JPS62108752A - Laminated glass - Google Patents

Abstract

PURPOSE:To obtain the titled glass without peeling under high-temp. and high- humidity conditions, having excellent impact resistance, and which is easy to produce by using the thin material of the cross-linked product of a mixture of the two kinds of specified ethylenic copolymers to bond the respective glass sheets. CONSTITUTION:(A) 1-99wt% ethylenic copolymer (e.g., an ethylene-acrylic copolymer) unit consisting of an ethylenic unit and a (di)carboxylic acid(anhydride) or a half ester unit and contg. 30-99.5wt% ethylenic unit and (B) 99-1wt% ethlenic copolymer (e.g., an ethylene-hydroxymethyl methacrylate copolymer) consisting of an ethylenic unit and a unit selected from a hydroxyl unit, an amino unit, and a glycidyl unit and contg. 30-99.5wt% ethylenic unit are mixed. Respective glass sheets are bonded by the thin material of the cross- linked product of the mixture to obtain the desired laminated glass.

Description

[Detailed Description of the Invention] f-no 1)! The present invention relates to a laminated glass characterized in that glass plates are adhered to each other by a thin crosslinked product of two types of ethylene copolymers. More specifically, the mutual glass plates are (A) an ethylene copolymer having at least ethylene units and at least one unit selected from the group consisting of carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and halfester units thereof; and (B) an uncrosslinked mixture of an ethylene copolymer having at least ethylene units and at least one unit selected from the group consisting of hydroxyl units, amino units and glycidyl units, or a thin film of a crosslinked product thereof. It relates to laminated glass characterized by
The purpose is to provide a laminated glass with excellent water resistance, impact resistance, and heat resistance.

Laminated glass used in vehicles such as automobiles, building materials, ships, and equipment that is subject to impact is light II glass.
laminated glass obtained by interposing a thermoplastic resin (e.g., butyral resin) as an intermediate layer between two glass plates for the purpose of improving vibration isolation, improving safety, etc., and then press-bonding them with a heated tube. It is now being used. However, in this type of laminated glass, the flexible thermoplastic resin intervening as the intermediate layer becomes fluid, and the initial thickness of the intermediate layer cannot be maintained due to slight external pressure, causing the resin to flow outside. It has drawbacks such as the possibility of leakage, and its usage conditions are extremely limited. In addition, because it has almost no adhesive properties at high temperatures, it will peel off from the glass, and since water-resistant resin is mainly used, water will enter from the terminal and cause it to peel off. However, it is difficult for the butyral resins and cellulose resins that are used to withstand deformation at around 80°C.
In addition, peeling is likely to occur due to poor water resistance.

From the above, the present invention does not have these drawbacks (problems); in other words, it not only provides excellent adhesion between the glass plate and the intervening thermoplastic resin layer using a simple method. ,
# To obtain laminated glass with good heat resistance, water resistance and impact resistance.

According to the present invention, these problems are solved when the mutual glass plates are (A)
consisting of at least ethylene and at least one type of unit selected from the group consisting of a carboxylic acid unit, a dicarboxylic acid unit, an anhydride unit thereof, and a halfester unit thereof,
and an ethylene copolymer having an ethylene unit content of 30 to 99.5% by weight (hereinafter referred to as "ethylene copolymer (A)") and (B) an ethylene unit content of 1 to 93% by weight. and at least one type of unit selected from the group consisting of hydroxyl units, amine 7 units, and glycidyl units, and the content of ethylene units is 30 to 9.5% by weight.'' [Hereinafter referred to as `` "Ethylene copolymer (B)"]99
A solution can be achieved by a laminated glass characterized in that it is glued by a crosslinked thin film of the mixture which is ~1% by weight. The present invention will be explained in detail below.

(A) Ethylene copolymer (A) The ethylene copolymer (A) used in the present invention contains at least ethylene units and a group consisting of carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and halfester units thereof. It is an ethylene copolymer containing 30 to 88.5% by weight of ethylene units.

This ethylene copolymer (A) contains at least the second component (
A) Copolymers that can be obtained by copolymerizing the following seven monomers, multicomponent copolymers of these and other monomers, and acid anhydride groups in these resonance polymers. Examples include those obtained by hydrolyzing and/or alcohol-denaturing.

Representative examples of such monomers include acrylic acid, methacrylic acid, and ethacrylic acid, which have at most 25 carbon atoms.
unsaturated monocarboxylic acids as well as maleic anhydride, tetrahydrophthalic anhydride, maleopimaric anhydride, 4-methylcyclohexan-4-ene-1,2-carboxylic anhydride and bicyclo(2,2,1)-hebutyric anhydride. -5-en-
4-50 carbon atoms such as 2,3-dicarboxylic anhydride
unsaturated dicarboxylic acid anhydrides.

Other monomers include unsaturated carbon atoms having at most 30 carbon atoms (preferably 10 or less) such as methyl (meth)acrylate, ethyl (meth)acrylate, hydroxymethyl (meth)acrylate and diethyl fumarate. Mention may be made of carboxylic acid esters and vinyl esters having at most 30 carbon atoms, such as vinyl acetate and vinyl propionate.

Among the above ethylene copolymers (A), copolymers of ethylene and unsaturated dicarboxylic anhydrides or multicomponent copolymers of these and unsaturated dicarboxylic esters and/or vinyl esters are hydrolyzed and The dicarboxylic acid anhydride units of these copolymers can be converted to dicarboxylic acid units or half ester units by modification with alcohol. Ethylene copolymers (A) obtained by replacing part or all of the acid anhydride units with dicarboxylic acid units or halfester units can also be preferably used.

To carry out the hydrolysis, the ethylene copolymer (A
) in the presence of a catalyst (e.g. tertiary amine) in an organic solvent (e.g. toluene) that dissolves the copolymer.
It can be obtained by reaction with water for 0.5 to 10 hours (preferably 2 to 6 hours, suitably 3 to 6 hours) at a temperature of ~100°C followed by neutralization with acid.

To perform alcohol modification, the ethylene copolymer (A) can be obtained by the solution method or kneading method described later.

The solution method is similar to the case of hydrolysis, in which the reaction is carried out in an organic solvent in the presence or absence of the above-mentioned catalyst (the reaction is slow in its absence).
2 minutes to 5 hours at the reflux temperature of the alcohol used in
The reaction time is preferably 2 minutes (7 to 2 hours, preferably 15 minutes to 1 hour).

On the other hand, in the kneading method, tertiary amine and Generally from 0.1 to dicarboxylic acid units in the copolymer.
3.0 times mole (preferably 1.0 to 2.0 times mole)
of saturated alcohol at a temperature above the melting point of the ethylene copolymer (A) but below the boiling point of the alcohol used, using a mixer such as the Banbury Mixer 1 extruder commonly used in the rubber and synthetic resin fields. This is a method in which the reaction is carried out while kneading for several minutes to several tens of minutes (preferably 10 to 30 minutes).

The saturated alcohol used in the above modification with alcohol is a linear or branched saturated alcohol having 1 to 12 carbon atoms, and includes methyl alcohol, ethyl alcohol, and -grade butyl alcohol.

In the case of the above hydrolysis and in the case of modification with alcohol, the conversion rate to dicarboxylic acid and the halfesterization rate are both 0.5 to 100%, and 1O80 to
100% is desirable.

The ethylene units in this ethylene copolymer (A) are 30
-99.5% by weight, preferably 30-99.0% by weight, particularly preferably 35-88.0% by weight. Also,
The proportion of carboxylic acid units, their anhydride units and halfester units in the copolymer is 0.1 to 70% by weight in total, preferably 0.5 to 70% by weight, particularly 0.5% by weight. ~60% by weight is preferred.

When using an ethylene polymer in which the proportion of carboxylic acid units, anhydride units, and halfester units in this ethylene copolymer (A) is less than 1%, the ethylene copolymer (A) described below may be used. When crosslinking with B) by heating, not only is the crosslinking incomplete, but also the adhesion to the glass is poor. There is no need to exceed %,
Unfavorable from manufacturing and economical standpoints.

In addition, when using a multicomponent copolymer containing the unsaturated carboxylic acid ester and/or vinyl ester, the total amount thereof is usually at most 70% by weight, and 6% by weight.
When using an ethylene copolymer in which the copolymerization ratio of unsaturated dicarboxylic acid ester and/or vinyl ester exceeds 70% by weight, which is preferably 0% by weight or less, the softening point of the copolymer becomes high, and the softening point is 150°C. The temperature below is not only undesirable because fluidity is impaired, but also economically unfavorable.

(B) Ethylene copolymer (B) In addition, the ethylene copolymer (B) used in the present invention (
B) contains at least ethylene units and hydroxyl units,
At least one unit selected from the group consisting of amino units and glycidyl units" [hereinafter referred to as [comonomer component (
2)", whose ethylene units are 30 to 30
99. It is an ethylene copolymer containing 41%.

This ethylene copolymer (B) is a copolymer that can be obtained by copolymerizing at least ethylene and the following monomers to constitute the comonomer component (2), and a multicomponent system of these and other monomers. Examples include saponified products obtained by saponifying polymers and copolymers of ethylene and vinyl esters (especially vinyl acetate).

These seven polymers include glycidyl alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates represented by the following general formula (the number of carbon atoms in the alkyl group is usually 1).
~25 carbon atoms), α-alkenyl alcohols having 3 to 25 carbon atoms, α-amines having 2 to 25 carbon atoms, and primary or secondary 7-minoalkyl (meth)acrylates (the number of carbon atoms in the alkyl group is usually 1 ~25 items).

(Here, R is H or a methyl group, and R2 is a linear or branched alkyl group having 1 to 12 carbon atoms.) Representative examples of this monomer component (2) include butene tricarboxylic acid monomer. glycidyl ester, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, itacon ugly glycidyl ester, hydroxymethyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate,
Hydroxyhexyl (meth)acrylate, allyl (a
llyl ) alcohol, allyl amine and aminoethyl (meth)acrylate.

Moreover, examples of other monomers include the unsaturated carboxylic acid esters and vinyl esters.

The ethylene unit in this ethylene copolymer (B) is 30
-99.5% by weight, preferably 30-99.0% by weight, particularly preferably 35-99.0% by weight. Further, the proportion of hydroxyl units, amino units and glycidyl units in the copolymer is 0.1 to 70% by weight for the same reason as in the case of the ethylene copolymer (A), and is 0.5%. -70% by weight is preferred, especially 0.5-60%
% by weight is preferred. Furthermore, when using a multicomponent copolymer containing the unsaturated carboxylic acid ester and/or vinyl ester, the total amount thereof is generally at most 70% by weight for the same reason as in the case of the ethylene copolymer (A). %, particularly preferably 60% by weight or less.

Melt index (JIS K-72t) of the ethylene copolymer (A) and ethylene copolymer (B)
o, measured under condition 4, hereinafter rM, 1. J) is generally 0.001 to 1000 g/10 minutes, preferably 0.05 to 500 g/10 minutes, and particularly preferably 0.1 to 500 g/10 minutes.
1. When these ethylene copolymers with a weight of less than 0.01 g 710 minutes are used, it is not only difficult to mix the copolymers uniformly, but also the moldability is poor.

Among these ethylene-based copolymers, when produced by a copolymerization method, the amount is usually 500 to 2500 Kg/cm.
Fast chain transfer agent (
For example, it can be obtained by copolymerizing ethylene and comonomer component (1) or comonomer component (2) or these and other components in the presence of an organic peroxide. It is well known. Furthermore, the method of manufacturing the ethylene copolymer (A) by hydrolysis and/or modification with alcohol and the method of manufacturing the ethylene copolymer (B) by saponification are also well-known methods. be.

(G) Production of mixture (1) Mixing ratio In producing the mixture of the present invention, ethylene copolymer (A) and ethylene copolymer (B
) Ethylene copolymer (A) in the total amount (total)
The mixing ratio of the ethylene copolymer (B) is 1 to 99% by weight [that is, the mixing ratio of the ethylene copolymer (B) is 99 to 1% by weight], and 5 to 99% by weight.
85% by weight is desirable, particularly 10-80% by weight. Ethylene copolymer (A) in the total amount of ethylene copolymer (A) and ethylene copolymer (B)
) Even if the mixing ratio is less than 1% by weight or more than 99% by weight, the crosslinking will be insufficient when the mixture is crosslinked by the method described later, and for example, the adhesion with the glass plate described later will not be good. It also has poor heat resistance.

(2) Mixing method To produce this mixture, it is sufficient to uniformly mix the ethylene copolymer (A) and the ethylene copolymer CB).The mixing method is generally used in the field of olefin polymers. Henschel mixer and tumbler being used
Tri-blending may be carried out using a mixer such as a mixer such as a blender, and a method of melt-kneading using a kneader such as a Banbury, an extruder, or a roll mill is exemplified. At this time, a more uniform mixture can be obtained by triblending in advance and melt-kneading the resulting mixture. When melt-crosslinking, it is necessary that the ethylene copolymer (A) and the ethylene copolymer CB) do not substantially undergo a crosslinking reaction (if they are crosslinked, the resulting mixture may be molded as described below). (This is undesirable because it not only deteriorates the moldability, but also reduces the shape of the desired molded product and the heat resistance when crosslinking the molded product.) Therefore, the melt-kneading temperature is Depending on the type and viscosity of the ethylene polymer used, room temperature (2
0°C) to 150°C, preferably 140°C or less.

As a guideline for ``substantially no crosslinking,'' ``an afterflame with a diameter of 0.1 micron or more after extraction in boiling toluene for 3 hours'' (hereinafter referred to as ``extraction afterflame'') is generally 15 It is preferably at most 10% by weight, most preferably at most 5% by weight.

In preparing this mixture, additives such as oxygen, light (ultraviolet) and heat stabilizers, antistatic agents, lubricants, processability modifiers and tack modifiers which are commonly used in the field of olefinic polymers are used. may be added within a range that does not impair the characteristics (physical properties) of the thin-walled material of the present invention.Furthermore, a crosslinking accelerator such as an epoxy compound, P-)luenesulfonic acid, and AI-impropoxide may be added. By doing so, the crosslinking between the ethylene copolymer (A) and the ethylene copolymer (B) can be further completed as described above. The amount added is 10% of these resins.
Usually at most 0.1 parts by weight (preferably 0.01 to 0.05 parts by weight) to 0 parts by weight.

(D) Production of thin-walled products When the thin-walled products of the present invention are used in the form of a film or sheet, T-Guy film, which is commonly used in the field of thermoplastic resins, is widely used when producing films by the inflation method. A thin-walled product can be obtained by extruding it into a film or sheet using an extruder. At this time, the extrusion temperature is 2
The temperature is below 50°C. On the other hand, when extruded at temperatures exceeding 250°C, parts of the ethylene copolymer (A) and ethylene copolymer (B) crosslink, producing small gel-like particles, resulting in a uniform shape. Extrudates cannot be obtained. For these reasons, the extrusion temperature is in the same temperature range as in the case of melt-kneading described above, regardless of whether a crosslinking accelerator is added (blended) or not.

In any of the above cases, after manufacturing the thin-walled objects, the thin-walled objects with good transparency are made by rapidly cooling them in a water-cooling roll or a water bath to prevent adhesion between the thin-walled objects or between the thin-walled objects and a take-up roll. can get. The thickness of the thin-walled material thus obtained is generally between 5 microns and 2 mm, preferably between 5 microns and 1.5 a+m, especially between 10 microns and 1.5 microns. Omm is preferred.

(E) Glass plate Furthermore, the glass plate used in the present invention may be washed or degreased in advance as necessary to make the adhesion with the crosslinked material of the mixture more effective. It is also possible to create an anchor effect by physically increasing the adhesion area by adding irregularities to the layer. Additionally, a primer can be used. The thickness of the glass plate is usually 0.5mm
It is preferably 0.511 m to 25 a+o, particularly preferably 1 m+e to 20 mm.

The glass types of this glass plate include soda lime glass, borosilicate glass, lead glass, quartz glass, phosphate glass,
Examples include tempered glass. These glasses are manufactured industrially and used in a wide variety of fields, and the manufacturing method 1, composition, 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) Production of laminated glass In the thin-walled mixture of the ethylene copolymer (A) and the ethylene copolymer (B), crosslinking has hardly progressed (the extracted afterflame is generally 15% by weight). (preferably 10% by weight or less, preferably 5% by weight or less), it exhibits the same behavior as ordinary thin-walled resin polymers (films, sheets).

Therefore, by subjecting this thin material and the glass plate to the heat and pressure treatment described below, the ethylene copolymer (
Comonomer component (1) of A) (i.e., carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and halfester units) and comonomer component (2) of the ethylene-based copolymer (B) (i.e., hydroxyl units, A crosslinking reaction (condensation reaction) occurs between the amino units and glycidyl units), and the laminated glass of the present invention not only has extremely high adhesive properties but also has significantly improved heat resistance of the thin-walled product.

The laminated glass of the present invention can be obtained by laminating a crosslinked product of the mixture on the intermediate layer. The manufacturing method includes a press molding method, a stamping moldability 2-dipping method, an injection method, a low-pressure transfer method, etc., which are generally used in the field of thermosetting thermoplastic resins, from the uncrosslinked mixture or thin-walled material. The most common method is
In this method, the uncrosslinked thin material is sandwiched between two glass plates, and bonding and crosslinking are simultaneously performed by press molding under the heating and pressure treatment conditions described below. For bonding, a one-stage adhesive method or a two-stage adhesive method is adopted. The one-stage bonding method is a method in which main bonding and crosslinking are directly performed without performing the first-stage temporary bonding described later.

In the two-step method, the uncrosslinked thin material is first sandwiched between glass plates, and then passed between two rubber rolls to be pressed together. The pressure at this time is usually 1 to 10 kg/cm'. Next, the second stage of final adhesion is carried out, and the temporary adhesive is finally bonded by heating and pressurizing using an electric heating plate press, or by vacuuming or pressurizing using an autoclave, heating and applying pressure. There are methods of pressure treatment and methods of combining these methods, in which adhesion and crosslinking are performed continuously. The temperature for bonding and crosslinking by heating is generally in the range of 120 to 240"C for bonding, and 180 to 360"C for crosslinking.The pressure for bonding is 0 to 1.
~30Kg/cm''; on the other hand, the higher the temperature, the shorter the crosslinking treatment is sufficient, but usually 160~2
30 seconds to 10 minutes at 00°C, and preferably 10 seconds to 2 minutes at 200 to 360°C. The important point is that the mixture or its thin material is placed between the glass plate and the pressure roll as shown in Fig. 1. The aim is to avoid getting involved.

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 impact resistance, but also has excellent heat resistance and furthermore has good water resistance.

The present invention will now be described in more detail with reference to Examples.

The mixture of ethylene copolymer (A) and ethylene copolymer (B) used in Examples and Comparative Examples is shown below.

Ethylene copolymer (A) and ethylene copolymer (B)
Tonneau mixture,! :LteM,1. is 300 g/10
Theal ethylene-acrylic acid copolymer (density 0.9
A saponified product obtained by saponifying an ethylene-vinyl acetate copolymer having an acrylic acid copolymerization rate of 20% by weight (hereinafter referred to as rEAAJ) and a vinyl acetate copolymerization rate of 28% by weight. Percentage 97.5%, 1.75g/10min, density 0.
M, 1. is 2
A mixture of an ethylene-methacrylic acid copolymer (density: 0.950 g/cm", methacrylic acid copolymerization ratio: 25% by weight) and the saponification degree described above [mixing ratio: 50:50 (weight ratio), Hereinafter, “Mixture (TI)
J], M, 1. terpolymer of ethylene-ethyl acrylate-maleic anhydride (ethyl acrylate copolymerization ratio 30.7% by weight,
Maleic anhydride copolymerization ratio 1.7% by weight, hereinafter r E
A) A terpolymer of ethylene-methyl methacrylate-hydroxy methacrylate (referred to as IJ) and M, i = 123 g/10 min (copolymerization ratio of methyl methacrylate 20.7% by weight, copolymerization of hydroxy methacrylate) (ratio 11.7% by weight) [mixing ratio 50:50 (weight ratio), hereinafter referred to as "mixture (II
I) J] and ■, are 105 g /
Ethylene-methyl methacrylate-maleic anhydride ternary copolymer (copolymerization ratio of methyl methacrylate 20.5% by weight, copolymerization ratio of maleic anhydride 3%)
．． 1% by weight) and a terpolymer of ethylene-methyl methacrylate-glycidyl methacrylate (copolymerization ratio of methyl methacrylate 18.8% by weight, copolymerization ratio of glycidyl methacrylate 12.7% by weight, hereinafter r GM
(referred to as AJ) [mixing ratio 30:70
(weight ratio], hereinafter referred to as "mixture (■)"). These mixtures were manufactured by tri-blending the respective copolymers or terpolymers for 5 minutes using a Henschel mixer. did.

The mixture dI) or IV) obtained as described above
and extrusion 4M with T-die for FAA and saponified products respectively! (Diameter 40m, die width 3゜C11,
A sheet having a thickness of 400 microns was molded using a rotational speed of 85 revolutions per minute) under the conditions where the cylinder temperature is shown in Table 1. The extracted afterflame of the obtained sheet was measured. In both cases, it was 0%.

Table 1 Examples 1 to 4, Comparative Examples 1.2 The above mixture (I) or rV) or EAA or saponified compound was added to the intermediate layer of two glass plates (thickness: 3 mm) whose surfaces had been degreased in advance. sheet (thickness
0.4 am), 10Kg/c at 180℃
Bonding was carried out under pressure of rn' (gauge pressure) for 5 minutes. Each laminate obtained was weighed at 20Kg/c at a temperature of 260℃.
A crosslinking treatment was performed for 3 minutes under pressure of rn' (gauge pressure) to produce a laminated glass.

The shear peel strength between each of the obtained laminated glasses was measured at a temperature of 80° C. according to JIS K6850. In addition, the visible light transmittance is determined according to JISR32.
12, and the impact resistance test was conducted according to JISR32.
12, the sample was dropped from a height of 8 m and measured.

Furthermore, a heat resistance test was performed at 65° C. according to JIS R3212. The results are shown in Table 2.

The results of the impact resistance test are shown below.

O: Not penetrated X: Penetrated In addition, the results of the heat resistance test are shown below. The laminated glass exhibits the following effects, including its manufacturing process.

(1) Since the intermediate adhesive layer (crosslinked 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) Since the intermediate adhesive layer has excellent adhesion and impact resistance, the laminated glass has good impact resistance.

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 for automobile windshields, window frames for buildings, glass for ships, and glass for vehicles other than automobiles.

Claims (1)

[Claims] The mutual glass plates (A) consist of at least ethylene and at least one type of unit selected from the group consisting of carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and half ester units, and the content of ethylene units is 30
-99.5% by weight of an ethylene copolymer; and (B) at least ethylene units and at least one unit selected from the group consisting of hydroxyl units, amino units and glycidyl units; 1. A laminated glass, characterized in that it is bonded by a thin crosslinked product of a mixture of 99 to 1% by weight of an ethylene copolymer having an ethylene unit content of 30 to 99.5% by weight.