JPS60222249A - Laminated safety glass and material therefor - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminated safety glass having a thermoplastic polyurethane resin layer on one side with excellent surface performance, and a material that is an intermediate raw material consisting of a sheet or film for manufacturing the same. be.

Laminated sheets of inorganic glass sheets or hard organic glass sheets and relatively soft synthetic resins are well known as laminated safety glass. Hereinafter, the hard substrate refers to these inorganic glass sheets or organic glass sheets, and simply glass refers to inorganic glass unless specifically called organic glass. Laminated safety glass (hereinafter referred to as laminated glass) in which both surfaces are glass, for example, a laminated sheet having a five-layer structure of glass-polyvinyl butyral-glass, is widely used as safety glass for automobiles. The synthetic resin layer laminated between such glass sheets is called an interlayer film, and various synthetic resins such as polyvinyl butyral, polyurethane, and others have been used or proposed. On the other hand, in laminated safety glass made of glass and synthetic resin, a laminated sheet with an exposed synthetic resin layer, such as glass-synthetic resin or glass-synthetic resin-glass-synthetic resin, has one side made of glass and the other side made of synthetic resin. Laminated sheets are attracting attention for applications such as automotive safety glass. This laminated safety glass is considered to be even safer than traditional double-sided glass laminated safety glass. For example, if this laminated safety glass is used as a car windshield with the synthetic resin side facing the inside of the car, there will be fewer lacerations and cuts when a driver collides with the 70-inch glass, and the glass will not break. It is thought that this will reduce the chance of glass shards flying into the interior of the car. Such sheet-shaped laminated safety glass, in which one side is glass and the other side is synthetic resin, is hereinafter referred to as "pylayer glass."

Regarding pie layer glass, for example, Japanese Patent Application Laid-Open No. 1986-
41423, JP-A-48-25714, JP-A-49-. Publication No. 54910, and JP-A-53-2
There is a description in Publication No. 7671. As can be seen from these known examples, the exposed synthetic resin layer (hereinafter referred to as "Pylayer") is usually made of polyurethane. Polyurethanes are also well known as interlayers in laminated glass. There are two types of polyurethane: thermoplastic polyurethane and thermosetting polyurethane; the former is a linear polymer;
It is usually obtained by reacting a high molecular weight diol, a chain extender and a diisocyanate compound, the latter being a crosslinked polymer), for example by reacting a high molecular weight diol, a crosslinker and a diisocyanate compound.

One of the important issues in pie layer glass is the surface properties of the pie layer layer. Compared to synthetic resin layer glass such as polyurethane, scratch resistance, abrasion resistance, stain resistance, etc. are inferior, and due to constraints such as molding conditions, the surface smoothness is often insufficient, and the surface characteristics Improving this is an extremely important issue. The invention described in JP-A-55-27671 is concerned with improving scratch resistance among surface properties. This invention proposes a thermosetting polyurethane resin as one layer of the pie layer, and since the thermosetting polyurethane resin is difficult to directly adhere strongly to glass, heat is applied between the glass layer and the thermosetting polyurethane resin layer. One of the main points is to provide a plastic polyurethane resin layer. Especially using certain raw materials. The resulting thermosetting polyurethane resin has self-healing properties and excellent scratch resistance. This thermosetting polyurethane resin with self-repairing properties is disclosed in Japanese Patent Publication No. 5, filed by the same applicant.
No. 8-29815, and the thermosetting polyurethane resin used in the examples described in the above publication is the one described in this publication.

Self-healing property refers to the property that scratches caused by scratches etc. disappear over time, and this solves the problem of scratch resistance. Self-healing property is not a property of all thermosetting polyurethane resins, but is thought to be a property unique to thermosetting polyurethane resins with a specific polymer structure.In fact, ordinary thermosetting polyurethane resins are self-healing. It has almost no repairability.

The biggest problem when using a thermosetting polyurethane resin for a pie layer #i "Thermosetting" itself is essentially a moldability problem. That is, the problem is that thermosetting polyurethane resins lose their plasticity after curing. For example, first of all, there are restrictions on the methods of molding thermosetting polyurethane resin sheets and films (
It is not possible to use extrusion molding, press molding, or other molding methods suitable for forming sheets or films (such as casting and curing, which is Haho's only method). It is difficult to obtain film. Furthermore, if the material has plasticity, it can be compressed with a mold material having a smooth surface to produce a smooth surface, but this cannot be applied to thermosetting polyurethane resins. In particular, as will be described later, when thermocompression bonding is employed in the manufacture of pie layer glass, when the surface of one layer of pie layer is heated and compressed using a molding material, it is possible to smooth the surface if the first layer of pie layer has thermoplasticity. This method cannot be used for thermosetting polyurethane resins. The lack of plasticity is also the reason why the thermosetting polyurethane resin has difficulty adhering firmly to glass. On the other hand, a specific thermosetting polyurethane resin with excellent abrasion resistance and hydrolysis resistance has been disclosed as a coating material that can be applied to a single layer of ultraviolet curable polyurethane resin.・Φ・I
! IwaO-...-Kai...Fist...@I@06
11...Fist...Fist 1-Statue...ee...@・16@@
...Export... (Refer to Japanese Patent Application Laid-open No. 149348/1983 and Japanese Patent Application Laid-open No. 57-!+1920). However, like thermosetting polyurethane resins, this composition, once cured, is difficult to perform secondary molding, and does not solve the above-mentioned problems.

The present inventors have conventionally studied the use of a thermoplastic polyurethane resin as a pie layer without using a thermosetting polyurethane resin. Thermoplastic polyurethane resin has excellent mechanical properties such as penetration resistance and impact resistance, and other than surface properties, it is considered to be the most excellent material for a pie layer. Among the surface properties, wear resistance and stain resistance could be solved by selecting a thermoplastic polyurethane resin and modifying the surface of the thermoplastic polyurethane resin. For example, JP-A No. 58-213660 and JP-A No. 58-21566 related to the invention of the present inventors.
No. 1 and Japanese Unexamined Patent Publication No. 59-3050 describe a method for improving the surface properties of a thermoplastic polyurethane resin by introducing a crosslinking group into the surface thereof and crosslinking the resin. 17 However, although thermoplastic polyurethane resins have some self-healing properties, they are insufficient compared to the self-healing properties of the specific thermosetting polyurethane resins described in the above-mentioned known examples.
Therefore, the scratch resistance was insufficient.

The present inventor conducted research and examination on the self-healing properties of thermoplastic polyurethane resins. As a result, it was found that the self-healing property of a thermoplastic polyurethane resin is not a property of the surface of the thermoplastic polyurethane resin, and therefore it is difficult to improve the self-healing property by any kind of surface treatment. Therefore, as a result of intensive research and study to improve the self-healing properties of thermoplastic polyurethane resins by improving the thermoplastic polyurethane resins themselves, we found that thermoplastic polyurethane resins with self-healing properties that are as good as, or superior to, the specific thermosetting polyurethane resins mentioned above. The present invention, which has led to the discovery of a resin, relates to laminated safety glass such as Pylayer glass, which has a layer of thermoplastic polyurethane resin having self-healing properties as the outermost layer, and also relates to an intermediate layer for manufacturing this laminated safety glass. It relates to sheets or films used as materials. That is,
The gist of the present invention is the following two inventions.

1. Transparent or translucent laminated safety glass having at least a two-layer structure of a hard base layer and a synthetic resin layer, with one exposed surface being the surface of the hard base layer and the other exposed surface being the surface of the synthetic resin layer. In this case, the synthetic resin layer has a thermoplastic polyurethane resin (A) described below as the outermost layer, and may optionally include an inner layer consisting of other synthetic resin layers. Laminated safety glass characterized by:

Thermoplastic polyurethane resin body): Molecular weight approximately son ~ 8
00 diol or a combination of a chain extender and a diol with a molecular weight of about 1200 or less in a ratio such that the average molecular weight is about 300 to aOO (however, the equivalent ratio of chain extender/diol is about 1.2 or less), and non-yellow A thermoplastic polyurethane resin obtained by reacting α9 to 1.1 equivalents of the latter with 1 equivalent of the former of a modified diisocyanate compound.

(5) A structure consisting of one layer of transparent thermoplastic polyurethane resin (aluminum), or one of which has one outermost layer of the thermoplastic polyurethane resin (A) and a transparent thermoplastic polyurethane resin (A) as shown below. A material for producing laminated safety glass, characterized in that it is a sheet or film consisting of a structure of at least two layers including a layer of plastic polyurethane resin (B).

Thermoplastic polyurethane resin (A): Molecular weight approximately 300~
800 diol or average molecular weight of about 300-800
A combination of a diol with a molecular weight of about 1200 or less and a chain extender in a ratio such that the equivalent ratio of chain extender/diol is about 1.2 or less, and a non-yellowing diiso7anate compound per equivalent of the former. A thermoplastic polyurethane resin obtained by reacting the latter a9 to t1 equivalents.

Thermoplastic polyurethane resin body): Molecular weight approximately 1500~
4000 diol and a chain extender and a non-yellowing diisocyanate compound for each equivalent of the former (
Thermoplastic polyurethane resin obtained by reacting L9 to 1.1 equivalents.

In the first aspect of the invention, if there is an internal layer, at least one of the inner layers, particularly the main layer, is most preferably made of the above-mentioned thermoplastic polyurethane resin. In addition, in the combination of diol and chain extender, which are the main raw materials of the thermoplastic polyurethane resin, and the combinations of diols and chain extenders described later, the average weight means the number average molecular weight, and is calculated using the following formula. It is something that will be done.

Mn: number average molecular weight M, molecular weight 111: number (=number of moles) In the following description of the present invention, a pie layer glass used as laminated safety glass, particularly as a window material for automobiles, will be mainly explained. However, the applications are not limited to this, and may also be used as window materials for other transportation equipment (for example, aircraft), window materials for buildings, and laminated safety glass for uses other than window materials. Good too. The pie layer glass of the present invention has a layer of the above-mentioned thermoplastic polyurethane resin having excellent self-repairing properties as the outermost layer of the pie layer. That is, one exposed surface of the pie layer glass is the surface of the thermoplastic polyurethane resin layer. The other surface consists of a hard substrate, preferably a glass surface. One layer of the pie layer may substantially consist only of the thermoplastic polyurethane resin (A) layer, but preferably has a thermoplastic polyurethane resin (CB) layer as an inner layer. The pie layer may also have other internal layers, but these are usually unnecessary.

An internal layer that may optionally be present is a thin adhesive layer to improve the adhesion between the hard substrate and the pie layer. The thermoplastic polyurethane resin (A) is responsible for the surface performance of the pie layer, and the thermoplastic polyurethane resin (ω) is responsible for the physical performance such as impact resistance and penetration resistance.

However, since the thermoplastic polyurethane resin (A) has superior physical performance compared to the known thermosetting polyurethane resin for one layer of the pie layer, the one layer of the pie layer is substantially composed of only the thermoplastic polyurethane resin (A). You can also. The thickness of the whole pie layer is at least 0
．． It is preferable that it is 2w or more. In the case of pie layer glass used as an automobile window material, the upper limit of its thickness is approximately 2cm.
It is preferable that The thickness of each layer of the pie layer will be described later.

The most significant feature of the present invention is that each pie layer can be made of substantially only thermoplastic resin. Thereby, there are fewer restrictions on the production of sheets or films for forming a single pie layer, and it becomes easy to continuously produce sheets or films with a uniform thickness and a smooth surface. Furthermore, when this sheet or film is laminated with a hard substrate by a lamination method, it is possible to further improve the surface smoothness of a single layer of the pie layer by applying heat and pressure using a mold material having a smooth surface. The most preferred method for producing the pie layer glass of the present invention is a method in which one or more sheets or films of single-layer or multilayer structure and a hard substrate are laminated by a lamination method. A sheet or film containing substantially a thermoplastic polyurethane resin (or the same substance as (A)) used for this purpose is the material for producing the laminated safety glass of the second invention.

Below, thermoplastic polyurethane resin (4), same (B),
The manufacturing method of the above-mentioned pie layer glass and its manufacturing materials will be explained in detail. As is clear from the description, the present invention is not necessarily limited to the preferred embodiments described above.

First, a specific thermoplastic polyurethane resin with excellent self-healing properties in the present invention, ie, the thermoplastic polyurethane resin (4) described above, will be explained. This thermoplastic polyurethane resin is made mainly from a combination of a diol in a specific molecular weight range and a specific proportion of a chain extender and a non-yellowing diisocyanate compound, or it is made mainly from a diol in a specific molecular weight range and a non-yellowing diisocyanate compound. It is obtained as a raw material.

In the present invention, the chain extender refers to a compound having a molecular weight of less than about 300 and having a divalent property for isocyanate groups. Preferred molecular weights are about 250 or less, especially about 200 or less. Furthermore, two or more types of chain extenders can be used in combination. The chain extender may be a divalent compound such as a diamine, but is preferably a diol, especially a dihydric alcohol (ie, a non-polymer such as a polyester diol or polyether diol). When the chain extender is a diol, the chain extender is not substantially different from higher molecular weight diols other than a difference in molecular weight. In the present invention, diols and diol chain extenders are distinguished by the difference in their molecular weights, and those with higher molecular weights than chain extenders are called diols (that is, those with a molecular weight of about 300 or more). Under this definition, the thermoplastic polyurethane resin body in the present invention is a combination of a diol with a molecular weight of about 1200 or less and a chain extender (however, the equivalent ratio of chain extender/diol is about 1.2 or less) or Molecular weight approximately 300
~800 diols are obtained as raw materials. Thermoplastic polyurethane resin bodies obtained using a combination of a diol and a chain extender have more favorable properties than those obtained using only a diol as a raw material.

The molecular weight of the diol used in combination with the chain extender must be about 1200 or less, and preferably about 980 or less.

A combination of two or more diols can be used as the diol, but in that case the average molecular weight of all the diols must be about 1,200 or less. In this case,
Diols which are considered chain extenders according to the above definition are not included. In addition, in the case of a combination of two or more diols, the molecular weight of some of the diols may exceed about 1200, but it is not preferable to use diols with extremely high molecular weights. In particular, diols with a molecular weight of about 1500 or more are It is preferable that the amount does not exceed the majority, particularly preferably about 30% by weight or less. The combination of two or more types of diols refers to a combination of tti and/or diols with different molecular weights.

In addition, in the present invention, the molecular weight of diol refers to the average molecular weight that exhibits the same statistical distribution as the molecular weight of ordinary polymers, and therefore, diols of the same type with different molecular weights have different statistical distributions. means. The lower limit of the molecular weight of the diol used in combination with the chain extender is preferably about 400, particularly preferably about 500.

Most preferably, when more than one diol is used, substantially all of the diols are within the range of about 400-1200.

In the combination of diol and chain extender, their average molecular weight should be within the range of about 300-800. A more preferable upper limit of this average molecular weight is about 750, and about 700. The lower limit of this average molecular weight is preferably about 350, particularly about 400.

Another condition for the combination ratio of diol and chain extender is that the chain extender/diol equivalent ratio is about 1.2 or less, preferably about 1.0 or less. The lower limit of this equivalent ratio is not particularly limited, but is preferably about 0.1
and in particular about 0.2. In the present invention,
A combination of at least two types of compounds, such as a combination of a diol and a chain extender, means that it is not necessarily necessary to use them in a mixture.

For example, if a diol and a non-yellowing diincyanate compound are first reacted to produce a prepolymer, then this prepolymer is reacted with a chain extender to produce 7. Of course, a mixture of a diol and a chain extender may be reacted with a non-yellowing diisocyanate compound.

The thermoplastic polyurethane resin (A) can be produced by reacting only the diol with a non-yellowing diisocyanate compound without using a chain extender. In this case, the equivalent ratio of the chain extender/diol corresponds to 0. In this case as well, two or more diols may be used in combination. The preferred molecular weight range is usually shifted lower when diols are used alone compared to when chain extenders are used. This is because there is no chain extender that acts as a hard block for the thermoplastic polyurethane resin, and by using only a diol with the same molecular weight as the average molecular weight of the chain extender and diol combination, it is easier to create a softer resin. It is from. Therefore, a more preferred molecular weight range for diols without the use of chain extenders is about 300-70.
0, especially about 300-600.

The types of non-yellowing diisocyanate compounds will be described later. This non-yellowing diisocyanate compound is used in an amount of approximately α9 to 1.1 equivalents per equivalent of the above-mentioned diol or the combination of diol and chain extender. It is manufactured by using a modified diisocyanate compound as the main raw material and reacting the two, but a small amount of auxiliary raw material other than this main raw material may be used as a raw material.These auxiliary raw materials will be described later.The heat obtained Plastic polyurethane resin (plastic polyurethane resin) must be a colorless or colored essentially transparent resin.However, as with embossed sheets using it, it may become opaque or translucent due to surface irregularities, etc. A pie layer glass may be made of a partially opaque material or a pie layer having a partially opaque portion.

In the pie layer glass, the thermoplastic polyurethane resin cA) constitutes the outermost layer of the pie layer, that is, the layer having an exposed surface. Thermoplastic polyurethane resin (
A) The self-healing property of the layer surface may depend on the thickness K of the layer.

For example, if the thermoplastic polyurethane resin (2) layer is thin and a scratch caused by scratching or the like is deep enough to penetrate the layer, the self-healing ability of the scratch will not be sufficiently exhibited. Therefore, the necessary thickness of the thermoplastic polyurethane resin (4) layer varies depending on the type of scratches that may occur. However, in the pie layer glass of the present invention, the thickness is about α1m01
1 if it's a degree! ? ! It can exhibit sufficient self-repairing properties.

A more preferable lower limit of the thickness of the thermoplastic polyurethane resin (A) layer is about α15-. The upper limit of the thickness of this layer is
It depends on whether the pie layer consists essentially only of thermoplastic polyurethane resin (A) or whether it has other internal layers, but it is usually about 10 m in common for both, and usually about 2 W. is often sufficient. On the other hand, thermoplastic polyurethane resin (A) obtained depending on the difference in raw materials such as the molecular weight of the above-mentioned diol, etc. and the type of the below-mentioned diol, etc.
The hardness may change. In terms of self-repairing ability,
If this thermoplastic polyurethane resin (A) is too hard or too soft, it is difficult to exhibit sufficient performance.

Therefore, the hardness of the thermoplastic polyurethane resin (4) is
Shore A hardness (according to A8TM D 2240-75) of about 70 to 90 is preferred, especially about 73 to 90.
88 is most preferred. The thickness of the thermoplastic polyurethane resin φ) layer to be described later is preferably about 0.1 to 10 mm, particularly preferably (L2 to 2 mm).

One pie layer layer of the pie layer glass of the present invention may consist only of the layer of the thermoplastic polyurethane resin (A), and may further include another synthetic resin layer as an inner layer. Other synthetic resin layers include layers of various synthetic resins and adhesives other than the thermoplastic polyurethane resin (c). Examples of this synthetic resin include thermoplastic polyurethane resins other than thermoplastic polyurethane resins, polyvinyl butyral resins, thermoplastic polyester resins, polyamide resins, and other hard substrates described below. , especially thermoplastic polyurethane resin (A)
Thermoplastic polyurethane resins other than these are preferred. The most preferable synthetic resin layer as the inner layer is the second thermoplastic polyurethane resin described below, that is, thermoplastic polyurethane resin ω).

Thermoplastic polyurethane resin (B) has a molecular weight of approximately 1500
It is a thermoplastic polyurethane resin obtained by reacting a combination of a diol of ~4000 and a chain extender with a non-yellowing diisocyanate compound as a main raw material. Molecular weight 1
The diol having a molecular weight of 500 to 4000 may be a combination of two or more diols having different types and molecular weights, but a combination of extremely different molecular weights is not preferred. For example, a diol with a molecular weight of about 1,200 or less and another diol can be combined in a ratio such that the average molecular weight is about 1,500 to 4,000, but in this case, the proportion of the diol with a molecular weight of about 1,200 or less to the total diol is about 30% by weight or less is preferred, especially about 10% by weight or less. As long as the diol with a molecular weight of about 1,200 or less does not exceed this proportion, the molecular weight of the diol with a higher molecular weight may exceed about 4,000 and the proportion is not particularly limited, but the proportion of diols exceeding about 4,000 is the total diol. It is preferable not to exceed more than half of the amount. Particularly in the case of one combination, it is preferred that each diol has a molecular weight of about 1500 to 4000. A more preferred molecular weight for a diol having a molecular weight of about 1,500 to 4,000 is about 1,600 to 3,000. The molecular weight of the chain extender which is the raw material for the thermoplastic polyurethane resin φ) is generally less than about 300, preferably about 250 or less, particularly preferably about 200 or less. As in the case of the chain extender, this chain extender may also be a combination of two or more types of compounds. In the combination of the diol having a molecular weight of about 1,500 to 4,000 and the chain extender, the total average molecular weight of both is preferably greater than about 300, but is not necessarily limited to this. In many cases, especially when obtaining products with excellent mechanical properties, the average molecular weight is usually within the range of 400 to 800. It is preferable that the thermoplastic polyurethane resin @) which has superior mechanical properties compared to the thermoplastic polyurethane resin (A) has a chain extender/diol ratio in the range of about 2 to B. y) The preferred equivalent ratio is preferably within the range of about Z2 to LO. If the equivalence ratio of the chain extender is too low, the thermoplastic polyurethane resin 03) tends to become too flexible, while if it is too high, it tends to become too hard. It becomes difficult to satisfy the required impact resistance and other mechanical properties. The average molecular weight (i.e. number average molecular weight) is the thermoplastic polyurethane resin body)
However, since the molecular weight of the diol is high in this case, there is a difference between the two when expressed in terms of weight average molecular weight. The weight average molecular weight of the diol chain extender in the thermoplastic polyurethane resin (03) is about 1200 or less, but the weight average molecular weight in the thermoplastic polyurethane resin 03) is often about 1400 or more. The combination of diol and chain extender for thermoplastic polyurethane resins is preferably such that in addition to the diol having a large molecular weight as described above, the equivalent ratio of chain extender/diol is approximately 2 or more. However, as described below, thermoplastic polyurethane resin (in thermoplastic polyurethane resin)
When the thermoplastic polyurethane resin Q3) is not particularly required to have mechanical properties, such as when the layer A) is used only for the purpose of adhering it to a hard substrate, the equivalent ratio of the chain extender is not limited to this range. For example, less than about 2 equivalents of chain extender may be used for each amount of diol.

The amount of the non-yellowing diisocyanate compound to be used per equivalent of the combination of the diol and chain extender is approximately (L9 to 1.1
Equivalent weight is required. This thermoplastic polyurethane resin 0
3) also needs to be essentially transparent like the thermoplastic polyurethane resin (A), but like the above, the sheet or film obtained using it may be opaque; This thermoplastic polyurethane resin layer in the glass may be partially opaque or translucent.

Below, the types of diols and chain extenders that are raw materials for the above two thermoplastic polyurethane resin bodies) and intermediate) will be explained. Examples of diols include polyester diol, polycarbonate diol, polyester ether diol, polyether diol, and hydrocarbon polymer diols having alcoholic hydroxyl groups at both ends, such as polybutadiene, which has hydroxyl groups at both ends; There are compounds that have a mainly linear molecular structure and have an alcoholic hydroxyl group. Polyester diol is a polymer having a divalent alcohol residue and a divalent carboxylic acid residue or a polymer having an oxycarboxylic acid residue, and is a polymer having a divalent alcohol or its reactive derivative and a divalent carboxylic acid or its reactive derivative. derivatives (e.g. acid anhydrides)
and cyclic esters (e.g. 8
-caprolactone) obtained by polymerizing ring-opening dioxycarboxylic acid. The production method is not particularly limited, and may be produced by, for example, a transesterification method. It may also be a copoly i- such as polyester diol having two or more types of dihydric alcohol residues or two or more types of polyhydric carboxylic acid residues. A highly preferred polyester diol is an aliphatic polyester diol (ie, a polyester diol containing no aromatic nuclei). Polycarbonate diols are polycarbonate diols having residues of dihydric alcohols, other diols, or dihydric phenols, and are produced by, for example, the reaction of these dihydroxy compounds with phosgene or the transesterification of dihydroxy compounds with carbonate compounds. Ru.

Preferred polycarbonate diols are aliphatic polycarbonate diols, especially polycarbonate diols having residues of dihydric alcohols or mono- or polyether diols having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms. Polyester ether diol is a diol having an ester group and an ether group, for example, one obtained by adding a cyclic ether to a polyester diol,
These are those obtained by adding a cyclic ester to polyether diol, and those obtained by reacting polyether diol or its reactive derivative with dihydric carboxylic acid or its reactive derivative. Preferred polyester ether diols include those in which more than half of the polyester residues are present, and those in which more than half of the polyether residues are composed of oxypolymethylene groups having 4 to 6 carbon atoms (particularly oxytetramethylene groups). Polyether diol is a compound obtained by adding a cyclic ether having a ring of 2 to 6 carbon atoms to a divalent initiator, and typical cyclic ethers include monoepoxides with 2 to 4 carbon atoms. Examples include ethylene oxide and propylene oxide) and dihydrofuran. Preferred polyether diol has 4 carbon atoms
Those having ~6 oxypolymethylene groups, especially polyoxytetramethylene diols, oxypropylene groups, or polyoxyalkylene diols having oxypropylene groups and oxyethylene groups, and those having oxyalkylene groups and oxytetramethylene groups It is a polyether diol. Hydrocarbon polymer diols include diene polymers such as butadiene, diene and styrene,
It is a hydrocarbon polymer diol made of acrylonitrile, a copolymer of other vinyl monomers, etc., and can be obtained by introducing a hydroxyl group into the terminal portion, for example by using a specific polymerization terminator. The type of diol is not limited to those mentioned above, and for example, diols obtained by adding the above cyclic ether to polycarbonate diols or hydrocarbon polymer diols may also be used. Also,
Of course, two or more diols can be used in combination.

As mentioned above, the thermoplastic polyurethane resin (A) is characterized by improved surface properties such as special self-healing properties. However, considering its polymer structure, this thermoplastic polyurethane resin (A) generally has lower impact resistance, penetration resistance, and other mechanical properties than thermoplastic polyurethane resin (B). Inferior. Therefore, one layer of the pie layer consists essentially entirely of thermoplastic polyurethane resin (B) or thermoplastic polyurethane resin (B
) is used as an internal layer, but its thickness is extremely thin, and when the mechanical properties of a single layer are mainly shared by the thermoplastic polyurethane resin (A), thermal As the diol for the raw material of the plastic polyurethane resin (A), it is preferable to select a diol that can impart high mechanical properties to the thermoplastic polyurethane resin (A). Such diols include
Among the diols, polyester diols, polycarbonate diols, polyether diols having an oxypolymethylene group having 4 to 6 carbon atoms, and the proportions of their structural units (i.e., ester groups, carbonate groups, oxypolymethylene groups) are Copolymer diols (for example, the above-mentioned polyester ether diols) that exceed a majority (i.e., exceed 50 weight percent) are preferred. Hereinafter, these diols will be referred to as diols imparting high physical properties.On the other hand, the thermoplastic polyurethane resin (A) mainly shares the effect of exhibiting surface properties, and the mechanical properties of the pie layer are the same as those of other high mechanical properties. Inner layer, especially thermoplastic polyurethane resinφ
), thermoplastic polyurethane resin (
The diol that is the raw material for A) does not necessarily have to be a diol that imparts high physical properties. However, for the following reasons, it is preferable to use a diol that imparts high physical properties in this case as well. As mentioned above, the thermoplastic polyurethane resin (A) in the present invention
has self-healing properties equivalent to or better than known thermosetting polyurethane resins having self-healing properties, and also has relatively excellent wear resistance. However, the abrasion resistance varies depending on the type of diol, and particularly high abrasion resistance can be exhibited by using a diol that imparts high physical properties. Therefore, it is preferable that the thermoplastic polyurethane resin (4) has excellent properties other than abrasion resistance and self-repairing properties, and therefore it is preferable to use a diol that imparts high physical properties. Further, in order to achieve high mechanical properties, the diol which is a raw material for the thermoplastic polyurethane resin CB) is preferably the above-mentioned diol imparting high physical properties.

The diols imparting high physical properties can be used alone, or two or more thereof can be used in combination.

The property-imparting diols may also be used in combination with small amounts of other diols, in which case the proportion of other diols is preferably less than 50 parts by weight, especially about 30 parts by weight or less. When the diol imparting high physical properties is the above-mentioned copolymer diol, it is preferable that the proportion of groups contributing to imparting high physical properties in this combination is within this range on average. The most preferred high physical property imparting diols are polyester diols, polycarbonate diols, and combinations thereof. Examples of diols imparting high physical properties include, but are not limited to, the following.

Poly(1,4-butylene adipate) diol, poly(
1,4-butylene azelate) diol, poly(1,6
-hexanediot) diol, poly(ethylene adipate) diol, poly((1,4-7' ethylene/ethylene) adipate) diol, poly(a-caprolactone) diol, poly(1,4-butylene/adipate) )−
(a-caprolactone) copolymerized diol, poly(1,6
-hexylene carbonate) di-ol, poly(1,4
-butylene carbonate) diol, poly(ethylene carbonate) diol, poly(oxytetramethylene)
Diol, poly(oxyethylene/oxypropylene) diol-(6-caprodicton) copolymer diol, ethylene oxide and hyfuropylene oxide adduct of poly(oxytetramethylene) diol.

As diols other than diols imparting high physical properties, compounds obtained by adding cyclic ethers to dihydric alcohols, dihydric phenols, and other divalent initiators are particularly suitable; for example, ethylene glycol, propylene glycol, Polyether diols obtained by adding propylene oxide and/or ethylene oxide to initiators such as diethylene glycol, dipropylene glycol, 1,4-butanediol, bisphenol A1 and bisphenol A1 are suitable. As the hydrocarbon polymer diol, for example, butadiene or a diol obtained by polymerizing it with styrene or acrylonitrile is suitable.

Chain extenders are low molecular weight compounds having two functional groups reactive with isocyanate groups and having a molecular weight less than about sun. Examples of this reactive functional group include an alcoholic hydroxyl group, an amino group, an imino group, a carboxylic acid group, and a mercapto group.

Examples of compounds having two of these functional groups (the functional groups may be different) include diols such as dihydric alcohols, diamines, divalent alkanolamines, and dithiols. Can be a chain extender.

Preferred chain extenders are diols and diamines, with diols being particularly preferred. The molecular weight of the chain extender in the present invention is preferably less than about 300 even in the case of the raw material for the thermoplastic polyurethane resin ω). When the chain extender is a diol, it is preferably about 250 or less, particularly about 200 or less. Examples of diol-based chain extenders include evapoethylene glycol, propylene glycol, 1,3-propylene diol, 1.
4-Pig.

Diol, 1.2-butanediol, 1.6-hexanediol, 1.4-cyclohexanediol, diethylene glycol, dipropylene glycol, bis(2-hydroxyethoxyphenyl)-2-propane, and the like. Preferred diol-based chain-extended rigid aliphatic diols having 2 to 8 carbon atoms, such as 1,4-butanediol,
Dihydric alcohols such as ethylene glycol, diethylene glycol, and diprohylene glycol, especially 1.
4-butanediol is preferred. Examples of diamine chain extenders include ethylene diamine, tetramethylene diamine, hexamethylene diamine, 4,4'-diaminodiphenylmethane, and inphorone diamine. In some cases, diols having carboxylic acid groups that do not react with isocyanate groups under normal reaction conditions can be used as chain extenders, such as dimethylolpropionic acid or dimethylolacetic acid. Thermoplastic polyurethane resin (A
) can apply the surface treatment according to the invention of the present inventors.

In addition, carboxylic acid group-containing thermoplastic resins may generally have favorable properties as a pie layer or an interlayer film for laminated glass.

The other main raw material of thermoplastic polyurethane resin body) and 03) is a non-yellowing diisocyanate compound. A non-yellowing diisocyanate compound is a diisocyanate compound that does not have an incyanate group bonded to an aromatic nucleus. For example, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds are preferred, but aromatic diisocyanate compounds such as xylylene diisocyanate may also be used. Furthermore, non-yellowing diisocyanate compounds modified by various methods and compounds can be used as the non-yellowing diisocyanate compound. For example, prepolymer type modified products, carbodiimide modified products, urea modified products, and other divalent modified products can be used. Examples of aliphatic diincyanate compounds include hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2, 2. ．． 4-) Limethylhexamethylene diisocyanate and the like. Examples of the alicyclic diisocyanate compounds include inphorone diisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate), bis(3-methyl-4-isocyanatecyclohexyl)methane, and λ2-bis(4-yne). Examples include cyclohexyl 7anate (cyclohexyl)propane and 1,4-cyclohexyl diisocyanate. An example of a non-yellowing aromatic diisocyanate is xylylene diisocyanate. Preferred non-yellowing diisocyanate compounds are aliphatic or alicyclic diisocyanate compounds, particularly alicyclic diisocyanate compounds, and among these, isophorone diisocyanate and 4.4'
-methylenebis(cyclohexyl isocyanate) is most preferred.

The thermoplastic polyurethane resins α) and @) are obtained by reacting the above-mentioned main raw materials. However, in addition to these main raw materials, other auxiliary raw materials can also be used for production.

Often one of the auxiliary materials used is a reaction catalyst. For example, organotin compounds such as dibutyltin dilaurate and stannous octoate, other metal compounds, and tertiary amines are suitable as catalysts.

The second auxiliary raw material is an ultraviolet absorber, a light stabilizer, an antioxidant,
Other stabilizers. Depending on the case, these may have a functional group (eg, hydroxyl group, amino group, incyanate group, etc.) that is reactive with at least one of the main raw materials. Examples of these stabilizers include benzotriazole compounds, benzoquino compounds, tetraalkylpiperidine compounds, hindered phenol compounds,
These include hindered amine compounds. Furthermore, other auxiliary raw materials include coloring agents such as the dyes mentioned above, silicone oil, and other antiblocking agents, which may be blended or impregnated after the thermoplastic polyurethane resin is produced. When these auxiliary raw materials are used, the amount used is usually about 5% by weight or less of each of the total raw materials, but reactive stabilizers and the like may be used in larger amounts depending on the case. In addition, as other auxiliary raw materials, polyols with a valence of 3 or more, functional groups reactive with incyanate groups may be added.
(hereinafter referred to as a crosslinking agent), 5
A polyinocyanate compound having a higher value than the above value can be used.

Examples of trivalent or higher polyols include polyester polyols and polyether polyols. Examples of crosslinking agents include polyhydric alcohols, polyamines, and compounds obtained by adding a small amount of alkylene oxide to these. Examples of the polyisocyanate compound include the above-mentioned non-yellowing diisocyanate compound modified with a trihydric or higher alcohol.

When these are used, the hardness of the thermoplastic polyurethane resin obtained increases, and the thermoplastic polyurethane resin (
A) may be preferable.

However, when these trivalent or higher-valent compounds are used in combination, the thermoplasticity of the thermoplastic polyurethane resin decreases, and if the amount used increases, the thermosetting polyurethane resin becomes a thermosetting polyurethane resin. Therefore, these compounds need to be used in small amounts to the extent that the resulting thermoplastic polyurethane resin does not lose its thermoplasticity. In normal cases, the use of this reactive compound having a valence of 3 or more is unnecessary, and it is preferable that it is not substantially used.

The method for producing the thermoplastic polyurethane resin (A) and 03) is not particularly limited. For example, according to the classification of conventional methods for producing polyurethane resins, a prepolymer method, a quasi-prepolymer method, a one-shot method, a reaction injection molding method, etc. can be used.

The method of forming the layers of thermoplastic polyurethane resin (A) and thermoplastic polyurethane resin (CB) is also not particularly limited. However, if this method, including the method for producing pie layer glass, can be roughly divided into two, indirect methods and direct methods as described below, it is preferable in the present invention to form layers by indirect methods. In the present invention, the indirect method is a method in which a sheet or film made of a laminate with a thermoplastic polyurethane resin (A) or a thermoplastic polyurethane resin (A) is first produced, and then this is laminated with a hard substrate or a sheet material having a hard substrate. means. The material for manufacturing laminated safety glass, which is the second aspect of the present invention, which will be described later, consists essentially of this thermoplastic polyurethane resin (A), or consists of this thermoplastic polyurethane resin (A) and the same 03). A sheet or film consisting of a multilayer structure containing at least two layers.

This preferred embodiment of the present invention will be described later.

In the present invention, the direct method refers to a method in which at least the thermoplastic polyurethane resin (A) is directly formed as a layer on the surface of a hard substrate or a sheet material containing a hard substrate, without passing through the form of a sheet or film. Let's go. That is, it refers to a method that does not involve the use of a laminated safety glass manufacturing material, which is the second aspect of the present invention, which will be described later. For example, one method for producing pie layer glass with a two-layer structure of thermoplastic polyurethane resin (A) and a hard substrate by a direct method is to mix the raw materials of thermoplastic polyurethane resin (4) on the surface of the hard substrate. (This also means a mixture of a prepolymer and a chain extender in the prepolymer method) or a method of forming a layer by applying a solution of a thermoplastic polyurethane resin (A). Another method is a casting method in which a liquid mixture of raw materials is injected into a cavity formed by arranging a hard substrate and a mold material in parallel with tV and sealing the pericrystal, and then removing the mold material after hardening. Similarly, three-layer structures can be produced by these methods using a sheet material consisting of a hard substrate and a laminated thermoplastic polyurethane resin. The sheet material itself consisting of a laminate of a hard substrate and a thermoplastic polyurethane resin (inside) may be produced by any method, such as the above-mentioned direct method, as well as the thermoplastic polyurethane resin (inside).
It may be manufactured by laminating a sheet or film and a hard substrate. These direct methods cannot be said to be any more advantageous than the indirect methods described below. For example, the above application method can be applied to curved car windshields, etc.
.

It is relatively difficult to form a layer of uniform thickness on a hard substrate having a surface, and the casting method described above has problems such as a complicated manufacturing process and not being economically advantageous. be.

The pie layer glass of the present invention is preferably manufactured by the above-mentioned indirect method. In adopting this indirect method, the material for manufacturing laminated safety glass (hereinafter referred to as pie layer sheet), which is the second invention, is used. Pylayer mm sheet ti consists essentially of only a thermoplastic polyurethane resin (A), or has at least a layer of said (A) on one side and has at least a two-layer structure containing a layer of thermoplastic polyurethane resin 03). A sheet or film. A sheet generally has a thickness of 0.2m or more, and a film has a thickness of 0.2m or more.
Although it refers to a sheet having less than two layers, in the present invention, unless otherwise specified, the term sheet is used to include a film. One of the pie layer sheets is made of thermoplastic polyurethane resin (A), but in some cases, a thin layer of other material (other than thermoplastic polyurethane resin ('B)) may be used on one side or on the inner layer. It may have layers. This pie layer sheet is hereinafter referred to as pie layer sheet (A). It is preferable that the sheet for pie layer cA) is manufactured by an extrusion molding method or a cast molding method. For example, a granular or powdery molding material made of thermoplastic polyurethane resin (A) is produced, and this is extruded to continuously produce a long pie layer sheet. A method of producing a sheet by directly supplying the raw material of the thermoplastic polyurethane resin (A) to an extrusion molding device is also known, and this method can also be used. In the cast molding method, a liquid material such as a liquid mixture of thermoplastic polyurethane resin (A) raw materials, its solution, or a solution of thermoplastic polyurethane resin (3) is spread on a flat surface and cured to form a sheet. The method also allows continuous production of long sheets using surfaces such as moving belts. The above two methods are preferable because they can produce a continuous long sheet (i.e., a sheet of substantially infinite length), but these methods are not necessarily applicable. It is not limited to.

For example, injection molding, calendar molding, and other molding methods may be used.

The pie layer sheet having a multilayer structure including a layer of thermoplastic polyurethane resin (1) is preferably substantially a two-layer structure of thermoplastic polyurethane resin (A) and thermoplastic polyurethane resin (CB). However, there is a third layer of another material between the two layers or on the surface of the thermoplastic polyurethane resin CB).
It may be a layered structure, or it may be a multilayered structure as long as it has a layer of thermoplastic polyurethane resin on one side. A pie layer sheet consisting of two layers of a thermoplastic polyurethane resin (A) and the same color) is hereinafter referred to as a pie layer sheet (A/B), and a method for producing it will be described below. One of the methods of manufacturing the pie layer sheet (A/B) is a sheet (hereinafter referred to as pie layer sheet (B)) consisting of the pie layer sheet (former) and thermoplastic polyurethane resin φ) as described above. There is a method in which these are manufactured separately by the extrusion molding method or cast molding method described above, and then the two are laminated by heating and pressing. A second method is an integral molding method using an extrusion molding method or a cast molding method.

For example, a sheet for a pie layer (A
/B) can be produced at once.

In addition, as an integral molding method using cast molding, the raw material mixture of one of the thermoplastic polyurethane resins is first cast onto a flat surface, and after it has hardened to some extent, the raw material mixture of the other thermoplastic polyurethane resin is cast. This is a method of manufacturing a sheet in which two layers are integrated by casting the same on the surface. Fire casting is performed after the initially cast raw materials have hardened to the extent that they do not mix with later cast materials or disturb the surface, but in order to increase the adhesive strength of both layers, KFi was cast first. It is preferable that the subsequent casting is performed at a stage before the raw materials etc. are completely hardened. By these coextrusion molding and integral cast molding, pie layer sheets (A/B) can be continuously manufactured. There are still other methods for continuous molding of pie layer sheets (A/B). for example,
There is a method in which a continuous sheet of pie layer sheet (4) or same Φ is first manufactured, and a layer is formed by continuously coating one side of the continuous sheet with a raw material for the other thermoplastic polyurethane resin. Of course, this pie layer sea)
(A/B) can also be produced in the form of a short sheet by an injection molding method or the like instead of a continuous method. The pie layer sheet @) is preferably manufactured by the same method as the pie layer sheet (A), such as an extrusion molding method or a cast molding method.

A pie layer glass is produced by laminating a pie layer glass (A) or a pie layer glass (A/B) and a hard substrate. At the time of lamination, a second synthetic resin sheet may be interposed between these two materials, or at least one material is laminated with the other material after the second synthetic resin layer is formed. Good too. A typical example of the second synthetic resin is thermoplastic polyurethane resin ω). For example, the pie layer sheet (A) can be interposed between the pie layer sheet (A) and the hard substrate, and the three can be laminated and integrated at the same time. Further, after laminating the pie layer sheet 03) and the hard substrate, the pie layer sheet 03) (A) can be laminated on the pie layer sheet 俤) to form a similar three-layer structure. Also, sea for pie layer)
One side of (A) or pie layer sheet (A/B)
After forming a thin adhesive layer on the surface of the thermoplastic polyurethane resin 03), it can be laminated with a hard substrate, or the adhesive layer may be formed on the surface of the hard substrate in advance.

Pie layer sheet (A) and pie layer sheet (
The surface of the thermoplastic polyurethane resin (A) layer, which is the non-laminated surface of A/B) (that is, the exposed surface of the pie layer glass), may be laminated with a hard substrate if necessary. Treatments such as surface treatment may be performed before being applied. For example, it can be colored in whole or in part by impregnating it with a dye solution. In addition, known surface treatments according to the invention of the present inventors can also be performed.

These surface treatments may of course be carried out after lamination, or in some cases may be carried out at the same time as lamination. In addition, such surface-treated pie layer sheets (A/B
), one side of pie layer sheet (A) may be first surface treated and then a layer of thermoplastic polyurethane resin Φ) may be formed on the other side.

The lamination method described above is not particularly limited, but it is usually preferably carried out by heating and pressurizing.

If adhesives are used, heating may not necessarily be required. One of the representative heating and pressurizing methods is a method that is similar to the manufacturing method of laminated glass that has been widely used in the past. Laminated glass is usually manufactured by interposing an interlayer between two glass sheets and heating and pressing the interlayer in an autoclave. In this method, a pie layer glass is obtained by replacing one glass sheet with a releasable mold and removing the mold after lamination. The mold material may be of course a release agent-coated glass sheet, but also metal, plastic, rubber, or other materials. Moreover, instead of this lamination method using an autoclave, a roll lamination method and other known pie layer glass manufacturing methods can be applied.

FIGS. 1 to 4 show schematic cross-sectional views of four examples of the pie layer glass of the present invention. FIG. 1 is a cross-sectional view of a two-layer structure of Pylayer glass, which consists of a thermoplastic polyurethane resin layer (1) and a hard substrate layer (2). Figure 2 is a cross-sectional view of Pylayer glass with a three-layer structure, consisting of a thermoplastic polyurethane resin (A) layer (1), a hard base layer (
2), and an inner layer of thermoplastic polyurethane resin @ff4 (S). FIG. 3 is a cross-sectional view of a pie layer glass consisting of a total of four layers having a thin adhesive layer (4) between a thermoplastic polyurethane resin elongated layer (3) and a hard base layer (2). Figure 4 shows two glass sheets (6) and (7) and an interlayer film (8) in place of the hard base (2) of Pylayer glass shown in Figure 2.
This is a pie layer glass with a total of 5 layers structure using a laminated glass (9) consisting of ) as a hard substrate. These 4
Although the examples show typical examples of the pie layer glass of the present invention, the pie layer glass of the present invention is not limited to only these structures. FIGS. 5 and 6 are schematic cross-sectional views showing three typical examples of combinations of materials when manufacturing layered glass by the lamination method. FIG. 5 is a diagram showing a combination of the pie layer sheet (A'> (10) and the hard substrate (11), and this combination
A pie layer glass having the structure shown in the figure is obtained. 86
Figure 16. A diagram showing the combination of pie layer sheet (A/B) (12) and hard substrate (11), Figure 7 shows pie layer sheet) (A) (10), pie layer sheet (A) (13) ) and a hard substrate (11). In each case, a pie layer glass having the structure shown in FIG. 2 above can be obtained.

The hard substrate is made of glass (ie, inorganic glass) or organic glass. This organic glass is made from thermoplastic polyurethane resin (
There are synthetic resins that are harder than 4) and (g)), such as polycarbonate resins and acrylic resins such as polymethyl methacrylate. It may be a laminate such as laminated glass having an intermediate film layer.The material of this intermediate film layer is made of a soft synthetic resin such as polyvinyl butyral resin.The intermediate film layer Fi2 made of this soft synthetic resin It refers to the material between the two hard substrates, and polyvinyl butyral resin and the like that are in contact with the first layer of the pie layer belong to the first layer of the pie layer.

Most preferably, the layer comprising the exposed surface of the rigid substrate is glass. In the case of a multilayered rigid substrate, the inner rigid substrate layer may be an organic glass. For example, the hard substrate may be a multilayer structure consisting of glass, interlayer film, and organic glass. In the present invention, the most preferred rigid substrate consists of a single glass sheet. The next preferred hard substrate is a laminated glass having a glass-interlayer-glass structure. The total thickness of the rigid substrate is at least approximately α21111
．． In particular, it is preferably about 15IIIB or more. When the rigid substrate is made of a glass sheet, the thickness of one layer is preferably about 15 to 5 mm. In the case of organic glass,
The thickness of one layer may exceed this range. Although there is no particular upper limit to the thickness of the entire hard substrate, it is approximately 10-10 mm or less for typical automotive window applications. However, in applications such as aircraft window materials, hard substrates with a multilayer structure of three or more layers are often used, and the thickness thereof may exceed about 10 mm.

Further, in laminated safety glass for uses other than window materials as described below, the thickness may be outside the range of the expansion range, and the hard substrate may not have a constant thickness.

As the glass for the hard substrate, silicate-based inorganic glass is suitably used, and silicate-based inorganic glass, which has conventionally been used as window materials for automobiles or architectural windows, is particularly preferred. However, depending on the application, lead glass, borosilicate glass, boric acid glass, silicate glass, other optical glasses, or other glasses may be used. These glasses may be strengthened by air-cooling strengthening, chemical strengthening, or the like. Further, the glass may be colored and may have a functional film such as an antireflection film or a heat ray reflective film on at least one side. Glass is normally preferably transparent, but may be translucent in applications such as architectural window materials. As the material for the organic glass, polycarbonate resins and acrylic resins are particularly preferable because of their excellent transparency. These may be stretched and may have a functional film such as a node coat film on the exposed surface.

The laminated safety glass of the present invention is particularly excellent as a window material for automobiles. However, it can also be used for architectural and other window materials. The hard substrate for the laminated safety glass used as the window material is made of a sheet-like material of a certain thickness or a molded product thereof. However, the rigid substrate may be of other shapes. A typical example is a lens. For example, a glass lens having a thermosetting polyurethane resin layer having self-repairing properties on one side is known as a lens for spectacles. The laminated safety glass of the present invention may also be used as such a lens for spectacles or other optical element. Further, as an example of other uses, for example, the above-mentioned Japanese Patent Application Laid-Open No. 55-27671 No. 9
The laminated safety glass of the present invention can also be used for applications such as those illustrated in the lower right column of the page.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Example I Production of thermoplastic polyurethane resin (A)1. Poly(oxytetramethylene) glycol with a molecular weight [hereinafter referred to as M] of approximately 8753 smHg
The mixture was stirred and degassed and dehydrated at 110° C. under vacuum. In addition to this, 80
0t of 1.4-butanediol [hereinafter 1.4-B D
], 5570f of 4,41-methylenebis(cyclohexyl isocyanate) [hereinafter referred to as H1! MD], and rJ, 49f dibutyltin dilaurate (
(hereinafter referred to as a catalyst) was added, and the mixture was stirred and mixed at 80° C. for 5 minutes. An exotherm was observed upon initiation of the reaction and a substantially homogeneous liquid reaction mixture was obtained. This was placed in a fluororesin-coated drying container and allowed to stand in a nitrogen purge oven at 120° C. for 15 hours until the reaction was essentially complete. The produced resin was pulverized into granules using a pulverizer.

This is then put into an extruder in the usual way and the maximum temperature of the cylinder is 1.
It was formed into a sheet at 80° C. and formed into a transparent sheet with a thickness of α2m. In this case, the chain extender/diol equivalent ratio [hereinafter simply referred to as equivalent ratio] is about 174, and the average molecular weight of the chain extender and diol [hereinafter referred to as Mn] is about 51a4.

Hereinafter, this sheet will be referred to as sheet (Mu-1).

2. 45.00 t of poly(oxytetramethylene) glycol having M of about 8313 was stirred and degassed and dehydrated at 110° C. under a vacuum of 5 Hg.

In addition, 1.4-BD of 560f, Hl of 25,07t
, MDI, and α002 f (adding D catalyst, 8
The mixture was stirred and mixed at 0°C for 5 minutes. An exotherm was observed upon initiation of the reaction and a substantially homogeneous liquid reaction mixture was obtained. This was placed on a 50xsoo glass plate whose surface had been subjected to mold release treatment, uniformly cast using a knife coater, and allowed to stand in a nitrogen purge oven at 160° C. for 1 hour until the reaction was essentially complete.

After being allowed to cool, it was peeled off from the glass plate to obtain a transparent sheet having a thickness of 0.2 mm and having a mirror surface.

In this case, the equivalent ratio is about 0.74, and Mn is about 51.
It is a1.

Hereinafter, this sheet will be referred to as sheet (mu-2).

5. Using the cast molding method described in 2 above, a sheet □ with a thickness of a and 6111K was manufactured using the same materials and conditions as in 2.

Hereinafter, this sheet will be referred to as sheet (A-3).

Tun Above 1. The extrusion molding method and the cast molding method described in 2 above were used, and the extrusion molding method had a thickness of Q, 311I11.
A transparent sheet with a thickness of α7m was produced using the cast molding method. Name of each sheet, molding method, type and amount of raw materials used (
parts by weight) are shown below. The E method refers to an extrusion molding method, and the C method refers to a cast molding method.

A-4: ] ii Method A-5: Q method Polycaprolactone diol (M approx. 526.0) 000 1.4-BD 240 Dan HMD Engineering 3764 Catalyst a, 30 (Equivalence ratio α23, Mn approx. 44 & 5) A- 6: Ilt method Mu 7: C method polycaprolactone diol (M approx. a 17.8) 6
000 1.4-BD 600 H1! , MDI 3744 Catalyst α31 (equivalence ratio α9, Mn approximately 471.1) A-8: E method A-9: Q method Polycaprolact/diol (M approximately 817.8) 50
00 Dipropylene glycol 800 H,, MDI 3231 Catalyst α27 (equivalence ratio a97, Mn about 48 (Ll) Mu-10 2H method Mu-11: (j method Polycaprolactone diol (M about 817.8) 000 1. 4-BD 500 Isophorone diisocyanate) 2645 Catalyst 0.24 (Equivalence ratio (190, Mn approx. 471.3) A-12: Method A-j 5:0 method Poly(oxypropylene) glycol (M approx. 700) 5000 1.4-BD 500 H1 Usu MD Engineering 3395 Catalyst α4゜(equivalent ratio [L78, Mn approx. 43 & 1) A-14:]l
[i-method A-15: O-method polyether diol (M about 820) 40001.4
-BD 320 H1 Tomi MD Engineering 2255 Catalyst a30 (equivalence ratio a, 72, Mn approximately 511.8) A-16:]
! f method A-17: O method poly(1,6-hexa/carbonate) diol (M about 950) 5000 dipropylene glycol 300 isophorone diisocyanate 1700 catalyst (L21 (equivalent ratio α42, Mn about 7047) A-18: Ti Method A-19: O method Polycaprolactone diol (M about 400) 4000 11, Mn engineering 2675 Catalyst 0.20 ■ Production of thermoplastic polyurethane resin @) 1, Poly(1,6-) with M of about 2003.6 hexane carbonate)
3 mlHg of diol 6000f and poly(butylene adipate) diol 40001F with M of about 2077.8.
The mixture was stirred at 110° C. under vacuum and dehydrated. This is busy,)I
f, Mn engineering 5310f, and catalyst α10t were added, and the mixture was reacted for 20 minutes at 8-0° C. under a nitrogen gas flow. Next, 1.4-BD1350F was added to this reaction mixture and the mixture was rapidly stirred and mixed.

An exotherm was observed upon initiation of the reaction, and a substantially homogeneous mixture was obtained. The liquid reaction mixture was charged into a fluororesin-coated drying vessel and left in a nitrogen-purged oven at 120° C. for 15 hours until the reaction was essentially complete.

The resulting resin was pulverized and granulated using a pulverizer, then put into an extruder in a conventional manner and formed into a sheet at a cylinder maximum temperature of 180°C, which was then molded into a transparent sheet with a thickness of α5cm. In this case, the equivalent ratio is about 505, and Mn is about 569.8.

Hereinafter, this sheet will be referred to as C (B-1).

2 Using the following raw materials in the same manner as above, the thickness is 16cm.
A transparent sheet was manufactured. See this sheet below)
It is called (B-2).

Poly(1,4-butylene adipate) diol (M approx. 2077.8) 4000f1.4-B
D 4081 H1tM D Engineering 174At Catalyst 0.04 f (equivalence ratio 2.35, Mn approximately 682.4) 5 Similarly, using the following raw materials, produce a transparent sheet (B-3) with a thickness of α61IIK. did.

Poly(ethylene adipate) diol (M approx. 20056) 1500f 1.4-BD 2341t isophorone diisozoane) 76X8f catalyst α15
Similarly,
A transparent sheet (B-4) having a thickness of α711Is+ was manufactured using the following raw materials.

Polyether diol (M approx. 2077.8) 000f 1.4-BD 204f H12M D engineering 872f Catalyst Q, 02t (equivalence ratio 2.36, Mn approx. 682.4) ■ Production of pie layer glass 1, 50 c' m x 30 crn sea) (A-1
) of the same size as 7-) (B-1), 3cm thick,
Size 30X30. It was sandwiched between two glass plates and introduced into an autoclave. At this time, the surface of the glass plate in contact with the sheet (A-1) was uniformly coated with polydimethylsiloxane in advance and heat-treated at 350° C. to perform mold release treatment. The surface of the other glass plate in contact with the sheet (B-1) was uniformly coated with γ-glycidoxyprobylsilane in advance.The autoclave was initially evacuated to remove air between the glass plate and the sheet. Subsequently, it was heated to 120° C. in a vacuum to perform preliminary pressure bonding. After opening the hole, autoclave at 140℃ and 13 to 9/car'' for about 30 minutes.
After keeping the glass plate and the sheet completely fused together, take it out of the autoclave and remove the glass plate that has been released from the mold. I got a pie layer glass. The structure of this pie layer glass will be shown below as (A-1)/(B-1)/G. The performance of this Pylayer glass is shown in Table 1.

2 By the same method as above, pie layer glass was manufactured from each sheet A, sheet B, and a glass plate, or from only sheet A and a glass plate. Table 1 shows the composition and performance of each pie layer glass. The configuration is shown in the same manner as above.

5. Using one sheet of Comparative Examples (B-1) to (B-5) and the same glass plate as above, a pie with a two-layer structure of thermoplastic polyurethane resin and glass plate was prepared by the above method. Manufactured layered glass. The structure and performance of this pie layer glass are shown in Table 1 as a comparative example.

4. Physical property test method The physical properties in Table 1 were measured by the following method.

Light transmittance: Based on rI8 R3212.

Taper wear: According to J1 day R3212.

Haze increase after 100 times.

Scratch test: Load at which scratches begin to appear. While changing the load continuously, scratch with a 10 μmφ diamond tip and measure the load when scratches start to appear.

Penetration resistance test: According to TI8 R3312. Passing means that the steel ball did not penetrate, the broken glass was adhered to the sheet, and no glass was observed to scatter.

Table 1 Table 1 (continued) Table 1 (continued) Table 1 (continued) Table 1 (continued)

[Brief explanation of drawings]

1 to 4 are schematic cross-sectional views showing examples of the laminated safety glass of the present invention.
Layered structure, FIG. 3 shows a four-layered structure with a thin adhesive layer;
FIG. 4 shows a five layer structure with laminated glass layers. Fifth
Figures 5 to 7 are schematic cross-sectional views showing the combination of sheets for manufacturing the laminated safety glass of the present invention.
The figure shows a combination for manufacturing the two-layer structure shown in FIG. 1, and FIGS. 6 and 7 show a combination for manufacturing the three-layer structure shown in FIG. 2. 1.10: Thermoplastic polyurethane resin (A) layer 3.1
3: Thermoplastic polyurethane resin 03) Layer 2.11: Hard base layer vIl Figure 2nd Figure 3 Military, Figure 4-Collection 5 Figure 6 Figure 7 Silkworm. 5] and 11

Claims (1)

[Claims] 1. A transparent or transparent material having at least a two-layer structure of a hard substrate layer and a synthetic resin layer, one exposed surface being the surface of a hard substrate and the other exposed surface being the surface of a synthetic resin layer. In semi-transparent laminated safety glass, the synthetic resin layer is a single layer or multiple layers, with the outermost layer consisting of a heat-warmable polyurethane resin below, and optionally an inner layer consisting of other synthetic resin layers. Laminated safety glass characterized by a synthetic resin layer in its structure. Thermoplastic polyurethane resin (A): Molecular weight approximately 300~
800 diol or average molecular weight of about 300-800
A combination of a diol with a molecular weight of about 1200 or less and a chain extender in a ratio such that the equivalent ratio of chain extender/diol is about 1.2 or less, and a non-yellowing diisocyanate compound for the former The latter is a thermoplastic polyurethane resin obtained by reacting the latter in an amount of about (L9 to 1.1). Laminated safety glass in scope 1. Thermoplastic polyurethane resin 03) Bi molecular weight approximately 1500
A thermoplastic polyurethane resin obtained by reacting a combination of a diol of ~4000 and a chain extender and a non-yellowing diincyanate compound in an amount of about 19 to 1.1 of the latter. (5) A structure consisting of substantially one layer of the transparent thermoplastic polyurethane resin (4) below, or one of the outermost layers of which is a layer of the thermoplastic polyurethane resin (A) and transparent as shown below. 1. A material for producing laminated safety glass, characterized in that it is a sheet or film consisting of at least two layers of structure, including a layer of (in a plastic polyurethane resin). Thermoplastic polyurethane resin (G): Molecular weight approximately 300~
80 diols or average molecular weight of about 300-800
A combination of a diol with a molecular weight of about 1200 or less and a chain extender in a ratio such that Thermoplastic polyurethane resin obtained by reacting α9 to 1.1 equivalents. (in thermoplastic polyurethane resin) molecular weight approximately 1500~
4000 diol and a chain extender and a non-yellowing diisocyanate compound for each equivalent of the former.
Thermoplastic polyurethane resin obtained by reacting 9 to 1.1 equivalents.