JPH0379186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a laminated safety glass that is transparent or translucent and has excellent physical properties such as shock absorption. A laminated sheet of an inorganic glass (hereinafter simply referred to as glass) sheet and a synthetic resin sheet is well known as laminated safety glass. For example, laminated safety glass having a three-layer structure of glass, polyvinyl petral, and 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 petral, 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 considered to be even safer than the conventional laminated glass described above. 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 windshield.
It is also thought that even if the glass breaks, there will be less glass fragments flying into the interior of the car. Such laminated safety glass, in which one side is glass and the other side is synthetic resin, is hereinafter referred to as "bilayer glass", and the exposed synthetic resin layer is referred to as "bilayer layer". These laminated safety glasses are not only used for automobiles, but also
It can also be used as a window material for other transportation equipment and buildings. Regarding laminated safety glass with a synthetic resin layer made of polyurethane polymer, for example, Japanese Patent Publication No. 43-3626
Publication No. 55-51744, Japanese Patent Publication No. 1973-
It is described in JP-A No. 25714, JP-A-53-27671, JP-A-56-127677, and the like. Many performances are required of polyurethane polymers used as interlayer films or bilayer layers. For example, physical properties such as transparency, adhesion to glass, and shock absorption are common requirements for both the interlayer film and the bilayer layer. Furthermore, surface performance such as solvent resistance is a required performance specific to the bilayer layer. The present inventors have studied polyurethane polymers that can satisfy the former required performance. A bilayer glass is known in which a thermosetting polyurethane polymer is used as the bilayer layer and glass is bonded to a thin thermoplastic polyurethane polymer (see Japanese Patent Laid-Open No. 53-27671). However, thermoplastic polyurethane is superior as a polyurethane polymer for interlayer films and bilayer layers, especially from the viewpoint of physical properties, and a thin thermosetting polyurethane polymer is applied to the surface of the bilayer layer to improve surface properties. In any case, a thermoplastic polyurethane polymer is considered to be most suitable for the main part of the interlayer film or bilayer layer. Thermoplastic polyurethane polymers used for interlayer films and the like are discussed in detail in the above-mentioned Japanese Patent Publication No. 51744/1982 and Japanese Patent Application Laid-open No. 127677/1982. As described in these publications, impact absorption (also referred to as energy absorption properties) is important for the physical properties required of thermoplastic urethane polymers. The shock absorbing properties of thermoplastic polyurethane polymers are highly dependent on the selection of raw materials for producing the polyurethane polymer. Similarly,
The optical property, which is an important performance, that is, the property of being uniform and transparent (hereinafter referred to as transparency) also depends on the selection of raw materials. It is also required that these properties change little over time; for example, polyurethane polymers using aromatic diisocyanates tend to turn yellow over time, making them difficult to use as raw materials for polyurethane polymers for laminated safety glass. be. Conventionally, Kochi's thermoplastic polyurethane polymers did not necessarily have sufficient performance. In particular, it has been found that there are problems with impact absorption, and that other physical properties, such as penetration resistance, need 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-isocyanatecyclohexyl)methane, which is a particular mixture of isomers, is particularly preferred as the diisocyanate compound. As a result of examining the above-mentioned physical properties, particularly regarding diisocyanate compounds, the present inventor found that
We have discovered that isophorone diisocyanate containing a urea-modified product is excellent as a raw material for thermoplastic polyurethane polymers for interlayer films or bilayer layers. The present invention relates to a laminated safety glass obtained using a sheet or film made of a thermoplastic polyurethane polymer obtained using this urea modified product or isophorone diisocyanate containing the same. That is, a thermoplastic polyurethane polymer obtained by reacting at least three components: a urea modified isophorone diisocyanate modified with water or isophorone diisocyanate containing the urea modified product, a high molecular weight diol, and a chain extender. A transparent or translucent laminated safety glass comprising at least one layer of one layer, a hard substrate, and at least one layer of a hard substrate. The laminated safety glass obtained using the thermoplastic polyurethane-based polymer of the present invention is compared to similar laminated safety glass using the thermoplastic polyurethane-based polymer obtained using isophorone diisocyanate without urea modification. Not only does it have excellent shock absorption properties, but also other physical properties such as penetration resistance are extremely good, and other properties such as transparency are also extremely high. Furthermore, compared to the above-mentioned known examples, since polyester diol with a high melting point is not essential and bis(4-isocyanatecyclohexyl)methane, which is a specific isomer mixture, is not essential, the range of raw material selection is wide and economical. It is also highly sexual. 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.
It is also highly economical. First, the thermoplastic polyurethane polymer and its raw material components will be explained below, and then the laminated safety glass will be explained. Isophorone diisocyanate (i.e. 3-isocyanate methyl-3,5,5
-trimethylcyclohexyl isocyanate)
is a typical non-yellowing diisocyanate compound, and by using this modified product as a raw material, thermoplastic polyurethane polymers with the best physical performance can be produced compared to the use of other non-yellowing diisocyanates. A union is obtained. The reason for this is not clear, but isophorone diisocyanate has some effect due to the difference in reactivity between two isocyanate groups with different properties (one is bonded to an aliphatic group and the other is bonded to an alicyclic group). It is assumed that there are. The above-mentioned urea form of isophorone diisocyanate is a compound in which two or more molecules of isophorone diisocyanate are bonded to each other through a urea bond (-NHCONH-). This modified product is usually obtained by reacting isophorone isocyanate with water. For example, as shown in the following formula, two molecules of isophorone isocyanate react through water to form a modified urea product (A is a residue obtained by removing two isocyanate groups from isophorone diisocyanate). (OCN-A-NCO) ₂ +H ₂ O→OCN-A-NHCONH-
When the amount of A-NCO+CO ₂ water is large, the reaction progresses further and a modified product in which three or more molecules of isophorone diisocyanate are bonded is also produced. Mixtures of this urea modification with unmodified isophorone diisocyanate can also be used. This mixture is usually obtained by adding a predetermined amount of water to isophorone diisocyanate and reacting the mixture. The content of the modified urea in the isophorone diisocyanate containing the modified urea is preferably 10% or more, particularly 30 to 80%. 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
~6000, preferably about 800-4000. The types include, for example, polyester diol, polyether diol, polyether ester diol,
Examples include polycarbonate diol, hydrocarbon polymer having two hydroxyl groups, and particularly preferred is polyester diol. 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 halogens, 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 dihydric alcohols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol,
Butylene glycol, 1,4-butanediol,
These include 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, polyethylene glycols such as diethylene glycol and triethylene glycol, polypropylene glycols such as dipropylene glycol, and cyclohexanedimethanol. ) include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, maleic acid, maleic anhydride, fumaric acid, and the like.
Examples of cyclic esters include s-calactone. Preferred polyester diols are poly(ethylene adipate), poly(1,4-butylene adipate), poly(1,6-hexane adipate), poly(ethylene azelate), poly(1,4-butylene azelate). , and poly(s-caprolactone). The high molecular weight diol in the present invention is not limited to these polyester diols, but may include other high molecular weight diols,
For example, polytetramethylene glycol, polyether diol obtained by adding epoxide, especially alkylene oxide having 2 to 4 carbon atoms, to dihydric alcohol or dihydric phenol, and other polyether diols are also preferred. Although dihydric alcohols and diamines can be used as chain extenders, 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 can be used alone or in combination with dihydric alcohols as chain extenders. Furthermore, other chain extenders include dihydric alcohols having a carboxylic acid group, such as dimethylolpropionic acid, as described in JP-A-56-127677, and dihydric alcohols and diamines. Can be used in conjunction with As described in this publication, thermoplastic polyurethane polymers having carboxylic acid groups not only improve adhesion to glass, but also improve the surface properties when used as a bilayer layer, as described later. This is because a carboxylic acid group can be used as a reactive group. Examples of diamines include ethylene diamine, tetramethylene diamine, diaminodiphenylmethane, tolylene diamine, and isophorone diamine. 2 with carboxylic acid group
Examples of the alcohol include dimethylolpropionic acid and dimethylolacetic acid. Particularly preferred chain extenders are dihydric alcohols with a molecular weight of 300 or less, particularly 62 (molecular weight of ethylene glycol).
~150 dihydric alcohols, such as ethylene glycol, 1,4-butanediol, 1,3-propanediol, propylene glycol, 1,6-
Hexanediol, neopentyl glycol, diethylene glycol and the like are preferred. Thermoplastic polyurethane polymers are obtained by reacting the above three components as main raw materials, but this reaction usually requires a catalyst. Representative catalysts include organometallic compounds and tertiary amines, but are not limited thereto. As the organic metal compound, organic tin compounds and organic lead compounds such as dibutyltin dilaurate, tin octoate, and lead octylate are preferred. The use of these catalysts is not necessarily essential, and the polymer can be produced without using a catalyst. Furthermore, various additives that may be present in the thermoplastic polyurethane polymer can be added during or after the production of the thermoplastic polyurethane polymer. Examples include stabilizers such as ultraviolet absorbers and antioxidants, anti-coloring agents, coloring agents, and agents for improving adhesion to glass. Further, in addition to the above-mentioned three bifunctional components, a trifunctional or higher functional reactive compound may be used in an amount that does not cause loss of thermoplasticity of the polyurethane polymer. For example, trifunctional or higher functional high molecular weight polyol, trifunctional or higher functional urea modified product,
A chain extender (ie, a crosslinking agent) having a higher functionality or the like can be used. The reaction ratios of the three components that are the main raw materials of the thermoplastic polyurethane polymer are not particularly limited, but the following ratios are preferred. The number of isocyanate groups (usually referred to as isocyanate index) per 100 hydroxyl groups (or hydroxyl groups and amine groups when diamines are used) of the high molecular weight diol and chain extender should be between 90 and 120, especially between 95 and 110. is preferable (if compounds having other reactive hydroxyl groups or amino groups are used together, those groups should be added to the calculation). The ratio of high molecular weight diol to chain extender is 1 equivalent of high molecular weight diol to 1 equivalent of chain extender.
The amount of the chain extender is preferably 0.5 to 5 times equivalent, and about 5 to 40 parts by weight of the 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 may be produced by a one-shot method, a prepolymer 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, casting liquid reactive mixtures, casting polymer solutions, extruding solid polymers,
Calendar molding or other molding methods may be used to form sheets or films. In particular, extrusion molding is suitable as a method for producing homogeneous sheets and films. What is a sheet in the present invention?
A film is a film with a thickness of 0.2 mm or more.
Thickness less than mm. The thermoplastic polyurethane polymer used in the present invention needs to be transparent or translucent. Although it may be colored if necessary, it is not preferable that the transparency changes over time. 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. The reason for this is that when laminated with glass, the surface is made smooth by heat compression or the like, and transparent or translucent laminated safety glass can be obtained. The thermoplastic polyurethane polymer sheet or film may be partially colored or partially opaque. for example,
"Dyeing" laminated glass is well known, and bilayer glass can also be dyed in the same way. Laminated safety glass is comprised 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 laminated glass, the interlayer film usually consists of only a thermoplastic polyurethane polymer, but the multilayer structure of the thermoplastic polyurethane polymer in the present invention or the thermoplastic polyurethane polymer in the present invention and other synthetic resins (for example, other (thermoplastic polyurethane polymers, polyvinyl butyral, etc.)
It may be a multilayer structure having more than one layer. The bilayer layer of bilayer glass similarly consists of a four-layer or multilayer structure. In particular, the surface characteristics of the bilayer layer are a problem, so even if the bilayer layer is composed of only one layer of the thermoplastic polyurethane polymer according to the present invention, surface treatment such as crosslinking is performed on the surface. It is preferable.
It is also preferable to provide a thin synthetic resin layer with excellent surface properties, such as a crosslinked polyurethane polymer layer, on the exposed surface of the thermoplastic polyurethane polymer layer in the present invention. The main parts of either the interlayer or the bilayer layer,
That is, the thickest portion is preferably made of the thermoplastic polyurethane polymer according to the present invention. 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 architecture.
This inorganic glass may be tempered glass strengthened by air-cooling strengthening or chemical strengthening. The rigid substrate may also be a multilayer structure, for example laminated glass can be used as a rigid substrate for bilayer glass. Although laminated safety glass can be manufactured by a variety of methods, the most common and preferred manufacturing method is thermocompression bonding. For example, by pre-pressing a thermoplastic polyurethane polymer sheet or film with a glass sheet, or directly without pre-pressing, thermo-compressing in an autoclave or using a roll, you can create laminated glass or bilayer glass. glass is obtained. The manufacturing method of laminated safety glass is not limited to this thermocompression bonding method; for example, laminated glass can be manufactured by casting the above-mentioned reactive mixture between two glass sheets, or by casting a single glass sheet and a mold material (for example, It is also possible to produce bilayer glass by casting a reactive mixture between the glass sheet and the mold release-treated glass sheet, and removing the mold material after the reactive mixture has hardened. Laminated safety glass must be entirely transparent or translucent, but may be partially opaque. Further, the hard substrate, intermediate film or bilayer layer may be entirely or partially colored. Although the total thickness of the hard base layer in laminated safety glass and the total thickness of the intermediate film or bilayer layer containing the thermoplastic polyurethane polymer in the present invention are not particularly limited, preferably the thickness of the hard base layer The length is 0.5mm or more, especially 1 to 50mm,
The thickness of the interlayer film or bilayer layer is 0.1 mm or more, especially
0.2 to 10 mm is appropriate. 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, but its uses are not limited to these. . EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Example 1 1000 g (0.482 mol) of polybutylene adipate having a molecular weight of 2074 and a hydroxyl value of 54.1 was heated and stirred at 110° C. for 2 hours under a vacuum of 3 mmHg to degas and dehydrate. To this, 550.4 g of isophorone diisocyanate (trade name: IPDI H-2921) containing 58% of the urea modified product of isophorone diisocyanate was added.
(1808 mol) and dibutyltin dilaurate 0.1g
(0.006% of the total reaction volume) and 80
The reaction was carried out at ℃ for 15 minutes. Next, 116.3 g (1.291 mol) of 1,4-butanediol was added to this reaction mixture, and the mixture was rapidly stirred and mixed. An exotherm was observed with the onset of the reaction, and after the reaction mixture was thoroughly mixed and substantially homogeneous, the reaction resin solution was poured into a dry container coated with polytetrafluoroethylene and heated to 130°C under a nitrogen atmosphere. The mixture was allowed to react 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.
A glass-like transparent sheet can be formed at a melting temperature of 180°C to 220°C. The performance of this sheet is shown in Table 1 below.

[Table] Place the 0.5 mm thick sheet obtained by the above method between two glass plates of 30 x 30 cm dimensions.
Introduce into a suitable autoclave. Apply a release treatment to the contact surface of a single piece of glass and the sheet, or
A release film is used, and the surface where the film contacts the other glass is treated with silane. The autoclave is initially evacuated to remove air between the glass and the sheet, and then heated to 100°C in a vacuum for preliminary crimping. After opening the hole, keep the autoclave at 140℃ and 13 to 14atm pressure for about 30 minutes to completely adhere the glass and sheet, and then remove the glass.
He created bilayer glass, which is a two-layer laminate of glass and plastic. For this bilayer glass, JIS R 3312
When a falling ball test was performed based on the penetration resistance test shown in the table, the steel balls did not penetrate, the broken glass was adhered to the sheet, and no glass was observed to scatter. Example 2 1000 g (0.482 mol) of polybutylene adipate having a molecular weight of 2074 and a hydroxyl value of 54.1 was heated and stirred at 110° C. for 2 hours under a vacuum of 3 mmHg to degas and dehydrate. In addition, isophorone diisocyanate (trade name IPDI H) containing 44% urea modified product obtained by modifying isophorone diisocyanate with water
-3150) and 0.1 g (0.006% of the total reaction amount) of dibutyltin dilaurate were added, and the mixture was reacted for 15 minutes at 80°C under a nitrogen stream. Next, 1,4-butanediol was added to the reaction mixture.
127.2 g (1.411 mol) was added thereto, rapidly stirred and mixed, and then the same method as in Example 1 was carried out to form a 0.5 mm thick sheet. The properties of this sheet are shown in Table 2 below.

[Table] 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 was adhered to the sheet. No glass shards were observed. Example 3 1000 g (0.482 mol) of polybutylene adipate having a molecular weight of 2074 and a hydroxyl value of 54.1 was heated and stirred at 110° C. for 2 hours under a vacuum of 3 mmHg to degas and dehydrate. To this, 571.9g of IPDI H-3150
(2.048 mol) and dibutyltin dilaurate 0.1
g (0.006% of the total reaction amount) was added, and the mixture was reacted for 15 minutes at 80°C under a nitrogen stream. Next, 94.7 g (1.526 mol) of ethylene glycol was added to this reaction mixture, and the mixture was rapidly stirred and mixed, and a sheet having a thickness of 0.5 mm was formed in the same manner as in Example 1. The properties of this sheet are shown in Table 3.

[Table] When this sheet was thermocompression bonded 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 scattering was observed. Comparative Example 1 1000 g (0.482 mol) of polybutylene adipate having a molecular weight of 2074 and a hydroxyl value of 54.1 was heated and stirred at 110° C. for 2 hours under a vacuum of 3 mmHg to perform deaeration and dehydration. This includes isophorone diisocyanate.
493.6 g (2.220 mol) and 0.10 g (0.006% of the total reaction amount) of dibutyltin dilaurate were added and reacted for 15 minutes at 80° C. under a nitrogen stream. Next, 129.8 g of 1,4-butanediol was added to the reaction mixture in advance.
(1.440 mol), isophoroshidiamine 43.3 g (0.255
mol) was added to the mixture, and the mixture was quickly stirred and mixed. Upon the start of the reaction, intense heat was generated and a gel-like substance precipitated. This reaction resin liquid was poured into a dry container coated with polytetrafluoroethylene, and reacted at 130° C. for about 15 hours under a nitrogen stream. The resulting polymer was non-uniform and unusable. (This is thought to be because the reactivity of isophoronediamine is too high, and a reaction occurs at the same time it is added, and a precipitate is formed due to the poor solubility of the urea group.In addition, consider lowering the reaction temperature and reducing the amount of catalyst. However, it was also impossible to use because a non-uniform polymer was obtained.) Comparative Example 2 1000 g (0.482 mol) of polybutylene adipate with a molecular weight of 2074 and a hydroxyl value of 54.1 was heated at 110°C for 2 hours under a vacuum of 3 mmHg. The mixture was stirred for deaeration and dehydration. This includes isophorone diisocyanate.
Add 493.6 g (2.220 mol) and 0.10 g of dibutyltin dilaurate (0.006% of the total amount of reaction resin),
The reaction was carried out at 80°C for 15 minutes under a nitrogen stream. Next, 2987 g of dehydrated methylene chloride was added, and the mixture was cooled to room temperature while stirring. Next, while stirring at room temperature in a nitrogen stream, 129.8 g (1.440 mol) of 1,4-butanediol, 43.3 g (0.255 mol) of isophoronediamine,
A mixture of 519.3 g of dehydrated methylene chloride was added dropwise over 1 hour. This reaction resin liquid was poured into a dry container coated with polytetrafluoroethylene and heated at 60°C for 2 hours under a nitrogen stream to remove the solvent methylene chloride, and then heated to 130°C for about 2 hours.
The reaction was allowed to proceed for 15 hours. Example 1 The produced polymer
A glass-like transparent sheet was formed in the same manner as above. The performance of this sheet is shown in Table 5 below.

[Table] As described above, this sheet had insufficient Taber abrasion resistance and could not be used for laminated safety glass.

Claims (1)

[Scope of Claims] 1. A thermoplastic polyurethane system obtained by reacting at least three components: a urea-modified product obtained by modifying isophorone diisocyanate with water, or isophorone diisocyanate containing the urea-modified product, a high molecular weight diol, and a chain extender. at least one of the polymers
Transparent or translucent laminated safety glass consisting of at least one layer and a rigid substrate. 2. The laminated safety glass according to claim 1, which uses isophorone diisocyanate with a modified content of 10% or more. 3. The laminated safety glass of claim 1, wherein the high molecular weight diol is a polyester diol having a molecular weight of about 500 to 6000. 4. The laminated safety glass according to claim 1, wherein the chain extender is a dihydric alcohol with a molecular weight of 300 or less. 5. The laminated safety glass according to claim 1, wherein the hard substrate is a sheet of inorganic glass.