JP7123673B2 - UV absorber, UV-absorbing resin, UV-absorbing resin composition, varnish, UV-absorbing film and method for producing the same - Google Patents

Description

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

As a method for preventing deterioration of 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 UV absorbers have insufficient UV absorption in the wavelength range of 300 nm to 400 nm.

The present invention provides an ultraviolet absorber, an ultraviolet-absorbing resin, an ultraviolet-absorbing resin composition, an ultraviolet-absorbing film and a method for producing the same, and the production of the ultraviolet-absorbing film, etc. The aim is to provide useful varnishes.

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).)

[2] The ultraviolet absorber of [1] above, which comprises an isomer mixture of the compound represented by formula (1) above.
[3] An ultraviolet-absorbing resin composed of a polymer of a monomer component containing the compound represented by the formula (1).
[4] The UV-absorbing resin of [3] above, wherein the monomer component contains an isomer mixture of the compound represented by formula (1) above.
[5] A UV-absorbing resin composition comprising a resin and the UV absorber of [1] or [2] above.
[6] A varnish containing the ultraviolet absorbing resin of [3] or [4] or the ultraviolet absorbing resin composition of [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 [6] above and drying the film.

According to the present invention, an ultraviolet absorber, an ultraviolet absorbing resin, an ultraviolet absorbing resin composition, an ultraviolet absorbing film and a method for producing the same, and the ultraviolet absorbing film, etc. A varnish useful in manufacturing 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 absorbency evaluation result when adding an ultraviolet absorber to resin. It is a graph which shows the UV absorption 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.

[Ultraviolet absorber]
The ultraviolet absorber of the present invention comprises a compound represented by the following formula (1) (hereinafter also referred to as "compound 1"). Compound 1 constituting the ultraviolet absorber of the present invention may be of one type or two or more types.

In 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. Alkyl groups and alkoxy groups may each 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 in which a hydroxyl group and a formyl group are bonded, it is excellent in ultraviolet absorption at a wavelength of 300 nm to 400 nm. In addition, it can absorb ultraviolet rays in a wide wavelength range including wavelengths of 300 nm to 400 nm.
It is considered that the reason why compound 1 is excellent in the absorption of ultraviolet rays in the wavelength region of 300 nm to 400 nm is that the benzene ring containing a hydroxyl group further contains a formyl group.
Moreover, since the compound 1 has a functional group such as a hydroxyl group and a formyl group, the functional group can be used to introduce a structure derived from the compound 1 into the resin. For example, a monomer component containing compound 1 can be polymerized to form a polymer, or a resin can be modified with compound 1.

The ultraviolet absorber of the present invention preferably comprises an isomer mixture 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 single compound 1. Therefore, it is possible to easily carry out operations such as polymerization and modification in the form of a solution, resulting in excellent workability.
The isomer mixture of Compound 1 constituting the ultraviolet absorber of the present invention may be one kind, or two or more kinds in which one or more of R ¹ , R ² , R ³ and X are different.

The isomeric mixture of compound 1 typically contains two or more isomers in which the bonding positions of X in the two benzene rings (OH and CHO bonded benzene rings) in formula (1) are different. Examples of such isomers include compounds in which the bonding position of X on one benzene ring and the bonding position of X on the other benzene ring are p-positions relative to the bonding position of OH (hereinafter referred to as "p,p'- (Also referred to as a compound"); a compound in which the bonding position of X on one benzene ring is the o-position with respect to the bonding position of OH, and the bonding position of X on the other benzene ring is the p-position with respect to the bonding position of OH. (Hereinafter, also referred to as “O, p-body”.); 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 at the OH position with respect to the bonding position of OH (hereinafter , Also referred to as "о,о'-body".);
For example, when X is a group (methylene group) represented by the formula (2), the p,p'-body, о,p-body, and о,о'-body 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% p,p'-isomer, 10 to 50% o,p-isomer, and 0 to 20% o,o'-isomer relative to the total mass of the isomer mixture. is preferred. If the proportions of the p,p'-isomer, о,p-isomer, and о,о'-isomer are within the above ranges, the workability and the solvent solubility of the polymer using the isomer mixture of compound 1 are improved. Excellent.
The ratio (compositional ratio) of the isomers constituting the isomer mixture is measured by ¹³ C-NMR (nuclear magnetic resonance spectroscopy). Moreover, % of composition is mol %.

When X is a group represented by the formula (2), the isomer mixture contains 50 to 80% of the p,p'-isomer and 15 to 15% of the o,p-isomer with respect to the total mass of the isomer mixture. 40%, more preferably 1 to 10% о,о'-body, 55 to 75% p,p'-body, 20 to 35% о,p-body, о,о'-body It is more preferable to contain 2 to 8%.

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

An isomeric mixture of compound 1 can be produced, for example, by the following method.
A group consisting of compounds represented by the following formula (11) (hereinafter also referred to as "salicylaldehydes"), formaldehyde and compounds represented by the following formula (13) (hereinafter also referred to as "xylylenes") and a cross-linking agent selected from , in the presence of orthophosphoric acid, and removing the orthophosphoric acid from the resulting reaction product.

In formula (11), R ¹ , R ² and R ³ are as defined above.
In formula (13), Y ¹ and Y ² each independently represent an alkoxy group having 1 to 4 carbon atoms or a halogen atom. Alkoxy groups may be straight or branched. A chlorine atom, a bromine atom, etc. are mentioned as a halogen atom.

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

Examples of xylylenes include 4,4′-, 2,2′-, and 2,4-isomers of bis(alkoxymethyl)xylene, and 4,4′-isomers and 2,2-isomers of bis(halogenated methyl)xylene. '-isomers, 2,4-isomers and the like can be mentioned. Among these, the 4,4'-form of bis(alkoxymethyl)xylene is preferable 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 produced. When formaldehyde is used as a cross-linking agent, X in compound 1 becomes a group represented by the formula (2). When xylylenes are used as the cross-linking agent, X in compound 1 becomes a group represented by the above formula (3).

Orthophosphoric acid functions as a catalyst in the reaction between salicylaldehydes and a cross-linking agent. When orthophosphoric acid is used as a catalyst, it is possible to suppress the reaction between the produced compound 1 and the cross-linking agent to produce a high molecular weight by-product, as compared with the case of using other acid catalysts. Since salicylaldehydes can be selectively reacted, the yield is improved.

The reaction of salicylaldehydes and cross-linking agents may be carried out in the presence of water.
Water may be added to the reaction system alone, or may be mixed with the cross-linking agent or orthophosphoric acid in advance and added to the reaction system in the form of an aqueous cross-linking agent solution or an aqueous orthophosphoric acid solution.

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

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

The amount of orthophosphoric acid is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 15.0% by mass, relative to salicylaldehydes. If the amount of orthophosphoric acid is more than the upper limit of this range, the formyl group of the salicylaldehyde reacts, possibly failing to obtain the desired product. If the amount of orthophosphoric acid is less than the lower limit of this range, the reaction rate will be slow, and unreacted cross-linking agent may remain.

The temperature at which the salicylaldehyde and the cross-linking agent are reacted (reaction temperature) is preferably 50 to 200°C, more preferably 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 group of the salicylaldehyde reacts, possibly failing to obtain the desired product.
The reaction time (reaction time) between the salicylaldehydes and the cross-linking agent may be, for example, 1 to 30 hours.

The reaction product obtained by reacting a salicylaldehyde with a cross-linking agent typically contains other components than the isomer mixture of Compound 1. Other components include salicylaldehydes, unreacted cross-linking agents, by-produced high molecular weight substances, and the like. Examples of high molecular weight substances include those in which three or more salicylaldehyde molecules are bonded through X.

By removing orthophosphoric acid from the resulting reaction product after reacting the salicylaldehydes with the cross-linking agent, it is possible to suppress the further reaction of the produced compounds 1 and the decrease in the purity of the compound 1.
Methods for removing orthophosphoric acid include, for example, a method of adding a base to the reaction product to neutralize the orthophosphoric acid, and then washing the reaction product with water (removing the orthophosphate). Any base can be used as long as it can neutralize orthophosphoric acid, and examples thereof include triethylamine, sodium hydroxide, potassium hydroxide and the like.

After removing the orthophosphoric acid, at least a portion of the unreacted material is removed from the reaction product, if necessary. Thereby, the content of the isomer mixture of compound 1 can be increased.
A method of removing at least part of the unreacted material includes, for example, a method of concentrating the reaction product. Salicylaldehydes, formaldehyde, and xylylenes volatilize and are removed from the reaction product when the reaction product is concentrated. Concentration can be performed by a conventional method.
If the reaction product contains water, the concentration can also remove (dehydrate) at least a portion of the water from the reaction product.

After removing at least part of the unreacted material as described above, it is preferable to further distill the reaction product to recover the vaporized component. When the reaction product is distilled, the isomer mixture of compound 1 evaporates and is distilled from the evaporator, while the high molecular weight product does not evaporate and becomes the bottom product. Therefore, distillation can separate the isomer mixture of compound 1 from the high-molecular-weight substance, and the content (purity) of the isomer mixture of compound 1 can be increased.

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

The distillation temperature (heat medium temperature) for thin film distillation is preferably 200 to 300°C, more preferably 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. descend.

The degree of vacuum in thin film distillation is preferably 20 mmHg or less, more preferably 10 mmHg or less. If the vacuum is too low, the isomeric mixture of compound 1 will not distill. The degree of vacuum may be 0 mmHg, but if the degree of vacuum is too high, even impurities may be distilled and the content of the isomer mixture of compound 1 in the evaporated components may decrease. is preferred.

The purity of the isomer mixture of compound 1 is preferably 80 area% or more, more preferably 85 area% or more, as a ratio of the peak area of the isomer mixture of compound 1 to the total peak area measured by gel permeation chromatography (GPC). It is preferably 90 area % or more, more preferably 95 area % or more, and most preferably 99 area % or more. 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 absorber of the present invention described above is composed of Compound 1, it is excellent in ultraviolet absorbability with a wavelength of 300 nm to 400 nm. In addition, it can absorb ultraviolet rays in a wide wavelength range including wavelengths of 300 nm to 400 nm.
In particular, when the UV absorber of the present invention comprises an isomer mixture of Compound 1, the UV 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 ultraviolet absorber of the present invention described above.

The resin is not particularly limited as long as it can be mixed with the ultraviolet absorber of the present invention.
As the resin, the ultraviolet absorbing resin of the present invention, which will be described later, may be used.
One of the resins may be used alone, or two or more of them may be used in combination.

The content of the ultraviolet absorber of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the resin. If the content of the UV absorber is too small, a sufficient UV absorbing effect may not be exhibited, and if the content of the UV absorber is too large, there is a concern that the UV absorber may be eluted or bleed out.

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

The UV-absorbing resin composition of the present invention can be molded into a molded article by a known molding method.
Examples of molded bodies include films and resin plates.
The molding method includes, for example, a method of dissolving the ultraviolet absorbing resin composition of the present invention in a solvent, forming the obtained varnish into a film, and drying the film.

Since the UV-absorbing resin composition of the present invention described above contains the UV-absorbing agent of the present invention, it has excellent UV-absorbing properties with a wavelength of 300 nm to 400 nm. In addition, it can absorb ultraviolet rays in a wide wavelength range including wavelengths of 300 nm to 400 nm.
In particular, when the ultraviolet absorbent of the present invention comprises an isomer mixture of compound 1, the ultraviolet absorbent of the present invention is excellent in solvent solubility, so that the ultraviolet absorbent resin composition of the present invention is easily dissolved in the solvent. can be varnished.

[Ultraviolet absorbing resin]
The UV-absorbing resin of the present invention comprises a polymer of monomer components containing compound 1 (hereinafter also referred to as "polymer I"). Polymer I contains structures derived from Compound 1. The polymer I constituting the ultraviolet absorbing resin of the present invention may be of one type or two or more types.

The monomer component may consist of Compound 1 only, or may further contain other monomers copolymerizable with Compound 1.
Compound 1 constituting the monomer component may be of one type or two or more types.

Preferably, the monomer component comprises an isomeric mixture of Compound 1. As described above, 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 single compound 1. Therefore, it is possible to easily carry out operations such as polymerization and modification in the form of a solution, resulting in excellent workability. Moreover, the polymer of the monomer component containing the isomer mixture of the compound 1 is also excellent in solvent solubility, and it is easy to increase the molecular weight of the polymer and form a varnish.
One of the isomer mixtures of Compound 1 may be used alone, or two or more of which one or more of R ¹ , R ² , R ³ and X are different may be used in combination.

Other monomers may be those that can be copolymerized with the compound 1, and can be appropriately selected according to the type of the polymer I.
Types of the polymer I include polycarbonate resins, phenoxy resins, urethane resins, and the like.
When the polymer I is a polycarbonate resin, other monomers include diol compounds other than the compound 1. Other diol compounds include bisphenol compounds such as bisphenol A and bisphenol F.
When the polymer I is a phenoxy resin, other monomers include bifunctional epoxy compounds such as bisphenol A type epoxy resins and bisphenol F type epoxy resins. If necessary, other diol compounds may be copolymerized.

The ratio of compound 1 to the total molar amount of compound 1 and other monomers is preferably 0.01 to 100 mol%, more preferably 0.5 to 10 mol%, even more preferably 0.2 to 5 mol%. If the ratio of compound 1 is too low, the ultraviolet absorption effect may become insufficient, and if the ratio is too high, there is concern about coloration derived from compound 1 and a decrease in strength.

Polymer I can be produced by polymerizing monomer components including Compound 1. A known polymerization method can be adopted as the polymerization method.
The method for producing the polymer I will be described below, taking as examples the case where the polymer I is a polycarbonate resin and the case where the polymer I is a phenoxy resin.

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

Examples of the carbonic acid diester include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate (preferably those having an alkyl group having 1 to 4 carbon atoms), alkylene carbonates having 1 to 4 carbon atoms (eg, ethylene carbonate), diphenyl carbonate, and the like. be done. Carbonic acid diesters may be used singly or in combination of two or more. As the diester carbonate, diphenyl carbonate is preferable from the viewpoints of good reactivity with the diol component, relatively low cost, and easy handling.

The diol component contains compound 1, and may further contain other diol compounds as necessary.
Other diol compounds are not particularly limited as long as the reaction proceeds, and bisphenol A and bisphenol F are preferred from the viewpoints of being relatively inexpensive and easy to handle. Other diol compounds may be used singly 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 0.5 to 10.0 mol%, even more preferably 0.2 to 5 mol%.

The molar ratio of the diester carbonate or phosgene to the diol component (diester carbonate or phosgene/diol component) is preferably 0.80 to 1.20, more preferably 0.95 to 1.05. If this molar ratio is too low or too high, a large amount of residual monomers may be present, possibly impairing the performance of the polycarbonate resin.

The reaction temperature for reacting the diester carbonate or phosgene with the diol component is preferably 130 to 300°C, more preferably 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 carbonic acid diester or phosgene 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. -n-butyl titanate, etc.), zinc oxide, lead oxide, manganese dioxide, tetraalkyl orthotitanate, zinc acetate, antimony oxide, germanium oxide, alkoxides (potassium-t-butoxide, sodium methoxide, etc.), alkali metals (lithium, sodium, etc.), alkali metal hydrides (lithium hydride, sodium hydride, etc.), alkali metal hydroxides (lithium hydroxide, sodium hydroxide, etc.), metal halides and the like. The catalyst may be used singly or in combination of two or more.

The amount of the catalyst used is preferably 0.00001 to 1.0% by mass, more preferably 0.0001 to 0.1% by mass, based on the total amount of the raw material compound (carbonic acid diester or phosgene and diol component). If the amount used is more than the upper limit of this range, turbidity may occur in the resulting polycarbonate resin. Resin may not be obtained.

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

Bifunctional epoxy compounds are not particularly limited as long as the reaction proceeds, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable from the viewpoints of being relatively inexpensive and easy to handle. The bifunctional epoxy compounds may be used singly or in combination of two or more.

The diol component contains compound 1, and may further contain other diol compounds as necessary.
Other diol compounds are not particularly limited as long as the reaction proceeds, and bisphenol A and bisphenol F are preferred from the viewpoints of being relatively inexpensive and easy to handle. Other diol compounds may be used singly 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 of the bifunctional epoxy compound to the diol component (bifunctional epoxy compound/diol component) is preferably 0.80 to 1.20, more preferably 0.95 to 1.05. If this molar ratio is too low or too high, a large amount of residual monomers may occur, which may impair the performance of the phenoxy resin.

The reaction temperature for reacting the bifunctional epoxy compound and the diol component is preferably 60 to 200.degree. C., more preferably 80 to 180.degree. 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.

A bifunctional epoxy compound and a diol component are usually reacted in the presence of a catalyst.
The catalyst is not particularly limited as long as the reaction proceeds. 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, etc.), alkali metals (lithium, sodium, etc.), alkali metal hydrides (lithium hydride, sodium hydride, etc.), alkali metal hydroxides (lithium hydroxide, sodium hydroxide, etc.), metal halides, etc. mentioned. The catalyst may be used singly or in combination of two or more.

The amount of the catalyst used is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass, based on the total amount of the raw material compound (total of the bifunctional epoxy compound and the diol component). If the amount used is more than the upper limit of this range, turbidity may occur in the phenoxy resin produced. Resin may not be obtained.

The UV-absorbing resin of the present invention can be formed into a molded article by a known molding method.
Examples of molded bodies include films and resin plates.
The molding method includes, for example, a method of dissolving the ultraviolet absorbing resin of the present invention in a solvent, forming a film from the obtained varnish, and drying the film.

The UV-absorbing resin of the present invention described above is composed of polymer I, which is a polymer of monomer components containing compound 1, and includes a structure derived from compound 1. Excellent for It can absorb ultraviolet rays in a wide wavelength range including wavelengths of 300 nm to 400 nm.
Further, in the ultraviolet absorbing resin of the present invention, since compound 1 is incorporated in the molecule of polymer I, there is no fear of elution or bleeding out of compound 1, and the ultraviolet absorbing property is less likely to deteriorate.
In particular, when the monomer component contains an isomer mixture of Compound 1, the UV-absorbing resin of the present invention is excellent in solvent solubility, and can be easily polymerized and varnished. A varnish containing high-molecular-weight polymer I is excellent in film-forming properties.
In addition, many of the conventional ultraviolet absorbents are mixed types that are used by being added to resins, and there is concern about elution and bleeding out from the resins. There are copolymer types that are used by copolymerizing with other monomers, but conventional copolymer type UV absorbers are acrylate-based, and copolymer type UV absorbers using hydroxyl groups such as polycarbonate resins and phenoxy resins. No drugs have been reported.

〔varnish〕
The varnish of the present invention contains the UV-absorbing resin or UV-absorbing resin composition of the present invention and a 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. alcohols, toluene, xylene and the like. One solvent may be used alone, or two or more 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 application, but is preferably 5 to 50% by mass, more preferably 20 to 35% by mass.
The solid content concentration of the varnish is the 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 contain other components, if necessary, 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.

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

The UV-absorbing film of the present invention can further contain other components, if necessary, as long as the effects of the present invention are not impaired. Other components are the same as those mentioned above.

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 comprising the varnish of the present invention and drying the film.
Examples of film-forming methods include a method of applying the varnish of the present invention onto a substrate. Examples of the coating method include a casting method and the like.
Drying the varnish film removes the solvent and forms a UV-absorbing film. The temperature for drying the film is preferably 40 to 200°C, more preferably 100 to 150°C.
When the varnish of the present invention is applied to a substrate to form a film, an ultraviolet absorbing film is formed on the substrate. get a sex film.

Since the UV-absorbing film of the present invention contains the UV-absorbing resin or UV-absorbing resin composition of the present invention, it has excellent UV-absorbing properties with a wavelength of 300 nm to 400 nm. It can absorb ultraviolet rays in a wide wavelength range including wavelengths of 300 nm to 400 nm.
In particular, when the UV-absorbing 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 bleeding out of compound 1, and the UV-absorbing property is less likely to deteriorate.

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

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

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

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

<Softening point>
Measured according to JIS K 6910.

<Ultraviolet (UV) transmittance>
Spectrophotometer: Using U-3900H manufactured by HITACHI, measurement mode: Wavelength scan 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, and 85% by mass of orthophosphoric acid were placed in a 1 L reaction vessel equipped with a thermometer, a stirrer and a cooling tube. After 24.4 g of the aqueous solution was charged and the temperature was raised to 100° C., the reaction was carried out for 2 hours. Then, the temperature was raised to 140° C. while dehydrating, and then the reaction was carried out for 3 hours. After cooling the reaction solution to 80° C., orthophosphoric acid was neutralized with triethylamine. Then, it was washed with water and concentrated to obtain crude methylenebissalicylaldehyde.
GPC was performed on the reaction product after neutralization, and the purity of methylenebissalicylaldehyde was 75.4%, and the consumption rate of 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 p,p'-methylenebissalicylaldehyde 69.58%, o,p-methylenebissalicylaldehyde 27%. 06%, and о,о'-methylenebissalicylaldehyde 3.36%.

A thin-film distiller (heating surface: 0.068 m ² , internal condenser surface: 0.019 m ² , with glass-filled polytetrafluoroethylene (PTFE) wiper) was set. C.° C. water was supplied, the rotor rotation speed was set to 350 rpm, and the operation was performed at a degree of vacuum of 1 to 5 mmHg. In this state, crude methylenebissalicylaldehyde was continuously supplied to the thin-film distiller at 600 g/hr for 1 hour, and the evaporated component and the bottom product were continuously withdrawn, and methylenebissalicylaldehyde was used as the evaporated component (distillate). got
GPC was performed on methylenebissalicylaldehyde, and the purity of methylenebissalicylaldehyde was 99.45%. Further, when the composition ratio of the isomer mixture was measured by ¹³ C-NMR, the composition ratio was p,p'-methylenebissalicylaldehyde 68.48%, o,p-methylenebissalicylaldehyde 28.36%, 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 cooling pipe, and the temperature was raised to 160°C. Then, 132.8 g (0.8 mol) of paraxylene glycol dimethyl ether was added dropwise over 3 hours. In addition, by-produced methanol was removed out of 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 the by-product methanol was completed, the mixture was cooled to 80°C. The orthophosphoric acid was then neutralized with triethylamine. Then, it was washed with water and concentrated to obtain crude xylylenebissalicylaldehyde.
When the reaction product after neutralization was subjected to GPC, the purity of xylylenebissalicylaldehyde was 82.37% and the consumption rate of 2-hydroxybenzaldehyde monomer was 93.35%.
When the composition ratio of the isomer mixture of crude xylylenebissalicylaldehyde was measured by ¹³ C-NMR, the composition ratio was p,p′-xylylenebissalicylaldehyde 73.43%, o,p-xylylenebissalicylaldehyde Salicylaldehyde was 26.57%.

A thin film evaporator (heating surface 0.068 m ² , internal condenser surface 0.019 m ² , with glass-filled PTFE wiper) was run with a heating medium of 265°C flowing through the heating jacket and heated water of 150°C flowing through the internal condenser. , the rotor rotation speed was set to 350 rpm, and the operation was performed at a degree of vacuum of 1 to 5 mmHg. In this state, crude xylylene bis-salicyaldehyde was continuously supplied to the thin-film distiller at 600 g/hr for 1 hour, and the evaporated component and the bottom product were continuously extracted. Salicylaldehyde was obtained.
GPC was performed on xylylene bissalicylaldehyde, and the purity of xylylene bissalicylaldehyde was 99.81%. Further, when the composition ratio of the isomer mixture was measured by ¹³ C-NMR, the composition ratio was p,p′-xylylenebissalicylaldehyde 71.41%, o,p-xylylenebissalicylaldehyde 28.59%. %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 cooling tube, and the temperature was raised to 120°C. Then, after adding 0.1 g of a 5% aqueous tetramethylammonium hydroxide solution, the temperature was raised to 180° C. and the reaction was allowed to proceed for 1 hour under normal pressure. Subsequently, while maintaining the temperature at 180° C., the pressure was slowly reduced to 10 mmHg, and the reaction was continued while removing the by-product phenol. Then, the temperature was raised to 230° C. under reduced pressure, and the reaction was allowed to proceed 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 9,121.
The obtained polycarbonate resin was dissolved in tetrahydrofuran so as to have a concentration of 10% by mass to obtain a varnish.

(Example 1)
The polycarbonate resin obtained in Comparative Example 1 was dissolved in tetrahydrofuran to a concentration of 10% by mass, and the methylenebissalicylaldehyde obtained in Synthesis Example 1 was added to 0.3 parts per 100 parts of the polycarbonate resin. and the 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 amount of methylenebissalicylaldehyde added was 1.0 parts per 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 were placed in a 1 L reactor equipped with a thermometer, a stirrer and a cooling tube. 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 tetramethylammonium hydroxide solution, the temperature was raised to 180° C. and the reaction was allowed to proceed for 1 hour under normal pressure. Subsequently, while maintaining the temperature at 180° C., the pressure was slowly reduced to 10 mmHg, and the reaction was continued while removing the by-product phenol. Then, the temperature was raised to 230° C. under reduced pressure, and the reaction was allowed to proceed 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 9,021.

(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 reactor 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. After adding 0.1 g of a 5% aqueous tetramethylammonium hydroxide solution, the mixture was heated to 180° C. and reacted under normal pressure for 1 hour. Subsequently, while maintaining the temperature at 180° C., the pressure was slowly reduced to 10 mmHg, and the reaction was continued while removing the by-product phenol. Then, the temperature was raised to 230° C. under reduced pressure, and the reaction was allowed to proceed under reduced pressure for 2 hours to obtain a polycarbonate resin. This polycarbonate resin had a softening point of 121.7° C. and a weight average molecular weight (Mw) of 8,985 by GPC.

(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 placed in a 1 L reaction vessel equipped with a thermometer, a stirrer and a cooling pipe. , and the temperature was raised to 80°C. Then, after adding 0.12 g of diazabicycloundecene, 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 a phenoxy resin ethyl cellosolve varnish. The weight average molecular weight (Mw) of this phenoxy resin by GPC was 50,061.

(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 cooling tube. ) and 320.6 g of ethyl cellosolve were charged, and the temperature was raised to 80°C. Then, after adding 0.12 g of diazabicycloundecene, 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 phenoxy resin. The weight average molecular weight (Mw) of this phenoxy resin by GPC was 32,589.

(UV absorption evaluation)
<1. UV absorbency of UV absorber (monomer)>
The methylene bis salicyl aldehyde obtained in Synthesis Example 1, the xylylene bis salicyl aldehyde obtained in Synthesis Example 2, and bisphenol A as a comparative example were each dissolved in tetrahydrofuran to 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).
As shown in FIG. 1, the methylenebissalicylaldehyde obtained in Synthesis Example 1 and the xylylenebissalicylaldehyde obtained in Synthesis Example 2 have a lower transmittance at a wavelength of 300 nm to 400 nm than bisphenol A. Excellent UV absorption.

<2. UV absorbency 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 a lower transmittance in the wavelength range of 300 nm to 400 nm than the varnish obtained in Comparative Example 1, and had excellent UV absorption in this wavelength region.

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

<4. UV absorbency of phenoxy resin copolymerized with UV absorber>
Each of the ethyl cellosolve varnishes obtained in Comparative Example 2 and Example 5 was applied onto a polyethylene terephthalate (PET) film and pre-dried in an oven at 80° C. for 1 hour. Then, it was heated to 180° C. and dried for 2 hours to form a phenoxy resin film. Then, the phenoxy resin film was obtained by peeling the phenoxy resin film from the PET film. The transmittance of the obtained phenoxy resin film was measured with a spectrophotometer. The results are shown in FIG.
As shown in FIG. 4, the phenoxy resin obtained in Example 5 had lower transmittance in the wavelength range of 300 nm to 400 nm than the phenoxy resin obtained in Comparative Example 2, and had excellent UV absorption in this wavelength region.

The isomer mixture of compound 1 has ultraviolet absorption in a wide wavelength range including wavelengths of 300 nm to 400 nm. In addition, it is possible to copolymerize with various resin raw materials, and by copolymerizing the isomer mixture of the compound 1 and the resin raw materials, an ultraviolet absorbing resin in which elution and bleeding out of the ultraviolet absorber are suppressed can be obtained. . Therefore, the isomer mixture of compound 1 is extremely useful as an ultraviolet absorber or as a raw material for ultraviolet absorbing resins.

Claims (10)

An ultraviolet absorber comprising an isomer mixture of compounds 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).)

The ultraviolet absorber according to claim 1 , wherein the isomer mixture contains two or more isomers in which the bonding positions of X in the two benzene rings in the formula (1) are different . R in the formula (1) ¹ , R ² and R ³ are all hydrogen atoms, the ultraviolet absorber according to claim 1 or 2. An ultraviolet-absorbing resin which is a polycarbonate resin, a phenoxy resin, or a urethane resin comprising a polymer of monomer components containing an isomer mixture of compounds 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).)

5. The ultraviolet absorbing resin according to claim 4 , wherein the isomer mixture contains two or more isomers having different bonding positions of X in the two benzene rings in the formula (1) . R in the formula (1) ¹ , R ² and R ³ are all hydrogen atoms, the ultraviolet absorbing resin according to claim 4 or 5. An ultraviolet absorbing resin composition comprising a resin and the ultraviolet absorbing agent according to any one of claims 1 to 3 . A varnish comprising the ultraviolet absorbing resin according to any one of claims 4 to 6 or the ultraviolet absorbing resin composition according to claim 7 and a solvent. An ultraviolet absorbing film comprising the ultraviolet absorbing resin according to any one of claims 4 to 6 or the ultraviolet absorbing resin composition according to claim 7 . A method for producing an ultraviolet absorbing film, comprising forming a film comprising the varnish according to claim 8 and drying the film.

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