JPH0610227B2 - Surface modification method of polyurethane-based thermoplastics - Google Patents

Description

The present invention particularly relates to a method for preliminarily modifying the surface of a polyurethane-based thermoplastic resin for laminated safety glass, and particularly to a method for preliminarily modifying physical properties such as solvent resistance of the surface. It is about.

As a laminated safety glass, a laminated sheet of an inorganic glass sheet or a hard organic glass sheet and a relatively soft synthetic resin is well known. Hereinafter, the hard substrate refers to these inorganic glass sheets or organic glass sheets, and the glass simply refers to inorganic glass unless specifically referred to as organic glass. Laminated safety glass having both surfaces made of glass, for example, glass-
Laminated sheets having a three-layer structure of polyvinyl butyral-glass are widely used as safety glass for automobiles. The synthetic resin layer laminated between such glass sheets is called an intermediate film, and polyvinyl butyral, polyurethane, and various other synthetic resins are used or proposed. On the other hand, in a laminated safety glass composed of glass and synthetic resin, a laminated sheet in which a synthetic resin layer is exposed, for example, glass-synthetic resin or glass-synthetic resin-
BACKGROUND ART Laminated sheets of glass-synthetic resin and the like, one side of which is glass and the other side of which is synthetic resin, are attracting attention for safety glass for automobiles and the like. This laminated safety glass is considered to be even safer than conventional laminated safety glass which is glass on both sides. For example, if this laminated safety glass is used as an automobile windshield so that the synthetic resin surface is on the inside of the car, there will be fewer tears or cuts when a driver or the like collides with the windshield, and even if the glass breaks. It is also believed that glass fragments are less likely to be scattered inside the vehicle. Such laminated safety glass having one surface made of glass and the other surface made of synthetic resin is hereinafter referred to as "bilayer glass".

Regarding the bilayer glass, for example, JP-A-48-
No. 41423, No. 48-25714, No. 49-34910, and No. 53-27.
No. 671 publication. As can be seen from these known examples, the exposed synthetic resin layer (hereinafter referred to as bilayer layer) is usually made of polyurethane. Polyurethane is also known as an interlayer for laminated glass. Polyurethanes include so-called thermoplastic polyurethanes and thermosetting polyurethanes, the former being a linear polymer,
Usually, it is obtained by reacting a high molecular weight diol, a chain extender and a diisocyanate compound, and the latter is a crosslinked polymer, for example, obtained by reacting a high molecular weight diol, a crosslinking agent and a diisocyanate compound. The bilayer layer needs to adhere strongly to the glass. However, when thermosetting polyurethane is used as the bilayer layer, there is a problem in that it does not adhere strongly to the glass. On the other hand, the thermoplastic polyurethane strongly adheres to the glass, but as long as it is used as a bilayer layer, the other surface is exposed, and the surface property becomes a problem. That is, thermoplastic polyurethane has insufficient weather resistance and is easily attacked by a solvent. These problems are described in detail in JP-A-53-27671, particularly pages 6 to 7.

In order to solve the above-mentioned problems, in the invention described in JP-A-53-27671, the bilayer layer is composed of two polyurethane layers, the surface is made of thermosetting polyurethane, and the adhesive surface to the glass is heat-treated. We are trying to solve the problem by using plastic polyurethane. Since both polyurethanes adhere strongly, the invention solves the problems of adhesion and surface properties of the bilayer layer with glass. However,
It is unlikely that the present invention could have completely solved all the problems. First of all, the invention requires the production of a sheet of two different polyurethanes, called a preformed sheet, which requires a relatively complex process. For example, page 10, lower right column, line 13 to line
As described on page 14, right upper column, line 14, the other method is required such as pouring the other onto one sheet to integrate it, or dissolving one in a solvent and coating it on the surface of the other.

The second problem is that thermosetting polyurethane loses plasticity after curing. First, there are limited methods for forming thermosetting polyurethane sheets and films (almost the only method is casting and curing), and it is suitable for extrusion, press forming, and other sheet and film forming. Can not use the molding method
Therefore, it is difficult to obtain a smooth sheet or film having a uniform thickness. Further, if it has plasticity, it can be compressed with a mold having a smooth surface to give a smooth surface, but this is also difficult. Of course, this is also due to the lack of adhesion. Third
A problem with the thermosetting polyurethane is that it has insufficient physical properties required for the bilayer glass, such as penetration resistance and impact resistance, as compared with the thermoplastic polyurethane. In the above-mentioned invention, many such problems have not yet been solved, and except for the problem of surface characteristics, a thermoplastic resin, particularly a polyurethane-based thermoplastic resin (hereinafter, polyurethane-based thermoplastic resin) is used as the bilayer layer of the bilayer glass. Plastic resin) is considered to be the best.

The present inventors used to modify the surface of a layer of a thermoplastic polyurethane resin to improve its surface properties, thereby producing a good bilayer glass without substantially using a thermosetting polyurethane. He found and filed a patent application. This surface modification method is a method in which a crosslinkable group is introduced into the surface of the polyurethane-based thermoplastic resin, and then the crosslinkable group is crosslinked, and the surface having the crosslink bond has a surface characteristic of the polyurethane-based thermoplastic resin. It was a solution to the problem. However, subsequent studies by the present inventor have led to the discovery of new problems in this method. In carrying out the above method, it is particularly preferable that the polyurethane-based thermoplastic resin has a reactive group such as a carboxylic acid group, and introduction of a crosslinkable group was not easy without this reactive group. However, this reactive carboxylic acid group may reduce the physical properties of the polyurethane-based thermoplastic resin, and the polyurethane-based thermoplastic resin may contain no carboxylic acid group except for the surface portion. It turned out to be preferable. As the polyurethane-based thermoplastic resin, polyurethane using polyester diol is preferable from the viewpoint of physical properties, but the presence of a carboxylic acid group has a function of decomposing the ester bond. Therefore, if a polyurethane-based thermoplastic resin that does not substantially contain a carboxylic acid group is used and a crosslinkable group can be introduced on this surface, it is considered that the problem due to the carboxylic acid group does not occur. .

As a result of various studies conducted by the present inventor, it was unexpectedly found that a compound having a polymerizable unsaturated group was grafted onto the surface of a polyurethane-based thermoplastic resin substantially containing no carboxylic acid group by the action of ultraviolet rays or the like. I found it easy. It is thought that this grafting reaction occurs when the surface of the polyurethane-based thermoplastic resin is irradiated with ultraviolet rays, etc., and hydrogen atoms are abstracted to form active sites, and the polymerizable unsaturated groups bond to these active sites. Be done. Therefore, it became possible to introduce a carboxylic acid group only on the surface of a polyurethane-based thermoplastic resin by using this method. Furthermore, a compound having a moisture-crosslinkable group can be directly used by utilizing this grafting reaction. Can be introduced. For example, a compound having a moisture-crosslinkable group such as a trialkoxysilyl group and a polymerizable unsaturated group can be grafted to directly form the moisture-crosslinkable group on the surface portion of the polyurethane-based thermoplastic resin. The compound having one polymerizable group and at least one carboxylic acid group or moisture crosslinking property is hereinafter referred to as a functional compound. Also, due to the characteristics of the polyurethane-based thermoplastic resin, the functional compound that comes into contact with the surface thereof is relatively easily impregnated into the polyurethane-based thermoplastic resin. Therefore, the impregnated functional compound is also grafted onto the polyurethane-based thermoplastic resin by irradiation with ultraviolet rays or the like, like the surface compound. In the present invention, the surface modification means not only the strict meaning of the surface of the polyurethane-based thermoplastic resin but also the modification of the surface part including the surface layer from the surface to the part where the functional compound is impregnated to a certain depth. To do.

The gist of the present invention is the preliminary surface modification for facilitating the surface cross-linking of the polyurethane-based thermoplastic resin by the above graft, and the preliminary surface modification of the polyurethane-based thermoplastic resin in the bilayer glass. Is the gist. That is, the present invention relates to a method for laminating transparent or translucent laminated safety glass having at least a two-layer structure in which one exposed surface is a surface of a thermoplastic polyurethane resin and the other exposed surface is a surface of a hard substrate. At any stage of production, the exposed surface or the surface of the polyurethane thermoplastic resin to be the exposed surface has one polymerizable unsaturated group and at least one carboxylic acid group or moisture-crosslinkable group. Surface of polyurethane-based thermoplastic resin in laminated safety glass characterized in that the functional compound is contacted or impregnated and irradiated with energy rays to graft the functional compound to the polyurethane-based thermoplastic resin on the surface or inside thereof. Partial modification method.

The modification method of the present invention is particularly suitable for surface modification of a polyurethane-based thermoplastic resin for laminated safety glass, particularly a sheet or film of a polyurethane-based thermoplastic resin used in the production of bilayer glass by the lamination method. That is, the carboxylic acid group-introduced polyurethane-based thermoplastic resin obtained by the present invention is applied to the surface modification using the carboxylic acid group-containing polyurethane-based thermoplastic resin in the invention of the present inventors. Is preferred. For example, a compound having a bondable group such as an epoxy group capable of bonding with a carboxylic acid group and a crosslinkable group capable of being crosslinked by moisture, light, heat or the like is bonded to the carboxylic acid group on the surface portion of the polyurethane-based thermoplastic resin. , Then crosslink the crosslinkable group,
Finally, a surface having excellent surface characteristics of solvent-resistant groups can be obtained (see Japanese Patent Application No. 57-147830). When a functional compound having a moisture-crosslinkable group is grafted, the moisture-crosslinkable group is then crosslinked to obtain a surface having similar excellent surface characteristics. Further, the present invention is
It can also be applied to a method for manufacturing bilayer glass by a method other than the laminating method. For example, a casting method is known as a method for manufacturing bilayer glass. That is, a liquid polyurethane-based thermoplastic resin material is injected between one glass sheet and a mold release material, usually a glass sheet treated with a mold release agent, and cured to remove the mold material, and a two-layer structure is formed. A method for manufacturing the bilayer glass of is known. The present invention can be applied to the case where the exposed surface of the polyurethane-based thermoplastic resin layer of the bilayer glass obtained by this method is surface-modified. However, preferably the lamination method described below, especially the lamination method by thermocompression bonding, the surface of the sheet or film of the polyurethane-based thermoplastic resin before lamination of the bilayer glass produced by the lamination method, or the bilayer glass produced by the lamination method. It is preferably applied to the surface of the polyurethane-based thermoplastic resin layer. Hereinafter, the application of the present invention in this laminating method will be mainly described.

The functional compound in the present invention means one polymerizable unsaturated group, particularly a polymerizable α, β-unsaturated double bond and at least one polymerizable unsaturated group.
It is a compound having one carboxylic acid group or a moisture-crosslinkable group. As the moisture-crosslinkable group, a silyl group having a hydrolyzable group, that is, -Si (A) _m (B) _3-m (A: an alkoxy group,
A hydrolyzable group such as a halogen or a phenoxy group, a non-hydrolyzable group such as B: an alkyl group, and a silyl group represented by m: an integer of 1 to 3) are suitable, and a trialkoxysilyl group is particularly preferable. Examples of the functional compound having a carboxylic acid group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, and examples of the functional compound having a moisture-crosslinkable group include Examples include acrylic or methacrylic monomers having the above hydrolyzable silyl group such as γ-methacryloyloxypropyltrimethoxysilane. It is known that the functional compound or a composition containing the functional compound is applied to the surface of a hard plastic such as a polycarbonate sheet and cured by heat or ultraviolet rays to form a hard coating layer, a so-called hard coat layer. The formation of this hard coat layer is inappropriate in the present invention. Because, the polyurethane-based thermoplastic resin in the present invention is relatively soft,
This is because even if a hard coat layer is formed on this surface, the hard coat layer is extremely easily broken by impact or the like. Therefore, the hard coat layer should not be substantially formed in the present invention. That is, in the present invention, the surface of the polyurethane-based thermoplastic resin does not substantially contain a layer having a uniform thickness of the polymer of the functional compound. Conventionally,
It is said that the thickness of the hard coat layer needs to be at least 1 micron. In the present invention, the thickness is less than 1 micron even though it may include a uniform layer of polymer of functional compound. Further, in the formation of the hard coat, the functional compound is usually hardly impregnated into the inside of the surface of the hard plastic. On the other hand, the polyurethane-based thermoplastic resin is relatively easily impregnated. In the present invention, various methods can be adopted as the method of grafting without forming a uniform layer of the polymer of the functional compound. For example, a functional compound applied to one side of a polyurethane thermoplastic resin sheet is irradiated with ultraviolet rays from the surface not coated with a polyfunctional compound through the polyurethane thermoplastic resin, and polymerization between the functional compounds does not occur so much. The objective can be achieved by using a method of removing the unreacted functional compound before proceeding. It is preferable to add a photosensitizer or the like to the functional compound, but it is not preferable to add a large amount of a compound that accelerates the polymerization. It should be noted that, in the present invention, it is not denied that the polymerization of the functional compound itself occurs as in the case of grafting, and the polymerization may occur to some extent.

Ultraviolet rays and electron beams are particularly preferable as the energy rays.
However, energy rays such as visible light having a relatively short wavelength, X-rays and γ-rays can also be used. As the ultraviolet ray source, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a xenon lamp, a metal halide lamp or the like can be used. Further, as the photosensitizer, an organic carbonyl compound,
Organic sulfur compounds, dyes, azo compounds, peroxide compounds, and other photosensitizers can be used, and two or more of them may be used in combination. Specific photosensitizers include, for example, benzophenone, methyl O-benzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin (n- Butyl) ether, benzoin isobutyl ether, 2-hydroxy-2-methylpropiophenone, 2-methylthioxanthone (2-
Methyl-9H-thioxanthene) -9-one, dibenzosuberone, benzoyl peroxide and the like are included, but are not particularly limited thereto.

In the present invention, the bilayer layer of the bilayer glass is made of a polyurethane-based thermoplastic resin that is softer than the hard substrate. This bilayer layer needs to be transparent to translucent, but the sheet or film that is the material itself is opaque that eventually becomes transparent to translucent (for example, having fine irregularities on the surface. The bilayer layer may be colored or partially opaque. The outermost layer that is the exposed surface of the bilayer layer is a polyurethane-based thermoplastic resin, but the inner layer is not necessarily the same. However, it is preferred that substantially all of the bilayer layers comprise a polyurethane-based thermoplastic resin, even though it may form a particularly thin adhesive layer. When the plastic resin is used for purposes other than the bilayer layer of the bilayer glass, it may be opaque and its shape etc. are limited. Not.

In the present invention, the polyurethane-based thermoplastic resin is a thermoplastic synthetic resin having a large number of urethane groups. In addition to the urethane group, this synthetic resin may have a urea group, an allophanate group, a buret group, and other groups formed by the reaction of an active hydrogen-containing group with an isocyanate group.

Further, it may have an isocyanurate group, a carbodiimide group, or another group derived from an isocyanate group.
Further, in addition to having an ester group, ether group, carbonate group, or other group that the high-molecular-weight polyol itself has, there is also a group having a group derived from a compound such as a chain extender or a cross-linking agent. . The polyurethane-based thermoplastic resin is basically a linear polymer obtained by reacting a high molecular weight diol, a chain extender, and an isocyanate compound. However, small amounts of branching may be present, for example, trifunctional or higher functional polyols, cross-linking agents, or polyisocyanates in combination with the above difunctional compounds resulting in the majority having small amounts of branching. It may be a polymer. In addition to the three main raw materials for high molecular weight diols, chain extenders, and isocyanate compounds,
If necessary, various auxiliary materials can be used to obtain a polyurethane-based thermoplastic resin. A catalyst is usually required as an auxiliary material. Depending on other purposes, cross-linking agents, colorants, stabilizers,
Ultraviolet absorbers, flame retardants, and other additives can be used as auxiliary materials.

As the high molecular weight diol, polyester diol, polyether diol, polyether ester diol, polycarbonate diol and other high molecular weight diols can be used, and particularly polyester diol obtained from dihydric alcohol and divalent carboxylic acid compound, or cyclic ester compound Is preferably a polyester diol obtained by ring-opening polymerization of poly (1,4-butylene adipate), poly (ethylene adipate), poly (1,4)
3-butylene azelate), poly (ε-caprolactone), and the like can be used. Also, water, dihydric alcohol,
It is rare that a polyether diol or a polycarbonate diol obtained by adding an epoxide such as an alkylene oxide or another cyclic ether having 4 or more membered rings to a dihydric phenol or other initiator is preferable. These high molecular weight diols are suitably low melting point compounds which can be liquid at room temperature or liquid at the time of reaction, and the molecular weight thereof is not particularly limited, but 600 to 8,000,
It is particularly preferably 800 to 4000. Chain extenders are divalent compounds of relatively low molecular weight, such as diols,
It is a compound having two diamines, a divalent alkanolamine, and other hydroxyl groups and amino groups. Its molecular weight is
Although not particularly limited, 300 or less, particularly 15
It is preferably 0 or less. As the diol, dihydric alcohol, polyester diol, polyether diol and the like can be used, and dihydric alcohol having 2 to 6 carbon atoms is particularly preferable. As the diamine, aliphatic, alicyclic, aromatic and other diamines can be used. As the alkanolamine, a divalent alkanolamine such as N-alkyldiethanolamine can be used. these,
In the combination of the high molecular weight diol and the chain extender, another divalent compound, for example, a diol having a molecular weight intermediate between the two can be used in combination. Of course, the high molecular weight diol and the chain extender can be used in combination of two or more kinds of compounds.

As the diisocyanate compound, aliphatic, alicyclic, aromatic and other diisocyanates and modified products thereof can be used, and it is also possible to use two or more of them in combination.
Since the isocyanate group directly bonded to the aromatic nucleus may cause yellowing of the obtained polyurethane, a diisocyanate having no such isocyanate group, which is usually called a non-yellowing type, is preferable. For example, hexamethylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and modified diisocyanates obtained by modifying them with various compounds and treatments are preferable diisocyanates.

The polyurethane-based thermoplastic resin is produced by using the above-mentioned raw materials by various methods such as a one-shot method, a prepolymer method, a quasi-prepolymer method and the like. It is of course possible to directly form a sheet or film by these methods, and also to form a sheet or film from the obtained polyurethane solution or powder to granular polyurethane. For example, a sheet or film can be formed by a casting method, an extrusion molding method, an injection molding method, a pressing method, or another method. In particular, it is preferable to extrude particles of a polyurethane-based thermoplastic resin obtained by various methods to produce a sheet or film, and to produce a bilayer glass using the sheet or film. In addition, in the present invention, a sheet refers to a sheet having a thickness of 0.2 mm or more, and a film refers to a sheet having a thickness of less than that.

In the present invention, the exposed surface of the bilayer layer of the bilayer glass is a single layer or a multi-layer structure having a polyurethane-based thermoplastic resin. The bilayer layer may be formed by directly casting the raw material of the polyurethane-based thermoplastic resin on the hard substrate surface as described above, but is preferably produced by a lamination method. The sheet or film for forming the bilayer layer used in the laminating method may have a multilayer structure. The surface side that is the exposed surface of the sheet or film of the multilayer structure is a polyurethane-based thermoplastic resin, but the other surface side is not necessarily limited thereto. When this multilayer structure is laminated with a hard substrate, the side in contact with the hard substrate must be firmly bonded to the hard substrate. Further, a sheet or film having a one-layer or multi-layer structure can be laminated by thermocompression bonding with a hard substrate via a second sheet or film. In this case, the entire bilayer layer is, of course, adjacent to the structural substrate. The layers also need to be tightly bonded. Further, the hard substrate and the bilayer layer, or adjacent layers of the bilayer layer may be bonded with an adhesive. In the present invention, the bilayer layer is preferably composed of only one layer of polyurethane-based thermoplastic resin or a multilayer of two types of polyurethane-based thermoplastic resin. Further, as the laminating method, a method of directly thermocompressing the hard substrate and the polyurethane-based thermoplastic resin is preferable. The total thickness of the bilayer layer is not particularly limited, but is preferably 0.2 mm or more, particularly 0.4 to 10 mm.

In the present invention, the hard substrate is a sheet material that is harder than the polyurethane-based thermoplastic resin, such as an inorganic glass sheet, polycarbonate, polymethylmethacrylate, or another organic glass sheet. These hard substrates may have a single-layer structure or a multilayer structure as described above. In the case of a multilayer structure, the surface to which the bilayer layer is bonded by thermocompression bonding and the surface of the outermost exposed layer are made of a hard material, but the two hard materials are made of a soft material such as butyral resin. Good. In the case of a glass sheet, it may be reinforced by air cooling strengthening or chemical strengthening. The glass sheet may be colored or may have a thin layer such as a heat ray reflective film. The organic glass sheet may be subjected to a treatment such as a stretching treatment, and may have a thin layer such as a hard coat layer.
The organic glass sheet may be colored or patterned, and may have a partially opaque portion. These hard substrates are preferably transparent to translucent as a whole, and particularly preferably have excellent optical characteristics. The thickness is 0.5 mm for the hard substrate layer as a whole
Above all, about 1 to 50 mm is particularly preferable. The hard substrate may be formed into various shapes used for a front window or a rear window of an automobile as well as a flat plate. Further, depending on the purpose, a lens such as a lens having a non-uniform thickness may be used. A particularly preferred rigid substrate is a transparent or colored transparent glass sheet having a one-layer or multi-layer structure.

In the present invention, the modification of the surface portion of the polyurethane-based thermoplastic resin in the production of the bilayer glass may be carried out after the production of the bilayer glass, but preferably the surface of the sheet or film having the surface of the polyurethane-based thermoplastic resin. A bilayer glass is manufactured by modifying a portion and then laminating it with a hard substrate. The most preferable lamination method is a thermocompression bonding method, but an adhesive or the like may be used for lamination. In the thermocompression bonding method, the surface-modified sheet or film and the hard substrate are stacked with the surface-modified surface as the outside, and the surface-modified surface is further stacked with a mold material having a smooth surface to form a laminated assembly. Is performed by heating and pressurizing. This thermocompression bonding can be carried out in one step, but preferably it is carried out in a multi-step method in which pre-compression bonding and then main compression bonding are carried out. Pre-compression bonding is performed by placing the laminated assembly in a rubber pre-compression bonding bag and degassing the inside, and main compression bonding is performed by heating and pressing the pre-compression bonding body in an autoclave. As such a thermocompression bonding method, various thermocompression bonding methods conventionally known as the production of laminated safety glass having an interlayer film between two glass sheets can be used as they are. Usually, the mold material is removed at the end to obtain bilayer glass. The mold material is preferably a glass sheet that has been subjected to a mold release treatment, but is not limited to this, and may be made of rubber, plastic, metal, or other material.

The preliminarily modified surface portion obtained according to the present invention, if it has carboxylic acid groups, γ-glycidoxytrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, a method of reacting a compound having a functional group capable of binding to other carboxylic acid groups and a moisture-crosslinkable group such as an alkoxysilyl group and then moisture-crosslinking, glycidyl cinnamate, glycidyl methacrylate, A compound having a group capable of binding to another carboxylic acid group and a photocrosslinkable group, a compound having a functional group capable of binding to another carboxylic acid group and a compound having a crosslinkable group are reacted, and then the crosslinkable group is crosslinked. The surface having the desired cross-linking can be obtained. A surface having a moisture-crosslinkable group can be moisture-crosslinked as it is to obtain a target surface.

The present invention is particularly suitable as a method for modifying the surface of a polyurethane-based thermoplastic resin for bilayer glass, but is not limited to this. For example, the application of the polyurethane-based thermoplastic resin requiring optical properties, for example, a lens It is also suitable as a surface modification method for, for example, laminated lenses.

The present invention will be described below with reference to examples and the like, but the present invention is not limited to these examples.

Reference Example [Production Example of Polyurethane Thermoplastic Resin] (a) 15000 g of poly (ethylene adipate) diol having a hydroxyl value of 56.7 is stirred and degassed at 110 ° C. under a vacuum of 3 mmHg.
Dehydrated. To this, 8007 g of 4,4′-methylenebis (cyclohexyl isocyanate) and 1.5 g of dibutyltin dilaurate were added, and the mixture was reacted at 80 ° C. for 20 minutes under a nitrogen stream. The reaction mixture is then added to 1,4 butanediol.
1993.5 g was added and immediately mixed with stirring. An exotherm was observed with the start of the reaction, and a substantially homogeneous mixture was obtained.
The liquid reaction mixture was charged to a fluororesin-coated drying vessel and placed in a nitrogen purged oven at 130 ° C. for 15 hours until the reaction was essentially complete. The produced polymer was cooled to room temperature and pulverized by a pulverizer to be granulated. This was formed into a sheet by an extruder at a cylinder maximum temperature of 180 ° C. by a usual method to form a glassy transparent sheet having a thickness of 0.6 mm.

(b) 7500 g of poly (1,6-hexane carbonate) diol having a hydroxyl value of 51.8, 7000 g of poly (butylene adipate) diol having a hydroxyl value of 54.4, 4,4 ′
-Methylenebis (cyclohexyl isocyanate) 79
59 g, dibutyltin dilaurate 1.5 g, 1,4-
A glassy transparent sheet having a thickness of 0.5 mm was produced in the same manner as in Reference Example (a) using 2041.5 g of butanediol as a raw material.

In the following (c) to (h), a urethane thermoplastic resin sheet was prepared by the same method.

(c) Copolymerized ester of polycaprolactone and polybutylene adipate (hydroxyl value 55) 1500 g 4,4'-methylenebis (cyclohexyl isocyanate) 969 g 1,4 butanediol 259 g dibutyltin dilaurate 0.2 g or more thick I made a 0.6mm thick sheet.

(d) Copolymer ester of polycaprolactone and polybutylene adipate (hydroxyl value 55) 1500g 4,4'-methylenebis (cyclohexyl isocyanate) 1035g ethylene glycol 193g dibutyltin dilaurate 0.6mm thick sheet with the above composition Made.

(e) Adipic acid ethylene glycol, diethylene glycol, 1,4 butanediol mixed ester diol (hydroxyl value 49) 1500 g 4,4'-methylenebis (cyclohexyl isocyanate) 834 g ethylene glycol 129 g trimethylolpropane 38 g dibutyltin A sheet with a thickness of 0.5 mm was made from the composition of dilaurate of 0.15 g or more.

(f) Polypropylene glycol (hydroxyl value 56) 750 g Polycaprolactone diol (hydroxyl value 56) 750 g 4,4'-methylenebis (cyclohexyl isocyanate) 1169 g 1,4 butanediol 332 g Dibutyltin dilaurate 0.18 g Thickness from the above composition I made a 0.6mm sheet.

(g) Poly (1,6-hexanediol carbonate ester) diol (hydroxyl value 56) 1500g 4,4'-methylenebis (cyclohexyl isocyanate) 800g 1,4 butanediol 200g dibutyltin dilaurate 0.15g or more A sheet having a thickness of 0.5 mm was made from the above composition.

(h) Polyhexylene adipate diol (hydroxyl value 44) 1500 g 4,4'-methylene bis (cyclohexyl isocyanate) 789 g 1,4 butane diol 211 g Dibutyltin dilaurate 0.15 g A 0.6 mm thick sheet is made from the above composition. It was

Example 1 A 0.6 mm thick sheet obtained by Reference Example (a)
It was placed between glass plates having a size of 30 cm and introduced into a suitable autoclave. At this time, one glass surface in contact with the film was uniformly coated with polydimethylsiloxane in advance and heat-treated at 350 ° C., and the other glass surface in contact with γ-glycidoxy Propyltrimethoxysilane was evenly applied. The autoclave is initially evacuated to remove the air between the glass and the sheet and subsequently heated to 120 ° C. in vacuum for preliminary crimping. After opening the autoclave at 150 ℃, 13kg /
A bilayer, which is a glass-plastic two-layer laminate, was prepared by keeping the film under the condition of cm ² for about 30 minutes to completely bond the glass and the film, and then removing one of the glasses. This bilayer was immersed in a solution of 1432 g of γ-methacryloyloxypropyltrimethoxysilane, 68 g of benzophenone, and 3000 g of ethanol and then pulled up, and then air-dried in air. This bilayer is 30
Using an air-cooled high-pressure mercury lamp of w / cm and 1000 w, light irradiation was performed while moving at a distance of 7 cm under a nitrogen stream at 1 m / min. Next, this bilayer was immersed in warm water at 50 ° C. for 3 hours and then left in the air for one day. The surface performance of this bilayer is shown in Table 1.

Example 2 A solution of 1432 g of γ-methacryloyloxypropyltrimethoxysilane, 68 g of benzophenone and 3000 g of ethanol was sprayed with an air gun on one surface of the sheet of Reference Example (a), and then dried. This sheet was irradiated with light from the side where it was sprayed under the same irradiation conditions as in Example 1. Next, Example 1 was laminated such that the treated surface of this sheet was in contact with the polydimethylsiloxane-treated glass surface and the non-treated surface of the sheet was in contact with the γ-glycidoxypropyltrimethoxysilane-treated glass surface. I made a bilayer in the same way. Next, this bilayer was immersed in warm water at 50 ° C. for 3 hours, and then left in the air for one day.
The surface performance of this bilayer is shown in Table 1.

Example 3 A solution of 518 g of acrylic acid, 77 g of benzophenone and 3000 g of ethanol was sprayed with an air gun on one side of the sheet of Reference Example (a), and then dried. This sheet was irradiated with light from the side where it was sprayed under the same irradiation conditions as in Example 1. Next, the treated surface was sprayed with a solution of 450 g of γ-glycidoxypropyltrimethylsilane, 10 g of N, N-dimethylaniline and 1100 g of ethanol, and then stored in a nitrogen purge furnace at 120 ° C for 20 minutes. Next, the sheet was laminated so that the treated surface of this sheet was in contact with the glass surface treated with polydimethylsiloxane and the untreated surface of the sheet was in contact with the glass surface treated with γ-glycidoxypropyltrimethoxysilane. Made a bilayer by the method. Next, the bilayer was immersed in warm water at 50 ° C. for 3 hours, and then left in the air for one day. The surface performance of this bilayer is shown in Table 1.

Examples 4 to 10 By using the sheets of Reference Examples (b) to (h), a bilayer was formed in the same manner as in Example 1 and a series of treatments were performed.
The surface performance of these bilayers is shown in Table 1.

Examples 11 to 17 Using the sheets of Reference Examples (b) to (h), pretreatment, bilayering, and posttreatment were performed in the same manner as in Example 2. The surface performance of these bilayers is shown in Table 1.

Examples 18 to 24 By using the sheets of Reference Examples (b) to (h), a bilayer was prepared in the same manner as in Example 3, and pretreatment, bilayer formation, and posttreatment were performed. The surface performance of these bilayers is shown in Table 1.

Example 25 On one surface of each of the sheets obtained in Reference Examples (b) to (h), γ-
Methacryloyloxypropylsilane 1288 g, acrylic acid 52 g, benzophenone 77 g, ethanol 3000
The solution consisting of g was sprayed with an air gun and then air dried.
This sheet was irradiated with light from the side where it was sprayed under the same irradiation conditions as in Example 1. Next, the processed surface of this sheet
Example 1 was laminated on a polydimethylsiloxane-treated glass surface so that the untreated surface of the sheet was in contact with the γ-glycidoxypropyltrimethoxysilane-treated glass surface.
I made a bilayer in the same way. Next, this bilayer is immersed in warm water at 50 ° C for 3 hours, and then 1
I left it in the air day and night. The resulting bilayer had anti-fogging properties. The surface performance of this bilayer is shown in Table 1.

Comparative Example 1 In Example (1). The test was carried out using the bilayer as it was before being immersed in the ethanol solution. The performance is shown in Table 1.

Comparative Example 2 The 0.5 mm thick sheet obtained in Reference Example (b) was thermocompression bonded in the same manner as in Example 1 to form a 30 × 30 cm bilayer. This bilayer is benzophenone 7
It was immersed in a solution of 7 g and 300 g of ethanol, then pulled up, and then air-dried in air. This bilayer was irradiated with light under the same conditions as in Example 1. Next, this bilayer was immersed in warm water of 50 ° C. for 3 hours and then left in the air for one day. The surface performance of this bilayer is shown in Table 1.

Reference Example [Penetration resistance test of bilayer body] The penetration resistance test described in JIS R 3312 was carried out for each bilayer of Examples 1 to 25. In each case, the steel balls did not penetrate and the broken glass adhered to the sheet, and the glass was not scattered.

In addition, the surface performance of the bilayer of each example is as follows.
Shown in the table.

Light transmittance: According to JIS R3212.

Taber abrasion: 〃 (Increase in haze after 100 times) Rubbing test: Ethanol / methanol = 10/1 Rubbing 500 times at a pressure of 330 g / cm ^{2 in} the presence of a solvent.

Claims (1)

[Claims] 1. A transparent or translucent laminated safety glass having at least a two-layer structure, wherein one exposed surface is a surface of a polyurethane-based thermoplastic resin and the other exposed surface is a surface of a hard substrate by a laminating method or the like. A function having one polymerizable unsaturated group and at least one carboxylic acid group or moisture-crosslinkable group on the exposed surface or the surface of the polyurethane-based thermoplastic resin to be the exposed surface at any stage of production. Of a polyurethane-based thermoplastic resin in a laminated safety glass, characterized in that the functional compound is grafted onto the polyurethane-based thermoplastic resin on the surface or inside thereof by contacting with or impregnating a functional compound with energy rays. Reforming method.