JPH01290542A - Laminated glass and its production - Google Patents

Abstract

PURPOSE:To obtain a laminated glass having less adhesive properly, high water resistance, and high resistance to penetration by interposing a specified mixture consisting of an OH group-contg. ethylenic copolymer and a blocked isocyanate between glass plates, and heating the laminated glass plates. CONSTITUTION:A mixture consisting of (a) an OH group-contg. ethylenic copolymer obtained by saponifying an ethylene/vinyl ester copolymer contg. 10-43mol.% vinyl ester, and (b) a blocked isocyanate having at least two blocked isocyanate groups in a molecule, is interposed between two glass plates, wherein the proportion of the blocked isocyanate group in the mixture per 100 mole sum of each monomer unit constituting the ethylenic copolymer is 0.2-10 mole, and the number of mole of the blocked isocyanate group in the constituting monomers per 1 mole vinyl alcohol unit is 0.02-1.0 mole. An aimed laminated glass is obtd. by heating the glass plate having said interposed mixture at the dissociation temp. or higher of the blocked isocyanate and <=30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminated glass and a method for manufacturing the same. More specifically, a thin cross-linked mixture of an ethylene copolymer and a protected block isocyanate is interposed between at least two glass plates to provide water resistance, heat resistance, impact resistance and The present invention relates to a laminated glass that not only has excellent workability but also good transparency, as well as excellent whitening resistance and penetration resistance, and a method for manufacturing the same.

[Conventional technology]

Windshields of automobiles, window glass of high-rise buildings, etc.
Laminated glass (laminated glass), which is used in ship windows and equipment that is subject to impact, is lightweight,
For the purpose of improving vibration isolation and safety, laminated glass is used, which is obtained by interposing a thermoplastic resin (for example, plasticized polyvinyl butyral resin) as an intermediate layer between two glass plates, and then heating and pressing them together. It is being

As an interlayer film for laminated glass, it has been proposed and put into practical use that 25 to 40 parts by weight of a plasticizer is added to 100 parts by weight of polyvinyl butyral resin to impart flexibility and improve impact resistance. It is well known that (For example, JP-A-47-1274
3) Furthermore, in addition to these butyral resins and cellulose resins, various ethylene copolymers have been proposed. Representative examples include ethylene-vinyl acetate copolymer (JP-A-49-28610) and ethylene-methyl methacrylate copolymer (JP-A-48-79).
817), ethylene-acrylic acid copolymer (JP-A-47-739G), saponified ethylene-vinyl acetate copolymer (JP-A-49-100105),
Metal salt of ethylene-acrylic acid copolymer (Japanese Patent Application Laid-Open No. 1987-
25842) and ethylene-methacrylic acid copolymer (Japanese Patent Laid-open No. 59115/1983).

[Problem to be solved by the invention]

Conventional commonly used butyral resins, cellulose resins, and the like have poor water resistance, so water enters from the terminals and peels off.

In addition, plasticized butyral resin films containing plasticizers have strong adhesion on the film surface, so it is necessary to spray powder such as bicarbonate of soda on the film surface or to store it at low temperatures to prevent blocking.

These problems are factors that increase costs in the distribution and storage stages or in the manufacturing process of laminated glass, and there is a need to resolve them. Furthermore, although plasticized butyral resin, which is currently in practical use as an interlayer film for automotive laminated glass, has a glass transition temperature lowered by a plasticizer, it has not yet achieved a sufficiently low glass transition temperature. . This seems to be the main reason, but although laminated glass with an interlayer film of plasticized butyral exhibits excellent penetration resistance near room temperature, it does not work at low temperatures (for example, -2
0° C.), the problem is that the penetration resistance is greatly reduced.

The present inventors have identified the problems of the current laminated glass as described above, and the current situation in which, although many proposals have been made to solve the problems, an appropriate solution has not always been found. As a background, as a result of extensive research, we have arrived at an interlayer film material that exhibits low adhesion during distribution and storage, excellent water resistance, and excellent penetration resistance over a wide temperature range. It is an object of the present invention to propose a novel laminated glass and manufacturing method based on this interlayer film.

[Means to solve the problem]

The gist of the present invention is as described below.

(1) (^) Copolymerization ratio of vinyl ester is 10 to 4
A hydroxyl group-containing ethylene copolymer obtained by saponifying a copolymer of ethylene and vinyl ester having a molecular weight of 3 mol 26, and (B) a block containing at least two protected isocyanate groups in one molecule. isocyanate, the number of protected blocked isocyanate groups is 0.2 to IO mol per 100 mol of total ffl of each monomer unit constituting the ethylene copolymer in the mixture, and the vinyl alcohol unit in the constituent monomers The number of moles of protected isocyanate group per mole is 0.0
A laminated glass comprising 2 to 1.0 mol of a crosslinked mixture interposed between at least two glass plates.

(2) (A) Copolymerization ratio of vinyl ester is 10
A hydroxyl group-containing ethylene copolymer obtained by saponifying a copolymer of ethylene and vinyl ester with a content of ~43 mol%, and (B) containing at least two protected isocyanate groups in one molecule. The number of protected block isocyanate groups is 0.2 to 10 moles per 100 moles of the total amount of each monomer unit constituting the ethylene copolymer in the mixture, and the vinyl The number of moles of protected isocyanate group per mole of alcohol unit is 0.02 to 1
．． 1. A method for producing laminated glass, which comprises interposing a 0 mol mixture between glass plates and heat-treating the mixture at a temperature above the dissociation temperature of pro-nquisocyanate and below 300°C.

(3) A thin material of the mixture according to claim (2) is heat-treated at a temperature above the dissociation temperature of pro-nquisocyanate and below 300°C, and then this thin material is interposed between glass plates, and the thin material is heated at a temperature of 50 to 200°C. A method for manufacturing laminated glass, characterized by heat treatment.

(4) A thin-walled product of the mixture according to claim (2) is irradiated with an electron beam, and then the thin-walled product is interposed between glass plates and heat-treated at a temperature above the dissociation temperature of the blocked isocyanate and below 300°C. Method of manufacturing laminated glass.

(5) A thin material of the mixture according to claim (2) is irradiated with an electron beam, then heat-treated at a temperature higher than the dissociation temperature of the blocked isocyanate and lower than 300°C, and then this thin material is interposed between glass plates. 1. A method for producing laminated glass, which comprises heat-treating at a temperature of 50 to 200°C.

The present invention claims that a laminate of glass and a specific crosslinked product obtained by crosslinking a hydroxyl group-containing copolymer obtained by partially saponifying an ethylene/vinyl ester copolymer with urethane bonds has extremely excellent properties. It is based on unexpected facts. This will be explained in detail below.

(A) Hydroxyl group-containing copolymer (A) The hydroxyl group-containing copolymer (hereinafter abbreviated as hydroxyl group-containing copolymer) obtained by saponifying the ethylene/vinyl ester copolymer used in the present invention is: It is obtained by copolymerizing ethylene and vinyl ester by a known method (high-pressure polymerization method, solution polymerization method, or emulsion polymerization method), and then hydrolyzing it by a known method. As the ethylene/vinyl ester copolymer, a copolymer containing 10 to 43 mol% of vinyl ester is used.

The vinyl ester monomer is a vinyl ester of an aliphatic or aromatic carboxylic acid, and includes vinyl acetate, vinyl propionate, vinyl benzoate, etc., with vinyl acetate being preferred.

Various methods are used to saponify ethylene/vinyl ester copolymers. For example, if the vinyl ester content is low, the polymer can be dissolved in a toluene/alcohol mixed solvent and saponified using sodium hydroxide; It is also possible to perform saponification in a heterogeneous system. These are all known techniques. The thus obtained hydroxyl group-containing copolymer used in the present invention has a mole fraction of constituent monomer units of ethylene 0.90 to 0.57 and vinyl ester 0.055 to 0.
30 and vinyl alcohol in the range of 0.045 to 0.34. The molar fraction of ethylene units is preferably in the range of 0.89 to 0.67.

Where the ethylene unit fraction exceeds 0.90, the influence of the presence of polyethylene crystals is strong, and the initial elastic modulus of the crosslinked product is too high, the transparency is reduced, or the plastic deformation region is wide. I don't like it.

Moreover, if the mole fraction is less than 0.57, the glass transition temperature of the material will be high and the low-temperature physical properties will tend to deteriorate, which is not preferable.

The mole fraction of vinyl ester units is 0.055-0.30
However, 0.06 to 0.28 is preferable. If it is less than 0.055, flexibility often decreases, which is undesirable.
．． If it exceeds 30, the low temperature properties tend to deteriorate, which is not preferable. The mole fraction of vinyl alcohol units is 0.04
5 to 0.34, preferably 0.05 to 0.30.

If the molar fraction is less than 0.045, not only the strength of the crosslinked product is insufficient, but also the crosslinking is insufficient, resulting in poor penetration resistance and poor heat resistance.

The melt index of the hydroxyl group-containing copolymer of the present invention is
0.05-500g/1O111n; preferably 0.1-300g/10mln.

If it is less than 0.05, it is difficult to ensure stable moldability, and 5
If it exceeds 00, sufficient strength and penetration resistance cannot be achieved.

(B) Blocked Isocyanate The blocked isocyanate (hereinafter abbreviated as "blocked isocyanate") having at least two protected isocyanate groups in one molecule used in the present invention is obtained by reacting an isocyanate group with a protecting agent according to a conventional method. It is a compound having a protected isocyanate group obtained by It is.

The blocked isocyanate used in the present invention is a compound having at least two such protected isocyanate groups in one molecule, but preferably one having two to three such protected isocyanate groups. Such blocked isocyanates are obtained by reacting polyisocyanates with protective agents.

Typical polyisocyanates include aromatic, aliphatic, and alicyclic diisocyanates, triisocyanates, and reaction products of excess amounts of these diisocyanates with polyols having a molecular weight of 60 to 2.000 as chain extenders. etc.

Typical examples of diisocyanates include alkylene diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, and diphenylmethane diisocyanate; 4,4'-methylene-bis(cyclohexyl isocyanate); ), ω, ω'-diisocyanate-1,4-dimethylcyclohexane, isophorone diisocyanate, and other alicyclic diisocyanates. Typical examples of triisocyanates include diisocyanate trimers, such as tolylene diisocyanate trimer and hexamethylene diisocyanate trimer.

A typical example of the polyisocyanate using a chain extender is a reaction product of an excess amount of the above diisocyanate and a polyol having a molecular weight of 60 to 2.000.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, pentaerythritol, and the like.

In the present invention, as the diisocyanate component, 2 mol of the above diisocyanate and 1 mol of the above diol are used.
It is advantageous to use blocked isocyanates, which are obtained by reacting the reaction product with a protective agent.

The blocked isocyanate is represented by general formula (1).

However, in formula (1), Bg is a residue of an isocyanate protecting agent, R1 is a residue of a divalent isocyanate,
A divalent hydrocarbon group having 2 to 20 carbon atoms; R2 is a hydrogen atom or a methyl group; m is an integer of 1 to 5; n is an integer of 1 to 30.

Among the above-mentioned diisocyanates, the diisocyanate as a starting material for the block isocyanate represented by the general formula (1) is preferably tolylene diisocyanate, diphenylmethane diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), or isophorone diisocyanate. Inphorone diisocyanate is preferred. Furthermore, among the above-mentioned tashiols, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and tetramethylene glycol are preferable as the diol as a starting material for the blocked isocyanate represented by formula (I).

In formula (1), BN is a residue of a protecting agent, and is a group obtained by removing a hydrogen atom from the protecting agent.

As the protective agent, any of phenol type, lactam type, active methylene type, acid amide type, imide type, amine type, imidazole type, urea type, imine type, and oxime type can be used, but among them, phenol type Protecting agents based on lactam, acid amide, active methylene, and oxime types are preferred, with lactam type protecting agents being preferred.

Examples of the phenolic protective agent include monohydric phenols such as phenol, cresol, xylenol, ethylphenol, and nonylphenol.

As lactam-based protective agents, β-propiolactam, γ
Examples include -butyrolactam, δ-valerolactam, ε-caprolactam, and ε-caprolactam is preferred.

Examples of acid amide protective agents include monocarboxylic acid amides such as acetanilide, acetic acid amide, and stearic acid amide.

As active methylene protective agents, dialkyl malonate,
Examples include alkyl acetoacetate and acetylacetone, but as alkyl, methyl and ethyl are preferred.

Examples of oxime-based protective agents include formaldoxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime.

The protective agent is advantageously one that is liberated into the composition at temperatures above the dissociation temperature but does not impair the appearance of the molded product, such as foaming of the crosslinked product.

The mixtures and crosslinked products of the present invention are composed of a saponified product of an ethylene/vinyl ester copolymer having a limited composition and a block isocyanate (indispensable) using a diol component represented by formula (1) as a chain extender. It is characterized by its use as a component.The blocked diisocyanate represented by formula (1) may be used alone, or two or more types may be used in combination.Also, the blocked diisocyanate represented by formula (I) The above-mentioned blocked isocyanates other than those of the formula (I
) It can also be used in combination with the blocked isocyanate shown by. In this case, the proportion of the blocked isocyanate represented by formula (1) in all blocked isocyanates is 10 mol% or more, preferably 20 mol% or more, and suitably 50 mol% or more.

The presence of the blocked isocyanate represented by formula (1) means that
This is extremely important for providing a balance in the physical properties of the crosslinked product. In order to maintain appropriate flexibility, ensure elongation, and increase breaking strength, the mechanism of the blocked isocyanate of formula (1) is not necessarily clear, but a chain extender is used. It is possible that the role of the chain extender as a spacer and the unique interaction between the urethane bonds at both ends of the chain extender and the OH groups present inside the crosslinked product lead to the excellent physical properties.

The mixture of the present invention is produced by mixing a hydroxyl group-containing copolymer and a block isocyanate. The quantitative ratio of both is limited by the relationship between the number of moles of monomer units constituting the hydroxyl group-containing copolymer and the number of moles of protected isocyanate groups in the blocked isocyanate.

That is, the number of moles of the protected isocyanate group in the block isocyanate is 0.2 to 10 moles, preferably 0.3 to 5 moles, with respect to 100 moles of constituent monomer units of the hydroxyl group-containing copolymer, and , the number of moles of protected isocyanate groups per mole of vinyl alcohol units in the constituent monomers is less than 1 mole, preferably from 0.9 to
It is 0.020 mol.

If the number of moles of protected isocyanate groups is greater than the number of moles of hydroxyl groups in the composition, not only will the crosslinking be incomplete, but the strength of the resulting crosslinked product will not necessarily be sufficient. . Furthermore, if the number of moles of protected isocyanate groups per 100 moles of constituent monomer units of the hydroxyl group-containing copolymer is less than 0.2 moles, the resulting crosslinked product will have insufficient heat resistance and poor penetration resistance. Even if more than 10 moles of stars are used, the strength of the crosslinked product does not improve, but rather decreases, and the resulting laminated glass not only has poor penetration resistance but also poor transparency.

(C) Mixing method Various means can be adopted for mixing the hydroxyl group-containing copolymer and the block isocyanate. toluene, xylene,
It may be mixed in a solvent such as ethyl acetate or methyl ethyl ketone, or it may be tri-blended using a mixer such as a Henschel mixer or tumbler, which is commonly used in the olefin field, or may be mixed using a roll mill, Panbali Misaki, etc. Examples include a method of melt-kneading using a kneader such as a kneader-1 extruder. At this time, a more uniform mixture can be obtained by melt-kneading the mixture obtained by triblending in advance. During melt crosslinking, it is necessary that the hydroxyl group-containing copolymer (A) and the blocked isocyanate (B) are not substantially crosslinked. For this purpose, it is important to knead at a temperature below the dissociation temperature of the blocked isocyanate. (If the mixture is cross-linked, the moldability will deteriorate when the resulting mixture is molded as described below, which is undesirable.) For this reason, the melt-kneading temperature varies depending on the type of blocked isocyanate, especially the type of protective agent, but it is generally is 80-140℃,
Preferably it is 90-130°C.

When melt mixing is used, lactam-based or protective agents are used.
Alternatively, it is advantageous to use blocked isocyanates with phenolic protective agents.

"Substantially no crosslinking" means "3
The residue after time extraction treatment (hereinafter referred to as "extraction residue") is 15 parts by weight or less, preferably 10% by weight or less, and optimally 5% by weight or less.

In producing this mixture, we use oxygen, light (ultraviolet) and heat stabilizers, antistatic agents, lubricants, nucleating agents, pigments (colorants), plasticizers, and processing agents commonly used in the field of olefinic polymers. Additives such as a property improver and an adhesion improver may be added to the extent that they do not impair the properties (physical properties) of the crosslinked product of the present invention.

(D) Production of thin-walled product When the thin-walled product of the present invention is used in the form of a film or sheet, the film is produced by a T-die film method, an inflation method, or a calendar method commonly used in the field of thermoplastic resins. A thin product can be obtained by extruding it into a film or sheet using a widely used extruder. At this time, the extrusion temperature is generally below 180°C, but cannot exceed the decomposition temperature of the blocked isocyanate.

When extruded above the decomposition temperature, part or all of the hydroxyl group-containing copolymer and blocked isocyanate are crosslinked and gel-like lumps are generated, making it impossible to obtain a uniform extruded product. Further, after producing the thin-walled article, a thin-walled article with good transparency can be obtained by rapidly cooling the thin-walled article in a water-cooling roll or a water bath to prevent adhesion between the thin-walled articles or between the thin-walled articles and a take-up roll or the like. The thickness of the thin-walled products thus obtained is generally between 5 microns and 2 mm, preferably between 5 microns and 1.5 mm, and particularly preferably between 10 microns and 1.0 mm.

This thin material may be passed through a grain roll to give the surface a grain in order to vent gas and prevent the sheet from blocking when bonded to glass. In addition, it may be uncrosslinked as described above before bonding with glass.
Further, it may be crosslinked as described below.

(E) Glass plate Furthermore, the glass plate used in the present invention may be washed and degreased in advance as necessary in order to make the adhesiveness with the crosslinked material of the mixture described later more effective. It is also possible to physically increase the adhesion area by adding irregularities to the surface layer, thereby creating an anchor effect. Additionally, you can use braimers. The thickness of the glass plate is usually 0.5 mu
30 m1, preferably 0.5 m to 25 m11, particularly preferably 1 mm to 20 mm.

The glass types of this glass plate include commercially available glass plates such as ordinary glass, polished plate glass, float plate glass, soda lime glass, borosilicate glass, lead glass, quartz glass, phosphoric acid glass, partially tempered glass, and tempered glass. . These glasses are manufactured industrially and used in a wide variety of fields, and their manufacturing methods, compositions, and various physical properties are well known.

The types and thicknesses of the glass plates used in the present invention do not necessarily have to be the same, and different types and thicknesses can be used in combination.

(F) Method of manufacturing laminated glass There are several methods for manufacturing the laminated glass of the present invention.

(2) A method in which the above-mentioned uncrosslinked thin material is interposed between the glass plates and bonded together, or after the glass plates are bonded together, a certain heat treatment is applied to produce a laminate of the crosslinked thin material and glass.

■The uncrosslinked thin material described above is irradiated with ionizing radiation in advance, and then heat treated as necessary, after which
A method of interposing glass plates and bonding them together, or after bonding, subjecting them to a certain heat treatment to form a crosslinked thin-walled material and glass laminate.

(2) A method of heat-treating the above-mentioned uncrosslinked thin material to allow crosslinking to proceed sufficiently, and then interposing the crosslinked material between glass plates and heat-treating it to form a laminate.

In the present invention, any of the methods (1) to (4) can be adopted. It is preferable to use method (1) above because the manufacturing process is simple and it is advantageous in terms of cost.

However, in order to obtain laminated glass with excellent performance and good penetration resistance, it is necessary to make a subtle difference between the strength of the intervening thin-walled material itself (mainly determined by the degree of crosslinking) and the adhesive strength between the glass and the thin-walled material. Sometimes a balance is required. That is, if the adhesive strength is too high, when the laminated glass is subjected to an impact, the impact absorption ability of the thin material will be reduced, and the penetration resistance may even be reduced. Furthermore, in method (2), the thickness of the thin-walled material may change during heat treatment.

In such cases, methods ① to ② can be effectively used. In other words, by partially crosslinking an uncrosslinked thin material using primary crosslinking in advance to control its strength and adhesive properties, and then interposing it between glasses and subjecting it to heat treatment, it is possible to create laminated glass with the required physical properties. Obtainable. Furthermore, in this secondary crosslinking, if an attempt is made to carry out inexpensive oven crosslinking of an uncrosslinked thin product, problems such as deformation and deformation may occur depending on the composition of the mixture. In this case, if partial crosslinking is performed in advance using ionizing radiation, primary crosslinking can be completed by heating in an oven without fear of deformation.

Examples of the ionizing radiation used in the present invention include electron beams, gamma rays, and X-rays, with electron beams being particularly preferred.

Methods for carrying out the electron beam crosslinking include Kotskucroft type, Kotskucroft-Walton type, Pandegraaf type,
Methods include emitting electron beams from various types of electron beam accelerators, such as insulated core transformer type, linear type, dynamidron type, high frequency type, and electrocurtain type. The irradiation dose can vary within a wide range depending on the required performance of the irradiated object. Generally, it is 1.0 to 60 Mrad,
1 to 50 Mrad, preferably 5 to 50 Mrad
is suitable.

1. If it is less than OMrad, even if the hydroxyl content copolymer (A) is attempted to be crosslinked with block isocyanate in an oven, the shape of the thin product will be distorted before crosslinking and no effect will be seen.

If it exceeds 160 Mrad, the degree of crosslinking will be too high and it will be difficult for the hydroxyl group-containing copolymer (A) to react with the block isocyanate. Also, the acceleration voltage is usually 50 to 1.000.
kV Te, special 1. : 100 to 750 kV is suitable.

The atmosphere during electron beam irradiation may be air or, if necessary, an inert gas atmosphere.

Lamination methods include a press molding method, a stamping molding method, a dipping method, an injection method, which are generally performed in the field of thermosetting thermoplastic resins by interposing the above-mentioned thin material between glasses.
Lamination can be performed by a roll method, a vacuum bag method, a low pressure transfer method, an oven method, or the like. For bonding, a one-stage adhesive method or a two-stage adhesive method is adopted. −
The method of performing adhesion in stages is a method in which main adhesion and crosslinking are directly performed without performing temporary adhesion in the first stage described later.

In the two-stage method, first, the uncrosslinked thin material is sandwiched between glass plates, and then passed between two rubber rolls to be pressed together. Also,
The method may also be carried out using a vacuum bag. The pressure at this time is usually 1 to 10 kg/cJ. Next, perform the second stage of main gluing. Methods for permanently bonding the temporarily bonded body include heating and pressurizing using an electric heating plate press device, vacuuming or pressurizing using an autoclave,
There are methods of heat/pressure treatment and methods of combining these methods, in which adhesion and crosslinking are performed continuously. The temperature for adhesion and crosslinking by heating is generally in the range of 80 to 240°C for adhesion, and for crosslinking it is 100 to 300°C depending on the type of blocked isocyanate, preferably in the range of 150 to 250°C. It is. Adhesion pressure is 0.1-30)cg/cl! It is.

On the other hand, the higher the temperature, the shorter the crosslinking treatment is sufficient, but usually at 100 to 200°C for 30 seconds to 60 minutes.
At 200 to 300°C, about 10 seconds to 30 minutes is preferable. Rather, the important point is to prevent air from being trapped between the mixture or its thin material and the glass plate at the inlet of the pressure roll.

In manufacturing the laminated glass of the present invention, two or more glass plates may be used, but the thin crosslinked material is interposed between the glass plates.

The laminated glass thus obtained not only has good penetration resistance, but also excellent heat resistance, water resistance, and transparency.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Examples 1-2. Comparative Example 1 Ethylene units 86.2 mol%, vinyl alcohol units 7
．． A 2=1 adduct of a partially saponified ethylene vinyl acetate copolymer (EVA) (abbreviated as A-1) containing 2 mol 96 and 8.8 mol % of vinyl ester units, isophorone diisocyanate, and ethylene glycol was ε- Blocked isocyanate protected with caprolactam (BIS-
It will be abbreviated as A.

The mixture was tri-blended for 5 minutes using a Henschel mixer so that the protected isocyanate group was 10H group-0,2 (molar ratio).

Each mixture thus obtained was transferred to a 30 m/mφ pent extruder (C1100℃, C2110℃, C3110℃
.

The mixture was uniformly mixed using a die (120° C.) and pelletized.

Each of the mixtures thus obtained was extruded using an extruder equipped with a T die (diameter: 401111%, die width: 45 cm).

The cylinder temperature is (CI
oooC, C2110°C) and die temperature is 110
Two types of sheets with thicknesses of 0.76 and 0.78 mu were molded at .degree. The extraction residue on the obtained sheet was measured. In both cases, it was 096.

This sheet was sandwiched between a Teflon-coated mold and a compression plate, compression molded at 180°C under a pressure of 50 kg/cJ (surface pressure), and heated for 30 minutes to create a cross-linked 0,
A transparent sheet with a thickness of 78 mm was obtained. Furthermore, two glass plates (thickness 2.5
A laminated glass was produced by sandwiching the 0.7 km long crosslinked sheet between the intermediate layers (mm) and bonding them together at a temperature of 120° C. under a pressure of 20 kg/cj (surface pressure) for 20 minutes. The laminated glass was evaluated by the method described below, and the haze (cloud value) was 1.3%. Further, in the penetration resistance test described later, it did not penetrate up to 5 m at -20°C and up to 4 m at 23°C. From the above, it is clear that the film has excellent penetration resistance at low temperatures. Also keep this sheet at room temperature~
Even when 10 sheets were stacked at 50°C, there was no stiffness.

Similarly, instead of BIS-A block isocyanate, m
-cresol protected blocked isocyanate (BI
It is abbreviated as SB.

Dissociation temperature: 160°C) was added so that the protected isocyanate group 10H group -〇, 2 (molar ratio), and the conditions for creating the crosslinked sheet were 190°C and 30 minutes, but the same procedure as in Example 1 was carried out. The laminated glass was manufactured by the method. (Example 2) A laminated glass was manufactured in the same manner as in Example 1, except that the blocked isocyanate (BIS-B) was not mixed. (Comparative Example 1) The haze (haze value) of each laminated glass obtained was determined by ASTM D.
-1003, and the penetration resistance test was conducted according to JIS
l? According to 32L2, it was dropped from a height of 4 m and n1 was determined. Furthermore, the hot water resistance test was conducted using JIS R321.
Measurements were made according to 2. Table 1 shows the haze and penetration resistance results of each glass plate.

Examples 3-5. Comparative Examples 2 to 4 Ethylene units 81.6 mol%, vinyl alcohol units 8
．． Partially saponified product of ethylene/vinyl acetate copolymer (EVA) (abbreviated as B-1) with 9 mol% of vinyl ester units and 9.5 mol% of vinyl ester units.81.6 mol% of ethylene units and 9 vinyl alcohol units.
．． Partially saponified product of ethylene/vinyl acetate co-ffi (EVA) (abbreviated as B-2) with 6 mol% of vinyl ester units and 8.8 mol% of vinyl ester units (abbreviated as B-2) 81.6 mol% of ethylene units and 6 vinyl alcohol units
．． A partially saponified product (abbreviated as B-3) of ethylene/vinyl acetate copolymer (EVA) containing 8 mol% and 11.6 mol% of vinyl ester units, and a blocked isocyanate (BI).
The molar ratio of the protected isocyanate group 10H group of S-A) was mixed in the ratio shown in Table 1, and sheet molding, compression molding, and crosslinking were performed under exactly the same conditions as in Example 1 to produce a laminated glass. (Example 3°4.5) The physical properties of the laminated glass were measured in the same manner as in Example 1. The results are shown in Table 1.

In addition, blocked isocyanate (B
A laminated glass without mixing IS-A) was produced in the same manner as in Comparative Example 1. (Comparative Examples 2, 3, 4) The physical properties of the laminated glass were determined in the same manner as in Example 1. Results first
Shown in the table.

Examples 6 to 8 Partially saponified product (A-1) of the ethylene/vinyl acetate copolymer ('EVA) used in Example 1 and block isocyanate (abbreviated as BIS-C) in which tolylene diisocyanate was protected with methyl ethyl ketone oxime do.

solution M temperature 130°C) and protected isocyanate group 1
Example 1 except that the 0H groups were added to -0,3 (molar ratio) and the conditions for creating the crosslinked sheet were 150°C and 30 minutes.
Laminated glass was manufactured using the same method. (Example 6) Partially saponified product (A-1) similarly used in Example 1
Blocked isocyanate (abbreviated as BIS-D) consisting of a 2:1 adduct of isophorone diisocyanate and propylene glycol protected with ε-caprolactam. Solution N&
? R degree 160°C) and protected isocyanate group 1
A laminated glass was produced in the same manner as in Example 1, except that the 0H groups were added so that the molar ratio was -0.1. (Example 7) Similarly to Example 7, blocked isocyanate (BIS-
D) Protected isocyanate group 10H group -0,32
(molar ratio), and a laminated glass was manufactured in the same manner as in Example 1. (Example 8) The physical properties of the laminated glass were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 9 - IO1 Comparative Example 5 Ethylene units 86.2 mol%, vinyl alcohol units 6
．． A partially saponified ethylene/vinyl acetate copolymer (EVA) containing 3 mol% and 7.5 mol% of vinyl ester units (abbreviated as C-1) and a 2=1 adduct of isophorone diisocyanate and ethylene glycol were ε- Blocked isocyanate protected with caprolactam (BIS-A
) and the protected isocyanate group 10H group -0,1
, 0.2 (molar ratio) using a Henschel mixer for 5 minutes.

Each mixture thus obtained was transferred to a 30 m/mφ vent extruder (0100°C, C2110°C, C3110°C1
The mixture was uniformly mixed using a die (120°C) and pelletized.

Each mixture thus obtained was heated to the same T as in Example 1.
A 0.76 mm sheet was molded under the same conditions using an extruder equipped with a die. The extraction residue on the obtained sheet was measured and found to be 0%. (Example 9.10) In the same manner, sheets were also formed without blending blocked isocyanate (BIS-A). (Comparative example 5
) The sheet of Examples 9 to 10 of the mixture or the sheet of Comparative Example 5 (thickness 0.78 mm) was placed between two glass plates (thickness 2.5 mm) whose surfaces had been previously degreased. 10kg/ci at 180℃ (
Crosslinking and adhesion were performed for 20 minutes under pressure (surface pressure) to produce a laminated glass.

Table 1 shows the results of measuring the physical properties of the laminated glass using the same method as in Example 1.

Example 11. Comparative Example 6 77.6 mol% ethylene units, 1 vinyl alcohol unit
A 2:1 adduct of a partially saponified ethylene/vinyl acetate copolymer (EVA) (abbreviated as D-1) containing 12 mol% O and 12.2 mol% vinyl ester units, isophorone diisocyanate, and ethylene glycol was ε - Blocked isocyanate protected with caprolactam (BT
S-A) and the protected isocyanate group 10H group -
0.2 (molar ratio), sheet-formed and crosslinked laminated glass was produced under the same conditions as in Example 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. (Example 11) For comparison, Table 1 also shows the physical properties of a laminated glass that does not contain blocked isocyanate (BIS-A). (Comparative Example 6) Comparative Example 7 Ethylene units 91 mol%, vinyl alcohol units 3.1
mol%, vinyl ester unit 5.9 mol% ethylene/
Partially saponified product of vinyl acetate copolymer (EVA) (abbreviated as E-1) and block isocyanate) (BIS
-A) and protected isocyanate group 10H group -0,
3 (molar ratio), and a laminated glass was manufactured in the same manner as in Example 1. Table 1 shows the physical properties of the laminated glass.

Example 12 The unlinked sheet of 0.76 m11 obtained in Example 1 was coated with a scanning type (E
Electron beam irradiation was performed in air using an electron beam irradiation device (model PS750) at an accelerating voltage of 500 kV and an irradiation beam ffi10 Mrad. This irradiated sheet was crosslinked in a constant temperature oven at 180° C. for 30 minutes, but the shape did not change.

This sheet was sandwiched and laminated between glass plates under the same conditions as in Example 1 to produce a laminated glass.

When the haze (haze value) of this laminated glass was measured, it was 1.
1%, and a penetration resistance test was conducted, but no penetration occurred.

Comparative Example 8 When the 0.76m+* uncrosslinked sheet obtained in Example 1 was crosslinked in a constant temperature oven (180°C, 30 minutes) without electron beam irradiation, the shape collapsed and it could not be bonded to glass. There wasn't.

Example 13 The 0°76 uncrosslinked sheet obtained in Example 7 was subjected to an acceleration voltage of 5 in air using the same electron beam irradiation device as in Example 12.
00. Electron beam irradiation was performed at kV and radiation H20 Mrad. This irradiated sheet was crosslinked in the same manner as in Example 12, but the shape did not change.

This sheet was sandwiched and laminated between glass plates under the same conditions as in Example 1 to produce a laminated glass.

The haze of this laminated glass was 1.2%, and a penetration resistance test was conducted, but no penetration occurred.

(Left below) A penetration resistance test was conducted on the laminated glass plates obtained in Examples 1 to 13, but no penetration occurred. On the other hand, the laminated glasses obtained in Comparative Examples 1 to 7 were
Both passed through. In addition, hot water resistance tests were conducted on the laminated glasses according to Examples 1 to 13, but no change was observed in any of them. On the other hand, in all of the laminated glasses obtained in Comparative Examples 1 to 7, the edge portions were peeled off.

〔Effect of the invention〕

The laminated glass of the present invention exhibits the following effects including its manufacturing process.

(1) Since the intermediate adhesive layer (thin material) has excellent heat resistance, peeling does not occur at high temperatures.

(2) Since the intermediate adhesive layer has almost no moisture content, moisture management is easy in the bonding process, and the manufacturing process is simple.

(3) Since the intermediate adhesive layer has excellent water resistance, peeling does not occur under high humidity or in water.

(4) The intermediate adhesive layer has excellent adhesion, and the laminated glass has good penetration resistance.

(5) Excellent transparency.

(6) Production efficiency is good because bonding can be performed even for a short time at relatively low temperatures.

The laminated glass of the present invention can be used in a wide variety of ways in order to exhibit the above-mentioned effects. Typical applications include glass such as automobile windshields,
Examples include window frames of buildings, glass for ships, and glass for vehicles other than automobiles.

Claims (5)

[Claims] (1) (A) The copolymerization ratio of vinyl ester is 10 to 43
A hydroxyl group-containing ethylene copolymer obtained by saponifying a copolymer of ethylene and vinyl ester in mol%, and (B) a block isocyanate containing at least two protected isocyanate groups in one molecule. The number of protected blocked isocyanate groups is 0.2 to 10 mol per 100 mol of the total amount of each monomer unit constituting the ethylene copolymer in the mixture, and 1 vinyl alcohol unit in the constituent monomers. The number of moles of protected isocyanate groups per mole is 0.02 to 1
．． A laminated glass comprising at least two glass plates and a cross-linked mixture having 0 moles interposed between at least two glass plates. (2) (A) The copolymerization ratio of vinyl ester is 10 to 43
A hydroxyl group-containing ethylene copolymer obtained by saponifying a copolymer of ethylene and vinyl ester in mol%, and (B) a block isocyanate containing at least two protected isocyanate groups in one molecule. The number of protected blocked isocyanate groups is 0.2 to 10 mol per 100 mol of the total amount of each monomer unit constituting the ethylene copolymer in the mixture, and 1 vinyl alcohol unit in the constituent monomers. The number of moles of protected isocyanate groups per mole is 0.02 to 1
．． 1. A method for producing laminated glass, which comprises interposing a 0 mol mixture between glass plates and heat-treating the mixture at a temperature above the dissociation temperature of a blocked isocyanate and below 300°C. (3) A thin product of the mixture according to claim (2) is heat-treated at a temperature above the dissociation temperature of the blocked isocyanate and below 300°C, and then the thin product is interposed between glass plates and heat-treated at a temperature of 50 to 200°C. A method for manufacturing laminated glass characterized by: (4) A thin-walled product of the mixture according to claim (2) is irradiated with an electron beam, and then the thin-walled product is interposed between glass plates and heat-treated at a temperature above the dissociation temperature of the blocked isocyanate and below 300°C. Method of manufacturing laminated glass. (5) A thin material of the mixture according to claim (2) is irradiated with an electron beam, then heat-treated at a temperature higher than the dissociation temperature of the blocked isocyanate and lower than 300°C, and then this thin material is interposed between glass plates. 1. A method for producing laminated glass, which comprises heat-treating at a temperature of 50 to 200°C.