JPH07117176A - Composite molded form - Google Patents

Abstract

PURPOSE:To improve resistance to shock and transparency without interposing any bonding layer and contrive the increase of hardness as well as the reduction of weight by a method wherein an inorganic glass plate and/or a high hardness transparent resin plate is bonded to one side or both sides of a special polyurethane resin layer. CONSTITUTION:A polyurethane resin layer is obtained by polymerizing at least one kind of polyisocyanate group, having (m) pieces (m is an integer of 2 or more) of isocyanate groups in one mole, polyol group, having (n) pieces (n is integer of 2 or more) of hydroxyl groups and/or thiol radical in one mole, polyol polythiol group or polythiol group. An inorganic glass sheet and/or high- hardness transparent resin plate are bonded on one side or both sides of the resin layer. The polyurethane resin layer can be obtained by polymerizing the polyisocyanate group and the polythiol group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composite molded body.
This composite molded body is a molded body with excellent transparency and can be used for cars, trains,
Also, it can be used as a glazing material for windows of aircrafts, windows of high-rise buildings, roof and ceiling parts of cultural education facilities and sports facilities. Further, it can be used as a protective wall or soundproof wall for highways, etc., and also as a front protective cover for vending machines and display devices, or as a protective cover for various lighting fixtures and lighting devices.

[0002]

2. Description of the Related Art A glass plate is used as a glazing material and various protective materials because it has excellent properties such as transparency. However, it has drawbacks such as high specific gravity and easy breakage. As a solution to this drawback, there has been proposed a composite material of glass and resin in which a resin plate having a light weight and excellent impact resistance is bonded to the surface of the glass plate via an adhesive layer. For example, a transparent silicone oil or a solvent-diluted wax-like silicon varnish is used as the adhesive layer (JP-A-56-73650), and a thermoplastic resin composition comprising a polyisobutylene resin and a tackifier is used (JP-A-56-76). 57-189846) and those using a thermoplastic resin composition of ethylene-acrylic acid ester copolymer (JP-A-58-28375). But,
In a composite material of a resin plate and a glass plate with such an adhesive layer interposed, there is no risk of whitening or cracks on the adhesive surface of the composite material or inside the resin layer due to deterioration of the adhesive layer due to adhesion of water or the like. Not really. In addition, due to the influence of the properties of the adhesive layer and the layer to be adhered, the adhesion conditions, etc., there are problems such as strict control of the adhesion conditions and a sophisticated and complicated adhesion technique.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composite molded article which is excellent in impact resistance and transparency, has high hardness and is lightweight, without interposing an adhesive layer.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, they have found that a composite molded body in which an inorganic glass plate and / or a high-hardness transparent resin plate are bonded to a polyurethane resin layer solves the problem, and completed the present invention. That is, the present invention provides polyisocyanates having m (m is an integer of 2 or more) isocyanate groups in one molecule, and n (n is an integer of 2 or more) hydroxyl groups in one molecule. And / or one or both surfaces of a polyurethane resin layer obtained by polymerizing a polyol having a thiol group, a polyol polythiols or at least one kind of polythiols, by bonding an inorganic glass plate and / or a high hardness transparent resin plate The present invention relates to a composite molded body comprising a polyurethane resin layer and an inorganic glass plate and / or a high hardness transparent resin plate. Further, in the above-mentioned composite molded body, the urethane resin layer has m in one molecule.
Polyurethane resin obtained by polymerizing polyisocyanates having a ke (m is an integer of 2 or more) isocyanate group and polythiols having n (n is an integer of 2 or more) thiol groups in one molecule The present invention relates to a composite molded body that is a layer.

Further, between the inorganic glass plate or the high-hardness transparent resin plate and the plate material having no bonding ability with the polyurethane resin, there are m (m is an integer of 2 or more) isocyanate groups in one molecule. Polyisocyanates and n in one molecule
Polyurethane obtained by injecting, polymerizing and curing a composition consisting of at least one of polyols having a hydroxyl group and / or thiol group (n is an integer of 2 or more) and / or thiol group, polyol polythiols or polythiols Composite molded body comprising one resin layer and one inorganic glass plate or one layer of high-hardness transparent resin plate, further inorganic glass plate and / or
Or, between two high-hardness transparent resin plates, m molecules (m
Is an integer of 2 or more) and polyisocyanates having an isocyanate group, and n (n is an integer of 2 or more) in one molecule.
Inorganic glass plate and / or high-hardness transparent resin obtained by injecting, polymerizing and curing a composition comprising a polyol having a hydroxyl group and / or a thiol group, at least one of polyol polythiols or polythiols The present invention relates to a composite molded body having one polyurethane resin layer between two layers of plates. Further, the present invention relates to a glazing material and a transparent protective material using these composite molded bodies.

The present invention is described in detail below. In the present invention, the term “join” means that the inorganic glass plate and / or the high-hardness transparent resin plate and the polyurethane resin layer are integrated without an adhesive layer. The polyisocyanates having m (m is an integer of 2 or more) isocyanate groups in one molecule used in the present invention include, for example, hexamethylene diisocyanate, isophorone diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
Diisocyanatocyclohexane, bis (isocyanatomethyl) cyclohexane, diisocyanatomethylcyclohexane, bicycloheptane triisocyanate,
Aliphatic or alicyclic polyisocyanates such as lysine isocyanate-β-isocyanate ethyl ester, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, etc. Polyisocyanates in which an isocyanate group is directly bonded to the aromatic ring of xylylene diisocyanate, mesitylene triisocyanate, bis (α, α-dimethylisocyanatomethyl) benzene, etc. Examples thereof include bound polyisocyanates, adduct reaction products of these polyisocyanates and trimethylolpropane, and isocyanurate compounds. Most of these compounds are commercially available.

As polyols having n (n is an integer of 2 or more) hydroxyl groups in one molecule,
These include: Examples of low molecular weight polyhydric hydroxy compounds include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5. -Pentanediol, 1,6-hexanediol, 1,2-hexane glycol, 1,2-hexylene glycol, 1,10-decanediol, neopentyl glycol, 1,2-cyclohexanediol, 2
-Butene-1,4-diol, 3-cyclohexane-
1,1-dimethanol, 4-methyl-3-cyclohexane-1,1-dimethanol, 3-methylene-1,5-pentanediol, (2-hydroxyethoxy) -1-propanol, 4- (2-hydroxy) Ethoxy) -1-butanol, 5- (2-hydroxypropoxy) -1-pentanol, 1- (2-hydroxypropoxy) -2-
Octanol, 3-acryloyloxy-1,5-pentanediol, 2-acryloyloxymethyl-2-methyl-1,3-pentanediol, [(4,4-pentylyloxy) -methyl] -1,3-propane Diol, 3-
(O-Propenylphenoxy) -1,2-propanediol, 2,2'-diisopropylidene-bis (p-phenyleneoxy) diethanol, glycerin, 1,2,6
-Hexanetriol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 3- (2
-Hydroxyethoxy) -1,2-propanediol,
3- (hydroxypropyl) -1,2-propanediol, pentaerythritol, sorbitol, sucrose, lactose, α-methyl glycoside, α-hydroxyalkyl glycoside, phosphoric acid, benzenephosphoric acid, tripolyphosphoric acid,
Such as tetrapolyphosphoric acid.

Examples of polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, neo. Pentyl glycol, hexamethylene glycol, decamethylene glycol, glycerin,
One or more compounds having at least two hydroxyl groups such as trimethylolpropane, pentaerythritol and sorbitol, and malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid. , Reaction products with one or more compounds having at least two carboxyl groups such as phthalic acid, terephthalic acid, trimellitic acid, and hemimellitic acid, ring-opening polymerization products of cyclic esters such as polycaprolactone, etc. Is.

Examples of the polyether polyols and polytetramethylene ether glycols include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, hexanetriol, diglycerin, pentaerythritol, sorbitol, sucrose and phosphoric acid. Polyols, phenol-aniline-formaldehyde ternary condensation products, aniline-formaldehyde condensation products, ethylenediamine, diethylenetriamine, triethylenetriamine, methylenebisorthochloroaniline, 2,4-diphenylmethanediamine, 4,4'-diphenylmethanediamine, 2,4-
Polyamines such as tolylenediamine and 2,6-tolylenediamine, alkanolamines such as triethanolamine and diethanolamine, and ethylene oxide, propylene oxide, butylene oxide,
A product obtained by adding one or more of tetrahydrofuran, styrene oxide and the like. Further, acrylic polyols, polybutadiene polyols, phenolic polyols, epoxy polyols and the like are included. Of these compounds, lower polyhydric hydroxy compounds are available as reagents, and other polyols are commercially available in many cases and can be easily prepared. Examples of the polyol polythiols having n (n is an integer of 2 or more) hydroxyl group and thiol group in one molecule include esterification products of mercaptopropionic acid and the above polyol, and addition of mercaptopropionic acid and epoxy resin. And the like.
Some of these compounds are commercially available and can be easily prepared.

Examples of the polythiols having n thiol groups (n is an integer of 2 or more) in one molecule include, for example, bis (2-mercaptoethyl) ether, 1,2-ethanedithiol and 1,4-butane. Dithiol, bis (2-mercaptoethyl) sulfide, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 2,2-dimethylpropanediol-bis (2-mercaptoacetate, 2, 2-Dimethylpropanediol-bis (3-mercaptopropionate), trimethylolpropane-
Tris (2-mercaptoacetate), trimethylolpropane-tris (3-mercaptopropionate),
Trimethylolethane-tris (2-mercaptoacetate), trimethylolethane-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2-mercaptoacetate), pentaerythritol-tetrakis (3-mercaptopropionate), Dipentaerythritol-hexakis (2-mercaptoacetate), Dipentaerythritol-hexakis (3
-Mercaptopropionate), 1,2-dimercaptobenzene, 4-methyl-1,2-dimercaptobenzene, 3,6-dichloro-1,2-dimercaptobenzene, 3,4,5,6-tetra Chloro-1,2-dimercaptobenzene, xylylenedithiol, 1,3,5-tris (3-mercaptopropyl) isocyanurate and the like. Most of these compounds are commercially available,
Moreover, it can be easily prepared. These polyols, polyol polythiols or polythiols may be used alone, or a plurality of compounds of the same kind or different kinds may be mixed and used.

Polyisocyanates and polyols,
The mixing of the polyol polythiols or at least one compound of the polythiols with each other is actually preferably performed immediately before the polymerization step from the viewpoint of the pot life of these mixtures. At this time, the polyisocyanates and these polyols, the proportion of the polyol polythiols or polythiols used are NCO and the equivalent ratio of the sum of (OH + SH), that is, NCO / OH, NCO / OH + SH,
Alternatively, the NCO / SH equivalent ratio is preferably in the range of 0.5 to 3.0, more preferably in the range of 0.5 to 1.5.

The inorganic glass plate used in the present invention may be so-called ordinary glass, but tempered glass or the like may be used depending on the application of the present composite molded body. The high-hardness transparent resin plate used in the present invention is a molded plate of the high-hardness transparent resin (Japanese Patent Laid-Open No. 2-84406) that the present inventors have already proposed. The molded plate has the following general formula (1) in one molecule.
Polymerization of a monomer (A) having a functional group represented by (Chemical formula 1) and a functional group represented by the following general formula (2) (Chemical formula 1) or the following formula (3) (Chemical formula 1) Or a cured molded plate, or a monomer (B) having at least one functional group selected from the group consisting of the monomer (A) and an acrylic group, a methacrylic group, and a styryl group. It is a molded plate obtained by copolymerizing and curing.

[0013]

[Chemical 1]

Specific examples of the monomer (A) include N- (3-isopropenyl-α, α-dimethylbenzyl) -2-acryloyloxyethyl carbamate and N- (3-iso). Propenyl-α, α-dimethylbenzyl) -2-methacryloyloxyethyl carbamate, N- (4-isopropenyl-α, α-dimethylbenzyl) -2-acryloyloxyethyl carbamate,
N- (4-isopropenyl-α, α-dimethylbenzyl) -2-methacryloyloxyethyl carbamate,
N- (3-isopropenyl-α, α-dimethylbenzyl) -1-acryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -1-methacryloyloxypropane-2
-Yl carbamate, N- (4-isopropenyl-α,
α-Dimethylbenzyl) -1-acryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -1,3-diacryloyloxypropan-2-ylcarbamate, N- ( Three
-Isopropenyl-α, α-dimethylbenzyl) -1,
3-dimethacryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -1-acryloyloxy-3-methacryloyloxypropan-2-ylcarbamate, N- (4
-Isopropenyl-α, α-dimethylbenzyl) -1,
3-Diacryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -2,2-diacryloyloxymethyl-3-
Acryloyloxypropyl carbamate, N- (4-
Isopropenyl-α, α-dimethylbenzyl) -2,2
-Diacryloyloxymethyl-3-acryloyloxypropyl carbamate and the like, and further, compounds in which the carbamate of these compounds is changed to thiocarbamate.

On the other hand, specific compounds of the monomer (B) include methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
Benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate Acrylate, dipropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tri (Acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, N, N', N - hexakis (acryloyloxyethyl) phosphazene, N, N
′, N-Hexakis (methacryloyloxyethyl)
Examples include phosphazene, styrene, chlorostyrene, bromostyrene, α-methylstyrene, divinylbenzene and the like.

The high-hardness transparent resin plate used in the present invention is obtained by homopolymerizing these monomers (A) or copolymerizing the monomers (A) and (B) with radical initiators. It can be obtained by a thermal polymerization method in the presence of a casting polymerization template. In addition, the ratio of the monomer used in the copolymerization of the monomer (A) and the monomer (B) is such that 1 equivalent of isopropenylphenyl group in the monomer (A) It is preferable that the total amount of the acrylic group, methacrylic group, styryl group and vinylbenzyl group in the body (A) and the monomer (B) is 0.5 to 10 equivalents. Further, the mixture of the monomers before the polymerization includes an ultraviolet absorber, an antioxidant, a near infrared absorber, a coloring inhibitor,
Fluorescent dyes and other reactive compounds may be appropriately added as needed. This high hardness transparent resin plate,
It is a useful resin plate that has excellent surface hardness, rigidity, chemical resistance, heat resistance, and also has impact resistance and weather resistance. The polyurethane resin used in the present invention and the plate material having no bonding ability,
The surface of an inorganic glass plate, a metal plate, an FRP plate, or the like is subjected to a release agent treatment using a silicone-based, varnish-based, or polyvinyl alcohol-based external release agent.

The composite molded article of the present invention comprises two inorganic glass plates and / or high-hardness transparent resin plates to be bonded, or one inorganic glass plate or high-hardness transparent resin plate and a polyurethane resin having no bonding ability. In the space portion of the casting polymerization mold combined at intervals, a mixture of polyisocyanates and polyols, polyol polythiols or polythiols is injected, and the mold is placed in a hot air oven for polymerization. Then, it is obtained by polymerizing under predetermined heating conditions. The heating conditions are not generally determined depending on the composition of the resin, but the heating temperature is 30 to 180 ° C., and the time is several tens of minutes to several days depending on the heating temperature. This polymerization is thermal polymerization,
A urethanization catalyst such as a tertiary amine type, an organometallic type or a quaternary ammonium fluoride is added to the prepared mixture of polyisocyanates and polyols, polyol polythiols or polythiols, and polymerization is carried out. At this time, the catalytic action is dull at around room temperature, and an organotin compound that exerts a strong catalytic action at the time of heat curing, for example, dibutyltin dilaurate, dibutyltin-bis (octylthioglycol ester), dibutyltin-bis (isooctylmercaptoacetate), etc. Select, 0.01
It is preferable to use ˜1.0% by weight. Further, in order to prevent the resin layer of the composite molded article of the present invention from being colored or deteriorated with time, an ultraviolet absorber, an antioxidant, an anti-coloring agent or the like may be added to this mixture in advance. Good. or,
In order to obtain a composite molded product having a colored resin layer, or to impart a heat-shielding effect to the composite molded product, a general dye, a fluorescent dye, or a near-infrared absorber is added to the mixture in advance. May be added as appropriate. The mixture thus prepared is sufficiently defoamed under reduced pressure to prepare for polymerization.

The polyurethane resin layer constituting the composite molded body of the present invention has the effect of imparting impact resistance to the composite molded body, and the thickness of the resin layer is 0.5 mm or more,
It is preferably 0.5 to 10 mm. On the other hand, the inorganic glass plate or the high-hardness transparent resin molded plate originally gives the composite molded body high hardness and rigidity at the same time, and in consideration of the weight reduction effect, the inorganic glass plate Has a thickness of 3.5 mm or less, preferably 0.5 to 3 mm, and in the case of a high-hardness transparent resin molded body that is expected to be more lightweight, the thickness is 5 mm or less, preferably 0.5 to It is 4 mm.

[0019]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The parts in the examples are parts by weight. here,
The evaluation method of this composite molded body will be described. -Evaluation method (1) Appearance: This composite molded body was observed with the naked eye. For polyurethane resin layer, glass plate, high hardness transparent plate, etc.,
The case where no cracks, surface roughening, or peeling was observed was marked (○), and the other cases were marked (x). (2) Impact resistance: This composite molded body is placed horizontally on a wooden frame so that the glass plate (arbitrary surface when both surfaces of the composite molded body are high-hardness transparent plates) face up, and above this, 1.2-2.3
A 225 g steel ball was naturally dropped from the position m (varied depending on the thickness of the plate). If none of the resin layer, the glass plate, the high-hardness transparent plate, etc., was cracked, damaged, or deformed, (○), and if not, (x). (3) Anti-urging property: Using the same four composite moldings, a square closed container (the outside is glass, but if the both surfaces of the composite molding is a high-hardness transparent plate, any surface) is prepared, A container containing water, a heating element (commercially available body warmer), and a thermo-hygrometer were installed in a closed container, and the container was left for 1 hour outdoors with good ventilation. At the end of standing, the presence or absence of bottles on the inner wall of the container was observed. When there is no bottle (○), when there is bottle (×). (4) Soundproofing: In a sealed container of the same type as above, at the center of the container, install a normal sound level meter specified by JIS C1502 method, and then install the container at the center of the room and 1.2m above the floor. It was installed at the height position, and the environmental noise inside the closed container, which was determined by JIS Z 8731 method, was measured. Also, the environmental noise near the closed container was measured. The average noise level (horn) within 1 hour of each measured value was compared.

Example 1 Two glass plates each having a thickness of 3 mm and a 310 mm square ordinary glass plate and a silicone rubber gasket having a thickness of 1.5 mm and a width of 10 mm arranged around one side thereof were prepared. The inner surface (the surface with the gasket) of one of the glass plates was treated with a silicone-based external release agent by a conventional method. Then, the two glass plates were combined so that the surfaces of the gaskets face each other, and then the periphery was fixed with clips to obtain a casting polymerization template. In a mixer equipped with a decompression device, a trimethylolpropane adduct of tolylene diisocyanate, which is a urethane prepolymer (Orestar P-75, manufactured by Mitsui Toatsu Chemicals, Inc.) is used.
Eight parts were charged, and degassing was sufficiently performed under reduced pressure while heating at 30 ° C. Next, 242 parts of polypropylene diol (PPG-Diol 3000, manufactured by Mitsui Toatsu Chemicals, Inc.) was added, and defoaming was performed again under the above conditions while stirring well. Then, 0.04 part of dibutyltin dilaurate was added to this composition, and the mixture was thoroughly stirred again. The polyurethane resin composition thus prepared was immediately poured into the space of the casting polymerization mold, and then placed in a polymerization hot-air stove to
Polymerization was carried out by heating at 0 ° C. for 2 hours. After completion of polymerization, remove the mold and apply 3 mm to only one side of the 3 mm thick polyurethane resin layer.
A composite molded body in which thick glass plates were joined was obtained. Appearance: (○) Impact resistance (fall height 1.8 m):
(○) Bottle-proof (Test environment: Outside the container: Temperature 22 ° C, Humidity 45% Inside: Container temperature 30 ° C, Humidity 53%): (○) Soundproofing: Outside the container 65 horns / Inside the container 57 horns

Example 2 A mold (made of glass) prepared by adjusting one glass plate having a thickness of 1 mm and a size of 300 mm square with a gasket so that the facing distance between the glass plate and the inner surface of the mold was 5 mm. After being placed inside, the periphery was fixed with a clip to obtain a casting polymerization mold.
The inner surface of the mold facing the glass plate was previously treated with a silicone-based external release agent by a conventional method. In a mixer equipped with a decompression device, a urethane prepolymer hexamethylene diisocyanate burette (manufactured by Mitsui Toatsu Chemicals, Inc., Olester NP
-1000) was charged in an amount of 402 parts and sufficiently defoamed under reduced pressure while heating to 30 ° C. Then pentaerythritol-tetrakis (β-mercaptopropionate)
100 parts of the above was stirred and mixed well, and then polypropylene diol (PPG-Diol 3000 manufactured by Mitsui Toatsu Chemicals, Inc.)
Was degassed under the above conditions while stirring well. Then, 0.06 parts of dibutyltin dilaurate was added to this composition, and the mixture was thoroughly stirred again. The composition of the polyurethane resin thus prepared was immediately injected into the space of the casting mold for casting, and then placed in a hot air oven for polymerization for 2 hours at 40 ° C. and further for 1 hour at 60 ° C. Polymerization was performed by heating. After the polymerization is completed, the mold is removed and the length is 5 mm.
A composite molded body was obtained in which a 1 mm thick glass plate was bonded to only one side of the thick polyurethane resin layer. Appearance: (○) Impact resistance (fall height 2.3)
m): (○) Bottle protection (test environment: outside the container: temperature 23 ° C, humidity 47% Inside container: temperature 32 ° C, humidity 55%): (○) Soundproofing: outside the container (70 horns) / inside the container (60 horns)

Example 3 Two glass plates each having a thickness of 3 mm and a 310 mm square ordinary glass plate around which one surface is provided with a silicone rubber gasket having a thickness of 1 mm and a width of 10 mm are prepared. The glass plates of (1) were assembled so that the surfaces of the gaskets were overlapped with each other, and the periphery was fixed with clips to obtain a casting polymerization mold. In a mixer equipped with a reducer, 109 parts of 1,3-xylylene diisocyanate, then 1 part of pentaerythritol-tetrakis (β-mercaptopropionate) was added.
41 parts were charged, and dibutyltin dilaurate was further added to 0.0
Charge 5 parts, with good stirring under cooling below 20 ° C,
Degassing was performed under reduced pressure for 1 hour. The composition of the polyurethane resin thus prepared was immediately injected into the space of the casting mold for casting, and then placed in a hot air oven for polymerization at 40 ° C.
It is heated for 2 hours at 100 ° C and then gradually heated to 100 ° C.
Polymerization was carried out at 0 ° C for 1 hour. After completion of polymerization, remove from the mold and remove 2mm
A composite molded body was obtained in which a glass plate having a thickness of 3 mm was bonded to both surfaces of a thick polyurethane resin layer. Appearance: (○) Impact resistance (fall height 1.5)
m): (○) Bottle protection (test environment: outside of container: temperature 23 ° C, humidity 54% Inside of container: temperature 35 ° C, humidity 62%): (○) Soundproofing: outside of container (68 horn) / inside container (61 horn)

Example 4 Between two mold materials (made of glass) with a thickness of 1 mm and 300 mm
One normal glass plate at the corner and on the side facing the glass plate,
One piece of high-hardness transparent resin plate with a thickness of 2 mm and 300 mm square manufactured by the following method is adjusted with a gasket so that the facing distance is 3 mm, and after inserting it, the mold materials are combined and the periphery is clipped. It was fixed and used as a casting polymerization template. (Production of high-hardness transparent plate) 3-isopropenyl-α, α-
Dibutyltin dilaurate 0.05 part to dimethylbenzyl isocyanate 116 parts and ethylene glycol 12 parts
Parts were added and the reaction was carried out at 40 ° C. for 1 hour. Then, 25 parts of 2-hydroxyethyl methacrylate was added thereto, and the reaction was carried out at 50 ° C. for 2 hours. Then, add 102 parts of pentaerythritol tetraacrylate to this,
Degassing was performed at 50 ° C. under reduced pressure while stirring well. Next, 0.26 parts of t-butylperoxy-2-ethylhexanoate as a radical initiator was added to this reaction mixture, and defoaming was again performed under the above conditions while stirring well. Then, this resin composition was molded into a casting mold made of glass (a different aspect from the above mold. Inner dimension: 2 mm
Immediately after pouring into the space of ( ^t × 305 mm × 305 mm), the mold was placed in a hot air oven and heated from 60 ° C. to 180 ° C. for 2 hours to carry out polymerization. Pencil hardness: 9H, Charpy strength: 2.4kg ・ cm / cm
² Flexural modulus: 465 kg / mm ² , chemical resistance, heat resistance: good Mixer with decompression device, trimethylolpropane adduct of tolylene diisocyanate, a urethane prepolymer (manufactured by Mitsui Toatsu Chemicals, Inc.) , Olester P-75)
158 parts were charged, and the mixture was thoroughly degassed under reduced pressure while heating at 30 ° C. Then, 242 parts of polypropylene diol (PPG-Diol 3000, manufactured by Mitsui Toatsu Chemicals, Inc.) was added, and defoaming was performed again under the above conditions while stirring well.
Then, dibutyltin dilaurate was added to this composition at a concentration of 0.
04 parts was added, and the mixture was stirred well again. The polyurethane resin composition thus prepared was immediately injected into the space of the casting mold for casting, and then placed in a hot air oven for polymerization and heated at 40 ° C. for 2 hours to carry out polymerization. After completion of the polymerization, remove the mold and apply 1 to one side of the 3 mm thick polyurethane resin layer.
A mm-thick glass plate was bonded to the other side of a 2 mm-thick high-hardness transparent resin molding plate to obtain a composite molding. Appearance: (○) Impact resistance (fall height 2.0m):
(○) Bottle protection (test environment: outside the container: temperature 20 ° C, humidity 47% Inside container: temperature 31 ° C, humidity 55%): (○) Soundproofing: 68 horn outside container / 60 horn inside container

Example 5 Between two mold materials (made of glass) with a thickness of 3 mm and 300 mm
One normal glass plate at the corner and on the side facing the glass plate,
Using a mold with internal dimensions of 3 mm ^t x 305 mm x 305 mm, adjust a gasket with a 3 mm thick, 300 mm square high hardness transparent resin plate manufactured by the following method with a gasket so that the facing distance is 2 mm. After incorporating, the mold materials were combined and the periphery was fixed with clips to obtain a casting polymerization mold. (Production of high-hardness transparent plate) 3-isopropenyl-α, α-
Dibutyltin dilaurate 0.08 in 182 parts of dimethylbenzyl isocyanate and ethylene glycol 19 parts.
Parts were added and the reaction was carried out at 40 ° C. for 1 hour. Then, 39 parts of 2-hydroxyethyl methacrylate was added thereto, and the reaction was carried out at 50 ° C. for 2 hours. Then, add 160 parts of pentaerythritol tetraacrylate to this,
Degassing was performed at 50 ° C. under reduced pressure while stirring well. Next, 0.41 part of t-butylperoxy-2-ethylhexanoate was added to this reaction mixture as a radical initiator, and defoaming was performed again under the above conditions while stirring well. Then, this resin composition was immediately poured into the space of a glass casting mold (internal dimensions: 3 mm ^t x 305 mm x 305 mm) for casting polymerization, and then the mold was placed in a hot stove and heated from 60 ° C to 18 ° C.
Polymerization was carried out by heating to 0 ° C. for 2 hours. Pencil hardness: 9H, Charpy strength: 2.2kgcm / cm
² Flexural modulus: 463 kg / mm ² , chemical resistance, heat resistance: good 109 parts of 1,3-xylylene diisocyanate, then pentaerythritol-tetrakis (β-mercaptopropionate) in a mixer equipped with a pressure reducing device. Was charged in an amount of 141 parts, and 0.05 part of dibutyltin dilaurate was further charged, and the mixture was degassed under reduced pressure for 1 hour while cooling well at 20 ° C. or lower with good stirring. The composition of the polyurethane resin thus prepared was immediately poured into the space of the casting mold for casting, then placed in a hot air oven for polymerization, heated at 40 ° C. for 2 hours, and then gradually raised. Warm and finally at 100 ° C 1
Polymerization was carried out for a time. After completion of the polymerization, the mold was removed to obtain a composite molded body in which a 3 mm thick glass plate was bonded to one side of a 2 mm thick polyurethane resin layer and a 3 mm thick high hardness transparent resin molded plate was bonded to the other side. Appearance: (○) Impact resistance (fall height 1.5m):
(○) Bottle protection (test environment: outside of container: temperature 22 ° C, humidity 54% Inside of container: temperature 34 ° C, humidity 61%): (○) Soundproofing: outside container (66 horns) / inside container (57 horns) )

Example 6 Two pieces of high-hardness transparent resin plate having a thickness of 3 mm and a size of 300 mm square manufactured by the following method are put between two pieces of mold material (made of glass) with a gasket so that the facing distance becomes 2 mm. After being adjusted and put in, the mold materials were combined and the periphery was fixed with clips to obtain a casting polymerization mold. (Production of high-hardness transparent plate) 3-isopropenyl-α, α-
Dibutyltin dilaurate 0.07 in 160 parts of dimethylbenzyl isocyanate and ethylene glycol 17 parts
Parts were added and the reaction was carried out at 40 ° C. for 1 hour. Then, 34 parts of 2-hydroxyethyl methacrylate was added thereto, and the reaction was carried out at 50 ° C. for 2 hours. Then, 141 parts of pentaerythritol tetraacrylate was added thereto,
Degassing was performed at 50 ° C. under reduced pressure while stirring well. Then 49 parts of pentaerythritol tetrakis (3-mercaptopropionate) were added to the reaction mixture,
Defoam under reduced pressure at 50 ° C. with good stirring, then add 0.36 parts of t-butylperoxy-2-ethylhexanoate to this and defoam again under the previous conditions with good stirring. I went. Then, this resin composition was applied to a glass casting mold (internal dimension: 2 mm ^t × 305 mm × 305 m).
Immediately after injection into the space of m), polymerization was carried out under the same conditions as in Example 4. Pencil hardness: 4H, Charpy strength: 5.4kg ・ cm / cm
² Flexural modulus: 450 kg / mm ² , chemical resistance, heat resistance: good Mixer with decompression device, 109 parts 1,3-xylylene diisocyanate, 141 parts pentaerythritol tetrakis (3-mercaptopropionate) Preparation,
Furthermore, 0.05 part of dibutyltin dilaurate was added,
With sufficient stirring, degassing was performed under reduced pressure for 1 hour at a temperature of 20 ° C. or lower. The composition of the polyurethane resin thus prepared was immediately poured into the space of the casting mold for casting, then placed in a hot air oven for polymerization, heated at 40 ° C. for 2 hours, and then gradually raised. The mixture was heated and finally polymerized at 100 ° C. for 1 hour. After completion of the polymerization, the mold was removed to obtain a composite molded body in which one layer of polyurethane resin having a thickness of 2 mm and a high hardness transparent resin plate having a thickness of 3 mm were bonded to both surfaces thereof. Appearance: (○) Impact resistance (fall height 2.3m):
(○) Bottle protection (test environment: outside the container: temperature 20 ° C, humidity 52% Inside container: temperature 35 ° C, humidity 64%): (○) Soundproofing: 70 horn outside container / 59 horn inside container

[0026]

The composite molded article of the present invention is one in which the polyurethane resin layer is firmly bonded and integrated with the surface of the inorganic glass plate and / or the high hardness transparent resin plate in the process of forming the composite molded article. Is. Since the composite molded article of the present invention does not have an adhesive layer, problems such as whitening and cracks between the layers of the composite surface caused by deterioration of the adhesive layer due to adhesion of water or the like do not occur.
The composite molded article of the present invention is imparted with high hardness and rigidity by the inorganic glass plate and / or the high hardness transparent resin plate,
Since the polyurethane resin layer absorbs or alleviates the deformation stress due to the impact from the outside, impact resistance is also imparted. Further, the high-hardness transparent resin plate used in the present invention has the same hardness as the glass plate (pencil hardness 9H <), and although it has a balance with the rigidity of the composite molded body itself, it has one of the thicknesses of the glass plate. It is possible to supplement the part with a high-hardness transparent resin plate, and by doing so, it contributes to weight reduction of the composite molded body. Furthermore, due to the difference in thermal conductivity between the polyurethane resin and the inorganic glass plate and / or the high-hardness transparent resin plate, and the elastic cross-linking structure of the polyurethane resin,
The composite molded article of the present invention also has a bottle-proof property and a sound-proof property. As described above, the present invention provides a lightweight composite molded article having excellent surface hardness, rigidity, impact resistance, chemical resistance, heat resistance, weather resistance, etc., and also having anti-jar and soundproof properties. It is possible to provide it, and further proposes a use as a glazing material or the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Fujii 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. A polyisocyanate having m (m is an integer of 2 or more) isocyanate groups in one molecule, and 1
One or both surfaces of a polyurethane resin layer obtained by polymerizing at least one of polyols, polyol polythiols or polythiols having n hydroxyl groups and / or thiol groups in the molecule (n is an integer of 2 or more) A composite molded body comprising a polyurethane resin layer obtained by joining an inorganic glass plate and / or a high hardness transparent resin plate, and an inorganic glass plate and / or a high hardness transparent resin plate. 2. The resin layer comprises polyisocyanates having m (m is an integer of 2 or more) isocyanate groups in one molecule, and n (n is an integer of 2 or more) in one molecule. The composite molded article according to claim 1, which is a polyurethane resin layer obtained by polymerizing the thiol group-containing polythiols. 3. An inorganic glass plate or a high-hardness transparent resin plate,
Between the polyurethane resin and the plate material that has no bonding ability, 1
Polyisocyanates having m (m is an integer of 2 or more) isocyanate group in the molecule and n (n) in one molecule
Is an integer of 2 or more), and a composition comprising a polyol having at least one hydroxyl group and / or a thiol group, a polyol polythiols or at least one kind of polythiols is injected, polymerized and cured to obtain one layer of polyurethane resin. A composite molded body composed of and one layer of an inorganic glass plate or a high hardness transparent resin plate. 4. A polyisocyanate having m (m is an integer of 2 or more) isocyanate groups in one molecule between two inorganic glass plates and / or high hardness transparent resin plates, and 1
A composition comprising n polyols (n is an integer of 2 or more) having at least one hydroxyl group and / or thiol group in the molecule, a polyol polythiols or a composition comprising at least one kind of polythiols is injected, polymerized and cured. A composite molded article having one layer of a polyurethane resin between two layers of an inorganic glass plate and / or a transparent resin plate having a high hardness obtained as described above. 5. A glazing material using the composite molded body according to claim 1. 6. A transparent protective material using the composite molded body according to claim 1.