JP2001294450A - Intermediate film for safety laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for safety laminated glass consisting of a vinyl alcoholic polymer composition which is excellent in adhesive power and its persistence, impact resistance and penetration resistant performance. SOLUTION: The vinyl alcoholic polymer composition of the intermediate film for the safety laminated glass consisting of the vinyl alcoholic polymer composition is a composition containing a vinyl alcoholic polymer and metal alkoxide or the metal oxide obtained by a polycondensation reaction of this oligomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer film for safety laminated glass used for laminated glass used for windshields and side glasses of automobiles, window glasses of buildings, and the like.

[0002]

2. Description of the Related Art Conventionally, a polyvinyl butyral resin has been most commonly used as an intermediate layer of a laminated glass. However, since a polyvinyl butyral resin is a thermoplastic resin, it has the following problems. .・ Since the softening point is relatively low, the glass plate is displaced or bubbles are generated by heat after bonding. -When left in a high-humidity atmosphere for a long period of time due to the susceptibility to the effect of moisture, the peripheral area gradually becomes white and a decrease in the adhesive strength to glass is recognized. The impact fracture resistance depends on the temperature, and particularly in a temperature region exceeding room temperature, that is, about 30 ° C. or more, the penetration resistance sharply decreases.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to overcome these disadvantages of the prior art, and to provide an adhesive and its durability, impact resistance, penetration resistance and the like in such a background. An object of the present invention is to provide an excellent interlayer film for safety laminated glass.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the above-mentioned problems have been solved by an intermediate film for safety laminated glass made of a specific vinyl alcohol-based polymer composition. It has been found that the present invention has been completed.

That is, an interlayer for safety laminated glass comprising a vinyl alcohol polymer composition, wherein the vinyl alcohol polymer composition is a polycondensation reaction of a vinyl alcohol polymer and a metal alkoxide or an oligomer thereof. An intermediate film for laminated safety glass, which is a composition containing a metal oxide obtained by the above method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The laminated glass of the present invention is obtained by interposing a vinyl alcohol-based polymer composition between glass plates, and integrating the vinyl alcohol-based polymer composition with the glass plate by curing or the like.
That is, for example, a vinyl alcohol-based polymer composition is interposed between glass plates, thermally cured, and integrated.

The vinyl alcohol polymer composition used in the present invention is preferably prepared by a polycondensation reaction of a metal alkoxide or an oligomer thereof and a saponification reaction of a vinyl carboxylate polymer, What is known as synthesis of an inorganic-organic composite by a general sol-gel method can be applied.

A more preferable method for producing the vinyl alcohol-based polymer composition used in the present invention is to use a solution (sol) containing a metal alkoxide or an oligomer thereof, a vinyl carboxylate-based polymer and an organic solvent to form an organic compound. A metal oxide is obtained by simultaneously performing the polycondensation reaction of the metal alkoxide or the oligomer and the saponification reaction of the vinyl carboxylate polymer in the same reaction system while removing low-boiling substances including a solvent. And a known method for producing a vinyl alcohol polymer composition (gel or solid organic / inorganic composite) comprising a vinyl alcohol polymer (hereinafter, this method is abbreviated as "in situ saponification sol-gel method"). In some cases).

The vinyl carboxylate-based polymer used in the present invention is a polymer having a vinyl carboxylate unit, and may be an addition polymer of vinyl carboxylate alone or an addition copolymer of vinyl carboxylate and another comonomer. Include.
As the vinyl carboxylate, vinyl acetate, vinyl propionate, vinyl 2-methylpropionate and the like are preferable, and vinyl acetate is particularly preferable. Examples of the comonomer include α-olefins such as ethylene, propylene and 1-butene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and t-butyl vinyl ether;
Allyl alcohol; vinyltrimethylsilane and the like can be used. Examples of the vinyl carboxylate polymer include polyvinyl carboxylate such as polyvinyl acetate and polyvinyl propionate; and ethylene-vinyl carboxylate such as ethylene-vinyl acetate copolymer and ethylene-vinyl propionate copolymer. Polymers and the like are used, and among them, polyvinyl acetate, ethylene-vinyl acetate copolymer and the like are particularly preferably used.

When polyvinyl carboxylate or ethylene-vinyl carboxylate copolymer is used as the vinyl carboxylate-based polymer, it is excellent in adhesiveness and persistence, and also in safety such as impact resistance and penetration resistance. Because of its superiority, its ethylene unit content is 0 to 7 based on all structural units.
It is preferably in the range of 0 mol%, more preferably in the range of 0 to 60 mol%, even more preferably in the range of 0 to 30 mol%. 20
It is particularly preferred that it is in the range of mol%.

[0011] The molecular weight of the vinyl carboxylate polymer used is not particularly limited, and can be used from low molecular weight to high molecular weight. A polymer having a degree of polymerization in the range of 300 to 6000 is preferably used in view of its excellent durability, and a polymer having a polymerization degree of 300 to 3000 is particularly preferably used. The vinyl carboxylate polymer used is,
As long as the effects of the present invention are not impaired, silyl group modification, boronic acid modification, modification such as carboxyl group modification may be performed, but the resulting vinyl alcohol-based polymer composition In view of particularly excellent impact resistance and penetration resistance, the amount of modification is preferably kept at 0.1 mol% or less, more preferably at 0.01 mol% or less, and unmodified. Is particularly preferred. Further, the vinyl carboxylate polymer used may be one in which a part of the acyloxy group derived from the vinyl carboxylate unit is saponified to a hydroxyl group, but the obtained vinyl alcohol polymer composition From the viewpoints of impact resistance and penetration resistance, the degree of saponification of the vinyl carboxylate polymer is preferably kept at 50 mol% or less, more preferably at 10 mol% or less, It is particularly preferable to keep the content at 1 mol% or less.

In the present invention, a metal alkoxide or an oligomer thereof (hereinafter, “metal alkoxide or oligomer” may be collectively referred to as “metal alkoxide-based component”) is used. In the present invention, the metal alkoxide-based component is selected from the group consisting of silicon alkoxide, metal alkoxide other than silicon alkoxide, oligomer of metal alkoxide having a unit derived from silicon alkoxide, and oligomer of metal alkoxide having no unit derived from silicon alkoxide. At least one component. In the present invention, it is not necessarily limited, and it is possible to use a silicon alkoxide or an oligomer of a metal alkoxide having a unit derived from a silicon alkoxide as at least one component of the metal alkoxide-based component, and obtain a vinyl alcohol-based polymer. It is preferable in terms of the high durability of adhesion in the composition.

The silicon alkoxide preferably has one silicon atom and has a chemical structure in which two, three or four alkoxy groups are bonded to the silicon atom. Here, the number of alkoxy groups is more preferably three or four, and particularly preferably four.
When the number of alkoxy groups is two or three, an alkyl group (eg, a methyl group), an aryl group (eg, a phenyl group), a halogen atom (eg, a chlorine atom), and the like are further bonded to the silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a butoxy group. Specific examples of silicon alkoxide include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,
Octyltrimethoxysilane, phenyltrimethoxysilane, chlorotrimethoxysilane and the like can be mentioned.

The metal alkoxide other than the above-mentioned silicon alkoxide has one or more (more preferably trivalent or tetravalent) metal atoms such as titanium, aluminum and zirconium, and has one or more (more than one) Preferably 2
(Preferably 3 or more, particularly preferably 3 or more) compounds having a chemical structure to which an alkoxy group is bonded. Specific examples of the alkoxy group include those exemplified above for the silicon alkoxide. The metal atom may have a substituent other than the alkoxy group, and examples of the substituent include an alkyl group (such as a methyl group), an aryl group (such as a phenyl group), and a halogen atom (such as a chlorine atom). . Specific examples of the metal alkoxide include alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and methyltriisopropoxytitanium; trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, and methyldiisopropoxy. Alkoxyaluminum compounds such as aluminum, tributoxyaluminum and diethoxyaluminum chloride; and alkoxyzirconium compounds such as tetraethoxyzirconium, tetraisopropoxyzirconium and methyltriisopropoxyzirconium.

The above-mentioned oligomers of metal alkoxides having units derived from silicon alkoxide include oligomers of the above-mentioned silicon alkoxides alone and co-oligomers of the above-mentioned silicon alkoxides with other metal alkoxides. Examples of the other metal alkoxide include titanium, aluminum, zirconium and the like.
One or more (more preferably trivalent or tetravalent) metal atoms
And a compound having a chemical structure in which one or more (more preferably two or more, particularly preferably three or more) alkoxy groups are bonded to the compound. Oligomers of metal alkoxides having units derived from silicon alkoxides can be produced by hydrolyzing / polycondensing a silicon alkoxide alone or in a mixture with other metal alkoxides by a known method, and having a low molecular weight hydroxyl group. It is preferably an oligomer containing. Preferred specific examples of the oligomer of the metal alkoxide having a unit derived from a silicon alkoxide include a silanol group-containing tetramethoxysilane dimer or an oligomer of a trimer or more thereof, a silanol group-containing tetraethoxysilane dimer or a trimer thereof The above oligomers, silanol-terminal-modified oligodimethylsiloxane, and the like can be mentioned. Although the degree of polymerization is not necessarily limited, it is preferably in the range of 2 to 25, and more preferably in the range of 2 to 10.

Examples of the metal alkoxide oligomer having no unit derived from silicon alkoxide include divalent or more (more preferably trivalent or tetravalent) metal atoms such as titanium, aluminum and zirconium.
One or two compounds having a chemical structure in which one or more (excluding silicon atoms) is bonded to one or more (more preferably two or more, particularly preferably three or more) alkoxy groups The above is preferably a low molecular weight hydroxyl group-containing oligomer which can be produced by hydrolysis and polycondensation by a known method. Preferred specific examples of the oligomer of the metal alkoxide having no unit derived from silicon alkoxide include a hydroxyl group-containing tetraisopropoxytitanium dimer or an oligomer of a trimer or more thereof. Although the degree of polymerization is not necessarily limited, it is preferably in the range of 2 to 25, and more preferably in the range of 2 to 10.

In the metal alkoxide component used in the present invention, the content of metal atoms on the basis of all metal atoms is at least 20 mol% from the viewpoint of the high persistence of adhesion in the obtained vinyl alcohol polymer composition. Is preferably, more preferably 50 mol% or more, and particularly preferably 80 mol% or more.

In the reaction for preparing the vinyl alcohol polymer composition of the present invention, a metal salt, a metal complex or a layered clay compound is added to the reaction system, if desired, as long as the effects of the present invention are not impaired. be able to. Examples of metal salts or metal complexes include fine powders of metal oxides produced by hydrolyzing / polycondensing the above metal alkoxides in a wet manner; metal oxides prepared by hydrolyzing / polycondensing or burning metal alkoxides in a dry manner Fine powder; carbonate, hydrochloride,
Metal salts of inorganic acids such as nitrates; metal salts of organic acids such as oxalates; metal complexes such as acetylacetonate metal complexes such as aluminum acetylacetonate and titanium acetylacetone; metal complexes such as cyclopentadienyl metal complexes and cyano metal complexes; Is mentioned. Examples of the layered clay compound include natural smectite, lipophilic treated smectite, hydrophilic treated smectite, natural mica, lipophilic treated mica, talc, and the like. The amount of use is not particularly limited, but is preferably in the range of 5 parts by weight or less based on 100 parts by weight of the vinyl alcohol-based polymer composition obtained because the adhesiveness and the durability are not impaired.

In the known sol-gel method, coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and γ-aminopropyltrimethoxysilane are generally used. Is often used for the purpose of improving the dispersibility of the metal oxide in the obtained vinyl alcohol-based polymer composition, but in the present invention, the obtained vinyl alcohol-based polymer composition has a higher water resistance. From the viewpoint of exhibiting the property, it is often better to not use such a coupling agent. However, metal salts as described above,
When a metal complex, a layered clay compound, or the like is used, the use of a coupling agent may be effective in improving their dispersibility. Therefore, when a coupling agent is used, the amount of the coupling agent is preferably limited to 0.1 mol% or less, and preferably 0.01 mol% or less based on the metal component in the metal alkoxide-based component used. It is more desirable to stop.

In the reaction according to the present invention, the above-described polycondensation reaction of the metal alkoxide-based component and the saponification reaction of the vinyl carboxylate-based polymer proceed in parallel in the same system, and are basically performed in situ. This is a known reaction in the saponification sol-gel method. The polycondensation reaction of the metal alkoxide-based component produces a macromolecularized metal oxide. When a compound containing an alkoxy group or an oligomer containing an alkoxy group is used, such as a metal alkoxide, the alkoxy group is used. The reaction proceeds by a dehydration-condensation reaction via a hydrolysis reaction that changes to a hydroxyl group. However, when an oligomer containing a hydroxyl group is used, the reaction may proceed by a dehydration-condensation reaction alone without a hydrolysis reaction. Either case is applicable to the present invention. On the other hand, the saponification reaction of the vinyl carboxylate polymer generates a vinyl alcohol polymer, and the acyloxy group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer is converted into a hydroxyl group, and at the same time, the carboxylic acid is converted into a hydroxyl group. An acid compound (one or more compounds of a carboxylic acid, a carboxylic acid ester and a carboxylate is usually produced as a by-product, although it differs depending on the type of the organic solvent and the catalyst used). It is assumed that in the vinyl alcohol-based polymer composition obtained by the reaction according to the present invention, a chemical bond may be partially formed between the vinyl alcohol-based polymer and the metal oxide.

In the reaction according to the present invention, the amounts of the vinyl carboxylate-based polymer and the metal alkoxide-based component are determined by converting the metal alkoxide-based component into an acyl group derived from a vinyl carboxylate unit in the vinyl carboxylate-based polymer. 1
It is necessary to use the metal alkoxide-based component in a proportion such that the metal atom in the metal alkoxide-based component is in the range of 0.01 to 100 mol with respect to 00 mol. The metal atom in the metal alkoxide component is 0.0 with respect to 100 mol of the acyl group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer.
When the amount is 1 mol or more, the resulting vinyl alcohol-based polymer composition has good adhesiveness. Further, when the metal atom in the metal alkoxide-based component is an acyl group 100 derived from a vinyl carboxylate unit in the vinyl carboxylate-based polymer,
When the amount is 100 moles or less, the obtained vinyl alcohol-based polymer composition can exhibit high safety such as impact resistance and penetration resistance. In that the safety and adhesiveness of the obtained vinyl alcohol-based polymer composition become more advanced, the amount of the metal alkoxide-based component used is reduced by the acyl derived from the vinyl carboxylate unit in the vinyl carboxylate-based polymer. The metal atom in the metal alkoxide-based component is 0.01 to 100 moles per group.
The ratio is preferably set to fall within the range of 80 mol, more preferably to the ratio falling within the range of 0.1 to 60 mol, and more preferably falls within the range of 0.1 to 40 mol. It is more preferable to set such a ratio.

In the reaction according to the present invention, in addition to the acid catalyst known in the in situ saponification sol-gel method, various catalysts known in the general sol-gel method can be used. Examples of usable catalysts include acidic catalysts such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, and carbonic acid; and sodium hydroxide, magnesium hydroxide,
Examples include basic catalysts such as potassium hydroxide, ammonia, triethylamine, ethylenediamine and the like, and these may be used alone or in combination. From the viewpoint of safety such as impact resistance and penetration resistance of the obtained vinyl alcohol polymer composition, it is generally preferable to use an acidic catalyst, and it is preferable to use a combination of an acidic catalyst and a basic catalyst. More preferred. However, when a low molecular weight hydroxyl group-containing oligomer which has been hydrolyzed or polycondensed to some extent in advance is used as the metal alkoxide-based component, it is preferable to use a basic catalyst. The amount of the catalyst used is not strictly limited, but the number of moles of the alkoxy group in the metal alkoxide component used and the moles of the acyl group derived from the vinyl carboxylate unit of the vinyl carboxylate polymer used It is preferably in the range of 0.001 to 0.1 gram equivalent relative to 1 mole of the sum of the numbers (total moles), and 0.01 to 0.1 gram equivalent.
More preferably, it is in the range of 05 gram equivalents.

In the reaction according to the present invention, a solution (sol) obtained by dissolving a vinyl carboxylate polymer and a metal alkoxide component in an organic solvent is used. The organic solvent used at this time is not particularly limited as long as it can sufficiently dissolve both the vinyl carboxylate polymer and the metal alkoxide component, and alcohols such as methanol, ethanol, propanol, and butanol are used. Amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide and the like are preferably used alone or in combination of two or more. Among them, methanol, ethanol, dimethylsulfoxide and the like are particularly preferable. The amount of the organic solvent used is not necessarily limited, but is preferably 20 to 2 parts by weight based on 100 parts by weight of the total weight of the vinyl carboxylate-based polymer and the metal alkoxide-based component.
000 parts by weight is preferred, and 100 to 1000 parts by weight.
More preferably, it is in the range of parts by weight. Acyl derived from vinyl carboxylate units in the vinyl carboxylate polymer used in the organic polymer in the reaction system (final target product or an intermediate thereof induced by saponification reaction of the vinyl carboxylate polymer used) When it is desired to reduce the residual ratio of groups, a uniform solvent containing 5% by weight or more of an organic solvent having an affinity for a predetermined vinyl alcohol-based polymer is preferably used.

In the reaction according to the present invention, if necessary, water may be present in the reaction system. For example, when a metal alkoxide having an alkoxy group or an oligomer having an alkoxy group is used as the metal alkoxide-based component, the presence of water is necessary for the hydrolysis reaction of the alkoxy group to proceed. The amount of water to be used is not necessarily limited, and as described above, can be appropriately set in consideration of the metal alkoxide-based component to be used, the type of catalyst, and the like. 1.5 to 4.5 with respect to the alkoxy group in the metal alkoxide-based component.
It is preferably within the range of 0 times mol. When a water-containing component such as hydrochloric acid is used, the amount of water to be used should be determined in consideration of the amount of water introduced by the component.

The reaction according to the present invention is carried out at least at a later stage while removing low-boiling substances outside the system by means such as evaporation. As the low-boiling point substance, an organic solvent, the above-mentioned carboxylic acid-based compound by-produced by saponification of a vinyl carboxylate-based polymer, a by-product (eg, water) by polycondensation of a metal alkoxide-based component, and excess water are added. In this case, excess water and the like are included.

In the reaction according to the present invention, at the beginning of the reaction,
That is, it is derived from the vinyl carboxylate unit in the vinyl carboxylate polymer used in the organic polymer in the reaction system (the final target product or its intermediate derived by the saponification reaction of the vinyl carboxylate polymer used). Before the residual ratio of the acyl group reaches 40 mol%, the dissipation of the organic solvent and the like to the outside of the system is suppressed, and the organic solvent and the carboxylic acid compound are removed to the outside of the system in the second half of the subsequent reaction. It is preferable to carry out the reaction while performing. For this purpose, the evaporation of the organic solvent and the like is suppressed by performing the reaction under normal pressure or under pressure in the early stage of the reaction, and the evaporation of the organic solvent and the carboxylic acid compound is promoted by shifting to the reduced pressure system in the latter stage of the reaction. It may be preferable to do so. In the reaction according to the present invention, the reaction mixture is in a solution state at the beginning of the reaction, but is in a solid state at the end of the reaction.

When the pressure in the reaction system is reduced to remove the carboxylic acid compound from the reaction system, if the pressure is lowered unnecessarily, the organic solvent evaporates too quickly to obtain a homogeneous composition, Since inconvenience may occur such that the composition cannot be obtained in a predetermined shape due to foaming, it is preferable to gradually lower the pressure while observing the state of the reaction system. From these facts, when the pressure reduction condition is adopted, the pressure condition at that time is generally 0.01 to 700 mmHg in absolute pressure.
Is preferably selected from the range of 0.1 to 400.
It is more preferable to select from the range of mmHg.

In the reaction according to the present invention, the vinyl alcohol polymer composition is obtained by using the carboxylic acid used in the organic polymer in the reaction system in that the excellent water resistance of the obtained vinyl alcohol polymer composition can be more highly expressed. It is preferably carried out until the residual ratio of acyl groups derived from vinyl carboxylate units in the vinyl oxypolymer reaches a stage of 30 mol% or less, and is preferably carried out within a range of 0.1 to 20 mol%. More preferably, the reaction is carried out so as to fall within the range of 1 to 10 mol%, and particularly preferably, the treatment is carried out within the range of 1 to 5 mol%. In order to highly reduce the residual ratio of the acyl group, for example, the water content in the reaction system in the reaction according to the present invention is 3% by weight or less, more preferably 1% by weight or less, further preferably 0.5% by weight or less. The amount of the solvent used is adjusted so that the amount of water in the reaction system is in the range of 30 to 100 mol%, more preferably 40 to 7 mol%, based on the alkoxy group derived from the metal alkoxide component.
The content is adjusted within a range of 5 mol%, and, as a metal alkoxide-based component, an alkoxy group and a hydroxyl group are mixed at a molar ratio of alkoxy group / hydroxyl group of from 1 / 0.5 to 1 / l.
2.0, more preferably 1 / 0.8 to 1/1.
It is desirable to employ one or more conditions of using a metal alkoxide or an oligomer thereof contained in the range of 25.

In the reaction according to the present invention, although not necessarily limited, if it is desired to obtain a vinyl alcohol-based polymer composition having a good color tone without coloring such as brown or black, an organic compound in the reaction system may be used. The residual ratio X of the acyl group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer in the polymer (the final target product or its intermediate derived by the saponification reaction of the vinyl carboxylate polymer used) is 40. In the range of not more than mol%, the carboxylic acid compound is represented by the following formula:

Y ≦ 0.9X + 5.0 (I)

(In the formula, X represents the residual ratio (unit: mol%) of the above acyl group, and Y represents the initial amount of the acyl group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer used. Relative ratio (unit: mol%) of the amount of the carboxylic acid compound contained in the reaction system on the basis of
Represents )

It is preferable to carry out the reaction while removing from the reaction system so as to satisfy the following. The residual ratio X (mol%) of the acyl group of the organic polymer in the reaction system is based on the organic weight contained in the reaction system based on the initial amount of the acyl group in the vinyl carboxylate polymer used. It is a relative ratio of the amount of the acyl group in the merging, and the degree of saponification of the organic polymer by only the saponification reaction according to the present invention is represented by Z (mol%).
It can be represented by 100-Z.

The above formula (I) qualitatively indicates that it is necessary to further reduce the content of the by-produced carboxylic acid compound in the reaction system as the reaction proceeds. This means that removal of the system compound from the reaction system needs to be performed more strictly. For the purpose of satisfying the formula (I), after the point in the middle of the reaction (the point when the residual ratio X of the acyl group in the organic polymer in the reaction system becomes 40 mol% or before), the reaction system It is generally preferable to accelerate the evaporation of the carboxylic acid compound by performing a reaction under reduced pressure conditions controlled based on the quantitative value while quantifying the carboxylic acid compound present in the carboxylic acid compound. However, since the carboxylate salt cannot be removed by evaporation among the carboxylic acid compounds, it is preferable to set conditions so that the formation of the carboxylate salt is suppressed and the carboxylic acid and / or carboxylic acid ester can be preferentially formed.

In the above formula (I), the residual ratio X of the acyl group and the abundance Y of the carboxylic acid compound are each determined at appropriate times during the reaction by quantitative analysis using a small sample collected from the reaction system. be able to. That is, the residual ratio X of the acyl group is, for example, a value obtained by quickly drying a small amount of a sample collected from a liquid (sol), gel or solid reaction system at a temperature of about 40 ° C. under reduced pressure. The composition containing the organic polymer of FT-I
The acyl group (acetyl group, propionyl group, etc.) is quantitatively analyzed by the diffuse reflection method using R, and the analysis value and the acyl group obtained by quantitatively analyzing the vinyl carboxylate polymer used in the same manner. It can be determined based on the value. Further, the abundance Y of the carboxylic acid compound is determined, for example, by dissolving a small amount of a sample collected from a liquid (sol), gel or solid reaction system in deuterated methanol,
^{Using 13} C-NMR, all acyl groups (acetyl group, propionyl group, etc.) of the organic polymer and by-produced carboxylic acid compound in the course of the reaction were quantitatively analyzed. The relative ratio (mol%) based on the analysis value of the acyl group of the vinyl carboxylate polymer obtained by quantitatively analyzing the vinyl polymer in the same manner was calculated, and the relative ratio and the acyl group were calculated. Can be determined by calculating the difference from the residual ratio X of

When the reaction is carried out so as to satisfy the above formula (I) for the purpose of obtaining a vinyl alcohol polymer composition having a good color tone, when the residual ratio X of acyl groups in the organic polymer is 40 mol% or less. In a certain region, it is not always necessary to always determine the residual ratio X and the abundance Y of the carboxylic acid compound, and if it is instantaneous, the condition of the formula (I) may be deviated. Therefore,
Under the above-mentioned purpose, as long as the conditions that can satisfy the above-mentioned formula (I) with a certain margin are adopted, both are quantified at appropriate time intervals, and if necessary, the pressure condition of the reaction system is adjusted. It is practical to control.

The temperature of the reaction system in the reaction according to the present invention is not necessarily limited, but is usually 20 to 1
It is in the range of 00 ° C, preferably in the range of 40-60 ° C. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.5 to 120 hours, preferably in the range of 1 to 60 hours, and more preferably in the range of 1 to 24 hours. Within range. The atmosphere of the reaction system is not necessarily limited, and conditions such as an air atmosphere and a nitrogen stream can be adopted.

In the reaction according to the present invention, the reaction is carried out using a solution (sol) containing a metal alkoxide-based component, a vinyl carboxylate-based polymer, an organic solvent and, if necessary, other components (catalyst, water, etc.). Although the reaction is started, the reaction is carried out while removing low-boiling substances such as organic solvents and carboxylic acid compounds out of the system, so that the state of the reaction system changes with the elapse of the reaction time. , A gel composition containing a metal oxide and a small amount of an organic solvent is formed, and finally, a solid composition is formed. In addition,
When the reaction system is liquid, stirring may be performed. In addition, heat treatment may be performed at the latter stage of the reaction and / or after the completion of the reaction, and the temperature is preferably in the range of 50 to 250 ° C, more preferably in the range of 60 to 200 ° C. is there.

The microphase-separated structure of the vinyl alcohol-based polymer composition used in the present invention is not necessarily limited. In many cases, the vinyl alcohol-based polymer composition is formed by saponification of a vinyl carboxylate-based polymer. The polymer and the metal oxide formed by the polycondensation of the metal alkoxide-based component each form a co-continuous structure, or the vinyl alcohol-based polymer and the metal oxide form a sea-island structure, and The component is composed of a vinyl alcohol-based polymer, and the island component has a form of a co-continuous structure in which the vinyl alcohol-based polymer is embedded in metal oxide particles.

The vinyl alcohol polymer composition obtained by the reaction according to the present invention is excellent in adhesive strength, durability, impact resistance and penetration resistance. For this reason, the vinyl alcohol-based polymer composition is usefully used as a laminated glass requiring excellent safety.

The vinyl alcohol polymer composition used in the present invention may be added with a cross-linking agent within a range that does not impair the safety, for the purpose of imparting higher adhesion. Examples of the crosslinking agent include an epoxy compound, an isocyanate compound, an aldehyde compound, a silica compound, an aluminum compound, a zirconium compound, and a boron compound. The amount of the crosslinking agent to be added is usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less based on 100 parts by weight of the vinyl alcohol polymer composition. It is preferable not to use it when it is necessary to express it.

Further, as long as the effects of the present invention are not impaired, various additives such as a polymer compound, a plasticizer, an antioxidant, an ultraviolet absorber and a flame retardant can be used. As the additive, those which can be dissolved or finely dispersed in the reaction solution during the preparation of the vinyl alcohol-based polymer composition are suitably used, and examples of the high molecular compound include polyacrylic acid and 2-hydroxyethyl polyacrylate. Acrylic resin; polymethacrylic acid, polymethacrylic acid 2
Methacrylic resins such as hydroxyethyl; starch, cellulose, and salts thereof; These additives may be added during the preparation of the vinyl alcohol-based polymer composition and separately added to and mixed with the vinyl alcohol-based polymer composition.

As a method for introducing the vinyl alcohol-based polymer composition into the laminated glass, an ordinary method for producing a laminated glass is adopted, and a sheet-shaped vinyl alcohol-based polymer composition is sandwiched between glass plates and heat-treated. And / or may be adhered by pressure treatment, the reaction liquid during the preparation of the vinyl alcohol polymer composition is applied on a glass plate,
Another glass plate may be bonded to the coated surface where the reaction has been performed on the glass plate, and may be adhered by heat treatment and / or pressure treatment. The reaction during the preparation of the vinyl alcohol polymer composition may be performed. The liquid may be applied on a glass plate, and the laminated body, which has undergone the reaction on the glass plate, may be adhered by a heat treatment and / or a pressure treatment with the coated surfaces facing each other. At this time, it is considered that a covalent bond is formed by a reaction between the vinyl alcohol-based polymer composition and the glass plate due to the heat treatment and / or the pressure treatment. For example, the vinyl alcohol-based polymer composition is sandwiched between two transparent glass plates, placed in a rubber bag and suctioned under reduced pressure for about 70 minutes.
It is manufactured by pre-adhesion at ~ 110 ° C, and then performing actual adhesion at about 120-150 ° C at a pressure of about 10-15 kg / cm2 using an autoclave or a press.

For the laminated glass of the present invention, a step of heat treatment and / or a step of irradiating ultraviolet rays or electron beams for the purpose of imparting adhesiveness and durability is suitably used. Specifically, a temperature of 80 ° C. or higher, preferably 120 to 200 ° C.
The heat treatment is performed at a temperature within the range. Irradiation with ultraviolet rays or electron beams such as ultraviolet rays (250 nm) or electron beams (0.1 to 50 megarads) is preferably selected in combination with heat treatment for the purpose of expressing adhesiveness and its durability to a higher degree. You.

The thickness of the film made of the vinyl alcohol polymer composition is not particularly limited, but may be 20 μm.
The above is preferable, 50 μm or more is more preferable, and 2
More preferably, it is in the range of 00 to 2000 μm.

As the glass plate, not only an inorganic glass plate but also an organic glass plate such as a polycarbonate plate and a polymethyl methacrylate plate can be used.

The laminated glass comprising the interlayer film for safety laminated glass of the present invention has excellent adhesiveness and durability, and also has remarkably excellent impact resistance and penetration resistance, and is safe even when broken by the action of external force. Provide laminated glass. The laminated glass comprising the interlayer film for safety laminated glass of the present invention is extremely useful as a windshield or a side glass of an automobile, a window glass of a building, and the like.

[0047]

EXAMPLES Hereinafter, the laminated film of the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The measurement or evaluation in the following examples and the like was performed by the following methods (1) to (3).

(1) Amount of acyl group: The vinyl carboxylate polymer used (polyvinyl acetate, polyvinyl propionate, ethylene-vinyl acetate copolymer, etc.) and the corresponding amount in the finally obtained composition For vinyl alcohol-based polymers (polyvinyl alcohol, ethylene-vinyl alcohol copolymer, etc.), an acyl group (acetyl group or propionyl group) is obtained by a diffusion reflection method using FT-IR (“FTIR8200” manufactured by Shimadzu Corporation). ) Was quantitatively analyzed. For the acyl group-containing organic polymer in the course of the reaction, a small amount of a sample is collected from a liquid (sol), gel or solid reaction system, dried quickly at 40 ° C. under reduced pressure, and then, similarly. Was quantitatively analyzed. The residual ratio of acyl groups (unit: mol%) in the organic polymer during the reaction and the final vinyl alcohol-based polymer was calculated based on the amounts of these acyl groups.

(2) Safety: For laminated glass, J
A shotback test was performed in accordance with IS R3205 (1983), and the presence or absence of a crack at a drop height of 120 cm was evaluated. (Less than 50 mm) was evaluated as “Slightly poor; Δ”, and when a large crack (crack length of 50 mm or more) was generated or cracked, “Defective; ×” was evaluated for safety.

(3) Adhesion: For laminated glass,
Leave at 18 ° C ± 0.6 ° C for 16 hours, hit the center of the laminated glass with a hammer having a 0.45kg head, pulverize until the particle size of the glass becomes 6mm or less, and partially peel the glass. The degree of exposure is determined by the Pummel value, and the adhesive strength of the glass can be determined. Pummel value is
When the degree of exposure of the vinyl alcohol-based polymer composition (intermediate film) is 100%, it is set to 0, and 95%, 90%, 85%, 6
In the cases of 0%, 40%, 20%, 10%, 5%, 2%, and 0%, 1, 2, 3, 4, 5, 6, 7, 8, 9,
It was expressed as 10.

Example 1 After dissolving 18.5 parts by weight of polyvinyl acetate having a polymerization degree of 1700 in 200 parts by weight of methanol, 1.26 parts by weight of tetramethoxysilane, 0.5 parts by weight of distilled water and 1N ( (Regulation)-Hydrochloric acid (1.0 part by weight) was added to prepare a sol, which was reacted at 60 ° C for 4 hours while stirring. The obtained sol is placed in a flat bottom container made of polytetrafluoroethylene (“Teflon” manufactured by DuPont) at a height of 2 μm.
mm, and then the upper open part of the container was covered with a polyvinylidene chloride film ("Saran Wrap" manufactured by Asahi Kasei Kogyo Co., Ltd.) and reacted at 60 ° C. for further 4 hours. Thereafter, a hole was formed in the coated film with a needle so that the porosity was 1% based on the area of the coated film, and the reaction was continued at 60 ° C. for 4 hours. Next, the residual ratio of acyl groups (the residual ratio of acetyl groups in this example) in the organic polymer in the system was 6%.
At 0 mol%, the inside of the reaction system was decompressed (pressure:
(100 mmHg), and the reaction was carried out at 60 ° C. while controlling the amount of the carboxylic acid compound (acetic acid compound in this example) in the reaction system to satisfy the above formula (I). After 4 hours, the pressure was changed to 20 mmHg, and the reaction was continued at 40 ° C for 4 hours. Thus, a colorless and transparent single-layer film (thickness: 50 μm) composed of the vinyl alcohol-based polymer / silica composite was obtained. Next, a transparent float glass (length 5 cm × width 5 cm × thickness 3 mm) is sandwiched from both sides of the vinyl alcohol-based polymer / silica composite film, placed in a rubber bag, and removed under a vacuum of 20 mmHg for 20 minutes. After being evacuated, it was transferred to a 90 ° C. oven while being degassed, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. Further, the laminated glass preliminarily bonded as described above is pressured at 12 kg / cm in an air type autoclave.
^{2. The} main bonding was performed at a temperature of 135 ° C. for 20 minutes. Table 1 also shows the results of evaluating the adhesiveness and safety of the laminated glass by a predetermined method.

<Examples 2 to 5> In Example 1, 18.5 parts by weight of polyvinyl acetate and 1.2 parts by weight of tetramethoxysilane were used.
6 parts by weight of a combination of 17.5 parts by weight of polyvinyl acetate and 2.5 parts by weight of tetramethoxysilane (Example 2), 6.6 parts by weight of polyvinyl propionate and 7 parts by weight of tetramethoxysilane 7 (Example 3), a combination of 16.5 parts by weight of an ethylene-vinyl acetate copolymer having an ethylene unit content of 32 mol% and 1.26 parts by weight of tetramethoxysilane (Example 3) 4) or Example 1 except that the combination was changed to 11.4 parts by weight of an ethylene-vinyl acetate copolymer having an ethylene unit content of 44 mol% and 7.6 parts by weight of tetramethoxysilane (Example 5). Similarly, a laminated glass was obtained by performing the reaction. Table 1 also shows the results of evaluating the adhesiveness and safety of the obtained laminated glass by a predetermined method.

Example 6 After dissolving 1.0 part by weight of polyvinyl acetate in 20 parts by weight of methanol in a flat-bottomed polypropylene container, 2.0 parts by weight of tetramethoxysilane and 0.1 part by weight of nitrogen were dissolved in a nitrogen atmosphere. A sol was prepared by adding 1.60 parts by weight of 1N hydrochloric acid, and then the upper open part of the container was covered with aluminum foil having a porosity of 1%, and the sol was prepared at a rate of 10 ° C./hr.
The temperature was raised to 0 ° C., and the reaction was continued for 168 hours. Thus, a brown single-layer film (thickness: 50 μm) composed of a vinyl alcohol polymer (residual ratio of acetyl group: 15 mol%) / silica composite was obtained. From both sides of the obtained film, transparent float glass (5cm × 5c)
mx 3mm thick), and put it in a rubber bag.
After degassing for 20 minutes at a degree of vacuum of 0 mmHg, the substrate was transferred to an oven at 90 ° C. while being degassed, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. Further, the laminated glass preliminarily bonded as described above was fully bonded in an air type autoclave at a pressure of 12 kg / cm ² and a temperature of 135 ° C. for 20 minutes. Table 1 shows the results of evaluating the adhesiveness and safety of the laminated glass by a predetermined method.

<Comparative Example 1> A transparent float glass (length 5c) was formed on both sides of a film (thickness: 50 μm) made of polyvinyl alcohol (“PVA117” manufactured by Kuraray Co., Ltd.).
mx 5cm x 3mm in thickness), put it in a rubber bag and deaerate at 20mmHg vacuum for 20 minutes.
While being degassed, it was transferred to a 90 ° C. oven, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. Further, the laminated glass preliminarily bonded as described above was fully bonded in an air type autoclave at a pressure of 12 kg / cm ² and a temperature of 135 ° C. for 20 minutes. Table 1 shows the results of evaluating the adhesiveness and safety of this laminated glass by a predetermined method.
Shown in

[0056]

[Table 1]

The "metal alkoxide-based component ratio" in Table 1 refers to the amount of metal atoms in a metal alkoxide such as a silicon alkoxide used or an oligomer thereof, and a vinyl carboxylate unit in a used vinyl carboxylate polymer. In terms of moles per 100 moles of acyl groups derived from The “acyl group residual ratio in the composition” refers to the residual amount of the acyl group in the organic polymer in the reaction system or the vinyl alcohol polymer in the finally obtained composition, and the carboxylic acid used It is represented by a mole fraction based on the acyl group in the vinyl polymer. Further, the “thickness of the intermediate layer” indicates the thickness of a film sandwiched between transparent float glass such as a used vinyl alcohol-based polymer / silica-based composite film. In Table 2, "metal alkoxide-based component ratio", "acyl group residual ratio in the composition", and "thickness of the intermediate layer" have the same meanings as described in Table 1, respectively.

According to Table 1 above, Example 1 according to the present invention was used.
According to Nos. 5 to 5, it can be seen that the laminated glass made of the vinyl alcohol-based polymer composition is excellent in adhesion performance and impact resistance, and is a safe laminated glass even when broken by the action of external force.

On the other hand, when the vinyl alcohol polymer alone was used as the intermediate layer of the laminated glass (Comparative Example 1), it was found that the adhesion and the impact resistance were extremely low. When the composition obtained when the polycondensation reaction of the metal alkoxide is performed in the presence of polyvinyl alcohol is used as the interlayer of the laminated glass (Comparative Example 2), both the adhesiveness and the safety are insufficient. I understand. Known i
When a composition obtained by reacting a vinyl carboxylate-based polymer and a metal alkoxide at a known ratio outside the range of the present invention according to the n-situ saponification sol-gel method is used as an interlayer of a laminated glass (Comparative Example 3) shows that the impact resistance is extremely low.

[0060]

As described above, the interlayer film of the laminated glass of the present invention is excellent in adhesiveness when manufacturing the laminated glass, and according to the laminated glass using the interlayer film of the laminated glass of the present invention, the external force is reduced. It is safe even if it is damaged by the action, such as the windshield and side glass of the car,
It is extremely useful as window glass for buildings.

Claims (4)

[Claims] 1. An intermediate film for safety laminated glass comprising a vinyl alcohol-based polymer composition, wherein the vinyl alcohol-based polymer composition is a polycondensation reaction of a vinyl alcohol-based polymer and a metal alkoxide or an oligomer thereof. An interlayer for safety laminated glass, which is a composition containing a metal oxide obtained by the method described in (1). 2. The safety laminated glass according to claim 1, wherein the vinyl alcohol polymer composition is a composition prepared by a polycondensation reaction of a metal alkoxide or an oligomer thereof and a saponification reaction of a vinyl carboxylate polymer. For intermediate film. 3. A low-boiling substance containing an organic solvent is removed by using a solution containing (1) a metal alkoxide or an oligomer thereof, a vinyl carboxylate polymer and an organic solvent. A metal oxide and a vinyl alcohol-based polymer obtained by performing a polycondensation reaction of the metal alkoxide or the oligomer and a saponification reaction of the vinyl carboxylate polymer in parallel in the same reaction system, And (2) the metal alkoxide or the oligomer has a metal atom in the metal alkoxide or the oligomer of 0.01 to 100 mol per 100 mol of the acyl group derived from the vinyl carboxylate unit in the vinyl carboxylate-based polymer. 3. A composition prepared using the composition in such a proportion as to be in the range of 100 mol.
4. The interlayer for safety laminated glass as described in 1. above. 4. A vinyl alcohol-based polymer composition wherein the residual ratio of acyl groups derived from vinyl carboxylate units in the vinyl carboxylate polymer in the organic polymer in the reaction system is 10 mol% or less. The intermediate film for safety laminated glass according to claim 2 or 3, wherein the reaction is continued until the reaction reaches.