JPH04301448A - Safety glass made of synthetic resin and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a safety glass made of a synthetic resin with excellent water resistance and moisture resistance without loss of clarity and without generating strain of a transmitted image and to provide a method for preparing thereof by improving adhesiveness between a transparent sheet made of the synthetic resin and an intermediate layer and by preventing the safety glass from peeling phenomenon generated with time. CONSTITUTION:A synthetic resin safety glass is manufactured by bonding a plurality of synthetic resin transparent sheet (A) and (C) consisting of a polycarbonate resin sheet, an acrylic resin sheet, etc., being adjacent each other through a thermoplastic polyurethane intermediate layer (B) consisting of a reaction product of a non-yellowing diisocyanate, a polyether diol and a curing agent. In addition, a method for manufacturing the safety glass made of the synthetic resin consists of heat-pressing of a laminated product of the synthetic resin transparent sheets (A) and (C) and a specified thermoplastic polyurethane intermediate layer (B) by means of a hot press under a condition at a temp. of 100-150 deg.C and a pressure of 5-50kg/cm<2>.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to synthetic resin safety glass having excellent impact resistance and durability, and a method for producing the same.

0002

2. Description of the Related Art In general, safety glass is widely used as glazing materials for public facilities, sports facilities, etc., partitions for bank counters, security doors, and glazing materials for various vehicles. Its structure consists of a plurality of sheets of inorganic glass, or a portion thereof replaced with organic glass, that is, a synthetic resin transparent plate, which are bonded together via a polyvinyl butyral resin sheet as an intermediate layer.

0003

[Problems to be Solved by the Invention] However, such conventional safety glasses do not necessarily have high impact resistance, and further improvements in safety have been desired.

[0004] Therefore, conventionally, safety glass has been developed which consists only of synthetic resin transparent plates instead of inorganic glass. Conventional safety glass made of synthetic resin is used, for example, as a windshield glass for aircraft, and is a product of a reaction between a plurality of transparent plates made of polycarbonate resin that are adjacent to each other, polyisocyanate, and polyester diol. They are joined via an intermediate layer made of thermoplastic polyurethane resin (see, for example, Japanese Patent Publication No. 12520/1983).

However, although such conventional synthetic resin safety glass is highly evaluated in terms of initial safety due to the inherent high impact resistance of the polycarbonate resin used, transparent glass made of polycarbonate resin Since the adhesive force between the plate and the intermediate layer is low, there are problems in that peeling occurs at the interface over time, resulting in devitrification and distortion of the transmitted image, and low water resistance and moisture resistance.

[0006] In order to solve the above-mentioned problems of the prior art, the inventors have made efforts to improve the adhesion between the synthetic resin transparent plate and the intermediate layer, particularly focusing on the constituent components of the intermediate layer and bonding conditions. As a result of repeated research, the adhesion between the synthetic resin transparent plate and the intermediate layer was improved by selecting a specific thermoplastic polyurethane for the intermediate layer and selecting specific temperature and pressure conditions using the hot press method. It was discovered that safety glass made of synthetic resin could be manufactured, and this invention was completed.

The purpose of the present invention is to improve the adhesion between the synthetic resin transparent plate and the intermediate layer, thereby preventing the peeling phenomenon that occurs over time as in the past, thereby preventing devitrification and distortion of the transmitted image. An object of the present invention is to provide a safety glass made of synthetic resin that has excellent water resistance and moisture resistance without causing any damage, and a method for producing the same.

[0008]

[Means for Solving the Problems] In order to achieve the above object, a first aspect of the present invention is to combine a plurality of synthetic resin transparent plates with mutually adjacent transparent plates, non-yellowing diisocyanate and polyester resin. The gist is a synthetic resin safety glass bonded via a thermoplastic polyurethane intermediate layer made of a reaction product of ether diol and a curing agent.

[0009] A second aspect of the present invention is a method for producing the above-mentioned synthetic resin safety glass, in which a plurality of synthetic resin transparent plates are bonded to the mutually adjacent transparent plates, non-yellowing diisocyanate, and polyether. A thermoplastic polyurethane intermediate layer made of a reaction product of a diol and a curing agent is interposed in between, and the laminate is heated to 10% by hot pressing.
The gist is a method for manufacturing safety glass made of synthetic resin, which is characterized by heating and pressurizing at a temperature of 0 to 150°C and a pressure of 5 to 50 kg/cm2.

In the above description, thermoplastic synthetic resin plates such as polycarbonate resin plates and acrylic resin plates are used as the synthetic resin transparent plates constituting the synthetic resin safety glass according to the present invention. These synthetic resin transparent plates are substantially transparent themselves, have smooth surfaces, and are flat as a whole. Note that the practical side of these synthetic resin transparent plates may be subjected to hardness treatment, antifogging treatment, or the like.

The thickness of the synthetic resin transparent plate is not particularly limited, but is usually selected within the range of 1 mm to 30 mm for practical reasons.

[0012] Furthermore, among the plurality of synthetic resin transparent plates constituting the synthetic resin safety glass according to the present invention, the thermoplastic polyurethane intermediate layer that joins the mutually adjacent transparent plates exhibits transparency. , which consists of a reaction product of a non-yellowing diisocyanate, a polyether diol, and a curing agent.

Examples of the non-yellowing diisocyanate include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexane diisocyanate,
Bis(4-isocyanatecyclohexyl)methane, 2
, 2-bis(4-isocyanatecyclohexyl)propane, 1,4-cyclohexyl diisocyanate, 1-
Examples include alicyclic diisocyanate compounds such as methyl-2,4-(or 2,6)-diisocyanate cyclohexane, and mixed aliphatic/alicyclic diisocyanate compounds such as isophorone diisocyanate.

Next, polyether diol is a compound formed by adding monoepoxide or tetrahydrofuran having typically 2 to 4 carbon atoms to two types of initiators, such as polyoxytetrahydrofuran having an oxymethylene group. They are methylene diol, polyoxyalkylene diol having an oxypropylene group or an oxyethylene group and an oxypropylene group, and a polyether diol having these oxyalkylene groups and an oxytetramethylene group.

[0015] Furthermore, the curing agent may be a fatty acid diol such as ethylene glycol, 1,3-propanediol, 1,4-butadiol, or 1,6-hexanediol;
Examples include amino alcohols such as monoethanolamine, and diamines such as 1,2-ethanediamine.

The intermediate layer of the synthetic resin safety glass according to the present invention is a film-like material made of a reaction product of the above-mentioned non-yellowing diisocyanate, polyether diol, and a hardening agent, and the manufacturing method thereof is as follows. There are no particular limitations, but ordinary methods for producing a film-like body of thermoplastic polyurethane resin,
For example, it may be manufactured by extrusion molding or the like.

[0017] The thickness of the intermediate layer is 0.03 mm to 8.0 m.
It is selected within the range of 0.5 mm to 5.0 mm, preferably 0.5 mm to 5.
The range is 0mm.

[0018] Here, if the thickness of the intermediate layer is too thin (less than 0.03 mm), uniform adhesion to the synthetic resin transparent plate will be difficult, and the shock absorption performance and internal stress relaxation performance will decrease, so it is preferable. do not have.

Furthermore, even if the thickness of the intermediate layer is too thick, exceeding 5.0 mm, it is no longer possible to expect an increase in shock absorption performance or internal stress relaxation performance, but rather the weight increases and the amount of material used decreases. This is not desirable because it becomes uneconomical if there are too many.

The thickness of the intermediate layer is appropriately determined within the above range depending on the performance required for the intermediate layer such as adhesive strength and impact strength, and the use of the resulting synthetic resin safety glass. It is something.

Next, the laminated structure and manufacturing method of the synthetic resin safety glass of the present invention will be described.

Referring to FIGS. 1 and 2, first, regarding the laminated structure of synthetic resin safety glass, for example, a thermoplastic polyurethane resin is placed between a polycarbonate resin transparent plate (A) and an acrylic resin transparent plate (C). An integrated structure is formed by heating and pressing through an intermediate layer (B) made of a film-like material.

As shown in FIG. 3, two or more intermediate layers (B) may be used to laminate three or more synthetic resin transparent plates.

[0024] Furthermore, the method for producing safety glass made of synthetic resin according to the present invention includes combining the plurality of synthetic resin transparent plates described above with mutually adjacent transparent plates, a non-yellowing diisocyanate, a polyether diol, and a curing agent. These laminates are heated to 100 to 150°C by hot pressing.
, and heat and pressurize and integrate under conditions of a pressure of 5 to 50 kg/cm2.

[0025]Heating conditions are such that the temperature of the laminate, especially the intermediate layer (B), is 100 to 150°C, preferably 120 to 140°C. here,
If the heating temperature is less than 100°C, the synthetic resin transparent plate (A) (
The adhesion with C) is insufficient, and good impact strength cannot be obtained. Also, if the heating temperature exceeds 150°C, the intermediate layer (
This is not preferable since B) may soften and flow, or in some cases, the synthetic resin transparent plates (A) and (C) themselves may flow. Therefore, it goes without saying that the heating temperature should be kept within a range that does not cause the intermediate layer (B) or the synthetic resin transparent plates (A) and (C) to melt and flow unnecessarily.

[0026] Regarding the pressurizing conditions, the laminate is
50kg/cm2, preferably 10-40kg/cm
2 pressure shall be applied uniformly. Here, if this pressure is less than 5 kg/cm2, the synthetic resin transparent plate (A
) (C) and the intermediate layer (B) become insufficient, air bubbles are generated between the layers, and the see-through performance is significantly reduced, which is not preferable.

Further, if the pressure exceeds 50 kg/cm2, the intermediate layer (B) becomes easy to flow, which is not preferable. Therefore, it goes without saying that in this case as well, the pressure should be kept within a range that does not cause the intermediate layer (B) to melt and flow unnecessarily.

[0028] When heating and pressing the laminate by hot pressing, a metal plated plate or the like having a mirror-like surface, which is slightly larger in size than the laminate material normally used for laminating thermoplastic synthetic resin transparent plates, etc. is used. The laminated materials stacked in the order shown in Figure 1 above are inserted between these metal plated plates, etc., and these are further inserted between the hot plates of a hot press and pressed together, under the above heating and pressing conditions. It is designed to be laminated and integrated.

In this case, a plurality of units of laminated material of synthetic resin safety glass are stacked by sequentially inserting them between a plurality of metal plated plates, etc., and these are inserted between a number of flat heating plates, so that the so-called It is also possible to adopt a method of improving productivity by integrating heating and pressing at once using a multi-stage press method.

[0030]

[Function] According to the synthetic resin safety glass of the present invention, mutually adjacent synthetic resin transparent plates are covered with a specific thermoplastic polyurethane intermediate layer obtained mainly by the reaction of a non-yellowing diisocyanate and a polyether diol. Since the synthetic resin transparent plate and the intermediate layer are bonded through the interlayer, uniform adhesion and high adhesive strength can be obtained, and peeling phenomenon that occurs over time can be prevented. In addition, synthetic resin safety glass does not cause devitrification or distortion of perspective images, and has excellent water resistance and moisture resistance.

The method of the present invention also includes stacking a plurality of synthetic resin transparent plates and a specific thermoplastic polyurethane intermediate layer obtained by a reaction containing the above-mentioned non-yellowing diisocyanate and polyether diol as main components. By heating and pressing these laminates under specific temperature and pressure conditions using a hot press, it is possible to manufacture synthetic resin safety glass with the excellent quality described above very efficiently and reliably. It is something.

[0032]

EXAMPLES Next, examples of the present invention will be described together with comparative examples.

Examples 1 to 4 and Comparative Examples 1 to 6 In these Examples and Comparative Examples, synthetic resin safety glasses shown in FIGS. 1 and 2 were investigated.

First, for each Example and Comparative Example, synthetic resin transparent plates (A) and (C) and an intermediate layer (B) were prepared according to the laminated structure shown in Table 1. The contents of the prepared laminated materials are as follows. In addition,
The dimensions of the laminated materials are 500mm x 1000mm.
And so.

A: Polycarbonate resin transparent plate (manufactured by Tsutsunaka Plastic Industries Co., Ltd., trade name Polycarbonate E)
C100) B1: Intermediate layer Thermoplastic polyurethane containing non-yellowing isocyanate and polyether diol as main reaction components (
This is abbreviated as polyether-based thermoplastic polyurethane) (manufactured by Molton International, trade name Molsen PE193) B2: Intermediate layer Thermoplastic polyurethane whose main reaction components are aromatic diisocyanate and polyester diol (
This is abbreviated as polyester thermoplastic polyurethane) (manufactured by Nippon Miractran Co., Ltd., trade name Miractran E780) C: Acrylic resin transparent plate (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumipex E000) Next, these laminates were , synthetic resin safety glass was manufactured by heating and pressurizing under specific temperature and pressure conditions.

As shown in the table, the heating and pressurizing means used a hot press method for Examples 1 to 4 and Comparative Examples 1 to 4, and an autoclave method for Comparative Examples 5 and 6. The heating and pressurizing conditions are summarized in Table 1.

[0037] In the autoclave method, the laminate was sandwiched between two glass plates larger in size than the laminate material, the inside of the autoclave was evacuated and preheated at 100°C, and then heated and pressurized under the above setting conditions. .

Initial performance evaluation and durability performance evaluation were conducted for each sample of the synthetic resin safety glass thus manufactured. The durability performance of the safety glass was evaluated by conducting a durability acceleration test of the safety glass, that is, a cold/heat test, a moisture resistance test, and a boiling test.

The test method for each performance evaluation item is as follows.

[0040] Initial performance evaluation ■ Check for layer peeling immediately after manufacturing.

■Appearance of safety glass immediately after manufacture.

[0042] Adhesive strength: Measured by the peeling (180°) method, and the measured value (kg/cm2) was recorded.

a interface=polycarbonate resin transparent plate (A
) and intermediate layer (B) adhesive interface b interface = adhesive interface between intermediate layer (B) and acrylic resin transparent plate (C) ■ Impact resistance: Weight 5 g, radius of curvature R of the striking center tip = 3/8 inch When a steel weight is dropped from a height of 2 m perpendicularly onto the surface of the acrylic resin transparent plate (C) side of each synthetic resin safety glass sample, the presence or absence of delamination, the presence or absence of penetration of the weight, and the presence or absence of whitening were determined. Observed.

[0044] Durability performance evaluation ■Cold heat test: After leaving the sample at 70°C for 2 hours,
After being left at -20℃ for 2 hours from ℃ to -20℃, and then exposed to an atmosphere of 2 hours from -20℃ to 70℃ for 10 cycles, the presence or absence of layer delamination and safety glass The appearance was observed.

■Humidity test: sample at 55°C, relative humidity 98
%RH for two weeks, the presence or absence of delamination and the appearance of the safety glass were observed.

[0046] Boiling test: After the sample was left in boiling water for 2 hours, the presence or absence of layer peeling and the appearance of the safety glass were observed.

The results of each performance evaluation are summarized in Table 2.

[0048]

[Table 1]

[0049]

[Table 2]

As is clear from Tables 1 and 2 above, the synthetic resin safety glasses according to Examples 1 to 4 of the present invention showed no delamination immediately after production and an excellent appearance in the initial performance evaluation. Of course, it also has high adhesive strength, and in the impact resistance test, there was no delamination, no penetration through the weight, and no whitening, indicating excellent quality. .

Further, according to the present invention, there was no layer peeling in any of the accelerated tests for evaluating durability performance, and the product had an excellent appearance.

On the other hand, with the synthetic resin safety glasses of Comparative Examples 1 and 2, immediately after manufacture, although no layer peeling was observed, cloudy appearance was observed. In addition, the adhesive strength was low, and although there was no delamination in the impact resistance test, whitening occurred, and in the accelerated test for evaluating durability performance, delamination occurred in all cases, and yellowing was observed in the appearance.

[0053] Regarding Comparative Examples 3 and 4, the synthetic resin transparent plates (A) and (C) and the intermediate layer (B) were not bonded together at the initial stage, resulting in layer peeling and poor appearance. Bubbles were generated, and the product could not be subjected to a durability test.

[0054] In addition, in the synthetic resin safety glass produced by the autoclave method of Comparative Examples 5 and 6, although no layer peeling was observed immediately after manufacture, bubbles were formed in the appearance. Furthermore, the adhesive strength was low, and delamination occurred in the impact resistance test. In addition, in an accelerated test for evaluating durability performance, although no layer peeling occurred, bubbles were observed in the external appearance.

The synthetic resin safety glass according to the present invention can be effectively used, for example, as a glazing material for public facilities and sports facilities, partitions for bank counters, security doors, and glazing materials for various vehicles. .

[0056]

Effects of the Invention As described above, the synthetic resin safety glass of the present invention comprises a plurality of synthetic resin transparent plates, each adjacent transparent plate, a non-yellowing diisocyanate, a polyether diol, and a curing agent. Because it is bonded through a thermoplastic polyurethane intermediate layer made of a reaction product of It has the effect of being able to prevent this phenomenon, not causing devitrification or distortion of a perspective image, and having excellent impact resistance and durability, as well as high water resistance and moisture resistance.

In particular, since a specific thermoplastic polyurethane obtained by a reaction containing non-yellowing diisocyanate and polyether diol as main components is used as the intermediate layer, there is an advantage that discoloration over time is small.

[0058] Furthermore, as described above, the method for producing safety glass made of synthetic resin according to the present invention is obtained by a reaction between a plurality of synthetic resin transparent plates and the above-mentioned non-yellowing diisocyanate and polyether diol as main components. According to the method of the present invention, a specific thermoplastic polyurethane intermediate layer is stacked, and these laminates are heated and pressed using a hot press at a temperature of 100 to 150°C and a pressure of 5 to 50 kg/cm2. This has the effect that synthetic resin safety glass having excellent quality as described above can be manufactured very efficiently and reliably.

[Brief explanation of drawings]

FIG. 1 is an enlarged exploded sectional view of essential parts of a synthetic resin safety glass according to the present invention.

FIG. 2 is an enlarged sectional view of a main part of the synthetic resin safety glass according to the present invention.

[Figure 3] Current state of synthetic resin safety glass according to the present invention
FIG. 3 is an enlarged cross-sectional view of main parts showing two specific examples.

[Explanation of symbols]

A Polycarbonate resin transparent plate B
Intermediate layer C made of polyether thermoplastic polyurethane resin Acrylic resin transparent plate

Claims (3)

[Claims] Claim 1: A plurality of synthetic resin transparent plates are interposed between adjacent transparent plates and a thermoplastic polyurethane intermediate layer made of a reaction product of a non-yellowing diisocyanate, a polyether diol, and a curing agent. Synthetic resin safety glass bonded together. 2. The synthetic resin safety glass according to claim 1, wherein the front synthetic resin transparent plate is a polycarbonate resin plate, and the back synthetic resin transparent plate is an acrylic resin plate. 3. A plurality of synthetic resin transparent plates are interposed between adjacent transparent plates and a thermoplastic polyurethane intermediate layer made of a reaction product of a non-yellowing diisocyanate, a polyether diol, and a curing agent. These laminates are heated to a temperature of 100 to 150°C by hot pressing.
and a method for producing safety glass made of synthetic resin, characterized by heating and pressurizing under conditions of a pressure of 5 to 50 kg/cm2.