JPS59135216A - Thermoplastic polyurethane polymer sheet or film and laminated safety glass - Google Patents

Abstract

PURPOSE:The titled (semi)transparent sheet or film of excellent impact absorption performance and perforation resistance, obtained by reacting a urea-modified product of a nonyellowing diisocyanate with a high-MW diol and a chain extender. CONSTITUTION:A thermoplastic polyurethane polymer is obtained by reacting (A) a urea-modified product obtained by reacting a non-yellowing diisocyanate (e.g., isophorone diisocyanate) with water, or a non-yellowing diisocyanate containing at least 10% this urea-modified product, with (B) a high-MW (500- 6,000) diol [e.g., poly(ethylene-adipate) and (C) a chain extender in the presence (absence) of a catalyst (e.g., dibutyltin dilaturate). This polymer is formed into a (semi)transparent sheet or film. At least one layer of this sheet or film is laminated with at least one layer of a rigid base comprising an organic or inorganic glass to produce a laminated safety glass.

Description

[Detailed Description of the Invention]: The present invention is characterized by transparent, translucent and shock absorbing properties.
etc.: M'□'□Excellent 1□・Relates to laminated safety glass, and sheets and films of thermoplastic polyurethane polymers suitable for the same. ′□：5
j"an'j:, i'fy -<;,, I, 1 inorganic #9.x (hereinafter: T1:, 1(,.

A laminated sheet of a glass sheet and a synthetic resin sheet is well known. For example, laminated safety glass consisting of a three-layer structure of glass-bo-livinyl-petitral-ru 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. Hereinafter, laminated safety glass having such an interlayer film will be referred to as "laminated glass." On the other hand, laminated safety glass made of glass and synthetic resin has a synthetic resin layer exposed, such as glass-synthetic resin or glass-synthetic resin-glass-synthetic resin, where one side is glass and the other side is synthetic resin. This laminated safety glass is attracting attention as a laminated safety glass for automobiles. This laminated safety glass is similar to the traditional laminated glass mentioned above and is also considered to be even safer. For example, this laminated safety glass has a synthetic resin surface: The inside of a car is used as an automobile windshield.

When used as a windshield, there are fewer lacerations and cuts when the driver hits the windshield, and even if the glass breaks, the inside of the car will be damaged. It is thought that this will also reduce the amount of flying debris.

In this way, one side is glass and the other side is synthetic resin, and the exposed synthetic resin layer is called ``one layer after another''. These laminated safety glasses can be used not only for automobiles but also as window materials for other transportation equipment, architecture, and other applications.

Regarding laminated safety glass having a synthetic resin layer made of a polyurethane polymer, for example, Japanese Patent Publication No. 43-s 626, Japanese Patent Publication No. 5-51744, Japanese Patent Application Laid-open No. 4
It is described in JP-A-8-25714, JP-A-53-27671, JP-A-56-127,677, and the like. Many performances are required of polyurethane polymers used as an interlayer film or pie layer.

For example, transparency, adhesion to glass,! Physical properties such as shock absorption are common requirements for both the intermediate film and the pie layer. In addition, surface performance such as solvent resistance is a requirement that is even more specific to Pylayer. The present inventors have studied polyurethane polymers that can satisfy the former required performance. A thermosetting polyurethane polymer is used as one layer of the pie layer, and this and glass are connected with a thin thermoplastic polyurethane polymer! A sheet layer glass is known (see Japanese Patent Application Laid-Open No. 53-27671). However, especially from the viewpoint of physical properties, thermoplastic polyurethane is superior as a single-layer polyurethane polymer for interlayer films and pie layers, and thin thermosetting polyurethane polymers are used to improve surface properties. Even if the erasure layer is provided on the surface, it is considered that thermoplastic polyurethane polymer is most suitable for the intermediate film and the main part of the pie layer.

Thermoplastic polymers used for interlayer films and the like are discussed in detail in the above-mentioned Japanese Patent Publication No. 55-5174 and Japanese Patent Application Laid-open No. 56-127677.
There are many. As described in these publications, one of the most important physical properties required for thermoplastic polyurethane polymers is impact hardness (also known as energy absorption properties). Polyurethane polymer is used for plasticity, and polyurethane polymer is used for shock absorption of the body.
It depends greatly. Similarly, the optical properties, which are important properties, are uniform, transparent, and dusty (hereinafter referred to as transparency).
) also depends on the choice of raw materials. Changes in these properties over time are often required; for example, hepolyurethane polymers using aromatic diincyanates tend to turn yellow over time.1. In the field of polyurethane-based polymer focusing for laminated safety glass, it is difficult to use it. Conventionally known thermoplastic polyurethane-based materials have a property that is not always sufficient. It was found that there was a particular problem with shock absorption, and that other physical properties such as penetration resistance needed to be further improved.

The present inventor conducted various research studies on the three components of a thermoplastic polyurethane polymer: a diisocyanate compound, a high molecular weight diol, and a chain extender. In the above two known examples, high molecular weight diols and chain lengthening agents are mainly studied. It is also stated that bis(4-incyanatocyclohexyl)methane, which is a particular mixture of isomers, is particularly preferred as the diisocyanate compound. As a result of examining diisocyanate compounds in particular from the viewpoint of the above-mentioned physical properties, the present inventor found that non-aromatic diisocyanates containing urea-modified compounds are excellent as raw materials for thermoplastic polyurethane polymers for interlayer films or pie layer calendars. I discovered this. The present invention relates to a sheet or film made of a thermoplastic polyurethane polymer obtained using this urea-rotor or a non-yellowing diisocyanate containing it, and a laminated safety glass obtained using the same. It is. That is, a thermoplastic polyurethane obtained by reacting three components: a urea-modified product of non-yellowing cyidicyanate or a non-yellowing diincyanate containing the urea-modified product, a high molecular weight diol, and a chain extender. Transparent or translucent laminated safety glass consisting of at least one layer of a polymer and at least one layer of a hard substrate, and a urea modified version of a non-yellowing diisocyanate, or a non-yellowing diisocyanate containing the modified product. A sheet or film of a transparent or translucent thermoplastic polyurethane polymer obtained by reacting at least three components: , a high molecular weight diol, and a chain extender.
□ ・ ・ □ The laminated safety glass obtained using the thermoplastic polyurethane polymer of the present invention is similar to the laminated safety glass obtained using the thermoplastic polyurethane polymer obtained using the non-yellowing diisocyanate which is not compatible with the urea modified product. Not only is the impact resistance and absorbency superior to that of laminated safety glass, but other physical properties such as penetration resistance are also comparable or better. In particular, as will be described later, the thermoplastic polyurethane polymer obtained using the urea modified product of inphorone diisotuanate has extremely excellent physical properties, and also has extremely high other properties such as transparency. Furthermore, when compared with the above-mentioned known examples, the polyester diol with a high melting point is not required;
Moreover, since bis(4-isocyanatecyclohexyl)methane, which is a specific isomer mixture, is not essential, there is a wide range of raw material selection and high economic efficiency. In addition, since a diamine-based chain extender is not essential and a normal dihydric alcohol can be used as a chain extender, the reaction can be easily controlled, and □It is highly economical. Below, the thermoplastic polyurethane polymer and its raw material components will be explained first, and then the laminated safety glass will be explained.・Non-yellowing diisocyanate is a diisocyanate compound that does not have an incyanate group directly bonded to an aromatic nucleus), and is usually a diisocyanate compound that does not have an aromatic nucleus. A non-yellowing diincyanate having an aromatic aroma and aromatic core,
There are also compounds, such as xylylene diisocyanate, that have an isocyanate group that is not directly bonded to an aromatic nucleus.

However, preferably aliphatic or alicyclic diisocyanate compounds.

More preferred compounds are compounds called mixed aliphatic, group □, alicyclic di, iso, and cyanates, as described below. Examples of fatty and aliphatic incyanates include ethylene diisocyanate and tetramethylene diiso. Cyanate 2. Hexamethylene diisocyanate, dodecamethylene diisocyanate, 2. , 4,4-trimethyl-1,6-hexane diisocyanate, -, cycloaliphatic diisocyanate, for example, bis(
4-, incyanate, cyclo, hexyl) methane, 2
, 2-bis(4-incyanatecyclohexyl), propane, 1-methyl-2,4(or 2,6)-diincyanatecyclohexane 1. ．． 1. , j,4-cyclohexyl diincyanate and the like. As mixed aliphatic and cycloaliphatic diisocyanates, isofluoride and ? , incyanate (i.e. 3=incyanate methyl L 3
．． , 5.5-)limethylcyclohexyl isocyanate) is a typical compound. The most effective non-yellowing diisocyanate in the present invention is inphorone diisocyanate, and a thermoplastic polyurethane polymer having excellent physical properties can be obtained. The reason for this is not clear, but in isophorone diisocyanate, the difference in reactivity of two isocyanate groups with different properties (one is bonded to an aliphatic group and the other is bonded to an aliphatic group) may have some effect. It is assumed that there are.

The urea modified product of the non-yellowing diisocyanate mentioned above is a compound in which two or more molecules of the non-yellowing diisocyanate are bonded to each other through a urea bond (-i+Hcona7). This modified product is usually obtained by reacting a non-yellowing diisocyanate with water. For example, as shown in the following formula, two molecules of non-yellowing isocyanate react through water to form a modified urea product.

(10,, 'C! IJ -A -N (j:, O),
,2 10H20, : :,, →,l0ION,'
When the amount of 1-A-NHcONH, -A-NOC) + co2 water is large, the reaction further progresses and a modified product in which three or more molecules of modified diinocyanate are bonded is also produced. Mixtures of modified urea and unmodified non-yellowing diincyanates can also be used. This mixture is usually obtained by adding a predetermined amount of a modifier such as water to a non-yellowing diisocyanate and reacting the mixture.

The modifier for urea modification is not limited to water, and diamines and the like can also be used, but water is most preferred. Commercially available? It is presumed that the urea modified product is also modified with water, but of course other modified products or urea modified or modified products modified by treatment can also be used. It is preferable that the content of the modified urea in the non-yellowing diisocyanate containing the modified urea is 10% or more, particularly 30 to 80%. Two or more S-yellowing diisocyanates may be used in combination, and two or more urea-modified products of non-yellowing diisocyanates may be used in combination.

As the high molecular weight diol, various high molecular weight diols can be used, and two or more types of high molecular weight diols can be used in combination. The molecular weight of the high molecular weight diol is not particularly limited, but is about 500 to 6,000, preferably about 800 to 4,00'O. The types include, for example, polyester diol, polyether diol, polyether ester diol, polycarbonate diol, and hydrocarbon polymer having two hydroxyl groups, but polyester diol is particularly preferred. Polyester diols are produced, for example, by the reaction of dihydric alcohols and dibasic acids or by ring-opening polymerization of cyclic esters. The former method can also be changed to a method in which acid anhydrides, acid chlorides, esters, etc. of dibasic acids are used and reacted with dihydric alcohols. The raw materials for these polyester diols may contain inert functional groups such as unsaturated groups and nitrogen, and therefore, the polyester diols may also contain these functional groups. . Preferred dihydric alcohols and dibasic acids are aliphatic compounds and substantially saturated compounds. Specific bivalent
Examples of alcohol include ethylene glycol, propylene glycol, 1.3-furo-banks alcohol,
Butylene glycol, 1,4-butanediol, 1,6
- Polypropylene glycols such as hexanediol, 1,8-octanediol, neopentyl glycol, diethylene glycol and triethylene glycol, diethylene glycol, etc.:
There are chlorhexanedimethanol, etc., and dibasic acids (and derivatives of 7) include cono-phosphoric acid, adipic acid,
Sperine, acid, azelaic acid, sebacic acid, phthalic acid,
Examples include in-7thalic acid, terephthalic acid, phthalic anhydride, maleic acid, maleic anhydride, and 7-malic acid. An example of a cyclic ester is 6-caprolactone. Preferred polyester diols include poly(ethylene adipate), poly(1,4-butylene adipate), poly(1,6-hexane adipate), poly(ethylene aze-ray 1=, ), poly( 1,4-butylere azelate) 1. and poly(ε-caprolactone). The high molecular weight diols used in the present invention are not limited to these double ester diols, but can also include other high molecular weight diols, such as polytetramethylene glycol, dihydric alcohols, dihydric phenols, and epoxides, especially □ carbon number diols. Polyether diols obtained by adding 2 to 4 alkidine oxides and other polyether diols are also preferred. As the 5-chain extender, dihydric alcohols and diamines can be used, but dihydric alcohols are particularly preferred. The dihydric alcohol is preferably the dihydric alcohol described as the raw material for the polyester diol, but is not limited thereto. -Diamines are used alone or in combination with dihydric alcohols as chain extenders. be able to. Furthermore, as other chain extenders, the above-mentioned JP-A-Sho 5.6-, . 1...2.7
6.7. ,．． 7. 1. Divalent atacols having a carboxylic acid group, such as dimethylo-lupro, as described in 1. Pionic acid can be used as a chain extender in combination with a dihydric alcohol, diamine, or cape. This publication (describes, describes, etc.) thermoplastics, polyurethane, tan-based polymers, glass, polyurethane, etc. ：And Ω contact! The sex is,
, if only the surface properties are improved, then the surface properties will be improved if the layers are layered, as will be explained later.
A carboxylic acid group is used as a reaction group. , because it is possible. Jiami・
For example, ethylene diamine, ethylene diamine,
Tramethylene diamine, shea, minoji 7 komi and methane 1. Tolylenediamine, inphorondiamine, etc. Examples of dihydric alcohols having a carboxylic acid group include ζ such as dimethylolpropionic acid and dimethylolacetic acid;
There is.

Particularly preferred chain extenders are dihydric alcohols having a molecular weight of 30.0 or less.5. Especially molecular weight 6? , (molecular weight of etching recall)'~2/1i of 1.5o
11i alcohols, such as 1, 1 ethylene glycol, 2. ．． Preferred are 1,4-butanediol, 1,6-propanediol, propylene glycol, 1,6-hexanediol, neohentyl glycol, diethyl astragalus, licor, and the like. .

Thermoplastic polyurethane polymers are obtained by reacting the above three components as main raw materials, but usually this reaction involves:
requires a catalyst. Typical catalysts include organometallic compounds and tertiary amines, but are not limited to these. As the organometallic compound, organotin compounds such as dibutyltin, dilauunt, octacyl, tin acid, lead octylate, and organic lead compounds are preferable.

The use of these catalysts is not necessarily essential, and the polymer can be produced with or without using a catalyst. Next, during or after the production of the thermoplastic polyurethane polymer, various additives that may be present in the polymer can be added. Examples include stabilizers such as ultraviolet absorbers and antioxidants, anti-coloring agents, colorants, and agents that improve adhesion to glass.

However, in addition to the above-mentioned three bifunctional components, it is also possible to use a trifunctional or higher functional reactive compound in a certain amount without causing loss of thermoplasticity during polyurethane polymerization. And,
For example, 3. Polyols with higher molecular weight than 3. More than sensory/no yellowing 5. poly,
, isocyanate, anene-7-ate and its modified derivatives, trifunctional or higher chain extenders (i.e. cross-linking agents), etc., are used. The reaction of the '33 compound, which is the main raw material of the polyurethane polymer, is
In particular, the following proportions are preferred, but not limited to. Insear for 100 of high molecular weight di-, ri-to-chain extension, long sword hydroxyl groups (if diamines are used, water, acid groups and/or groups): Nate Ei-no-Tsugu, (usually It is preferable that the isocyanane index is 90 to 12.0, especially 95 to 110 (when using in combination with other reactive hydroxyl groups or compounds having amii groups) Add these groups to the calculation) δ high molecular weight di-ol, chain extender 90%, high molecular weight di-ol, chain extender 0.5 to 5% per equivalent Double equivalent (also preferably about 5 to 4.0 parts by weight of the seven-chain extender per 100 parts by weight of the high molecular weight diol).

The method for producing the thermoplastic polyurethane polymer is not particularly limited, and can be produced by a one-shot method, a greborimer method, a quasi-prepolymer method, or other methods. Similarly, there are no particular limitations on the method for producing sheets or films of thermoplastic urethane polymers using these methods.

□ For example, how to cast a liquid reactive mixture,
A method of casting a polymer solution, a method of forming a solid polymer into a sheet or film by extrusion molding, calendar molding, or other molding methods can be adopted. In particular, extrusion molding is suitable as a method for producing homogeneous sheets and films. In the present invention, a sheet is 0. ``A film is a film with a thickness of 2+ inches or more, and a film is a film with a thickness of less than 0.2 inches.

The thermoplastic polyurethane polymer used in the present invention needs to be transparent or translucent. It may be colored if necessary, but it is undesirable for the transparency to change over time.8
The thermoplastic polyurethane polymer sheet or film does not necessarily have to be transparent or translucent. for example,
It may be a ground glass sheet or film having fine irregularities on the surface. This is because when laminated with glass, it can be heated and compressed to create a smooth surface and can be made into transparent or translucent laminated safety glass. The thermoplastic polyurethane polymer sheet or film may be partially colored or partially opaque. For example, it is well known that laminated glass can be dyed differently, and it is possible to dye it in the same way with layered glass.

Laminated safety glass is composed of at least one layer of the thermoplastic polyurethane polymer sheet or film and at least one layer of a rigid substrate. In the case of labe-nate glass, the interlayer film is usually made only of a thermoplastic polyurethane polymer, but the multilayer structure of the thermoplastic polyurethane polymer in the present invention, It may also be a multi-layered structure of two or more layers of and other synthetic resins (for example, other thermoplastic polyurethane polymers, polyvinyl butyral, etc.). The pie layer of pie layer glass also tends to have a single layer or multilayer structure.

In particular, the surface properties of a single layer of pie layer are problematic, so even if the single layer of pie layer is composed of only one layer of the thermoplastic polyurethane polymer according to the present invention, the surface may be cross-linked, etc. Preferably, the treatment is carried out. Further, in the present invention, it is also preferable to provide a thin synthetic resin layer with excellent surface characteristics, such as a crosslinked polyurethane polymer layer, on the exposed surface of the thermoplastic polyurethane polymer layer. In either the intermediate film or the pie layer, the main portion, ie, the thickest portion, preferably consists of the thermoplastic polyurethane-based polymer of the present invention described above.

The hard substrate is made of glass (ie, inorganic glass), polycarbonate, polymethyl, methacrylate, or other hard organic glass. Particularly preferred is inorganic glass, which is widely used as a window material for automobiles and other transportation equipment or for buildings. This inorganic glass may be tempered glass strengthened by air-cooling or chemical strengthening. The rigid substrate may also be a multilayer structure, for example laminated glass,
□-Can be used as a hard substrate for glass.

Laminated safety glass can be manufactured by various methods□
However, the most common and preferred manufacturing method is the thermocompression bonding method. For example, a sheet or film of thermoplastic polyurethane polymer and a glass sheet are pre-pressed or pre-pressed. □ Lamination is often carried out directly by heat-pressing in an autoclave or by heat-pressing with a roll. You can get glass and pie layer glass. The manufacturing method for laminated safety glass is limited to the thermocompression bonding method of □
For example, between two glass sheets.
The reactive mixture was cast on □□ to produce laminated glass, one glass sheet and a mold (
For example, it is also possible to adopt a method in which a reactive mixture is cast between a glass sheet that has been subjected to a mold release treatment, and after the reactive mixture has hardened, the mold material is removed to produce pie layer glass.

Laminated safety glass must be transparent or translucent as a whole, but may be partially opaque. In addition, the hard substrate and the interlayer layer may be entirely or partially colored. The total thickness of the intermediate film or layer containing the polymer is particularly limited. Preferably, the thickness of the hard base layer is O, 5 tan or more, although not a
Especially when the thickness of the intermediate film or eraser layer is 0.
1 w or more, especially 0.2 to 10 watts is suitable.

The laminated safety glass of the present invention is suitable as a window material for automobiles, trains, aircraft, ships, and other transportation equipment, or as a window material or partition material for buildings, etc., but its use is limited to these. It's not a thing. The present invention will be explained below with reference to Examples.
This will be explained concretely, but it is limited to these examples. '? (0:”
4's' 2 moles) to 3-seg'o□□□□Q under vacuum
``Heat at 110°C for 2 hours □ Stir to remove water with sharp air □. -2
921) 5 '5 'o, 4""'? ”(”'1
808 mol): Th' and dibutyltin dilaure Lyto
, it' (o, o a 6% of the total reaction amount) were added, and the mixture was reacted for 15 minutes at 80°C under a nitrogen stream. Next, add 1,4-butane to this reaction mixture. Q
Add ``'i'' (1,291 moles) and mix gently. After the reaction started and the reaction mixture was thoroughly mixed and became substantially homogeneous, the reaction resin solution was poured into a polytetrafluoroethylene-coated drying container and heated to 130°C under a nitrogen atmosphere. The mixture was reacted for about 15 hours. The produced polymer was cooled to room temperature, pulverized using a pulverizer, and further granulated using a pelletizer. This is done in the usual way using an extruder at υ, 180°C to 2°C.
A glassy transparent sheet can be formed at a melting temperature of 20°C. The performance of this sheet is shown in Table 1 below.

Table 1 A sheet of 0.5 wn thickness obtained by the above method was placed between two glass plates having dimensions of 3.0 x 5.0 cm. Introduce it into a suitable autoclave.

The surface where one piece of glass and the sheet come into contact is subjected to a release treatment, or a release film is used, and the surface where the other glass and the film come into contact is subjected to a silage treatment. The autoclave was initially evacuated 76, to remove air between the glass and the sheet, and then evacuated in vacuum for 1 hour.
Heat to 00°C and perform preliminary pressure bonding. After opening the hole, autoclave at 140η, pressure 13~1, at
The glass sheet was maintained for about 30 minutes under the conditions of 1.m to completely adhere the glass sheet, and then the glass was removed to produce a pie layer glass, which is a two-layer glass-plastic laminate.

When a falling ball test was conducted on this Pylayer glass based on the penetration resistance test specified in J.K. S R3312, the steel balls did not penetrate, and the broken glass was glued to the sheet and replaced. Hii was an unacceptable 4.

Example 2 Polybutylene adibate with a molecular weight of 2074 and a hydroxyl value of 541) 1o, o o,, y (, o, 482
mol) was heated and stirred at 110° C. for 2 hours under a vacuum of 5 mnHg to deaerate and dehydrate. In addition, inphoron diisocyanate (trade name: PD engineering a-s1s) containing urea modified inphoron diisocyanate, 44
o ) to j59. ．． To the mixture were added dibutyltin dilaurate (t, q, 32 mol) and dibutyltin dilaurate (0.006% of the total reaction amount), and the mixture was reacted at 80° C. for 15 minutes under a nitrogen stream. Next, 1.2, 1,4-butanediol, . 7.22 (1,+, t1 mol) was added thereto, and the mixture was quickly stirred and mixed, and a sheet having a thickness of 0.5fi was formed using the i method similar to that in Practical Example 1. The properties of this sheet are shown in Table 2.

Construction 2 Table.

This sheet was heat-pressed to a glass plate in the same manner as described in Example 1, and a falling ball test was conducted in the same manner as in Example 1. When the steel ball did not penetrate, the broken glass was removed by adhering the sheet to a glass plate. No scattering of moths or grass was observed. .

Example 3 Polybutylene adipate 1'0002 (α482 mol) with a molecular weight of 2.97.4 and a hydrocarbon value of 54.1 was
Degassing and dehydration were carried out by heating and stirring at 110°C for 2 hours under a vacuum of "m'E g".
15'o 5.71.91 (2,:048 mo attack) and dibutyltin dilaurate 0. 1 f (o, 'oo6 h of the total reaction volume) was added and heated at 80°C under a flow of drilling wax for 15 min.
Next, 94.7 mol of ethylene glycol (526 mol) of ethylene glycol was added to the reaction mixture, and the mixture was quickly stirred and mixed, and then a sheet with a thickness of 0.5 mm was prepared in the same manner as in Example 1. Formed.

The properties of this sheet are shown in Table 3.

Table 3 □ When this sheet was thermocompressed to a glass plate in the same manner as shown in Example 1 and a similar falling ball test was conducted, the steel balls did not penetrate and the broken glass adhered to the sheet. No glass was observed.

Example 4 Molecule i2074, polybutylene adipate with 54.1 hydroxyl groups) 1000F (0,482 mol) at 5 msH
The mixture was heated and stirred at 110° C. for 2 hours under a vacuum of 1.5 g to degas and dehydrate. This was synthesized from bis(4-incyanatecyclohexyl)methane and water. -Urea modified product of bis(4-incyanatecyclohexyl)methane 4
565.3 P (1,662 mol) of bis(4-incyanatocyclohexyl)methane containing 7q6 and 0.1 t (0.3006% of the total reaction amount) of dibutyl tin dilaure were added, and the mixture was heated at 80°C under a nitrogen stream. The mixture was reacted for 15 minutes. Next, 103.4 mol of 1°4-butanediol (t 14 a mol) was added to this reaction mixture, and the mixture was rapidly mixed to form a 0.5-thick sheet in the same manner as in Example 1. . The properties of this sheet are shown in Table 4.

Table 4

Claims (1)

[Claims] 1. The non-yellowing diisocyanate has three components: the non-denatured diisocyanate, a high-molecular-weight diol, and the three components of the non-yellowing diisocyanate. Sheet or film made of transparent or translucent thermoplastic polyurethane (transparent or translucent thermoplastic polyurethane) obtained by reacting. ' 12
The sheet or film according to claim 1, wherein the non-yellowing diisocyanate is inphorone diisocyanate. 5 Non-yellowing cyidicyanate: urea-modified product i Non-yellowing 1 □□ socyanate containing the urea-modified product, □high; Thermoplastic polymer obtained by reacting at least 4 components 1) At least 1' layer of urethane polymer and 1' layer of urethane polymer must be opaque or translucent. laminated safety glass. 4. A patent "Claims" characterized in that the non-yellowing tie isocyanate is an isophorone diisocyane.
□ Surroundings 1'5m'α' Seminar safety glass □Glass. □５、”””
Assume that the proportion of i-form containing □ is □・10% or more:
"htd+'m'"* is the range: ・Laminated safety glasses in Section □.3. l l::,,,,,,,,,
'□. Layering of safety materials. ′□
′ □l @□Prolongation agent is molecular honor 3□00
□'The following ・2・valent alcohol']' The scope of the patent claim is characterized by the following.・ □＆□−□Hard base: 1 turnip machine □Glass plate
- Features: ``Claim 1
3. Laminated low """pot" □ Glass "o" ・ ・
: