JP2000128587A - Intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for a laminated glass which maintains excellent basic performance required for a laminated glass such as transparency, proper adhesion strength, impact absorbing property, resistance against penetration, moisture resistance, light resistance, weather resistance and durability, and which is suitable to obtain a laminated glass showing excellent antistatic performance, and to provide a laminated glass produced by using the intermediate film. SOLUTION: This intermediate film for a laminated glass consists of a polyvinylacetal resin film which is plasticized with a diester-based plasticizer and contains N-polyoxyalkylene-N,N,N-trialkylammonium salt expressed by the formula. In the formula, R1, R2 and R3 are 1-18C alkyl groups, A is a 2-4C alkylene group, n is an integer of 1 to 10, and X- is one of chlorine ion, chlorate ion and perchlorate ion. The laminated glass is produced by interposing the intermediate film for a laminated glass described above between at least a pair of glass sheets for integration.

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 laminated glass and a laminated glass manufactured using the interlayer film.

[0002]

2. Description of the Related Art Conventionally, laminated glass has been widely used for vehicles such as automobiles, window glasses of aircraft, buildings and the like. As a typical example of the laminated glass, an interlayer film for laminated glass made of plasticized polyvinyl butyral resin is interposed between at least two pieces of glass,
And those manufactured integrally.

[0003] The interlayer film for laminated glass made of the plasticized polyvinyl butyral resin has a proper adhesive strength with glass, a tough film strength, and excellent transparency, and is particularly suitable for window glass of vehicles. It is preferably used and the obtained laminated glass has excellent basic performance required as a laminated glass such as transparency, adhesive strength, shock absorption, penetration resistance, moisture resistance, light resistance, weather resistance, durability and the like. It will have both functions.

[0004] On the other hand, with the increase in performance required for laminated glass, in recent years, adhesion of dust and foreign matter due to static electricity has been regarded as a problem. There is a strong demand for a laminated glass interlayer and laminated glass having properties.

However, the above-mentioned conventional intermediate for laminated glass
The film has a surface resistance of 10¹³Ω / cm ^TwoAbout high
Generally easy to charge and can fully satisfy the above requirements
Was not.

In order to improve the antistatic property of the interlayer film for laminated glass, when an ordinary antistatic agent conventionally used for a transparent plastic plate or the like is contained in the interlayer film for laminated glass, for example, Adhesive strength and transparency,
There is a problem that the durability and the like are impaired, and the practicality of the laminated glass becomes poor.

As a specific method for improving the antistatic property of the interlayer film for laminated glass, for example, Japanese Patent Application Laid-Open No.
JP-A-223849 discloses "an interlayer film for antistatic laminated glass characterized in that a nonionic antistatic agent is kneaded or applied to the interlayer film for laminated glass". .

However, in the method using a nonionic antistatic agent as disclosed in the above-mentioned disclosure, a sufficient amount of the nonionic antistatic agent cannot be obtained unless the amount of the nonionic antistatic agent is generally used. It is necessary to increase the amount of kneading and application to the intermediate film for use, and as a result, there is a problem that the adhesion to glass and the toughness of the intermediate film tend to decrease.

That is, an interlayer film for laminated glass and a laminated glass suitable for obtaining a laminated glass having the basic performance required for a laminated glass and having excellent antistatic properties have not been put to practical use at present. .

[0010]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention provides transparency, proper adhesive strength, shock absorption, penetration resistance, moisture resistance, light resistance, weather resistance, and durability. An interlayer film for laminated glass suitable for obtaining a laminated glass exhibiting excellent antistatic properties while retaining excellent basic performance required as a laminated glass such as a laminated glass, and a laminated glass produced using the intermediate film The task is to provide

[0011]

The interlayer film for laminated glass according to the invention described in claim 1 (hereinafter referred to as "first invention") is obtained by forming a polyvinyl acetal resin film plasticized by a diester plasticizer on a laminated film. It is characterized by containing an N-polyoxyalkylene-N, N, N-trialkylammonium salt represented by the following general formula (1).

Embedded image (Wherein, R ¹ , R ² or R ³ represents an alkyl group having 1 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms,
n represents a positive integer of 1 to 10, and X ⁻ represents any of a chloride ion, a chlorate ion and a perchlorate ion)

The interlayer film for laminated glass according to the invention described in claim 2 (hereinafter referred to as “second invention”),
In the interlayer film for laminated glass according to the present invention, the polyvinyl acetal resin has an average degree of butyralization of 60 to 75 mol%.
And N-polyoxyalkylene-N, N, N represented by the following general formula (1) and 20 to 60 parts by weight of a diester plasticizer with respect to 100 parts by weight of the polyvinyl butyral resin. -0.01 to 2 parts by weight of a trialkylammonium salt is contained.

Embedded image (Wherein, R ¹ , R ² or R ³ represents an alkyl group having 1 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms,
n represents a positive integer of 1 to 10, and X ⁻ represents any of a chloride ion, a chlorate ion and a perchlorate ion)

[0013] The interlayer film for laminated glass according to the invention of claim 3 (hereinafter referred to as "third invention") is obtained by adding a polyoxyethylene alkyl monolayer to a polyvinyl acetal resin film plasticized by a diester plasticizer. ether,
It is characterized by containing at least one surfactant selected from the group consisting of alkylphenyl monoethers and fatty acid monoesters.

The interlayer film for laminated glass according to the invention described in claim 4 (hereinafter referred to as “fourth invention”) is provided by the third invention.
In the interlayer film for laminated glass according to the present invention, the polyvinyl acetal resin has an average degree of butyralization of 60 to 75 mol%.
And at least one surfactant 0 selected from the group consisting of alkyl monoethers, alkyl phenyl monoethers and fatty acid monoesters of polyoxyethylene with respect to 100 parts by weight of the polyvinyl butyral resin. .1 to 10 parts by weight.

The interlayer film for laminated glass according to the invention of claim 5 (hereinafter referred to as "fifth invention") is obtained by adding an alkali metal salt and an alkaline earth to a polyvinyl acetal resin film plasticized by a diester plasticizer. It is characterized by containing a metal salt.

The interlayer film for laminated glass according to the invention described in claim 6 (hereinafter referred to as “sixth invention”),
In the interlayer film for laminated glass according to the present invention, the polyvinyl acetal resin has an average degree of butyralization of 60 to 75 mol%.
Of polyvinyl butyral resin, and 0.005 to 0.5 parts by weight of an alkali metal salt and 0.005 to 0.5 parts by weight of an alkaline earth metal salt with respect to 100 parts by weight of the polyvinyl butyral resin. It is characterized by becoming.

Further, the invention according to claim 7 (hereinafter referred to as “7th
The laminated glass according to the present invention is characterized in that an interlayer film for laminated glass according to any one of the first to sixth inventions is interposed between at least a pair of glasses and integrated.

The main component of the polyvinyl acetal resin film plasticized with a diester plasticizer constituting the interlayer film for laminated glass according to the first, third and fifth inventions (hereinafter simply referred to as "intermediate film"). The method for producing the polyvinyl acetal resin is not particularly limited. For example, polyvinyl alcohol (hereinafter, referred to as “PV
A) is dissolved in hot water, and the resulting aqueous solution is maintained at a predetermined temperature, for example, about 10 to 20 ° C., and the required aldehyde and acid catalyst are added thereto. The reaction is then completed by raising the temperature of the reaction system to about 70 ° C. and maturing, and then neutralizing, washing and drying to obtain a polyvinyl acetal resin powder. Adopted.

Specific examples of the polyvinyl acetal resin are not particularly limited.
A, a polyvinyl formal resin obtained by reacting formaldehyde, a polyvinyl acetal resin in a narrow sense, obtained by reacting PVA with acetaldehyde, PV
A polyvinyl butyral resin (hereinafter, referred to as “PVB”) obtained by reacting A with butyraldehyde may be mentioned, and is preferably used. Among them, PVB is more preferably used.

The polyvinyl acetal resin may be used alone or in combination of two or more.

The average degree of polymerization of PVA used for producing the polyvinyl acetal resin is not particularly limited, but is preferably 800-3000. P
When the average degree of polymerization of VA is less than 800, the strength of the obtained intermediate film is too weak, and the penetration resistance of the laminated glass may be reduced.
If it exceeds 0, the strength of the obtained interlayer film becomes too strong, and the shock absorbing properties of the laminated glass may decrease.

The degree of saponification of the PVA is not particularly limited, but is preferably at least 95 mol%. When the degree of saponification of PVA is less than 95 mol%, the transparency, heat resistance, light resistance and the like of the obtained interlayer film may be insufficient. Incidentally, the average degree of polymerization and saponification degree of the PVA,
For example, it can be measured according to JIS K-6726 "Testing method for polyvinyl alcohol".

The polyvinyl acetal resin thus obtained is composed of a vinyl acetal component, a vinyl alcohol component and a vinyl acetate component. When the polyvinyl acetal resin is a polyvinyl acetal resin other than PVB, the amount of the vinyl alcohol component and the amount of the vinyl acetate component are measured, and the amount of the remaining vinyl acetal component can be calculated by subtracting the amounts of both components from 100. .

When the polyvinyl acetal resin is PVB, the amounts of the vinyl butyral component, the vinyl alcohol component, and the vinyl acetate component are, for example, JI
It can be measured according to SK-6728 "Testing method for polyvinyl butyral", nuclear magnetic resonance method (NMR) or the like.

The average degree of butyralization of the PVB is not particularly limited, but is preferably from 60 to 75 mol%, more preferably from 64 to 71 mol%.

The average degree of butyralization of PVB is 60 mol%
If it is less than, the hygroscopicity of the obtained interlayer becomes large,
A whitening phenomenon due to moisture absorption may easily occur in the peripheral portion of the laminated glass, and conversely, the average butyral degree of PVB is 7%.
If it exceeds 5 mol%, the mechanical strength of the obtained interlayer film may decrease.

In the first, third and fifth inventions, the diester plasticizer used for plasticizing the polyvinyl acetal resin is a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol. Any plasticizer can be used as long as it is obtained by an esterification reaction, and the type is not particularly limited.

Specific examples of the diester plasticizer (hereinafter, simply referred to as "plasticizer") are not particularly limited. For example, di-n-hexyl adipate, di2
-Ethylhexyl adipate, diisodecyl adipate, octyldecyl adipate, heptylnonyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, butyl benzyl sebacate Kate, di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dilauryl phthalate, diethylene glycol di-2-ethyl butyrate ,
Triethylene glycol di-2-ethyl butyrate (3G
H), tetraethylene glycol di-2-ethyl butyrate (4GH), diethylene glycol dipentylate,
Diethylene glycol dihexylate, triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4
GO), tetraethylene glycol di-n-heptanoate, dihexyl adipate, dibenzyl phthalate, and the like, and are preferably used. Among them, 3GH and 4G are preferable.
H, 3GO, 4GO and the like are more preferably used.

The above plasticizers may be used alone or in combination of two or more.

The content of the plasticizer in the intermediate film is as follows:
Although not particularly limited, the plasticizer is preferably 20 to 60 parts by weight, more preferably 30 to 55 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin.

If the content of the plasticizer is less than 20 parts by weight based on 100 parts by weight of the polyvinyl acetal resin, the resulting laminated glass may have a reduced penetration resistance. If the content exceeds 60 parts by weight, the plasticizer may bleed out on the surface of the intermediate film, and the transparency of the intermediate film, the adhesive strength to glass, and the like may decrease.

The interlayer film for laminated glass according to the first invention comprises:
In the plasticized polyvinyl acetal resin film composed of the polyvinyl acetal resin and the plasticizer described above,
It contains an N-polyoxyalkylene-N, N, N-trialkylammonium salt represented by the following general formula (1) as an antistatic agent.

Embedded image

In the general formula (1), R ¹ , R ² or R ³ represents an alkyl group having 1 to 18 carbon atoms. When the carbon number of the alkyl group exceeds 18, it becomes difficult to dissolve in PVB or a plasticizer, and it becomes difficult to produce an intermediate film, or the transparency of the intermediate film decreases. Note that R ¹ , R ² or R ³ is
It may be the same alkyl group having 1 to 18 carbon atoms,
Each may be a different alkyl group.

A represents an alkylene group having 2 to 4, preferably 2 to 3 carbon atoms. When the number of carbon atoms of the alkylene group is less than 2 or more than 4, the antistatic effect becomes weak.

N represents a positive integer of 1 to 10. n is 10
If it exceeds, the hydrophilicity becomes strong, so that the transparency and moisture resistance of the interlayer film decrease.

X ^- represents a counter anion, and specifically represents any of a chloride ion, a chlorate ion and a perchlorate ion.

Since the N-polyoxyalkylene-N, N, N-trialkylammonium salt represented by the above general formula (1) exhibits excellent antistatic performance with a small amount of use, various types of intermediate films can be used. An excellent antistatic property can be imparted to the interlayer film without impairing the performance.

The above N-polyoxyalkylene-N, N,
The N-trialkylammonium salt may be used alone or in combination of two or more.

The content of the N-polyoxyalkylene-N, N, N-trialkylammonium salt in the intermediate film is not particularly limited, but the content of N-polyalkylene resin is 100 parts by weight of polyvinyl acetal resin. Oxyalkylene-N, N, N-trialkylammonium salt
It is preferably from 01 to 2 parts by weight.

If the content of the N-polyoxyalkylene-N, N, N-trialkylammonium salt is less than 0.01 part by weight based on 100 parts by weight of the polyvinyl acetal resin, sufficient antistatic performance cannot be obtained. There is
Conversely, N based on 100 parts by weight of polyvinyl acetal resin
If the content of the polyoxyalkylene-N, N, N-trialkylammonium salt is more than 2 parts by weight, the resulting interlayer may have poor adhesion to glass and durability.

The interlayer film for laminated glass according to the second invention is
In the interlayer film for laminated glass according to the first aspect, the polyvinyl acetal resin has an average butyralization degree of 6
0 to 75 mol% of PVB, and the PVB 10
It is characterized by comprising 20 to 60 parts by weight of the plasticizer and 0.01 to 2 parts by weight of the N-polyoxyalkylene-N, N, N-trialkylammonium salt with respect to 0 parts by weight.

In the second invention, if the average degree of butyralization of PVB is less than 60 mol%, the hygroscopicity of the obtained interlayer film is increased, and higher prevention of the whitening phenomenon due to moisture absorption at the periphery of the laminated glass is obtained. The effect is difficult to obtain, and conversely, the average butyral degree of PVB is 75 mol%.
When it exceeds, it is difficult to obtain higher mechanical strength of the obtained interlayer film.

In the second invention, if the content of the plasticizer is less than 20 parts by weight based on 100 parts by weight of PVB,
Higher penetration resistance of the obtained laminated glass becomes difficult to obtain, and conversely, when the content of the plasticizer with respect to 100 parts by weight of PVB exceeds 60 parts by weight, the plasticizer easily bleeds out on the surface of the obtained intermediate film. , It is difficult to obtain higher transparency and higher adhesion to glass.

Further, in the second invention, N-polyoxyalkylene-N, N, N-
When the content of the trialkylammonium salt is less than 0.01 part by weight, it is difficult to obtain a higher antistatic property of the obtained interlayer film.
When the content of the polyoxyalkylene-N, N, N-trialkylammonium salt is more than 2 parts by weight, it is difficult to obtain higher adhesive strength and durability with respect to glass of the obtained interlayer film.

Next, the interlayer film for laminated glass according to the third invention comprises a plasticized polyvinyl acetal resin film composed of the above-mentioned polyvinyl acetal resin and a plasticizer.
At least one surfactant selected from the group consisting of polyoxyethylene alkyl monoethers, alkylphenyl monoethers and fatty acid monoesters (hereinafter simply referred to as “surfactant”) is contained as an antistatic agent. Become.

The above surfactant is excellent in a relatively small amount of use by dissociating hydrogen in the terminal hydroxyl group of the oxyethylene portion or hydrogen in the ethylene portion to become a proton and moving within a molecule or between molecules. Since the antistatic properties are exhibited, excellent antistatic properties can be imparted to the intermediate film without deteriorating various properties of the intermediate film.

Among the above surfactants, the alkyl monoether of polyoxyethylene is represented by the following general formula (2). The alkylphenyl monoether of polyoxyethylene is represented by the following general formula (3). Furthermore, the fatty acid monoester of polyoxyethylene is represented by the following general formula (4)
It is represented by

[0048]

Embedded image

Embedded image

Embedded image

In the general formulas (2), (3) and (4), R represents an alkyl group. Although the carbon number of the alkyl group is not particularly limited, it is preferably 1 to 20 in the general formulas (2) and (3), and 1 to 19 in the general formula (4). Is preferred.

When the number of carbon atoms of the alkyl group in the general formulas (2) and (3) exceeds 20, and when the number of carbon atoms of the alkyl group in the general formula (4) exceeds 19, the compatibility with the polyvinyl acetal resin is increased. , The transparency of the interlayer may be reduced, or the surfactant may easily bleed out to the surface of the interlayer.

In the general formulas (2), (3) and (4), n represents a positive integer. The number of n is not particularly limited, but is preferably 1 to 10, and more preferably 3 to 8. When the number n exceeds 10, the hydrophilicity becomes too strong, and the whitening phenomenon due to elution into moisture or moisture absorption may easily occur.

The balance between R and n is represented by the HLB value indicating the hydrophilic-lipophilic balance of the surfactant.
In the present invention, the HLB value is preferably 14 or less. When the HLB value exceeds 14, the hydrophilicity of the surfactant becomes too strong, and the whitening phenomenon due to elution into moisture or moisture absorption may easily occur.

The surfactants represented by the general formulas (2), (3) and (4) may be used alone or in combination of two or more.

Specific examples of the alkyl monoether of polyoxyethylene represented by the general formula (2) are not particularly limited. For example, polyoxyethylene mono-2-ethyl butyl ether, polyoxyethylene mono2 -Ethylhexyl ether, polyoxyethylene monolauryl ether, polyoxyethylene monostearyl ether, polyoxyethylene monooleyl ether, and the like are preferably used.

The above alkyl monoethers of polyoxyethylene may be used alone or in combination of two or more.

Specific examples of the alkylphenyl monoether of polyoxyethylene represented by the general formula (3) are not particularly limited. For example, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl Phenyl ether, polyoxyethylene lauryl phenyl ether and the like are exemplified, and are preferably used.

The above alkylphenyl ethers of polyoxyethylene may be used alone or in combination of two or more.

Further, specific examples of the fatty acid monoester of polyoxyethylene represented by the general formula (4) are not particularly limited. For example, polyoxyethylene 2-ethylbutyrate, polyoxyethylene Examples thereof include 2-ethylhexanoate, polyoxyethylene laurate, polyoxyethylene stearate, and polyoxyethylene oleate, which are preferably used.

The above polyoxyethylene fatty acid monoesters may be used alone or in combination of two or more.

The content of the above surfactant in the intermediate film is not particularly limited, but the content of the surfactant is 0.1 to 10 with respect to 100 parts by weight of the polyvinyl acetal resin.
It is preferably in parts by weight.

If the content of the surfactant is less than 0.1 part by weight with respect to 100 parts by weight of the polyvinyl acetal resin, sufficient antistatic performance may not be obtained. If the content of the activator exceeds 10 parts by weight, the resulting interlayer may have reduced adhesive strength to glass and durability.

The interlayer film for laminated glass according to the fourth invention comprises:
In the interlayer film for laminated glass according to the third aspect, the polyvinyl acetal resin has an average degree of butyralization of 6
0 to 75 mol% of PVB, and the PVB 10
It is characterized by containing 20 to 60 parts by weight of the plasticizer and 0.1 to 10 parts by weight of the surfactant with respect to 0 parts by weight.

In the fourth invention, when the average degree of butyralization of PVB is less than 60 mol%, the hygroscopicity of the obtained interlayer film is increased, and the prevention of whitening caused by moisture absorption in the peripheral portion of the laminated glass is improved. The effect is difficult to obtain, and conversely, the average butyral degree of PVB is 75 mol%.
When it exceeds, it is difficult to obtain higher mechanical strength of the obtained interlayer film.

In the fourth invention, if the content of the plasticizer is less than 20 parts by weight based on 100 parts by weight of PVB,
Higher penetration resistance of the obtained laminated glass becomes difficult to obtain, and conversely, when the content of the plasticizer with respect to 100 parts by weight of PVB exceeds 60 parts by weight, the plasticizer easily bleeds out on the surface of the obtained intermediate film. , It is difficult to obtain higher transparency and higher adhesion to glass.

Further, in the fourth invention, if the content of the surfactant is less than 0.1 part by weight with respect to 100 parts by weight of PVB, it is difficult to obtain a higher antistatic property of the obtained intermediate film, and conversely, PVB 100 When the content of the surfactant with respect to parts by weight exceeds 10 parts by weight, it is difficult to obtain higher adhesive strength and durability with respect to the glass of the obtained interlayer film.

Next, the interlayer film for laminated glass according to the fifth invention comprises a plasticized polyvinyl acetal resin film composed of the above-mentioned polyvinyl acetal resin and a plasticizer.
It contains an alkali metal salt as an antistatic agent and an alkaline earth metal salt as an adhesion regulator.

The alkali metal salt exhibits excellent antistatic performance with a small amount of use by dissociating and moving into ions in the intermediate film, so that various properties of the intermediate film are not impaired. Excellent antistatic properties.

Further, the alkaline earth metal salt functions as an adhesion regulator, and maintains the adhesion between the interlayer and the glass within a proper range with a small amount of use. It is excellent in penetrability and hardly causes peeling or whitening of the peripheral portion due to moisture absorption.

The metal used for the alkali metal salt is not particularly limited. For example, the mobility when an alkali metal having a relatively small atomic weight, such as lithium, sodium and potassium, is dissociated into ions. It is more preferably used because it exhibits higher and more excellent antistatic performance. Examples of the alkali metal salt include, but are not limited to, halides of these alkali metals; inorganic salts such as acetates, nitrates, sulfates, and carbonates; carboxylic acids, organic sulfonic acids, and phosphoric acids ester,
Salts of organic acids such as fatty acids and the like are mentioned, and are preferably used. Among them, alkali metal salts of carboxylic acids having 1 to 20 carbon atoms such as potassium salts of carboxylic acids having 1 to 20 carbon atoms are more preferable. Used.

The above alkali metal salts may be used alone or in combination of two or more.

The content of the alkali metal salt in the intermediate film is not particularly limited, but the alkali metal salt is added to 100 parts by weight of the polyvinyl acetal resin.
It is preferably from 005 to 0.5 part by weight, more preferably from 0.01 to 0.1 part by weight.

If the content of the alkali metal salt is less than 0.005 parts by weight based on 100 parts by weight of the polyvinyl acetal resin, sufficient antistatic performance may not be obtained. When the content of the metal salt exceeds 0.5 parts by weight,
The interlayer film easily absorbs moisture, and the whitening phenomenon may easily occur in the peripheral portion of the laminated glass.

The alkaline earth metal salt is not particularly restricted but includes, for example, halides of alkaline earth metals; inorganic salts such as acetates, nitrates, sulfates and carbonates; Organic sulfonic acids, phosphoric acid esters, salts of organic acids such as fatty acids and the like, and are preferably used. Among them, carboxylic acids having 1 to 20 carbon atoms such as magnesium salts of carboxylic acids having 1 to 20 carbon atoms are preferable. Alkaline earth metal salts are more preferably used.

The above alkaline earth metal salts may be used alone or in combination of two or more.

The content of the alkaline earth metal salt in the intermediate film is not particularly limited. However, the content of the alkaline earth metal salt is 0.005 to 0.5 part by weight based on 100 parts by weight of the polyvinyl acetal resin. Is preferably
More preferably, it is 0.01 to 0.1 part by weight.

When the content of the alkaline earth metal salt is less than 0.005 parts by weight based on 100 parts by weight of the polyvinyl acetal resin, the effect of adjusting the adhesive strength is poor, and the penetration resistance of the laminated glass may be reduced. Conversely, if the content of the alkaline earth metal salt with respect to 100 parts by weight of the polyvinyl acetal resin exceeds 0.5 parts by weight, the interlayer film easily absorbs moisture, and the whitening phenomenon easily occurs in the peripheral portion of the laminated glass. There is.

The interlayer film for laminated glass according to the sixth invention is
In the interlayer film for laminated glass according to the fifth aspect, the polyvinyl acetal resin has an average degree of butyralization of 6
0 to 75 mol% of PVB, and the PVB 10
20 to 60 parts by weight of the plasticizer, 0.005 to 0.5 parts by weight of the alkali metal salt, and 0.005 to 0.5 parts by weight of the alkaline earth metal salt with respect to 0 parts by weight. It is characterized by.

In the sixth invention, if the average degree of butyralization of PVB is less than 60 mol%, the hygroscopicity of the obtained intermediate film is increased, and the prevention of whitening caused by moisture absorption in the periphery of the laminated glass is improved. The effect is difficult to obtain, and conversely, the average butyral degree of PVB is 75 mol%.
When it exceeds, it is difficult to obtain higher mechanical strength of the obtained interlayer film.

In the sixth invention, if the content of the plasticizer is less than 20 parts by weight based on 100 parts by weight of PVB,
Higher penetration resistance of the obtained laminated glass becomes difficult to obtain, and conversely, when the content of the plasticizer with respect to 100 parts by weight of PVB exceeds 60 parts by weight, the plasticizer easily bleeds out on the surface of the obtained intermediate film. , It is difficult to obtain higher transparency and higher adhesion to glass.

Further, in the sixth invention, if the content of the alkali metal salt is less than 0.005 parts by weight with respect to 100 parts by weight of PVB, it is difficult to obtain a higher antistatic performance, and conversely, the content of the alkali metal with respect to 100 parts by weight of PVB When the content of the salt exceeds 0.5 parts by weight, the interlayer film easily absorbs moisture, and it is difficult to obtain a higher effect of preventing the whitening phenomenon due to moisture absorption generated in the peripheral portion of the laminated glass.

In the sixth invention, if the content of the alkaline earth metal salt is less than 0.005 parts by weight with respect to 100 parts by weight of PVB, it is difficult to obtain a higher effect of adjusting the adhesive force, and the laminated glass has a higher resistance. When the content of the alkaline earth metal salt with respect to 100 parts by weight of PVB exceeds 0.5 part by weight, the interlayer film easily absorbs moisture, and the penetration of the interlayer film due to the moisture absorption generated in the peripheral portion of the laminated glass becomes difficult. It becomes difficult to obtain a higher prevention effect against the whitening phenomenon.

In the interlayer film for laminated glass according to the first to sixth aspects of the present invention, besides the essential components, the adhesive strength between the interlayer film and the glass may be properly adjusted within the range not hindering the achievement of the object of the present invention. (The first invention to the fourth invention), an adhesion regulator other than the alkaline earth metal salt (the fifth invention and the sixth invention), and prevent deterioration of the interlayer film. Or one or more of various additives such as an ultraviolet absorber and a light stabilizer for improving the light resistance of the interlayer film.

Examples of the adhesion regulator include, but are not particularly limited to, carboxylic acid metal salts such as alkali metal or alkaline earth metal salts of monocarboxylic acid and dicarboxylic acid, and modified silicone oil. One or more of these are suitably used.

Specific examples of the metal salt of a carboxylic acid which may be used as an adhesion regulator are not particularly limited. For example, magnesium butyrate, magnesium propionate, magnesium 2-ethylbutyrate, valeric acid Magnesium, magnesium hexanoate, magnesium heptanoate, magnesium malonate, magnesium succinate, magnesium glutarate, magnesium adipate, potassium propionate, and the like, and one or more of these are preferably used. However, magnesium salts are more preferably used.

The content of the metal salt of the carboxylic acid in the intermediate film is not particularly limited, but is 0.01 to 0.1 part by weight of the metal salt of the carboxylic acid per 100 parts by weight of the polyvinyl acetal resin. And more preferably 0.03 to 0.08 parts by weight.

If the content of the metal salt of carboxylic acid is less than 0.01 part by weight based on 100 parts by weight of the polyvinyl acetal resin, the effect of adjusting the adhesive strength cannot be sufficiently obtained.
In some cases, the penetration resistance of the laminated glass is insufficient, and when the content of the metal salt of the carboxylic acid exceeds 0.1 part by weight based on 100 parts by weight of the polyvinyl acetal resin, the adhesive strength between the interlayer and the glass is reduced. May be too low, or the transparency of the laminated glass may be reduced.

The modified silicone oil which may also be used as an adhesion regulator is not particularly limited. For example, polysiloxane is reacted with a compound having a functional group to be introduced therein. And a viscous liquid generally obtained from polysiloxane, which is a pale yellow transparent viscous liquid.
More than one species is preferably used.

Specific examples of the modified silicone oil are not particularly limited, and examples thereof include epoxy-modified silicone oil, ether-modified silicone oil, ester-modified silicone oil, carboxyl-modified silicone oil, and amine-modified silicone oil. One or more of these are suitably used.

The molecular weight of the modified silicone oil is not particularly limited, but is preferably from 800 to 5000, more preferably from 1500 to 4000.

If the molecular weight of the modified silicone oil is less than 800, localization on the surface of the intermediate film is reduced, so that a sufficient adhesive force adjusting effect may not be obtained. If it exceeds 5,000, the compatibility with the polyvinyl acetal resin becomes poor, so that bleeding out to the surface of the intermediate film is liable to occur, and the adhesive strength to glass may decrease.

The content of the modified silicone oil in the interlayer is not particularly limited, but may be 0.01 to 0.2 parts by weight of the modified silicone oil based on 100 parts by weight of the polyvinyl acetal resin. Preferably, it is more preferably 0.03 to 0.1 part by weight.

If the content of the modified silicone oil is less than 0.01 part by weight with respect to 100 parts by weight of the polyvinyl acetal resin, the effect of adjusting the adhesive strength cannot be sufficiently obtained, so that the penetration resistance of the laminated glass becomes insufficient. On the contrary, when the content of the modified silicone oil per 100 parts by weight of the polyvinyl acetal resin exceeds 0.2 parts by weight, the compatibility with the polyvinyl acetal resin becomes poor, so that the bleed out to the surface of the interlayer film becomes easy. , The adhesive strength to glass may be reduced.

Examples of the antioxidant include, but are not particularly limited to, for example, t-butylhydroxytoluene (for example, trade name “Sumilyzer B” manufactured by Sumitomo Chemical Co., Ltd.)
HT "), tetrakis- [methylene-3- (3'-5 '
-Di-t-butyl-4'-hydroxyphenyl) propionate] methane (for example, trade name "Irganox 1010" manufactured by Ciba-Geigy), and one or more of these are suitably used.

The ultraviolet absorber is not particularly limited, but for example, 2- (2′-hydroxy-5 ′)
-Methylphenyl) benzotriazole (for example, trade name "Tinuvin P" manufactured by Ciba Geigy), 2- (2'-
Hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (for example, trade name “Tinuvin 320” manufactured by Ciba-Geigy), 2- (2′-hydroxy-3 ′)
-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole (for example, trade name "Tinuvin 326" manufactured by Ciba Geigy), 2- (2'-hydroxy-
3 ′, 5′-di-amylphenyl) benzotriazole (for example, trade name “Tinuvin 32 manufactured by Ciba Geigy)
8 ") and the like, and one or more of these are suitably used.

Examples of the light stabilizer include, but are not particularly limited to, hindered amine light stabilizers such as “ADEKA STAB LA-57” (trade name, manufactured by Asahi Denka Kogyo KK). Alternatively, two or more types are suitably used.

The method for producing the interlayer film for laminated glass according to the first to sixth aspects of the present invention is not particularly limited. For example, each of the predetermined amounts of each essential component and one of various additives to be contained as necessary. Seeds or two or more kinds are mixed with each other and uniformly kneaded, then formed into a sheet by extrusion, calendering, pressing, casting, inflation, etc., and plasticized with a plasticizer. The formed PVB film may be formed and used as an intermediate film.

The plasticized PVB film may be used as an intermediate film as a single layer or as an intermediate film in a state where two or more films are laminated. The intermediate film may be used as a single layer, or may be used in a state where two or more sheets are stacked.

The total thickness of the intermediate film is not particularly limited. However, considering the minimum required shock absorption, penetration resistance, light resistance, weather resistance, etc., as a laminated glass,
In practice, it is generally preferable that the thickness be in the range of 0.3 to 1.6 mm, similarly to the film thickness of an ordinary interlayer film for laminated glass.

Next, in the laminated glass according to the seventh invention, the interlayer film for a laminated glass according to any one of the first invention to the sixth invention described above is interposed between at least a pair of glasses.
It is characterized by being integrated.

The above glass includes not only ordinary inorganic transparent glass but also organic transparent glass such as polycarbonate plate and polymethyl methacrylate plate.

The type of the above glass is not particularly limited. For example, various types of inorganic glass such as a float plate glass, a polished plate glass, a template plate glass, a net plate glass, a line plate glass, a heat ray absorption plate glass, a colored plate glass, etc. Glass or organic glass is mentioned, and one or more of these are suitably used. The thickness of the glass may be appropriately selected depending on the application, and is not particularly limited.

The manufacturing method of the laminated glass according to the seventh invention is not special, and the same manufacturing method as in the case of the ordinary laminated glass is employed. For example, an interlayer film for laminated glass according to any of the first to sixth inventions is interposed between two transparent glass plates, placed in a rubber bag, and suctioned under reduced pressure at a temperature of about 70 to 110 ° C. Pre-adhesion and then using an autoclave or press at a temperature of about 120-150 ° C and about 10-15 kg /
A desired laminated glass can be obtained by performing actual bonding at a pressure of cm ² and integrating them.

[0103]

The interlayer film for laminated glass according to the first to fourth aspects of the present invention is a polyvinyl acetal resin film plasticized with a diester-based plasticizer, and an antistatic agent exhibiting excellent antistatic performance with a small amount of use. Since it is contained, it is suitable for obtaining a laminated glass having excellent antistatic properties while maintaining the basic performance required as a laminated glass.

The interlayer film for laminated glass according to the fifth and sixth aspects of the present invention is an antistatic film which exhibits excellent antistatic performance with a small amount of use on a polyvinyl acetal resin film plasticized with a diester plasticizer. Contains an adhesive agent and an adhesive agent that exerts an excellent adhesive force adjusting effect with a small amount of use, so that the adhesive force between the intermediate layer and the glass is kept within an appropriate range, and therefore, shock absorption Resistance and penetration resistance,
It is suitable for obtaining a laminated glass having excellent whitening resistance and the like and excellent antistatic properties.

The laminated glass according to the seventh invention is characterized in that
Since it is manufactured by using the interlayer film for laminated glass according to any one of the inventions to the sixth invention, it is excellent in basic performance required as a laminated glass such as shock absorption, penetration resistance, whitening resistance and the like, and excellent in charging. Has prevention properties.

[0106]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

(Example 1)

(1) Production of interlayer film for laminated glass As polyvinyl acetal resin, polyvinyl butyral resin (PVB) 10 having an average degree of butyralization of 65 mol% was used.
0 parts, 40 parts of triethylene glycol di-2-ethyl butyrate (3GH) as a diester plasticizer,
As an antistatic agent, N-trioxyethylene-N, N,
0.2 part of N-trioctylammonium perchlorate [in the general formula (1), R ^{1 to} R ³ = octyl group, A = ethylene group, n = 3, X = perchloric acid] It was supplied to a roll and kneaded uniformly. Next, using a press molding machine, the kneaded material obtained above was heated to a temperature of 150.
Press molding was performed at a temperature of 120 ° C. and a pressure of 120 kg / cm ² for 10 minutes to produce an interlayer film for laminated glass having a thickness of 0.8 mm.

(2) Evaluation The performance (surface resistance) of the interlayer film for laminated glass obtained above was evaluated by the following method. The results were as shown in Table 1.

Surface resistance: After drying the interlayer film for laminated glass in a desiccator for 24 hours, the interlayer film for laminated glass was measured using a surface resistance measuring device (model “DSM-8103”, manufactured by Toa Denpa Kogyo Co., Ltd.). Surface resistance (Ω / c
m ² ) was measured.

Example 2 In the production of an interlayer film for laminated glass, instead of 0.2 parts of N-trioxyethylene-N, N, N-trioctylammonium perchlorate as an antistatic agent, N -Oxyethylene-N, N, N
- In lauryl dipropyl ammonium perchlorate [Formula ^(1), R 1 = lauryl group, R ² and R ³ = propyl, A = ethylene group, n = 1, X = perchloric acid)
Except that 0.2 parts were used, the same as in Example 1
An interlayer for laminated glass was obtained.

Example 3 In the production of an interlayer for laminated glass, instead of 0.2 parts of N-trioxyethylene-N, N, N-trioctylammonium perchlorate as an antistatic agent, N -Oxyethylene-N, N, N
-An interlayer film for laminated glass was obtained in the same manner as in Example 1 except that 0.6 part of lauryldipropylammonium perchlorate was used.

Example 4 100 parts by weight of PVB having an average degree of butyralization of 65 mol% as a polyvinyl acetal resin and triethylene glycol di-2-ethylhexanoate (3GO) 40 as a diester plasticizer were used.
And 0.5 part of triethylene glycol lauryl ether as an antistatic agent, and the mixture was supplied to a mixing roll and uniformly kneaded. Then, using a press molding machine,
The kneaded material obtained above was heated at a temperature of 150 ° C. and a pressure of 120 kg.
/ Cm ² for 10 minutes, and the film thickness is 0.8
mm interlayer film for laminated glass was manufactured.

Example 5 In the production of an interlayer film for laminated glass, except that 0.5 parts of tetraethylene glycol octyl phenyl ether was used as an antistatic agent instead of 0.5 parts of triethylene glycol lauryl ether. In the same manner as in Example 4, an interlayer film for laminated glass was obtained.

(Example 6) In the production of an interlayer film for laminated glass, 0.5 parts of tetraethylene glycol laurate monoester was used as an antistatic agent instead of 0.5 parts of triethylene glycol lauryl ether. Except for the above, an intermediate film for laminated glass was obtained in the same manner as in Example 4.

Example 7 In the production of an interlayer film for laminated glass, 0.5 parts of triethylene glycol 2-ethylhexanoate was used as an antistatic agent instead of 0.5 parts of triethylene glycol lauryl ether. Except having used it, it carried out similarly to Example 4, and obtained the interlayer film for laminated glass.

Comparative Example 1 An interlayer film for laminated glass was obtained in the same manner as in Example 1 except that no antistatic agent was added in the production of the interlayer film for laminated glass.

(Comparative Example 2) In the production of an interlayer film for laminated glass, instead of 0.2 parts of N-trioxyethylene-N, N, N-trioctylammonium perchlorate as an antistatic agent, N An intermediate film for laminated glass was obtained in the same manner as in Example 1 except that 0.2 part of -lauryl-N, N, N-trimethylammonium perchlorate was used.

Comparative Example 3 An interlayer film for laminated glass was obtained in the same manner as in Example 4 except that no antistatic agent was added in the production of the interlayer film for laminated glass.

The performance (surface resistance) of the nine types of interlayer films for laminated glass obtained in Examples 2 to 7 and Comparative Examples 1 to 3 was evaluated in the same manner as in Example 1. The results were as shown in Table 1.

[0121]

[Table 1]

As is clear from Table 1, the interlayer films for laminated glass of Examples 1 to 7 according to the present invention each had a low surface resistance value and exhibited excellent antistatic properties.

On the other hand, the interlayer films for laminated glass of Comparative Examples 1 and 3 which did not contain an antistatic agent, and Comparative Example 2 which contained an antistatic agent not falling under the general formula (1) All of the interlayer films for laminated glass had a high surface resistance and were inferior in antistatic properties.

(Example 8) As a polyvinyl acetal resin, 100 parts by weight of PVB having an average degree of butyralization of 65 mol%, and 3GH40 as a diester plasticizer
Parts, 0.05 parts of potassium 2-ethylhexanoate as an antistatic agent and 0.1 parts of magnesium 2-ethylbutyrate as an adhesion regulator were supplied to a mixing roll and kneaded uniformly. Next, using a press molding machine, the kneaded material obtained above was heated at a temperature of 150 ° C and a pressure of 120 kg /
Press molding under the condition of cm ² for 10 minutes, the film thickness is 0.8 m
m was manufactured as an interlayer film for laminated glass.

The interlayer film for a laminated glass obtained above was
Moisture content of 0.4 in constant temperature and humidity room (20 ℃ -65% RH)
After adjusting the humidity to 0.5% by weight, it was sandwiched between two pieces of float glass (2.4 mm thick) and preliminarily bonded by a roll method. Next, the preliminarily bonded laminate was permanently bonded in an autoclave at a temperature of 140 ° C. and a pressure of 13 kg / cm ² to produce a laminated glass.

The performance (surface resistance value) of the interlayer film for laminated glass obtained above was evaluated in the same manner as in Example 1. The results were as shown in Table 2.

The performance (peripheral peelability) of the laminated glass obtained above was evaluated by the following method. The results were as shown in Table 2.

Peripheral peeling property: constant temperature and humidity chamber (50 ± 2 ° C.)
(−95% RH) for 4 weeks, then take out, −18 ±
The laminated glass, which had been left at a temperature of 0.6 ° C. for 16 hours and temperature-controlled, was beaten with a hammer having a head of 0.45 kg, and pulverized until the glass particle diameter became 6 mm or less. Next, it was visually observed whether or not a portion where the glass was completely peeled off due to moisture absorption occurred in the peripheral portion of the laminated glass, and the peripheral portion peelability was evaluated.

Example 9 In the production of an interlayer film for laminated glass, 0.02 parts of potassium 2-ethylhexanoate was used as an antistatic agent instead of 0.05 parts of potassium 2-ethylhexanoate. Except for the above, an intermediate film for laminated glass was obtained in the same manner as in Example 8.

Example 10 In the production of the interlayer film for laminated glass, the procedure was carried out except that 0.05 parts of potassium laurate was used instead of 0.05 parts of potassium 2-ethylhexanoate as an antistatic agent. In the same manner as in Example 8, an interlayer film for laminated glass was obtained.

Example 11 In the production of the interlayer film for laminated glass, the procedure was carried out except that 0.05 parts of potassium oleate was used instead of 0.05 parts of potassium 2-ethylhexanoate as an antistatic agent. In the same manner as in Example 8, an interlayer film for laminated glass was obtained.

Comparative Example 4 In the production of an interlayer film for laminated glass, an antistatic agent (potassium 2-ethylhexanoate) and an adhesion regulator (magnesium 2-ethylbutyrate) were used.
In the same manner as in Example 8 except that
An interlayer for laminated glass was obtained.

Comparative Example 5 An interlayer film for laminated glass was produced in the same manner as in Example 8 except that an antistatic agent (potassium 2-ethylhexanoate) was not contained in the production of the interlayer film for laminated glass. Obtained.

(Comparative Example 6) An interlayer film for laminated glass was produced in the same manner as in Example 8 except that no adhesiveness regulator (magnesium 2-ethylbutyrate) was contained in the production of the interlayer film for laminated glass. Obtained.

Using the six types of interlayer films for laminated glass obtained in Examples 9 to 11 and Comparative Examples 4 to 6, six types of laminated glass were obtained in the same manner as in Example 8. .

The performance (surface resistance value) of the six types of interlayer films for laminated glass obtained in Examples 9 to 11 and Comparative Examples 4 to 6 was evaluated in the same manner as in Example 1. The results were as shown in Table 2.

Examples 9 to 11 and Comparative Examples 4 to 6
The performance (peripheral peelability) of the six types of laminated glass obtained in the above was evaluated in the same manner as in Example 8. The results were as shown in Table 2.

[0138]

[Table 2]

As is clear from Table 2, the interlayer films for laminated glass of Examples 8 to 11 according to the present invention each had a low surface resistance value and exhibited excellent antistatic properties. Further, the laminated glasses of Examples 8 to 11 according to the present invention did not show any peeling around the laminated glass, and exhibited excellent adhesive strength and moisture resistance.

On the other hand, the interlayer film for laminated glass of Comparative Example 4, which did not contain the antistatic agent and the adhesive force adjusting agent, had a high surface resistance and was inferior in antistatic properties. or,
In the laminated glass of Comparative Example 4 manufactured using the interlayer film for a laminated glass of Comparative Example 4, peeling was observed around the laminated glass, and the adhesive strength and the moisture resistance were poor.

The interlayer film for laminated glass of Comparative Example 5, which did not contain an antistatic agent, had a high surface resistance and was inferior in antistatic properties. Furthermore, in the laminated glass of Comparative Example 6 manufactured using the interlayer film for a laminated glass of Comparative Example 6 which did not contain the adhesive strength modifier, peeling was observed at the periphery of the laminated glass, and the adhesive strength and moisture resistance were poor. Was inferior.

[0142]

As described above, the interlayer film for laminated glass according to the present invention has excellent antistatic properties, excellent adhesive strength to glass, and excellent moisture resistance. Lamination that retains excellent basic performance required for laminated glass such as proper adhesive strength, shock absorption, penetration resistance, moisture resistance, light resistance, weather resistance, durability, etc., and also exhibits excellent antistatic properties Suitable for obtaining glass.

Further, since the laminated glass according to the present invention is produced using the interlayer film for laminated glass, the laminated glass retains the excellent basic performance required for laminated glass, and
Demonstrates excellent antistatic properties. Therefore, it is suitably used as a window glass for vehicles such as automobiles, aircraft, buildings, and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 29/14 C08L 29/14

Claims (7)

[Claims] An N-polyoxyalkylene-N, N, N-trialkylammonium salt represented by the following general formula (1) is contained in a polyvinyl acetal resin film plasticized by a diester plasticizer. An interlayer for laminated glass. Embedded image (Wherein, R ¹ , R ² or R ³ represents an alkyl group having 1 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms,
n represents a positive integer of 1 to 10, and X ⁻ represents any of a chloride ion, a chlorate ion and a perchlorate ion) 2. The polyvinyl acetal resin is a polyvinyl butyral resin having an average degree of butyralization of 60 to 75 mol%, and based on 100 parts by weight of the polyvinyl butyral resin, 20 to 60 parts by weight of a diester plasticizer and the following general formula: N-polyoxyalkylene-N, N, N-trialkylammonium salt represented by (1) 0.01 to 0.01
2. The interlayer film for laminated glass according to claim 1, comprising 2 parts by weight. 3. Embedded image (Wherein, R ¹ , R ² or R ³ represents an alkyl group having 1 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms,
n represents a positive integer of 1 to 10, and X ⁻ represents any of a chloride ion, a chlorate ion and a perchlorate ion) 3. A polyvinyl acetal resin film plasticized by a diester-based plasticizer, wherein at least one surfactant selected from the group consisting of alkyl monoethers, alkyl phenyl monoethers and fatty acid monoesters of polyoxyethylene. The interlayer film for laminated glass characterized by containing. 4. The polyvinyl acetal resin is a polyvinyl butyral resin having an average degree of butyralization of 60 to 75 mol%, and based on 100 parts by weight of the polyvinyl butyral resin, an alkyl monoether, an alkyl phenyl monoether of polyoxyethylene and The interlayer film for laminated glass according to claim 3, further comprising 0.1 to 10 parts by weight of at least one surfactant selected from the group consisting of fatty acid monoesters. 5. An interlayer film for laminated glass, wherein an alkali metal salt and an alkaline earth metal salt are contained in a polyvinyl acetal resin film plasticized by a diester plasticizer. 6. The polyvinyl acetal resin is a polyvinyl butyral resin having an average degree of butyralization of 60 to 75 mol%, and 0.005 to 0.5 parts by weight of an alkali metal salt and 100 parts by weight of the polyvinyl butyral resin. The interlayer film for laminated glass according to claim 5, comprising 0.005 to 0.5 parts by weight of an alkaline earth metal salt. 7. The method according to claim 1, wherein at least between the pair of glasses.
A laminated glass, wherein the interlayer for laminated glass according to any one of claims 6 to 6 is interposed and integrated.