Tosoh Corporation.
Column: TSKgel G3000H + G2000H + G2000H, manufactured by Tosoh Corporation.

<Composition ratio>
It measured using the following NMR apparatus.
NMR measuring device: JEOL RESONANCE made ECZ500R ¹³ C measurement mode.
When X in the formula (1) is a group represented by the formula (2), the structures of the p, p′-form, о, p-form, and о, о'-form are as described above. . When X in the above formula (1) is a group represented by the above formula (3), a compound having a structure represented by the following formula (1d) is converted into a p, p′-form compound by the following formula (1e). The composition ratio was determined using the compound having the structure represented as о, p-form.

<Weight average molecular weight (Mw) of polycarbonate resin>
The weight average molecular weight (Mw) of the polycarbonate resin was measured by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene.
GPC measuring device: HLC8120GPC manufactured by Tosoh Corporation.
Column: TSKgel G3000H + G2000H + G2000H, manufactured by Tosoh Corporation.

<Weight average molecular weight (Mw) of phenoxy resin>
The weight average molecular weight (Mw) of the phenoxy resin was measured in terms of standard polystyrene by gel permeation chromatography (GPC) under the following conditions.
GPC measuring device: HLC8120GPC manufactured by Tosoh Corporation.
Column: TSKgel G3000H + G2000H + G2000H, manufactured by Tosoh Corporation.

<Softening point>
It was measured according to JIS K 6910.

<Ultraviolet (UV) transmittance>
Spectrophotometer: Using U-3900H manufactured by HITACHI, measurement mode: Measured with a wavelength scan of 900 nm to 250 nm.

(Synthesis Example 1: Synthesis of methylenebissalicylaldehyde)
244.2 g (2.0 mol) of 2-hydroxybenzaldehyde, 19.6 g (0.60 mol) of 92% by mass formaldehyde, 85% by mass of orthophosphoric acid were placed in a 1 L reaction vessel equipped with a thermometer, a stirrer, and a condenser. After 24.4 g of an aqueous solution was charged and the temperature was raised to 100 ° C., the reaction was performed for 2 hours. Next, after the temperature was raised to 140 ° C. while performing dehydration, the reaction was performed for 3 hours. After cooling the reaction solution to 80 ° C., orthophosphoric acid was neutralized with triethylamine. Thereafter, the resultant was washed with water and concentrated to obtain a crude methylenebissalicylaldehyde.
When GPC was performed on the reaction product after the neutralization, the purity of methylenebissalicylaldehyde was 75.4%, and the consumption rate of the 2-hydroxybenzaldehyde monomer was 65.78%.
When the composition ratio of the isomer mixture was measured by ¹³ C-NMR for the crude methylenebissalicylaldehyde, the composition ratio was 69.58% of p, p′-methylenebissalicylaldehyde, о, p-methylenebissalicylaldehyde 27 0.06% and 3.36% of о, о'-methylenebissalicylaldehyde.

A thin-film evaporator (heating surface 0.068 m ² , internal condenser surface 0.019 m ² , with glass-containing polytetrafluoroethylene (PTFE) wiper) was passed through a heating jacket at 220 ° C., and 150 μm was passed through the internal condenser. C., and the system was operated at a degree of vacuum of 1 to 5 mmHg at a rotor rotation speed of 350 rpm. Crude methylene bissalicylaldehyde was continuously supplied at 600 g / hr for 1 hour to the thin film still in that state, and the evaporating component and the bottom component were continuously extracted, and methylene bissalicylaldehyde was evaporated as the evaporating component (distillate). I got
GPC of methylenebissalicylaldehyde revealed that the purity of methylenebissalicylaldehyde was 99.45%. When the composition ratio of the isomer mixture was measured by ¹³ C-NMR, the composition ratio was 68.48% for p, p′-methylenebissalicylaldehyde, 28.36% for о, p-methylenebissalicylaldehyde, о, о'-methylenebissalicylaldehyde was 3.16%.

(Synthesis Example 2: Synthesis of xylylenebissalicylaldehyde)
244.2 g (2.0 mol) of 2-hydroxybenzaldehyde and 24.4 g of an 85% by mass orthophosphoric acid aqueous solution were charged into a 1 L reaction vessel equipped with a thermometer, a stirrer, and a condenser, and the temperature was raised to 160 ° C. Next, 132.8 g (0.8 mol) of para-xylene glycol dimethyl ether was added dropwise over 3 hours. Methanol by-produced was removed outside the system. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 160 ° C., and after confirming that the distillation of by-produced methanol was completed, the system was cooled to 80 ° C. The orthophosphoric acid was then neutralized with triethylamine. Thereafter, the resultant was washed with water and concentrated to obtain crude xylylenebissalicylaldehyde.
The reaction product after neutralization was subjected to GPC. As a result, the purity of xylylenebissalicylaldehyde was 82.37%, and the consumption rate of the 2-hydroxybenzaldehyde monomer was 93.35%.
When the composition ratio of the isomer mixture was measured by ¹³ C-NMR for the crude xylylenebissalicylaldehyde, the composition ratio was 73.43% for p, p′-xylylenebissalicylaldehyde, о, p-xylylenebis Salicylaldehyde was 26.57%.

A thin-film still (heating surface 0.068 m ² , internal condenser surface 0.019 m ² , with glass-containing PTFE wiper) is passed through a heating jacket at 265 ° C. and a heating medium at 150 ° C. is passed through the internal condenser. The operation was performed at a rotor speed of 350 rpm and a degree of vacuum of 1 to 5 mmHg. Crude xylylenebissalicylaldehyde was continuously supplied at 600 g / hr for 1 hour to the thin film distillation apparatus in that state, and evaporated components and bottom components were continuously extracted, and xylylenebis was distilled off as an evaporated component (distillate). Salicylaldehyde was obtained.
When GPC was performed on xylylenebissalicylaldehyde, the purity of xylylenebissalicylaldehyde was 99.81%. When the composition ratio of the isomer mixture was measured by ¹³ C-NMR, the composition ratio was 71.41% for p, p′-xylylenebissalicylaldehyde and 28.59 for о, p-xylylenebissalicylaldehyde. %Met.

(Comparative Example 1)
228.0 g (1.000 mol) of bisphenol A and 203.5 g (0.950 mol) of diphenyl carbonate were charged into a 1-L reaction vessel equipped with a thermometer, a stirrer, and a condenser, and the temperature was raised to 120 ° C. Then, after adding 0.1 g of a 5% aqueous solution of tetramethylammonium hydroxide, the temperature was raised to 180 ° C., and the reaction was carried out at normal pressure for 1 hour. Then, the pressure was slowly reduced to 10 mmHg while maintaining the temperature at 180 ° C., and the reaction was continued while removing by-product phenol. Next, the temperature was raised to 230 ° C. under reduced pressure, and the reaction was performed under reduced pressure for 2 hours to obtain a polycarbonate resin. The softening point of this polycarbonate resin was 122.5 ° C., and the weight average molecular weight (Mw) by GPC was 9121.
The obtained polycarbonate resin was dissolved in tetrahydrofuran to a concentration of 10% by mass to obtain a varnish.

(Example 1)
The polycarbonate resin obtained in Comparative Example 1 was dissolved in tetrahydrofuran so as to have a concentration of 10% by mass, and the methylene bissalicylaldehyde obtained in Synthesis Example 1 was added thereto in an amount of 0.3 part based on 100 parts of the polycarbonate resin. And methylenebissalicylaldehyde was dissolved at room temperature to obtain a varnish.

(Example 2)
A varnish was obtained in the same manner as in Example 1 except that the addition amount of methylenebissalicylaldehyde was changed to 1.0 part with respect to 100 parts of the polycarbonate resin.

(Example 3)
227.4 g (0.997 mol) of bisphenol A, 0.72 g (0.003 mol) of methylenebissalicylaldehyde obtained in Synthesis Example 1, and diphenyl carbonate in a 1-L reaction vessel equipped with a thermometer, a stirrer, and a condenser. 203.5 g (0.950 mol) was charged and the temperature was raised to 120 ° C. Then, after adding 0.1 g of a 5% aqueous solution of tetramethylammonium hydroxide, the temperature was raised to 180 ° C., and the reaction was carried out at normal pressure for 1 hour. Then, the pressure was slowly reduced to 10 mmHg while maintaining the temperature at 180 ° C., and the reaction was continued while removing by-product phenol. Next, the temperature was raised to 230 ° C. under reduced pressure, and the reaction was performed under reduced pressure for 2 hours to obtain a polycarbonate resin. The softening point of this polycarbonate resin was 121.7 ° C., and the weight average molecular weight (Mw) by GPC was 9021.

(Example 4)
225.8 g (0.990 mol) of bisphenol A, 2.42 g (0.010 mol) of methylenebissalicylaldehyde obtained in Synthesis Example 1, and diphenyl carbonate were placed in a 1-L reaction vessel equipped with a thermometer, a stirrer, and a condenser. 203.5 g (0.950 mol) was charged and the temperature was raised to 120 ° C. Then, after adding 0.1 g of a 5% aqueous solution of tetramethylammonium hydroxide, the temperature was raised to 180 ° C., and the reaction was carried out at normal pressure for 1 hour. Then, the pressure was slowly reduced to 10 mmHg while maintaining the temperature at 180 ° C., and the reaction was continued while removing by-product phenol. Next, the temperature was raised to 230 ° C. under reduced pressure, and the reaction was performed under reduced pressure for 2 hours to obtain a polycarbonate resin. The softening point of this polycarbonate resin was 121.7 ° C., and the weight average molecular weight (Mw) by GPC was 8985.

(Comparative Example 2)
190.0 g (0.5 mol) of bisphenol A type epoxy resin, 116.3 g (0.51 mol) of bisphenol A, and 320.6 g of ethyl cellosolve were charged into a 1 L reaction vessel equipped with a thermometer, a stirrer, and a cooling tube. The temperature was raised to 80 ° C. Next, 0.12 g of diazabicycloundecene was added, and the mixture was reacted at 110 ° C. for 2 hours. Next, the temperature was raised to 160 ° C., the reaction was continued for 5 hours, and the mixture was cooled to obtain an ethyl cellosolve varnish of a phenoxy resin. The weight average molecular weight (Mw) of this phenoxy resin measured by GPC was 5,0061.

(Example 5)
190.0 g (0.5 mol) of bisphenol A type epoxy resin and 130.6 g (0.51 mol) of methylenebissalicylaldehyde obtained in Synthesis Example 1 were placed in a 1 L reaction vessel equipped with a thermometer, a stirrer, and a condenser. ) And 320.6 g of ethyl cellosolve, and the temperature was raised to 80 ° C. Next, 0.12 g of diazabicycloundecene was added, and the mixture was reacted at 110 ° C. for 2 hours. Then, the temperature was raised to 160 ° C., the reaction was continued for 5 hours, and the mixture was cooled to obtain an ethyl cellosolve varnish of a phenoxy resin. The weight average molecular weight (Mw) of this phenoxy resin by GPC was 32589.

(UV absorption evaluation)
<1. UV Absorbency of UV Absorber (Monomer)>
A solution obtained by dissolving methylene bissalicylaldehyde obtained in Synthesis Example 1, xylylene bissalicylaldehyde obtained in Synthesis Example 2, and bisphenol A as a comparative example in tetrahydrofuran so as to have a concentration of 10% by mass. Was measured for transmittance with a spectrophotometer. The results are shown in FIG. The horizontal axis in FIG. 1 is the wavelength (nm) and the vertical axis is the transmittance (% T), which is the same in FIGS.
As shown in FIG. 1, the methylene bissalicylaldehyde obtained in Synthesis Example 1 and the xylylenebissalicylaldehyde obtained in Synthesis Example 2 have lower transmittance at a wavelength of 300 nm to 400 nm than bisphenol A. Excellent UV absorption.

<2. UV absorption when UV absorber is added to resin>
The transmittance of each of the varnishes obtained in Comparative Example 1 and Examples 1 and 2 was measured with a spectrophotometer. The results are shown in FIG.
As shown in FIG. 2, the varnishes obtained in Examples 1 and 2 had lower transmittance at wavelengths of 300 nm to 400 nm than the varnishes obtained in Comparative Example 1, and were excellent in UV absorption in this wavelength region.

<3. UV Absorption of Polycarbonate Resin Copolymerized with UV Absorber>
The polycarbonate resins obtained in Comparative Example 1 and Examples 3 and 4 were each dissolved in tetrahydrofuran so that the concentration became 10% by mass, and the transmittance was measured with a spectrophotometer. The results are shown in FIG.
As shown in FIG. 3, the polycarbonate resin obtained in Examples 3 and 4 has a lower transmittance at a wavelength of 300 nm to 400 nm than the polycarbonate resin obtained in Comparative Example 1, and is excellent in UV absorption in this wavelength region. Was.

<4. UV Absorption of Phenoxy Resin Copolymerized with UV Absorber>
Each of the ethyl cellosolve varnishes obtained in Comparative Example 2 and Example 5 was applied on a polyethylene terephthalate (PET) film, and pre-dried in an oven at 80 ° C. for 1 hour. Next, the temperature was raised to 180 ° C. and dried for 2 hours to form a phenoxy resin film. Thereafter, the phenoxy resin film was peeled off from the PET film to obtain a phenoxy resin film. The transmittance of the obtained phenoxy resin film was measured with a spectrophotometer. FIG. 4 shows the results.
As shown in FIG. 4, the phenoxy resin obtained in Example 5 had a lower transmittance at a wavelength of 300 nm to 400 nm than the phenoxy resin obtained in Comparative Example 2, and was excellent in UV absorption in this wavelength region.

  The isomer mixture of the compound 1 has an ultraviolet absorbing property in a wide wavelength range including a wavelength of 300 nm to 400 nm. Further, it is copolymerizable with various resin raw materials, and by copolymerizing the isomer mixture of the compound 1 and the resin raw material, it is possible to obtain an ultraviolet absorbent resin in which elution of an ultraviolet absorbent and bleed out are suppressed. . Therefore, the isomer mixture of the compound 1 is extremely useful as an ultraviolet absorber or a raw material of an ultraviolet absorbing resin.

Claims (8)

An ultraviolet absorber comprising a compound represented by the following formula (1).

(Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and X represents the following formula: A group represented by (2) or a group represented by the following formula (3) is shown.)

  The ultraviolet absorbent according to claim 1, comprising an isomer mixture of the compound represented by the formula (1). An ultraviolet absorbing resin comprising a polymer of a monomer component containing a compound represented by the following formula (1).

(Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and X represents the following formula: A group represented by (2) or a group represented by the following formula (3) is shown.)

  The ultraviolet absorbent resin according to claim 3, wherein the monomer component includes an isomer mixture of the compound represented by the formula (1).   An ultraviolet absorbent resin composition comprising a resin and the ultraviolet absorbent according to claim 1.   A varnish comprising the ultraviolet absorbent resin according to claim 3 or 4, or the ultraviolet absorbent resin composition according to claim 5, and a solvent.   An ultraviolet absorbing film comprising the ultraviolet absorbing resin according to claim 3 or 4 or the ultraviolet absorbing resin composition according to claim 5.   A method for producing an ultraviolet-absorbing film, comprising forming a film comprising the varnish according to claim 6 and drying the film.

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