JPS642057B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a lightweight transparent material, and more particularly to a method for manufacturing a lightweight transparent material made of a composite material of glass and polyurethane resin.

Conventionally, it has been known to use polyurethane resin as an intermediate layer of laminated safety glass used for automobile windshields and the like. For example, special public service in 1977-
Publication No. 9582 describes a high molecular weight ( 2 linear polyurethane polyurea films with a molecular weight of 10,000 or more)
Either by inserting the polyurethane polyurea solution between two glass sheets, or by applying the polyurethane polyurea solution on the glass sheet and physically drying it to form a film, heating (100-200°C),
It is described that the film is melted under pressure (5-20 bar) and combined with glass to produce composite glass. However, with this method, sufficient glass adhesion strength cannot be obtained unless the linear polymer is produced using a special reaction component (dihydroxycarboxylic acid), so the physical properties of the polyurethane polyurea are limited. Although it is possible to manufacture laminated glass with an intermediate layer of a certain thickness, which requires melting and bonding under heat and pressure, it cannot be applied to the manufacture of composite materials with complex shapes and different thicknesses, etc. There is.

The inventors of the present invention have arrived at the present invention as a result of intensive studies on a method for manufacturing a lightweight transparent material that does not have the above-mentioned drawbacks. That is, the present invention injects and fills a room temperature curing or thermosetting non-yellowing urethane resin stock solution into the gap between two thin glass plates with a thickness of 2 mm or less that are juxtaposed with an interval of no more than 20 mm, and then This is a method for producing a lightweight transparent material consisting of a urethane resin layer and a thin glass plate surface layer, which is characterized by reacting with and curing the material.

In the glass thin plate used in the present invention, the glass (material) is not particularly limited, and various oxide glasses (manufactured by cooling a melt of metal oxides such as silicon, sodium, potassium, lead, etc.)
can be used. Examples include silicate glasses such as silicate glass, alkali silicate glass, soda lime glass, potash lime glass, lead (alkali) glass, barium glass, and borosilicate glass. Preferred is soda-lime glass, especially that commonly used for safety glass such as automobile windshields (tempered glass). The thickness of the thin glass plate used in the present invention is 2 mm or less, preferably 0.1 to 2 mm.
It is 1.0mm. If the thickness exceeds 2 mm, the resulting transparent material becomes heavy and the goal of weight reduction cannot be achieved, and the reaction heat of the urethane resin stock solution causes a temperature difference between the inner and outer surfaces of the thin glass plate, causing distortion inside the glass. This results in disadvantages such as an increased tendency to occur. The shape of the thin glass plate is not particularly limited and may be planar, curved, or spherical.

The distance between the two juxtaposed thin glass plates is 20 mm or less, preferably 10 mm or less. If it exceeds 20 mm, the overall thickness of the transparent material becomes too large to be practical. This spacing may be the same or different at each location as long as it does not exceed 20 mm. In addition, it is preferable that this interval (if not the same at each position, the average interval) is 0.5 mm or more, especially 1.0 mm or more; if it is narrower than 0.5 mm, the proportion of the urethane resin layer will decrease, so that the purpose of weight reduction cannot be achieved. Moreover, it becomes difficult to uniformly inject and fill the urethane resin stock solution.

The weight ratio of the urethane resin intermediate layer to the thin glass plate surface layer is usually 100:1 to 1:20, preferably 50:1 to
It was 1:10.

The urethane resin stock solution used in the present invention contains a non-yellowing polyisocyanate and a polyfunctional active hydrogen-containing compound as main components, is liquid at the time of casting, and is then solidified by reaction.

Examples of non-yellowing polyisocyanates include aliphatic polyisocyanates (polyisocyanates in which all NCO groups are bonded to non-aromatic carbon atoms), such as carbon numbers (excluding carbons in NCO groups).
2-12 aliphatic polyisocyanates, carbon number 4-
15 alicyclic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 12 carbon atoms, and modified products of these polyisocyanates (carbodiimide groups,
uretdione group, uretimine group or isocyanurate group, modified products containing them, etc.) can be used. Such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI),
Dodecamethylene diisocyanate, 1,6,11-
Undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-
2,6-diisocyanate hexanoate; isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanate ethyl) 4-cyclohexene-1 , 2-dicarboxylate; xylylene diisocyanate, diethylbenzene diisocyanate; water-modified products of HDI, trimerized products of IPDI, etc.;
and mixtures of two or more thereof.
Preferred among these are HDI, IPDI and hydrogenated MDI.

As the polyfunctional active hydrogen-containing compound, compounds having two or more active hydrogen-containing groups (hydroxyl group, amino group, etc.) such as polyols, polyamines, amino alcohols, and mixtures of two or more thereof can be used. Here, as polyols,
Low molecular polyols (difunctional polyols such as ethylene glycol, propylene glycol, 1,4-butanediol; trifunctional or higher functional polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc.) High molecular polyols (OH value, Usually 20-700)
For example, polyether polyols [the above-mentioned low molecular polyols or/and amines (alkanolamines such as triethanolamine, N-methyldiethanolamine, aliphatic polyamines such as ethylenediamine, diethylenetriamine, aromatic diamines such as tolylenediamine, diphenylmethanediamine, etc.)] Alkylene oxide [alkylene oxide having 2 to 4 carbon atoms, e.g., one or more of ethylene oxide, propylene oxide, butylene oxide, etc. (random and/or block)] adducts, ring-opening polymers of alkylene oxide, etc. (opening of tetrahydrofuran) polyester polyols [polycarboxylic acids (aliphatic polycarboxylic acids such as adipic acid, maleic acid, dimerized linoleic acid, aromatic polycarboxylic acids such as phthalic acid, etc.) Polyester polyols, lactone polyesters, etc. whose terminals are hydroxyl groups with low-molecular polyols or polyether polyols],
Examples include polybutadiene polyol and acrylic polyol. As polyamines,
Aliphatic (aliphatic, cycloaliphatic or araliphatic) polyamines, preferably having a molecular weight of 60 to 300, such as ethylene diamine, tetramethylene diamine, hexamethylene diamine; 4,4'-diaminocyclohexylmethane, 1,4- Diaminocyclohexane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, isophoronediamine,
Hydrogenated products of the following aromatic polyamines; such as xylylene diamine; and aromatic polyamines such as 4,4'-methylenebisaniline, 4,4'-methylenebis(2-chloroaniline), 2,3,2',
3'-tetrachloro-4,4'-diaminodiphenylmethane, 1,2-bis(3-chloro-4-aminophenylthio)ethane, 1,3-bis(4-aminobenzoyloxy)propane, 3 , 5-diamino-4-chloroisobutylbenzoate and the like. Preferred are aliphatic polyamines, particularly 4,4'-diaminodicyclohexylmethane and isophorone diamine. Examples of amino alcohols include mono- or di-ethanolamine, propanolamine, and the like. Among these compounds having two or more active hydrogen groups, polyether polyols are preferred, and polypropylene ether polyols (propylene oxide adducts and alkylene oxide coadducts mainly composed of propylene oxide) are particularly preferred. .

Two or more active hydrogen-containing compounds may be used in combination. For example, one or more polymer polyols (preferably polyether polyols) (OH
It is possible to use a combination of compounds having different values, a combination of polyether and polyester, etc.) and a low-molecular active hydrogen-containing compound (such as a low-molecular polyol and/or polyamine). In this case, the ratio of the two can be varied depending on the molecular weight and required physical properties, but generally the low-molecular active hydrogen-containing compound is less than 30% (equivalent) of the total of both, especially less than 20% (polyamine). 20% or less, especially 10% or less).

The equivalent weight (molecular weight per active hydrogen atom content) of the polymer polyol (polyether polyol) used and the active hydrogen-containing compound as a whole (molecular weight per active hydrogen atom content) and the average number of functional groups can be changed depending on the required physical properties.
Generally, the equivalent weight is preferably 29 to 1000, particularly preferably 40 to 100, and the average number of functional groups is preferably 2 to 6, particularly 2.1 to 4.0.

Furthermore, by using a polyol having a valence of 3 or higher as at least a part of the polyol (polymer and/or low molecule), a polyurethane having excellent water resistance, boiling resistance, solvent resistance, hardness, and other physical properties can be obtained.

In the present invention, when a urethane resin stock solution containing a non-yellowing polyisocyanate and a polyfunctional active hydrogen-containing compound as main components is used for gap filling, any method may be used.

The polyisocyanate may be used as is (one-shot method), or it may be reacted with a portion of the active hydrogen-containing compound (high molecular polyol and/or low molecular polyol) in advance.
It may also be used as an NCO-containing urethane prepolymer (complete prepolymer or quasi prepolymer) (prepolymer method). When producing NCO-containing prepolymers, the NCO/OH ratio is usually 100/1.
~1.1/1 preferably 15/1 ~ 1.5/1, and the viscosity of the prepolymer (at 20°C) is particularly 10,000 cps or less.
It is preferably 5000 cps or less, and the NCO content is preferably 2 to 40%, particularly 5 to 25%. In addition, a part of the polyisocyanate is reacted with an active hydrogen-containing compound to synthesize a terminal active hydrogen prepolymer, which is then reacted (with another active hydrogen-containing compound if necessary) with the polyisocyanate or the NCO-containing prepolymer. You can also do so. The viscosity (at 20° C.) of the active hydrogen component (active hydrogen-containing compound or/and active hydrogen-containing prepolymer) used for mixing and filling with the isocyanate component (polyisocyanate or NCO-containing prepolymer) is preferably 10,000 cps or less, particularly 5,000 cps or less.

The mixing ratio of the isocyanate component and the active hydrogen component is usually 1.5/NCO/active hydrogen-containing group equivalent ratio.
1 to 0.8/1, preferably 1.3/1 to 1/1.
In addition, the proportion of NCO is higher than the above [isocyanate index 150-300 or higher (e.g.
1000)] can also be used to form polyisocyanurate resins. (In this case, an isocyanate trimerization catalyst such as a metal salt such as potassium acetate, sodium acetate, or potassium naphthenate, or an amine such as trisdimethylamino or propylhexahydro-S triazine is used.) As the urethane resin stock solution, the above-mentioned is used. A so-called two-component type in which an isocyanate component and an active hydrogen component are stirred and mixed and then injected is preferred, but other types can also be used. For example, masking agents [oxime compounds, lactams,
Inject a stirred mixture (mixture or reaction product) of an active hydrogen component and an active hydrogen component blocked with active methylene compounds, phenols, etc.; for example, acetoxime, ε-caprolactam, malonic acid dialkyl ester, monomethylaniline, phenol, etc. A method in which polymerizable double bonds are introduced into at least a part of the urethane resin stock solution (for example, maleic acid, itaconic acid as at least a part of the raw material carboxylic acid) Polyester polyols produced using unsaturated dicarboxylic acids such as polyethers, polyethers produced using double bond-containing oxides such as allyl glycidyl ether as at least a part of the raw material alkylene oxide, or polyesters produced by reacting these with polyisocyanates. (NCO or active hydrogen-containing prepolymer)], double bonds in the liquid during injection filling are sensitized by a photosensitizer (e.g. benzophenone, benzoin ethyl ether, benzoin isobutyl ether, benzyl, benzoyl peroxide, etc.).
Examples include a method of curing with ultraviolet rays in the presence of.

Furthermore, in the present invention, other components that do not reduce the glass adhesive strength can be optionally added to the urethane resin stock solution, if necessary. Other ingredients include
Plasticizers (dibutyl phthalate, dioctyl phthalate, dioctyl sebacate, etc.), solvents (toluene, xylene, methyl ethyl ketone, ethyl acetate, butyl acetate, etc.), catalysts (lead octylate, dioctyl dilaurate, stannath octoate,
triethylamine, triethylenediamine, etc.)
Examples include dyes and anti-aging agents.

The method of casting and filling the non-yellowing polyurethane resin is not particularly limited, and can be arbitrarily selected such as manual casting, casting using a discharge casting machine, etc. After casting, it is optional to heat the entire body to accelerate curing of the polyurethane resin. Heating temperature is usually 30
-150°C, preferably 40-120°C.

In the present invention, in order to improve the adhesion between the glass thin plate and the non-yellowing type urethane resin, the glass thin plate (inner surface side) is treated with a primer in advance before applying the polyurethane resin. I can do it. As the primer, an organosilicon compound having both a reactive group capable of chemically bonding with an inorganic substance and a reactive group capable of bonding with an organic substance in its molecule, a so-called silane coupling agent, or a solution containing the same as a main component are effective. As the silane coupling agent and its solvent, Japanese Patent Application No. 55-120316 and
Examples include those described in specification No. 120317. The primer may be applied to the glass plate by any method such as application with a brush, dipping, and spraying. When a solution containing a solvent is applied, it is necessary to thoroughly dry the solvent by air drying or heating after application.

According to the present invention, when injecting and filling the non-yellowing urethane resin stock solution into the gap between the thin glass plates, the two thin glass plates are faced in parallel with a predetermined distance (20 mm or less) to form a gap. After placing a holding member (e.g., a rubber plate, urethane elastomer plate, plastic plate, wooden board, etc.) and holding it at a predetermined interval, apply a means to prevent the resin solution from flowing out on the periphery (both sides and bottom) (e.g., vinyl tape). A resin stock solution injection space is formed by sealing with a tape such as, etc., and the stock solution can be injected and filled into the space. In the above, it is also possible to insert a slightly thicker holding member (such as rubber), seal the periphery, and then tighten it from the outside to provide a predetermined spacing. The spacing member (rubber, urethane elastomer, etc.) may be left as is or may be peeled off after the resin intermediate layer is formed. (When peeling, use a mold release agent coated on the surface or a mold releasable material such as Teflon.) The method for manufacturing the lightweight transparent material of the present invention involves heating a conventional polyurethane film (100 to 200°C). And compared to the method of manufacturing composite glass that is melt-bonded under pressure (5 to 20 bars), transparent materials can be manufactured with simple equipment and operations without the need for heating or pressurizing equipment.
The shape and thickness of the urethane resin layer can be changed arbitrarily, the reaction components can be selected arbitrarily, and the urethane resin layer has excellent glass adhesion strength and various physical properties without using special reaction components. This has the advantage of being able to obtain a transparent material having the following characteristics.

The glass adhesion of the transparent material obtained by the present invention and the physical properties of the urethane resin layer can be varied over a wide range by selecting the resin stock solution. For example, when high glass adhesion is required, the content of the isocyanate component can be changed. Hydrogenated as a component
This can be achieved by using MDI, or if a high degree of heat resistance and water resistance is required, by using a polyfunctional isocyanate component or active hydrogen component.

In addition, the transparent material manufactured by the present invention is lighter than conventional materials made only of inorganic glass or laminated glass made of inorganic glass plates with a thickness of 3 mm or more, and moreover, it is made only of conventional organic synthetic resin. It overcomes the disadvantage that its surface is easily damaged compared to other materials, and it is a material that is extremely useful in practical terms because it has excellent physical properties, glass adhesion, light resistance, edge stability, transparency, and energy absorption.

Because it achieves the above effects, this material is lighter than conventional inorganic glass materials and laminated glass, and has the same functionality, so it can be widely applied to windshield glass for vehicles such as automobiles and trains, as well as lightweight lenses. I can do it.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.
The parts described below indicate parts by weight.

Production Example 1 100 parts of polypropylene ether triol with a hydroxyl value of 168 and isophorone diisocyanate are placed in a four-necked flask equipped with a stirring bar and a thermometer.
180 parts of the copolymer were added, and the reaction was carried out at 100° C. for 5 hours under a nitrogen gas stream to obtain Prepolymer A.

Production Example 2 Primer A was obtained by dissolving 1 part of γ-aminopropyltrimethoxydylane in 99 parts of ethanol.

Example 1 Two square glass thin plates with a thickness of 0.2 mm and a side of 10 cm were prepared. Primer A obtained in Production Example 2 was applied thinly and evenly to one side of each using a brush, and air-dried for 30 minutes at room temperature. I let it happen.

Next, as shown in FIGS. 1 and 2, the primer-treated surfaces P ₁ and P ₂ of each glass are set on the inside,
Two thin glass plates 1 and 2 were erected parallel and perpendicularly with a gap of 10 mm, the gap was maintained with a 10 mm wide Teflon plate 3, and both sides and the bottom were sealed with vinyl tape 4.

In a poly beaker with a capacity of 1, 200 parts of the prepolymer obtained in Production Example 1 preheated to 40°C, 71.9 parts of polypropylene ether triol with a hydroxyl value of 673 and 0.1 part of lead octylate preheated to 40°C were charged, and the mixture was heated with a propeller blade. After stirring and mixing thoroughly, 3mm
The mixture was sufficiently degassed using a Hg vacuum line.

The mixed solution 5 was quickly injected through the upper opening 6 of the glass pair, cured at 60°C for 3 hours, and further cured at room temperature for 1 week, forming a glass thin plate layer and urethane resin as shown in FIG. A composite material consisting of layers was obtained.

The remainder of the mixture was poured into a mold preheated to 60°C and cured in the same manner to obtain a test plate with a thickness of 2 mm.
It was subjected to physical property tests.

The obtained composite material had excellent transparency, was lightweight, and had high scratch resistance and impact resistance, and was sufficiently durable for practical use.

The results of physical property tests of the polyurethane resin were as follows.

Hardness (Shore D) 70
(based on JIS K6301) Tensile strength (Kg/ ^cm2 ) 350
(〃) Growth (%) 10
(〃) Specific gravity 1.06

[Brief explanation of drawings]

FIG. 1 is a perspective view, and FIGS. 2 and 3 are side sectional views. In the figure, 1, 2,,, 3 are thin glass plates, 3 is a Teflon plate, 4 is tape, 5 is urethane resin stock solution, 6
indicates an open opening, and indicates a urethane resin layer.

Claims (1)

[Scope of Claims] 1. Inject and fill the gap between two thin glass plates with a thickness of 2 mm or less juxtaposed with a distance of no more than 20 mm, by injecting a room temperature curing or thermosetting non-yellowing urethane resin stock solution, A method for producing a lightweight transparent material consisting of a urethane resin layer and a thin glass plate surface layer, which is characterized by reacting and curing on the spot. 2. The manufacturing method according to claim 1, wherein the urethane resin stock solution is a two-component urethane resin stock solution comprising an aliphatic polyisocyanate or its NCO-containing prepolymer, a polyol, and/or an aliphatic polyamine. 3. The manufacturing method according to claim 2, wherein a polyether polyol is used as at least a part of the polyol. 4 NCO obtained by reacting a prepolymer with a low molecular weight polyol and/or a polyether polyol and an excess of aliphatic polyisocyanate
The method according to claim 2 or 3, wherein the prepolymer has a content of 2% or more. 5. The manufacturing method according to any one of claims 1 to 4, wherein a glass thin plate having a silane coupling agent applied to its inner surface is used. 6 The thickness of the urethane resin layer is 0.5 to 20 mm,
A manufacturing method according to any one of claims 1 to 5. 7 Claims 1 to 1, wherein the weight ratio of the urethane resin layer to the glass thin plate surface layer is 50:1 to 1:10.
The manufacturing method described in any of Item 6.