JPH03200956A - Photochromic resin composition and molded body thereof - Google Patents

Abstract

PURPOSE:To improve weather resistance by using specified polyvinyl butyral resin. CONSTITUTION:Polyvinyl butyral resin (PVB) having >=75% transmissivity at 230 nm wavelength and >=90% transmissivity at 280 nm per 1 cm optical path length when dissolved in ethanol by 0.1 wt.% is used. This PVB is obtd. by removing impurities having absorption at about 200-300 nm in ordinary PVB by purification. For example, PVB obtd. in the conventional purifying stage is dissolved in dioxane, the resulting soln. is dropped into hexane to purify the PVB by reprecipitation and this work is repeated at least twice. The weather resistance of a photochromic resin molded body can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a photochromic resin string acid product having particularly excellent weather resistance and a molded product thereof.

(Prior Art) Recently, vehicle-mounted light control materials using optically variable materials, particularly photochromic materials, have been proposed. Among such photochromic materials, spirooxazine compounds are
It absorbs ultraviolet light of 350 to 380 nm and develops a blue color,
It returns to its original colorless state when ultraviolet light is blocked, and is considered promising because it has excellent repeatability of coloring and decoloring between colorless and blue.

Photochromic automotive light control materials include those in which a transparent polymer film having a photochromic photosensitive layer containing a photochromic material is sandwiched between transparent glass substrates to form a laminate. Resin is used.

(Problems to be Solved by the Invention) Generally, polyvinyl butyral resin is obtained by reacting butyraldehyde with polyvinyl alcohol produced by the hydrolysis (ester exchange) reaction of polyvinyl acecool; however, polyvinyl alcohol is insoluble in organic solvents. Since polyvinyl butyral is soluble, a considerable amount of impurities having absorption in the vicinity of 200 to 300 nm are present in the usual manufacturing method.

When this conventional polyvinyl butyral resin is used as a binder for photosensitive materials, no particular adverse effects due to the residual impurities have been found, but in the case of the spirooxazine compound used in the present invention, which has excellent light resistance, There is a problem in that impurities having absorption in the vicinity of 200 to 300 nm have a negative effect on the color retention rate of spirooxazine compounds, accelerating deterioration of weather resistance.

(Means for Solving the Problem) The present inventors have discovered that in order to improve the light resistance of a photochromic resin composition containing a spirooxazine compound and a polyvinyl butyral resin as main components and a molded article thereof,
The inventors have discovered that such problems can be solved by reducing impurities having absorption in the vicinity of 0 to 300 nm to a certain amount or less, and have arrived at the present invention.

That is, in the present invention, in a molded article consisting of a photochromic resin and a compound whose main components are a spirooxazine compound and a polyvinyl butyral resin, the polyvinyl butyral resin has an optical path length of 1 cffi when dissolved in 0.1% by weight in ethanol. A photochromic resin molded article characterized by having a transmittance of 75% or more at 230 nm and a transmittance of 90% or more at 280 nm, and a photochromic resin for coating containing a spirooxazine compound, a polyvinyl butyral resin, and a solvent as main components. In things,
As the polyvinyl butyral resin, 0.0% is added to ethanol.
230n per clll of photofurnace length when dissolved at 1% by weight
A photochromic resin composition for coating, characterized in that a polyvinyl butyral resin having a transmittance of 90% or more at 230 nm per 1 cm of optical path length when the transmittance of m is used, and spirooxazine on the polyvinyl butyral resin film. In a photo black resin molded product formed by forming a film mainly composed of a polyvinyl butyral compound and a polyvinyl butyral resin, the shape of the film and the polyvinyl butyral resin which is a film forming component are added by 0.1 weight to ethanol. %2 per 1 cm of optical path length when dissolved
23 per cm of optical path length when transmittance is 30 nm
The gist of the present invention is a photochromic resin molded article characterized by using a polyvinyl butyral resin having a transmittance of 90% or more at 0 nm.

The present invention will be explained in detail below.

The photochromic resin molded article of the present invention is one in which a spirooxazine compound is kneaded into a specific polyvinyl butyral resin at a high temperature, and then molded and molded. At this time, the spirooxazine compound is added to the polyvinyl butyral resin in an amount of 0.001 to 15% by weight, preferably 0.01 to 5% by weight. The temperature of polyvinyl butyral resin (abbreviated as PVB) into which the spirooxazine compound is kneaded is in the range of 150 to 250°C.

In addition, molding methods include extrusion molding to form a film, injection molding, vacuum molding, blow molding, breath molding, thermosetting resin injection molding, pultrusion molding, RIM Kaigata 1RTM Kaigai molding, molding that requires high temperature. The law is given.

The photochromic resin molded article of the present invention may be made into a film by the above molding method and used alone, but it may also be used by pasting the molded article on a substrate or by sandwiching it between substrates at least one of which is transparent. .

The photochromic resin composition for coating of the present invention includes:
A spirooxazine compound and a specific PvB are dissolved in an appropriate solvent (an alcoholic solvent such as ethanol or butanol, or a mixed solvent of these and a ketone solvent such as methyl ethyl ketone, or a cellosolve solvent such as methyl cellosolve). Here, the appropriate solvent is one that dissolves the spirooxazine compound and polybutyral resin,
This is a solvent that can be easily evaporated after application.

In this photo black ivy resin m* product for coating, spirooxazine compounds are added at a ratio of 0.1 to 50% relative to PVB.
% by weight, preferably 0.5-20% by weight. If the spirooxazine compound is less than 0.1% by weight, sufficient optical density will not be obtained when colored, and if it is added in excess of 50% by weight, no improvement in optical density will be seen and the cost will be high. Undesirable.

This photochromic photosensitive composition for coating is made of glass,
It is used by coating on base materials such as plastic, paper, boards, and metal foil.

As a coating method, conventional methods such as screen printing, a doctor blade method, a casting method, a spinner method, and a dipping method are used.

A substrate such as a plate, glass, or plastic coated with this coating composition may be used as it is or by further laminating a transparent substrate, transparent film, etc. thereon. In addition, it is also possible to apply the composition on glass, overlay a film such as PVB, and sandwich it between another glass plate.

In addition, the photochromic resin molded article of the present invention includes a spirooxazine compound on a specific PVB film,
It is provided with a photosensitive layer whose main component is the same specific PVB as the film.

Specifically, a specific PVB film may be coated entirely or partially with the above-mentioned photoblack ivy composition for coating.

The PVB film may or may not be embossed.

The thickness of the photochromic photosensitive layer is 0.5 μm to 1n, preferably 10 to 250 μm.

This photochromic device is used as an intermediate film by being sandwiched between substrates, at least one of which is transparent.

Specifically, an interlayer film for photochromic laminated glass may be mentioned.

The specific PV used in the coating photochromic resin composition or photochromic resin molded article of the present invention
B needs to satisfy the following conditions.

That is, the PVB used in the present invention is
．． 23 per cflI optical path length when dissolved at 1% by weight
The transmittance at 0 nm is 75% or more, and 28
The transmittance at 0 nm is 90% or more.

However, the 230 nm and 280 nm referred to here may have a width of approximately ±3 nm in consideration of the measurement accuracy of the spectrometer.

This kind of PVB contains 200~
It is obtained by removing impurities having absorption near 300 nm through purification treatment.

For example, in addition to the usual purification process, it can be obtained by repeating at least twice a process of dropping PVB dissolved in dioxane into hexane and performing reprecipitation purification.

On the other hand, spirooxazine compounds used in the present invention include, for example, the following general formula (1) (where R1, R1 and R3 are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, It represents a cycloalkyl group or an aryl group, and R2 and R3 may be bonded to each other to form a cyclization. R4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R1 represents an alkylene group or an arylene group. It may have another spirooxazine ring to form 21 compounds as a whole. Rings X and Y represent an optionally substituted hydrocarbon aromatic ring or a heteroaromatic ring. Z is an oxygen atom or a sulfur atom) is used.

In the compound represented by the above formula (1), R1R2 and R3 are alkyl groups such as alkyl groups having 1 to 28 carbon atoms, alkoxyalkyl groups such as methoxyethyl group and ethoxyethyl group, methoxyethoxyethyl group, n-butoxyethoxy Substituted alkoxyalkoxyalkyl groups such as ethyl groups, alkoxyalkoxyalkoxyalkyl groups such as methoxyethoxyethoxyethyl groups, ethoxyethoxyethoxyethyl groups, phenyloxyethyl groups, naphthyloxyethyl groups, p-chlorophenyloxyethyl groups, etc. Aryloxyalkyl group, benzyl group, phenethyl group, p~chlorobenzyl group, p-
An optionally substituted arylalkyl group such as nitrobenzyl, a cycloalkylalkyl group such as a cyclohexylmethyl group, a cyclohexylethyl group, a cyclopentylmethyl group, an allyloxyethyl group, a 3-bromoallyloxyethyl group, etc. Substitution of alkenyloxyalkyl groups, cyanoalkyl groups such as cyanoethyl groups and cyanomethyl groups, hydroxyalkyl groups such as hydroxyethyl groups and hydroxymethyl groups, and tetrahydrofuryl alkyl groups such as tetrahydrofurfuryl groups and tetrahydrofurylethyl groups; Unsubstituted alkyl groups; substituted or unsubstituted alkenyl groups such as allyl group and 2-chloroallyl group; substituted or unsubstituted aryl groups such as phenyl group, p-methylphenyl group, naphthyl group, m-methoxyphenyl group; Examples include cycloalkyl groups such as cyclohexyl group and cyclopentyl group. Also, Rt and R3
may be linked to each other to form a ring such as a cyclohexyl group, a cyclopentyl group, or a cycloheptyl group. Examples of R1 include compounds in which another spirooxazine ring is bonded via an alkylene group or an arylene group to form a dimeric compound as a whole.

R4 represents a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, such as a methyl group or an ethyl group.

Examples of the optionally substituted hydrocarbon aromatic ring or heteroaromatic ring of rings x and y include a benzene ring, a naphthalene ring, a quinoline ring, and a phenanthrene ring. Substituents for these rings include a chlorine atom, Halogen atoms such as bromine atoms and iodine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups, alkoxycarbonyl groups, methoxysulfonyl groups,
Examples include alkoxysulfonyl groups such as ethoxysulfonyl groups, cyano groups, amino groups, dimethylamino groups, and nitro groups.

Specific examples of these compounds include JP-A-6330486.
No., JP-A-63-30487, JP-A-63-3048
No. 8, JP-A-63-30489, JP-A-63-303
Examples include compounds described in No. 984 and the like.

In the present invention, among the spirooxazine compounds represented by the above formula [I], the following general formula (II) (wherein R1 is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group, and R4 is a hydrogen atom or It is preferable to use a spirooxazine compound represented by a methyl group, X and Y each representing an optionally substituted hydrocarbon aromatic ring, or a heteroaromatic ring.

Among the preferred compounds of formula (If) above, those with the following structures are more preferably used.

(In the formula, R'=CH1, R''=H and R1=H
, R"=CH,) Also, the spirooxazine compound used in the photochromic resin molded article whose main components are spirooxazine compound and PVB is kneaded into the resin at high temperature. Therefore, those with good heat resistance are preferable. For example, R in the above-mentioned hole (1)
Preferably, 1 has another spirooxazine skeleton and is a dimer as a whole. As a specific example of this dimeric structure sugorooxazine compound, JP-A-33-1
No. 4786, JP-A-63-1) No. 5884, JP-A-63
-1) Compounds described in each publication of No. 5885 are mentioned.

The photosensitive layer of the photochromic resin composition or photochromic resin molded article of the present invention may contain a plasticizer and other various additives, if necessary.

The photosensitive composition of the present invention may also contain a plasticizer, if necessary.

Examples of this plasticizer include phthalates such as dibutyl phthalate and dioctyl phthalate, adipates such as dioctyl adipate, phosphates such as tricresyl phosphate, and ethylene glycol diesters such as triethylene glycol hexanoate. plasticizers and mixtures thereof.

Examples of other various additives include light resistance improvers such as hindered compounds, antioxidants, and nitroxy free radicals. Radicals are preferred. These additives are 0.1 to 50% by weight based on the polyvinyl butyral resin (which may contain a plasticizer),
Preferably, it is used in an amount of 0.5 to 20% by weight.

(Function) The photochromic resin composition of the present invention has significantly improved coloring properties. This effect was 2 when dissolved at 0.1% by weight in ethanol together with spirooxazine compounds.
This is probably because the use of a PVB resin and PVB film with a transmittance of 75% or more at 30 nm and a transmittance of 90% or more at 280 nm had less adverse effect on the spirooxazine compound and reduced the rate of deterioration.

<Examples> The present invention will be further explained by the following Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example-1] (Purification of PVB) 5 g of commercially available polyvinyl butyral (abbreviation: PVB) was completely dissolved in 100 ml of dioxane, and when this was gradually added to 500 ml of hexane with stirring, PVB was precipitated. It was filtered and the same operation was repeated again.The obtained PVB was washed with hexane and dried in a vacuum dryer.The yield at this time was 4.6 g.

The obtained PVB was dissolved in ethanol as shown in Figure 1■.
．． Optical path length 230n per lam when dissolved at 1% by weight
Transmittance at m is 82%, transmittance at 280 nm is 93
%Met. (Measuring device: Hitachi spectrophotometer U-3400) [Preparation of photochromic laminated glass] PVB obtained by the above method: 9.6% by weight, and plasticizer (triethylene glycol di-2-ethyl butyrate): 1 .1% by weight, spirooxazine compound (A) having the above structure = 2
．． 1% by weight (In the above formula, the compound where R' = H, R" = CH3 and the compound where R' = CH3, R" = H:
1), a light resistance improver (2, 2,
5,5-tetramethyl-1-pyrrolidinyloxy-3-
Carboxamide): 2.1% by weight was dissolved in a solvent (ethanol:toluene:n-butanol=50:45:5) to prepare a photochromic resin composition. The resulting composition was printed by screen printing on an interlayer film made using PVB purified in the same manner as in the above purification method, and air-dried to produce a photochromic molded body. This molded body was sandwiched between two sheets of clear glass having a thickness of 2-2, and vacuum pressure bonded to produce a laminated photochromic laminated glass having a layer of a photochromic compound between the substrates.

[Weather resistance test]

In order to evaluate the weather resistance of these samples, the initial coloring performance was measured using a xenon lamp, and then light irradiation was performed in a xenon fade meter to measure the change in coloring performance over time.

As a result, the laminated glass of this example retained 70% of its initial coloring performance even after 2000 hours of irradiation.

[Comparative Example-1] Next, as a PVB interlayer film, an interlayer film using unpurified PVB with a transmittance of 23Qnm of 71% and a transmittance of 280nm of 71% and 88% at 280nm, as shown in ■ in Figure 1, was used. Similar PV
A laminated glass (Comparative Example 1) was produced under the same conditions as in Example 1 except for using B binder.

[Weather resistance test]

Weather resistance was evaluated in the same manner as in Example 1. As a result, the coloring performance was 10% of the initial value after 1000 hours of irradiation, and furthermore, changes in coloring and decoloring were difficult to judge visually.

[Example-2] Purification of CPVB] When 5 g of commercially available PVB was completely dissolved in 100 ml of ethanol and gradually added to 500 ml of hexane with stirring, PVB was precipitated. This was filtered and the same operation was repeated again. The obtained PVB was washed with hexane,
It was dried in a vacuum dryer. As a result, the yield was 4.7 g.

The transmittance of this PVB was measured using a Hitachi spectrophotometer U-3400 in the same manner as in Example-1, and as shown in Figure 1-■, it was 82% at 230 nm and 91% at 280 nm.
Met.

[Production of photochromic laminated glass] The above PVB
A laminated glass (
Example 2) was produced.

[Weather resistance test]

Weather resistance was evaluated in the same manner as in Example 1, and the coloring performance remained at 70% of the initial value even after 2000 hours of irradiation.

(Effect of the invention) The photochrome ivy resin composition and molded article of the present invention are PV
B is a photochrome ivy resin composition that does not have a negative effect on spirooxazine compounds and has good weather resistance by using an interlayer film using polyvinyl butyral that has significantly reduced impurities having absorption in the vicinity of 200 to 300 nm. and a molded body can be obtained.

This composition and molded product are used in various applications as optically variable laminated structures such as photochromic laminated glass.

[Brief explanation of drawings]

Figure 1 is a transmission spectrum diagram per optical path length of 10 when each of the PVB used in the examples of the present invention is dissolved in ethanol at 0.1% by weight. The vertical axis is the transmittance (%), and the horizontal axis is the transmission spectrum. represents wavelength (nm). In the figure, ■ indicates Comparative Example-1, ■ indicates Example-1, and ■ indicates Example-2.
represents the PVB used respectively.

Claims (3)

[Claims] (1) In a molded article made of a photochromic resin composition whose main components are a spirooxazine compound and a polyvinyl butyral resin, the optical path length is 1 c when the polyvinyl butyral resin is dissolved in ethanol at 0.1% by weight.
Transmittance of 230nm per m is 75% or more and 280n
A photochromic resin composition characterized by using a polyvinyl butyral resin having a transmittance of 90% or more. (2) In a photochromic resin composition for coating containing a spirooxazine compound, a polyvinyl butyral resin, and a solvent as main components, the optical path length 1 when the polyvinyl butyral resin is dissolved in ethanol at 0.1% by weight
A photochromic resin composition for coating, characterized by using a polyvinyl butyral resin having a transmittance of 75% or more at 230 nm per cm and a transmittance of 90% or more at 280 nm. (3) In a photochromic resin molded article formed by forming a film mainly composed of a spirooxazine compound and a polyvinyl butyral resin on a polyvinyl butyral resin film, the polyvinyl butyral resin which is a forming component of the film and a film forming component , 230n per 1cm optical path length when dissolved in ethanol at 0.1% by weight
A photochromic resin molded article characterized in that a polyvinyl butyral resin having a transmittance of 75% or more at m and a transmittance of 90% or more at 280 nm is used.