JPS63109049A - Laminated glass - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to laminated glass. More specifically, it is made by integrating a special resin layer with excellent adhesive properties and temporary glass, and is useful as window glass, lighting material, and shielding material in various fields, especially automobile windshields, aircraft,
This invention relates to laminated glass that is useful as window glass for vehicles such as trains and high-rise buildings.

(b) Conventional technology Recently, it has been recommended to use laminated glass instead of conventional partially tempered glass for automobile windshields from the point of view of safety, and laminated glass is used not only in luxury cars but also in popular cars. It has come to be used. Such laminated glass is a type of safety glass that is made by laminating at least two sheets of glass together and bonding them together using a soft resin as an interlayer film.Even if the glass sheets break due to the action of an external force, the interlayer film absorbs the impact. This prevents most of the debris from scattering. Furthermore, in order to reduce weight and reduce injury to the human body in the event of breakage, the negative side of the soft resin (interlayer film) is made of temporary glass, and the other side is made of hard wood instead of temporary glass. Laminated glass coated with a layer is also I
It has come to be recommended.

Conventionally, the lat interlayer film for the above laminated glass is
Synthetic resins such as cellulose sulfate and cellulose acetate have been used in the past, but now plasticized butyral resin is exclusively used. The manufacturing method for this laminated glass is to sandwich the resin interlayer between glass plates and to
Usually, the materials are heated and crimped, or they are degassed by reducing the pressure to a vacuum to remove air bubbles, and crimped at high temperature and low pressure.

(c) Problems to be Solved by the Invention The plasticized butyral resin described above exhibits excellent properties as an interlayer film material, but it has a high specific gravity and becomes extremely hard and brittle at low temperatures, especially below -20°C, and its shock absorption ability decreases. It has the physical property of being significantly reduced. Therefore, laminated glass using this as an interlayer film has problems in terms of weight and effectiveness in use in cold regions.

Regarding this point, the present inventors have previously prepared polymer blocks of an aromatic vinyl compound at both ends of a hydrogenated conjugated diene polymer block, and the conjugated diene polymer block has 10
We proposed a laminated glass with excellent low-temperature impact resistance in which multiple pieces of temporary glass are laminated and integrated using a copolymer that accounts for ~40% by weight as a soft resin interlayer film (Patent Application No. 60-9037).
No. 6). Furthermore, in order to further reduce injuries to the human body when the plate glass breaks, we proposed a laminated glass constructed in the same manner as above, with the plate glass on the - side replaced with a hard resin layer (Patent Application 1983- No. 257255). These laminated glasses have many features compared to existing laminated glasses, but depending on the application, the adhesion between the soft resin film and the plate glass may be insufficient, so surface treatment, adhesive coating, or heat treatment may be required. Temporary glass, adhesive film coating, etc.
In some cases, it may be necessary to apply it to a soft resin film.

This invention was made in view of the above situation, and can greatly improve the problem of high pressure and low temperature use, and reduce human injuries. The aim is to provide an improved laminated glass.

(d) Means for Solving the Problems Thus, according to the present invention, a hydrogenated diconjugated diene polymer block is provided with aromatic vinyl compound polymer blocks at both ends of the conjugated diene polymer block. The hydrogenated copolymer content accounts for 10 to 40% by weight of the total, and 0.3 to 40% by weight
Block copolymer (a) into which 5% by weight of acrylic acid or methacrylic acid residue is introduced or this block copolymer (
There is provided a laminated glass characterized in that a plate glass and a temporary glass or a hard resin layer are laminated and integrated via a soft resin film made of a resin composition mainly composed of a).

The base hydrogenated copolymer of the block copolymer (a) used in this invention is a conjugated diene linear polymer such as polybutadiene, polyisoprene, polychloroprene, etc. (
A linear polymer having a polymer chain (end blocks) of an aromatic vinyl compound such as polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, polychlorostyrene, etc. at both ends of the intermediate block) is hydrogenated. It is obtained by processing. At this time, it is preferable to use a material that has been sufficiently hydrogenated so that the hydrogenation ratio of the intermediate block is 90% or more, from the viewpoint of heat resistance, weather resistance, etc., and more preferably 95% or more. Even if such sufficient hydrogenation treatment is carried out, the hydrogenation ratio of the aryl groups in both end blocks is usually suppressed to within 105 and has no substantial effect.

In addition, the average molecular weight of the intermediate block is usually 5000 to 1
25,000, and the average molecular weight of both end blocks is usually
It should be 10,000 to 300,000. The most suitable hydrogenated copolymer structure is polystyrene on both ends and middle block. The block has an ethylene-butylene copolymer structure (hydrogenated polybutadiene), and the block at both ends is polystyrene and the middle block has an ethylene-propylene copolymer structure (hydrogenated polyisoprene). Such hydrogenated copolymers themselves include Kraton G-1650, G-1652
, G-1657, G-16511 (all manufactured by Shell Chemical) and other names and model numbers.

Although the copolymer before hydrogenation is transparent and flexible, it shows significant yellowing during weathering tests and is not suitable for the purpose of this invention.

Furthermore, if the hydrogenated conjugated tzene polymer block exceeds the range of 10 to 40% by weight of the total weight, it will not be suitable as an intermediate resin film because it will not have adequate softness.

The block copolymer (a) used in the present invention can be obtained by introducing a small amount of acrylic acid or methacrylic acid residue into the hydrogenated copolymer chain.

The form in which such acrylic acid or methacrylic acid residues are introduced into the chain may be random, block, or grafted. Such block copolymer (a) is easily available, for example, under the name and product number HTr (-HR3201 (trade name of Asahi Kasei Corporation)).

The amount of acrylic acid or methacrylic acid residue introduced into the chain is 0.3 to 5% by weight. If it is less than 0.3 parts by weight or 1%, the adhesion improving effect is insufficient, and if it exceeds 5 parts by weight, the thermal stability during molding will be insufficient, and, for example, transparency will decrease, so it is not suitable. From this point of view, the preferred introduction amount is particularly 06 to 3! Il [amount%.

The soft resin film of the present invention may be comprised essentially only of the block copolymer (a). However, as long as the transparency, flexibility, weather resistance, and adhesion to the glass plate are not impaired, it is sufficient that the resin is mixed with Ike's resin. Can be applied. At this time, as the other resin to be mixed, it is best to use a block copolymer into which no acrylic acid or methacrylic acid residue has been introduced, that is, a block copolymer corresponding to the hydrogenated copolymer chain. This is a preferred embodiment.

As mentioned above, such a block copolymer for mixing is easily available under the name of Kraton G series (manufactured by Shell Chemical Co., Ltd.). At this time, the block copolymer in the mixed resin (
The amount of a) should be at least 50% by weight.

Other resins that can be mixed include polypropylene, polypropylene copolymers, low density polyethylene, high density polyethylene, ethylene-vinyl ester (vinyl acetate, etc.) copolymers, ethylene-acrylate (ethyl acrylate, etc.) copolymers, ethylene-acrylic acid (or methacrylic acid) copolymer, its salt, polybutene-
Various resin components such as 1, poly-4-methylpentene-1 are listed, and two or more of these may be used in combination. The mixing ratio of these is not particularly limited, but the resin composition is 100TL! A ratio of about 10 parts by weight or less to 1 part is usually suitable.

In addition, a small amount (usually 10% by weight or less of the total) of a low-molecular modifier such as mineral oil or a plasticizer is further added to the above copolymer (a) or a resin composition mainly composed of the copolymer (a). In addition, small amounts of various additives such as heat stabilizers, antioxidants, ultraviolet absorbers, lubricants, anti-setting agents, and colorants may be added as necessary. In particular, if weather resistance is required, it is preferable to add an ultraviolet absorber.
Further, a coloring agent may be added to the whole or part of the composition. Particularly when the glass is used as a windshield for an automobile, the addition of such ultraviolet absorbers and colorants is a preferred embodiment.

The soft resin film of the present invention can be formed by extrusion molding the copolymer (a) or the resin composition to form a sheet, or by molding it into a sheet by low flow from a solution (cast ). Normally, for reasons of economy, it is appropriate to form sheets using the pre-cut method.

The laminated glass of the present invention can be produced by sandwiching the above-mentioned soft resin film between plate glasses or between a plate glass and a hard resin layer and bonding them under pressure and heat, or by heating under reduced pressure, as with conventional laminated glass. It can be manufactured by crimping.

These may have not only a three-layer structure but also a multi-layer structure. However, when using a hard resin layer, the hard resin melts,
If it is difficult to form the glass to the specified thickness using pressure, you can either laminate the sheet glass and the soft resin membrane in advance and then bond the hard resin together in a separate process, or coat the soft resin membrane in advance as described below. All you have to do is keep it that way. In any case, it is possible to obtain a laminated glass in which the glass plate and the soft resin film are closely integrated in each layer without performing any pretreatment to improve adhesion on the surface of the glass plate or the soft resin film.

At this time, the thickness of the soft resin film may be adjusted as appropriate, but since it is used for automobile windshields, JIS R32
11 (Automotive safety glass) regulations (0.38 to 0.7
It is preferable to set the thickness according to 6 mm).

Note that the plate glass that is the raw material for the laminated glass may be formed into a desired shape depending on the purpose, and does not particularly need to be flat. Generally, various glass materials such as ordinary plate glass, float temporary glass, frosted glass, and heat ray absorbing glass can be used. Furthermore, it is also possible to use temporary glass that has been colored or roughened, or that has been partially or entirely strengthened.

Further, the hard resin layer that can form one surface of the laminated glass in the present invention preferably has the same transparency as the soft resin film (usually, light transmittance of 70% or more). Furthermore, this resin layer has surface hardness (hardness) that is greater than that of the soft resin film.
It is necessary to have a pencil hardness of about 3 to 5H) and excellent scratch resistance.

Formation of a resin layer that satisfies these requirements includes: forming a hard resin by bonding a hard resin film to a soft resin film;
In addition, after forming a primer layer on the surface of the soft resin film, an external wire curing paint with excellent adhesion to the primer film and excellent abrasion resistance is applied, and then cured with ultraviolet rays to form a hard film and form a hard resin layer. The appropriate method is to Here, as the former hard resin, polymethyl methacrylate resin, polyethylene terephthalate resin, polycarbonate resin, etc. are preferable. The thickness of these resin layers is 5 to 500
μm is suitable, preferably 10-200 μm.

Note that this hard resin layer may consist of two or multiple layers of different types (in particular, an ultraviolet curing resin (?! cloth) may be further applied on top of the hard resin film adhered to the soft resin film). It is also possible to further improve the weather resistance and abrasion resistance by forming the hard resin layer into a two-layer structure, and this is a particularly useful embodiment when using a film having insufficient weather resistance, such as a polycarbonate resin, for example.

(e) Function According to the laminated glass of the present invention, the soft resin film serving as the intermediate layer has appropriate flexibility and excellent weather resistance and low temperature resistance, so it is suitable for use at low temperatures. This results in improved impact resistance.

Moreover, the soft resin film has extremely excellent adhesion and adhesion to sheet glass due to its acrylic acid or methacrylic acid component, and is effective in improving the durability of laminated glass and simplifying the manufacturing process. do.

Furthermore, the soft resin film has a low specific gravity, which is advantageous in terms of weight.

(f) Examples Example 1 A blend of the following composition was mixed in a blender and then extruded in an extruder to produce pellets.

Kraton 01657 40 parts by weight Soft resin TR-HR3201 (hereinafter referred to as resin A) 60 parts by weight Tinuvin P (manufactured by Ciba Geigy) 0.4 ff parts - Butylene copolymer is a hydrogenated block copolymer in which the weight ratio of the former to the latter is approximately 14/36, and HTR-HR3201 (Asahi Kasei Corporation) is a hydrogenated block copolymer in which the weight ratio of the former to the latter is approximately 28/72. It is a hydrogenated block copolymer containing 1% by weight of acrylic acid component. In addition, Tinuvin P is an ultraviolet absorber, and 2-
(Composed of 2'-hydroxy-5'-methylphenylbenzotriazole.) Using this pellet, a sheet with a thickness of 0.81 mm was produced by extrusion using a T-die.
The laminated glass of the present invention was produced by sandwiching the glass between ordinary plate glasses of 75 mm and width 50+11+11 and pressing under reduced pressure at a temperature of 240°C. The adhesive strength between the glass and the resin film was 7.5 kg/25I width (T-peel strength), which was satisfactory.

On the other hand, for comparison, a conventional plasticized butyral resin (thickness: 0.8 am) was used as an intermediate layer, and a laminated glass was produced in the same manner as above except that it was press-bonded at 200°C. In this case, the T-peel strength between glass and resin is 6.0 kg/
It was 25 mm 1 J (Comparative Example 1).

Also, instead of the tree MW-A, Clayton G1.652 (
A laminated glass was produced in the same manner as above using a laminated glass containing no acrylic acid component. In this case, the T-peel strength between the glass and the resin was as poor as 4.2 kg/25+nm width (Comparative Example 2).

Each of the obtained laminated glasses was measured for its light transmittance and subjected to crushing tests using a DuPont impact tester at various temperatures. The crushing test method is as follows.

The temperature was set at -20''Cl2O°C and 60°C, and a drop test was conducted using a DuPont impact tester (300 g of heavy weight, 20 cm height drop) to observe the state of crushing.

Further, after soaking in hot water at 95° C. for one hour, the sample was taken out and changes in appearance were observed.

The results are shown in the table below.

(The following is a blank space, continued on the next page.) Table 1 [Note] In Table 9, A indicates the state of glass fragmentation and B indicates the state of scattered fragments (the same applies hereinafter). Example 2 The following composition is used as a resin for an interlayer film. The materials were mixed in a blender and then extruded in an extruder to create pellets.

Kraton 01657 30℃ parts by weight Resin-A? Part by weight of O3i Tinuvin P Part by weight of O34 (manufactured by Ciba Geigy) Using this pellet, a thickness of 0.8Il1 was formed using a T-die.
Eleven sheets were produced by extrusion. This sheet is used as an intermediate layer, and has a thickness of 2.75 mm, a width of 50111 m, and a length of 5.
This invention is made by sandwiching ordinary plate glass of 0IllII with a 50 micron thick polyethylene-terephthalate resin film whose surface has been subjected to corona discharge treatment, and pressing it under reduced pressure at a temperature of 230°C, so that one side is made of plate glass and the other side is made of hard resin. A laminated glass was produced.

On the other hand, for comparison, a conventional plasticized butyral resin and a sort of 0.81 thickness each for the above-mentioned interlayer film were used as interlayer films, both sides of which were sandwiched between temporary glasses, and the former was heated at 200°C.
Two types of double-sided plate glass type laminated glasses were prepared by press-bonding the latter at 230° C. (the former is Comparative Example 4, and the latter is Comparative Example 3).

Examples of physical properties of these laminated glasses! It was measured in the same manner. The results are shown in Table 2.

(The following is a blank space, continued on the next page.) In Table 2, A indicates a broken glass state, and B indicates a hearing loss with scattered fragments (
same as below).

Example 3 Using a formulation with the following composition, a thickness of 0 was obtained in the same manner as in Example 1.
．． An 8 mm sheet (intermediate 11K) was produced.

Kraton 01657 40 parts by weight Resin-A 60 parts by weight Tinuhin P
0.411ttlifIn The results of measuring various physical properties of this sheet are shown in the comparative example (
Commercially available plasticized butyral resin for laminated glass;
0.8m1) are shown in Table 3.

(The following is a blank space, continued on the next page.) Table 3 As is clear from this table, the interlayer film in this invention (
Soft resin film) has a low specific gravity and is superior to conventional intermediate a(
It has many advantages over plasticized butyral.

In addition, the light transmittance is practically acceptable compared to conventional products, and the weather resistance is also excellent. In particular, the low specific gravity is a great advantage in reducing the weight of the laminated glass, and the low dynamic elastic modulus at low temperatures is advantageous in terms of low-temperature impact absorption.

(G) Effects of the Invention The laminated glass of the present invention has improved shock absorption ability when used at low temperatures compared to the conventional glass, and is also lightweight. Moreover, the adhesion between the soft resin film (intermediate Fa) and the temporary glass is excellent, which is advantageous in terms of durability and manufacturing. Therefore, the laminated glass of this invention is
It can be used for the same purposes as in the past, and is also expected to be applied to purposes not previously used.

Procedure Masa Neyama e-) May 22, 1988 Patent Application No. 25428G 2, Title of Invention Laminated Glass 3, Relationship with the Amendment Case Patent Applicant Address Awaji-cho, Higashi-ku, Osaka City 2-44 address name
Dainippon Brass Dicks Co., Ltd. Representative Tsunsaku Sakauchi 4, Agent 530 Address 1-3 Quarter, 51 Nishitenma, Kita-ku, Osaka
One Building Phone (06)365-0718 ,,'-+
Name Patent Attorney <6524) Shintabe Nogawa ・
5. Date of the amendment order. 6. Contents of the amendment in the "Detailed Description of the Invention" section of the amendment against China Mei M. Correct with system J.

2. In lines 8 to 6 from the bottom of page 6 of the same book, "(all manufactured by Shell Chemical Co., Ltd.)...Available." was replaced with "(both manufactured by Shell Chemical Co., Ltd.) and Toughtic HR- 1041(
It is easily available under the name and model number such as (manufactured by Asahi Kasei Kogyo Co., Ltd.). Correct it with J.

3, r HT R-1-I R32 on page 7, line 8 of the same book
Correct the month of 0 to IR-3201J.

4. Correct "loan" in line 6 from the bottom of No. 11 of the same book to "J".

5. Delete "(coating)" on page 112, line 10 of ff.

6. Same book, page 14, line 9 r 7.5kl' 25mm
Correct the width to r7.5kQ/1 in 50mm.

7. In the 15th line of the same page, correct [6,0k (1/25m+n width)] to "6.0kQ150tlllll width".

8. Correct "4.2kg/25II 1m width" in the second line from the bottom of the same page to f 4.2kQ/50t*ta width J.

9. In Table 1 on page 16 of the specification, "water-bearing resistance test" in the bottom column of the test items is amended to "hot water resistance test."

10. “Adhesive strength between glass and resin (kg/25ml/1l)” at the bottom of the test items in Table 2, page 19 of the same book.
J is the adhesive strength between glass and resin (ko/50++
n+) Corrected as J.

11. “1Ii4” at the bottom of the test items in Table 2
"Water carrying test" is corrected as "Hot water resistance test J.

12, Specification M, page 21, Table 3, the value of heating loss rate (%) of the comparative example "115J" is corrected to "11.5J.

Claims (1)

[Claims] 1. A hydrogenated copolymer chain having aromatic vinyl compound polymer blocks at both ends of the hydrogenated conjugated diene polymer block, in which the conjugated diene polymer blocks account for 10 to 40% by weight of the whole, Through a soft resin film made of a block copolymer (a) into which 0.3 to 5% by weight of acrylic acid or methacrylic acid residues have been introduced or a resin composition mainly composed of this block copolymer (a) A laminated glass characterized in that a plate glass and a plate glass or a hard resin layer are laminated and integrated.