JP3151062B2 - Aromatic polycarbonate laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an aromatic polycarbonate layer, an adhesive layer, and a glass layer or a transparent resin layer.
The invention relates to a novel laminate comprising at least three layers.

[0002]

2. Description of the Related Art Many attempts have been made to bond an aromatic polycarbonate to glass or another transparent resin to form a laminate, but a satisfactory one has not been obtained. And most of these attempts involved the development of adhesives. For example, various adhesives have been studied for the purpose of obtaining a laminated body of aromatic polycarbonate and glass suitable for applications such as so-called safety glass or lightweight glass or security glass.

Such an adhesive is indispensable for transparency, weather resistance and water resistance in addition to adhesiveness to glass and aromatic polycarbonate, and is also required to have heat resistance and hot water resistance. Furthermore, when manufacturing a laminate of a large-area plate having a different coefficient of thermal expansion, such as a glass plate and an aromatic polycarbonate sheet, it is soft and has mechanical properties after curing to absorb distortion due to thermal expansion or contraction. In particular, it is necessary that an adhesive layer having a large elongation can be obtained.

As such an adhesive, for example, Japanese Patent Application Laid-Open
As described in JP-A-2-132096, it has been proposed to mold a polycarbonate diol-modified polyurethane into a film and use it as an adhesive layer between glass and an aromatic polycarbonate sheet. When used as an agent, it must be cured and adhered by heating at a high temperature or for a long time. Under such adhesive conditions, the aromatic polycarbonate sheet is soaked by the adhesive and devitrified, There was a problem that the layer foamed and was not suitable for use as safety glass.

JP-A-56-28213 discloses that acrylated polycarbonate-based urethane is cured by ultraviolet irradiation and used as a solventless paint. However, when such a copolymer is used as an adhesive for a glass plate or the like, there is a problem that sufficient adhesiveness cannot be obtained. Also, Japanese Patent Application Laid-Open
Japanese Patent Application No. -69182 discloses that a block copolymer of polysiloxane and aromatic polycarbonate is used as an adhesive for a laminate of glass and aromatic polycarbonate. However, the layer made of the above adhesive has a problem that although it has extremely excellent impact resistance, it has low adhesion to glass.

Further, JP-A-60-51766 discloses a polycarbonate-modified urethane acrylate adhesive for bonding an aromatic polycarbonate sheet and a glass plate. However, since the polycarbonate diol used is crystalline, the cured product does not have sufficient elasticity, and the polyester diol or polyether diol is used to absorb the distortion caused by thermal expansion or contraction of the glass plate and the aromatic polycarbonate sheet. Must be used together. Thus, despite the use of polycarbonate diols having good hydrolysis resistance, satisfactory physical properties were not obtained as a result.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate excellent in transparency and impact resistance.

[0008]

Means for Solving the Problems The inventors of the present invention focused on eliminating such disadvantages of future adhesives and conducted various studies. As a result, the present inventors have found that they have excellent flexibility, heat resistance, hydrolysis resistance and glass. And an urethane acrylate adhesive having excellent adhesion to an aromatic polycarbonate sheet can be found, and have been filed earlier (Japanese Patent Application No. 3-49443). In order to obtain a more excellent laminate, the present inventors have conducted detailed studies on aromatic polycarbonate which is a main component material which has been hardly studied so far, and as a result, the adhesion found together with a special aromatic polycarbonate. It has been found that a desired laminate can be obtained by combining the agent with the agent, and the present invention has been completed.

That is, the present invention relates to a laminate comprising at least three layers including (a) an aromatic polycarbonate layer, (b) an adhesive layer, and (c) a glass layer or a transparent resin layer. The aromatic polycarbonate is a high molecular weight aromatic polycarbonate having a weight average molecular weight of 35,000 or more, and (2) the adhesive is as follows:
A) a urethane acrylate oligomer (I) obtained by reacting a), a) a repeating unit comprising
Is 7: 3 to 3: 7, and the total of one or more of (c) is 0 with respect to the total amount of (a), (b), and (c).
10 to 2000% by weight (provided that the percentage and the percentage are represented by the number of repeating units).

[0010]

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100 parts by weight of acrylate or methacrylate containing a hydroxyl group, 0.05 to 50 parts by weight of an alkoxysilane containing an active hydrogen group, corresponding to 70 to 100 mol% based on the total number of moles of active hydrogen atoms contained in An organic polyisocyanate containing an amount of isocyanate groups, and a reactive diluent (II), wherein (II) is (I)
The present invention provides an aromatic polycarbonate laminate characterized by being a urethane acrylate-based adhesive which is blended in an amount of 10 to 500% by weight based on the weight of the adhesive.

The aromatic polycarbonate used for the aromatic polycarbonate layer constituting the laminate of the present invention must have a weight average molecular weight of 35,000 or more. Such an aromatic polycarbonate has a higher molecular weight than a commercially available aromatic polycarbonate resin or sheet. Aromatic polycarbonates having a weight average molecular weight of less than 35,000 may be attacked and whitened by components forming the urethane acrylate adhesive, but aromatic polycarbonates having a weight average molecular weight of 35,000 or more have improved chemical resistance. , It became difficult to whiten. The higher the weight average molecular weight, the better the chemical resistance, the upper limit of the weight average molecular weight of the aromatic polycarbonate used in the present invention is not particularly limited, is about 300,000,
If it is larger than this, the melt viscosity becomes too high, and the moldability in forming into a sheet or the like deteriorates.

For these reasons, the aromatic polycarbonate used in the present invention has a weight average molecular weight of 35,000.
~ 300,000, preferably 40,000 ~
100,000, more preferably 40,000-8000
0, particularly preferably in the range of 45,000 to 70,000. Such a high-molecular-weight aromatic polycarbonate may be manufactured by a known method, for example, a phosgene method or a melting method, but in any case, it is difficult to industrially manufacture the high-quality aromatic polycarbonate, and high quality Is difficult to obtain. For example, in the case of the phosgene method, the polymerization reaction must be carried out under high dilution using a large amount of a chlorine-based solvent such as methylene chloride, and the polymerization solvent and by-product sodium chloride are separated from the polymer. Since it is very difficult to carry out the process, substantially low-quality products containing a large amount of chlorine-based impurities and sodium compounds can be obtained.

Although aromatic polycarbonates containing such chlorine-based impurities are inferior in heat resistance and weather resistance and are not preferred, any polymers having a molecular weight within the range required for the present invention can be used in the present invention. . In addition, in the case of the melting method, the polymerization reaction proceeds, and as the molecular weight increases, the melt viscosity of the aromatic polycarbonate extremely increases. For this reason, it has drawbacks such that only a colored polymer can be obtained, and it is substantially difficult to obtain a high molecular weight aromatic polycarbonate required for the present invention. However, if the molecular weight can be increased, those produced by this method can also be used.

As described above, it is substantially difficult to obtain a high-molecular-weight aromatic polycarbonate required for the present invention by the existing method, but the solid-state polymerization method previously proposed by the present inventors (Japanese Patent Laid-Open No. 1-158033). JP, JP-A-1-271426, JP-A-3-68627, etc.), a high-quality, high-molecular-weight aromatic polycarbonate can be easily obtained, and if necessary, this resin can be used. JP-A-4-
By the method described in JP-A-28716, a high-molecular-weight aromatic polycarbonate sheet can be formed.

The aromatic polycarbonate used in the present invention comprises a polycarbonate having a main chain comprising a repeating unit represented by the formula (1).

[0017]

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[In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene,
Examples include pyridylene and those represented by the formula (2). ] ^{-Ar 1 -Y-Ar 2 - (} 2) wherein, Ar ¹ and Ar ² is a respective arylene radical, such as phenylene, naphthylene, biphenylene, a group such as pyridylene, Y is represented by the following Chemical Formula 4 Or a substituted or unsubstituted alkylene group. ]

[0019]

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The divalent aromatic residue represented by the formula (3)
A group may be contained as a copolymer component. -Ar¹-Z-Ar^Two-(3) [wherein, Ar¹, Ar^TwoIs the same as above, and Z is a simple
Or -O-, -CO-, -S-, -SO_Two−,
-CO_Two-, -CON (R¹) (R^Two)-(R ¹, R^Two
Is the same as described above). ] These divalent fragrances
Examples of the aromatic residue include, for example,
7 and the like.

[0021]

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[0022]

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[0023]

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Wherein R ⁵ and R ⁶ are hydrogen, halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₅ -C ₁₀ cycloalkyl or phenyl, respectively. m and n are integers of 1 to 4; when m is 2 to 4, each R ⁵ may be the same or different; and when n is 2 to 4, each R ⁶ is the same. However, they may be different. Among them, a compound represented by the following formula is a preferable example.

[0025]

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In particular, those containing 85 mol% or more of a repeating unit in which the above-mentioned chemical formula 8 is Ar are preferable. Further, the aromatic polycarbonate of the present invention may contain a trivalent or higher aromatic residue as a copolymer component. Although the molecular structure of the polymer terminal is not particularly limited, a hydroxyl group,
One or more terminal groups selected from an aryl carbonate group and an alkyl carbonate group can be bonded.

The terminal of the aryl carbonate group is represented by the following formula:

[0028]

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[In the formula, Ar ³ is a monovalent aromatic residue. The aromatic ring may be substituted. ], As a specific example, for example,

[0030]

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And the like. The terminal of the alkyl carbonate group is represented by the following formula

[0032]

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In the formula, R ⁷ is a straight-chain or branched alkyl group having 1 to 20 carbon atoms.

[0034]

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And the like. Among these, a phenyl carbonate group, a pt-butylphenyl carbonate group, a p-cumylphenyl carbonate group, and the like are preferably used. The hydroxyl group terminal is preferably as small as possible to reduce heat resistance and hot water resistance. The aromatic polycarbonate used in the present invention may contain commonly used additives such as a heat stabilizer, a release agent, a colorant, and a weather resistance improver.

As such a heat stabilizer, for example, phosphorus stabilizers described in JP-A-3-163160, JP-A-3-163161 and the like are particularly preferably used. Examples of the weather resistance improver include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4
Benzophenones such as -octyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) 5-chlorobenzotriazole, 2- (3,5'-t-amylhydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octyl Phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-bis (α,
α-dimethylbenzyl) phenyl-2H-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'-lauryl-5'-methylphenyl)
Examples thereof include benzotriazoles such as benzotriazole and hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. These weatherability improvers can be used alone or in combination of two or more. If the laminate of the present invention is used in a place receiving sunlight, it is necessary to have high weather resistance, and in particular, in order to prevent yellowing due to ultraviolet rays or the like, such a weather resistance improver Particularly preferred are those containing

The weight average molecular weight (Mw) of the aromatic polycarbonate used in the present invention is a value measured by a gel permeation chromatography (GPC) method. It is determined from a calibration curve of standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following equation.

M _pc = 0.3591M _ps ^1.0388 (M _pc is the molecular weight of aromatic polycarbonate, M _ps is the molecular weight of polystyrene) The urethane acrylate adhesive used as the adhesive layer constituting the laminate of the present invention is as follows. A urethane acrylate oligomer (I) obtained by reacting (a), (b) with a repeating unit consisting of the following formula (13), wherein the ratio of (a) and (b) is 7: 3 to 3: 7 and (a), (b) ),
The total amount of one or more of (c) is 0 to 10% with respect to the total amount of (c) (however, the% and the ratio indicate the number of repeating units.) Aliphatic polycarbonate diol 10 ~ 2000 parts by weight,

[0039]

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Hydroxyl-containing (meth) acrylate 100
Parts by weight, 0.05 to 50 parts by weight of the active hydrogen group-containing alkoxysilane.
An organic polyisocyanate containing an isocyanate group in an amount corresponding to 0 to 100 mol%, and a reactive diluent (II), wherein (II) is (I)
Urethane acrylate-based adhesive characterized by being blended in an amount of 10 to 500% by weight based on the weight of the adhesive.

The aliphatic polycarbonate diol used for producing the urethane acrylate adhesive may be produced by any method.
For example, 2 selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol
The diols are mixed at a predetermined ratio, and if necessary, have an ether bond represented by the following formula 4 HO—R ¹ —OR ″ —OH (4) (where R ′ and R ″ are as described above). It can be easily obtained by reacting a diol mixture containing a predetermined amount of diols with a carbonylating agent. Examples of such carbonylation reagents include phosgene and multimers thereof; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkyl carbonates such as methyl phenyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate; -Cyclic carbonates such as propylene carbonate and 1,4-butylene carbonate; carbon monoxide and an oxidizing agent. When cyclic carbonates are used as the carbonylating agent, those having the structure of the repeating unit (c), which is a carbonate group containing an ether bond, are introduced without using the ether bond-containing diol represented by Formula 4. Sometimes.

The process for producing such aliphatic polycarbonate diols is described in Shell Review, Polymer Review, Vol.
-20 (1964). When the urethane acrylate adhesive used in the present invention is produced, the blending amount of the aliphatic polycarbonate diol is 10 to 100 parts by weight of the hydroxyl group-containing (meth) acrylate.
To 2000 parts by weight, preferably 100 to 1000 parts by weight.
Parts by weight. If the amount is less than 10 parts by weight, the adhesive has insufficient hydrolysis resistance, heat resistance and adhesion to aromatic polycarbonate, and if it exceeds 2,000 parts by weight, the fluidity of the oligomer becomes a problem.

The hydroxyl group-containing (meth) acrylate used for producing the urethane acrylate adhesive required for the present invention includes, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate and 2-hydroxypropyl acrylate. Hydroxy-3-
Butoxypropyl acrylate, 2-hydroxy-3-
(Meth) acryloyloxypropyl acrylate, 2-
Hydroxy-3-phenyloxyacrylate, 1,4
-Butylene glycol monoacrylate, glycerin monoacrylate, glycerin diacrylate, trimethylolpropane diacrylate, tetramethylolmethane triacrylate, triethylene glycol monoacrylate, polypropylene glycol monoacrylate, polycaprolactone glycol monoacrylate,
And methacrylates corresponding to these acrylates.

Among them, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate and methacrylates corresponding to these acrylates are preferably used. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

The alkoxysilane having an active hydrogen group used for producing the urethane acrylate adhesive required for the present invention includes an alkoxysilane having a mercapto group or an alkoxysilane having an amino group. Specifically, 3-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane And the like. The amount of the active hydrogen group-containing alkoxysilane is 0.05 to 50 parts by weight based on 100 parts by weight of the hydroxyl group-containing (meth) acrylate.
If the amount is less than 0.05 part by weight, adhesion to glass cannot be obtained, and if it exceeds 50 parts by weight, the adhesion to aromatic polycarbonate decreases. Preferably 0.1 to 3
It is in the range of 0 parts by weight, more preferably in the range of 1 to 10 parts by weight.

The organic polyisocyanate used for producing the urethane acrylate adhesive required for the present invention includes organic diisocyanates such as 2,4.
-Tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3-dimethyl-4, 4-biphenylene diisocyanate, crude TDI, polymethylene polyphenyl diisocyanate,
Aromatic diisocyanates represented by crude MDI, etc .; Aromatic alicyclic diisocyanates represented by xylylene diisocyanate (XDI), phenylene diisocyanate, etc .; Examples thereof include aliphatic diisocyanates represented by diisocyanate (HDI), isophorone diisocyanate (IPDI), and cyclohexane diisocyanate (hydrogenated XDI). Further, a burette derivative or an isocyanurate derivative of these organic diisocyanates, and an organic polyisocyanate obtained by reacting a bifunctional or trifunctional alcohol with these organic diisocyanates may be mentioned. Above all, TDI, MDI, hydrogenated MDI, HD
I and IPDI are preferably used. These polyisocyanates may be used alone or in combination of two or more. Among them, a combination of organic diisocyanates is preferable.

The compounding amount of the organic polyisocyanate is 70 to 100%, preferably 80 to 98% of the theoretical amount in which the amount of isocyanate groups contained in the polyisocyanate reacts with the total amount of active hydrogen atoms contained therein. It is blended to be in the range. When the amount of the isocyanate group is less than 70% of the theoretical amount, the molecular weight of the urethane acrylate oligomer decreases, and the mechanical strength of the cured adhesive decreases. On the other hand, if it exceeds 100% of the theoretical amount, an excess of isocyanate groups will remain, and the stability of the adhesive during storage will decrease.

The urethane acrylate oligomer (I), which is a component of the urethane acrylate adhesive used in the present invention, may be produced by any method. There is a method of adding and reacting an organic polyisocyanate to a liquid, and a method of adding and reacting a prepolymer having an isocyanate group at a terminal obtained by adding and reacting an organic polyisocyanate to a mixed solution with the liquid. Preferably, these reactions are usually performed at a temperature in the range of 20 to 150 ° C.

In this case, if necessary, a catalyst for the urethanization reaction, for example, dibutyltin dilate, or the like, or a polymerization inhibitor for a vinyl monomer, for example, methyl ether hydroquinone, may be added. If necessary, the reaction may be carried out using a solvent inert to the reaction. The reactive diluent (II), which is another component of the urethane acrylate adhesive used in the present invention, is a liquid compound having a polymerizable double bond and reduces the viscosity of the adhesive to be adhered. It is intended to improve workability such as the process of applying to objects and the process of filling gaps between adherends.Moreover, at the time of adhesion, it is polymerized by its polymerizable double bond and acts as a component of the adhesive. is there. Since the high molecular weight aromatic polycarbonate used in the present invention is hardly affected by such a reactive diluent, various compounds can be used as the reactive diluent.

Examples of such a reactive diluent include:
The aforementioned hydroxyl group-containing (meth) acrylates, 2-ethylhexyl acrylate, propylene glycol diacrylate, butylene glycol diacrylate, 1,4-
Butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, butoxyethylene glycol acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl carbitol acrylate, butoxyethyl acrylate, butoxydiethylene glycol monoacrylate, Or an acrylate represented by glycidyl acrylate, etc., and a methacrylate corresponding to the acrylate, and N
And vinyl compounds such as -vinyl-2-pyrrolidone. Among them, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate
Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate and methacrylates corresponding to these acrylates are preferably used.

When these reactive diluents (II) do not have a functional group which reacts with the isocyanate group, they can be added at any time during or after the synthesis of the urethane acrylate oligomer (I). However, when it has a functional group that reacts with an isocyanate group, it must be added after the synthesis of the urethane acrylate oligomer (I).

The amount of the reactive diluent (II) is from 10 to 50 based on the urethane acrylate oligomer (I).
0% by weight. If it is less than 10% by weight, it is difficult to obtain good workability during filling or coating, and
If it exceeds 500% by weight, the mechanical strength of the cured product and the adhesion to the aromatic polycarbonate are significantly reduced. The urethane acrylate adhesive used in the present invention has a viscosity at room temperature of 1,000,000 cps when used.
Or less, more preferably 100000 cps or less, and most preferably 10,000 cps or less.

For the purpose of improving the weather resistance, a known ultraviolet absorber, antioxidant or antioxidant may be added to the adhesive. In the urethane acrylate adhesive used in the present invention, the oligomer component has a double bond of a (meth) acrylate group. Therefore, when a thermal polymerization initiator is added, heating is performed, and when a photopolymerization initiator is added, ultraviolet fluorescent light is used. Curing can be easily performed in a short time by ultraviolet irradiation or electron beam irradiation using a lamp or a high-pressure mercury lamp. When it is desired to avoid heating the object and the adhesive, ultraviolet irradiation is preferred.

When the adhesive is cured by heating, it can be cured by heating at room temperature to about 90 ° C. after filling between the bases constituting the layer or coating on the surface of the base constituting the layer. It is. When the base material is a glass plate and an aromatic polycarbonate resin sheet, it is preferable to cure at room temperature to about 70 ° C. Examples of the thermal polymer initiator include benzoyl peroxide, lauroyl peroxide, succinic peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide and the like.

Examples of the photopolymerization initiator include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether and benzoin. -N-butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
Examples thereof include 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl sulfide, thioxanthone, and 2-chlorothixant.

Glass or transparent resin is used as another layer component constituting the laminate of the present invention. As such glass, glass generally used for plate glass or laminated glass can be used. For example, there are soda lime glass, phosphosilicate glass, borosilicate glass, quartz glass, potassium lime glass, lead alkali glass, alumina silicate glass, barium glass, and the like.
Semi-tempered glass, partially tempered glass, untempered glass, and the like can be used. Although not particularly limited, among them, soda lime glass is preferably used.

Further, the shape of the glass may be not only a plate shape but also various curved surfaces. Examples of the transparent resin that can be used as a layer component include an aromatic polycarbonate resin, an acrylic resin containing polymethacrylate as a main component, a vinyl chloride resin, a vinylidene chloride resin, a polystyrene resin, polyethylene terephthalate, and polybutylene. Polyester resins such as terephthalate, polyethylene naphthalate and polybutylene naphthalate, polyarylate resins, polysulfone resins, polyethersulfone resins, polyetherimide resins, polyacrylonitrile resins, amorphous polyolefin resins, etc. . Above all, an acrylic resin mainly containing an aromatic polycarbonate resin and polymethacrylate is preferably used. Of course, these glasses or transparent resins may be colored in various colors.

The laminate of the present invention comprises at least three layers including (a) the aromatic polycarbonate layer, (b) the adhesive layer, and (c) the glass layer or the transparent resin layer. A layered body of five or more layers in which these layer components are further multiply stacked may be used. Further, a layer having another function, for example, a layer having a light reflection or light control function may be further included.

The thickness of each layer constituting the laminate of the present invention is not particularly limited, but usually, the aromatic polycarbonate layer is 0.1 to 100 mm, and the adhesive layer is 0.01 to 5 mm.
mm, the glass layer or the transparent resin layer ranges from 0.1 to 200 mm. The method for producing the laminate of the present invention is not particularly limited, for example, an aromatic polycarbonate as a base material constituting a layer, between a glass or a transparent resin, filling a urethane acrylate adhesive. According to the method as described above, a method of curing the adhesive by thermal polymerization or photopolymerization and bonding the substrates, and applying a urethane acrylate adhesive to at least one surface of the substrate. After that, the surfaces of the substrates to be bonded are brought into close contact,
Then, a method of curing the adhesive by heat polymerization or photopolymerization and bonding the substrates to each other is preferably used.

The shape of the laminate of the present invention may be any shape, but it is particularly preferable to have a shape such as a flat shape, a plate shape, a flat shape having a curved surface, and a curved shape. The laminate of the present invention is preferably used as a glazing material for windows of general buildings and high-rise buildings, windows and doors of cars, buses, windows of transportation vehicles such as railroad vehicles and windows of aircrafts. it can. In addition, it can be used for decorative articles, various lighting fixtures, advertising boards, signboards, various building materials, and the like.

[0061]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example means a weight part.

[0062]

Synthesis Example 1 In a reactor equipped with a stirrer, a thermometer, a fractionating tower, and a vacuum pump, 2261 parts (21.74 mol) of 1,5-pentanediol and 1,6-hexanediol 2 were added.
33 parts (19.75 mol), ethylene carbonate 34
0 parts (40.0 mol) were charged and reacted at 130 ° C. and 30 to 4 mmHg while flowing a small amount of N ₂ gas into the system. During this time, ethylene glycol and ethylene carbonate were distilled from the top of the column. Thereafter, the reaction temperature was set to 200 ° C.
And reacted at 4-2 mmHg. At this time, the system was evacuated without using a fractionation tower, and ethylene glycol,
Ethylene carbonate, 1,5-pentanediol,
1,6-hexanediol was distilled off. After the reaction,
A polymer having a number average molecular weight of 1,000 was obtained.

This polymer was analyzed by C-NMR [GX270 manufactured by JEOL Ltd.] to find that
The terminal was a hydroxyl group and the content of the ether bond was 3%. PCD the polymer
LI.

[0064]

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[0065]

[Synthesis Example 2] The number average molecular weight was 200 in the same manner as in Synthesis Example 1.
No polymer was obtained. The polymer having a number average molecular weight of 2,000 is designated as PCDL-II. This polymer is represented by the following formula 1.
It had the structure shown in FIG. 5, the terminal was a hydroxyl group, and the ether bond content was 2.3%.

[0066]

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[0067]

Synthesis Example 3 360 parts (4.0 mol) of 1,4-butanediol was placed in a reactor equipped with a stirrer, a thermometer and a distillation tube.
And 416 parts of 1.5-pentanediol (4.0 mol)
Was added, and 1.84 parts (0.08 mol) of metallic sodium was added at 70 to 80 ° C. with stirring. After the sodium had completely reacted, 472 parts (8.0 mol) of diethyl carbonate were introduced. As the reaction temperature was raised to 95-100 ° C, ethanol began to distill. Gradually increase the temperature by 1
60 ° C. During this time, ethanol containing about 10% diethyl carbonate was distilled off. Thereafter, the pressure in the reactor was further reduced to 10 mmHg or less, and the reaction was performed at 200 ° C. under strong stirring. After cooling, the obtained polymer was dissolved in dichloromethane, neutralized with a dilute acid, washed repeatedly with water several times, dehydrated with anhydrous sodium sulfate, distilled off the solvent, and further distilled at 2-3 mmHg at 140 ° C. Dry for several hours. The obtained polymer had the structure shown in the following chemical formula 16, the number average molecular weight was 1,000, the terminal was a hydroxyl group, and the content of the ether bond was 0%. The polymer is converted to PC
DL-III.

[0068]

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[0069]

Synthesis Example 4 A polymer having a number average molecular weight of 1,000 was obtained in the same manner as in Synthesis Example 1 using 1,6-hexanediol and ethylene carbonate. PCDL-I
V. The terminal of the PCDL-IV was a hydroxyl group, and the ether bond content was 3%. Its structural unit was as shown in the following chemical formula 17.

[0070]

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[0071]

Synthesis Example 5 550 parts of PCDL-I obtained in Synthesis Example 1,
182 parts of 2-hydroxypropyl acrylate, 200 parts of 2-ethylhexyl acrylate, 0.5 parts of dibutyltin dilaurate as a catalyst, and 1.0 part of hydroquinone monomethyl ether as a polymerization inhibitor were charged into a four-necked flask equipped with a stirrer, The mixture was heated and mixed at 50 ° C. with stirring. Next, 5 parts of γ-aminopropyltrimethoxysilane was added, and isophorone diisocyanate 27 was added.
0 parts was added dropwise to the reaction system over 1 hour. The temperature was raised to 80 ° C. with further stirring, and the urethanization reaction was performed for 10 hours.

After confirming that the conversion of NCO was 99% by determining the amount of residual NCO by titration, the reaction temperature was lowered to obtain urethane acrylate oligomer A. The urethane acrylate oligomer A500
Parts: 250 parts of 2-hydroxypropyl acrylate, 125 parts of tetrahydrofurfuryl acrylate, and 12 parts of 2-hydroxyethyl methacrylate as reaction diluents
5 parts, 2-hydroxy-2-methyl- as a photopolymerization initiator
20 parts of 1-phenylpropan-1-one was added and stirred,
A photopolymerizable urethane acrylate adhesive A was obtained.

[0073]

Synthesis Example 6 Using PCDL-II, III, and IV, and using the urethane acrylate oligomer prepared in the same manner as in Synthesis Example 5 except that the mixing ratio shown in Table 1, was used.
In the composition shown in the above, urethane acrylate adhesives B, C,
D was obtained.

[0074]

Examples 1, 2, 3 and Comparative Example 1 By using a plate glass having a thickness of 3 mm and a method described in JP-A-3-68627,
The weight average molecular weights produced from diphenyl carbonate and 2,2-bis (4-hydroxyphenyl) propane were 40,000 (Example 1), 56000 (Example 2), 68000 (Example 3), and 28000 (comparative). A sheet having a thickness of 1 mm obtained by melt-extruding the aromatic polycarbonate of Example 1) was placed in the order of glass / gap / aromatic polycarbonate sheet / gap / glass using a spacer so that a gap of 0.5 mm was formed. Superimposed. The three side surfaces are sealed with tape so that the adhesive does not flow off, and the opening side is filled up, and the gap is filled with urethane acrylate adhesive A so that air bubbles do not enter. We stopped with tape. The laminated product was irradiated with ultraviolet rays for 30 seconds from a distance of 15 cm from both sides of the glass using an ultraviolet irradiation device equipped with a high-pressure mercury lamp with an output of 30 W / cm to cure the urethane acrylate adhesive. A laminate composed of an aromatic polycarbonate sheet / adhesive / glass was obtained.

The obtained laminate was evaluated for transparency and a ball drop test (performed in accordance with JIS R3205). Table 3 shows the evaluation results.

[0076]

Example 4 Using the aromatic polycarbonate sheet of Example 2 (thickness: 3 mm) and a commercially available 1 mm thick acrylic sheet, using a spacer so as to have a gap of 0.5 mm, an aromatic polycarbonate sheet / gap / acrylic The sheets were superimposed in the order. A laminate composed of an aromatic polycarbonate sheet / adhesive / acrylic sheet was obtained in the same manner as in Example 1 except that the urethane acrylate adhesive B was used. Table 3 shows the evaluation results. In addition, the falling ball test was implemented from the acrylic sheet side.

[0077]

Example 5 Using a 3 mm-thick ordinary plate glass and the aromatic polycarbonate sheet of Example 2 (2 mm in thickness),
Using a spacer so that a gap of 1.0 mm is created,
The glass / gap / aromatic polycarbonate sheet was overlaid in this order. A laminate composed of glass / adhesive / aromatic polycarbonate sheet was obtained in the same manner as in Example 1 except that urethane acrylate adhesive C was used. Table 3 shows the evaluation results. The ball drop test was performed from the glass side.

[0078]

Example 6 Using the aromatic polycarbonate sheet of Example 3 (thickness: 3 mm), using a spacer so as to form a gap of 1.0 mm, superposing the aromatic polycarbonate sheet / gap / aromatic polycarbonate sheet in this order. Was. Example 1 using urethane acrylate adhesive A
Aromatic polycarbonate sheet / adhesive /
A laminate composed of an aromatic polycarbonate sheet was obtained.
Table 3 shows the evaluation results.

[0079]

Comparative Example 2 A laminate was obtained in the same manner as in Example 2 except that urethane acrylate adhesive D was used as the adhesive. Table 3 shows the evaluation results.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

As shown in Table 3, the laminate of the present invention is excellent in transparency and impact resistance (adhesion), and is used for glazing applications, for example, window glass for buildings, show windows and doors, especially glass area. Can be suitably used as glass for high-rise buildings having a large size, and as glass for vehicles such as automobiles, buses, trucks, and railways. Furthermore, it can be suitably used as safety glass used for window glasses and doors of schools, gymnasiums, hospitals, and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-51766 (JP, A) JP-A-3-251448 (JP, A) JP-A-4-29844 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C09J 175/00 -175/16

Claims (1)

(57) [Claims] (1) an aromatic polycarbonate layer,
(B) In a laminate comprising at least three layers including an adhesive layer and (c) a glass layer or a transparent resin layer, (1) the aromatic polycarbonate has a high molecular weight aromatic having a weight average molecular weight of 35,000 or more. (2) the adhesive is a urethane acrylate oligomer (I) obtained by reacting the following: (a) and (b)
Is 7: 3 to 3: 7, and the total amount of one or more of (c) is 0 to 1 with respect to the total amount of (a), (b), and (c).
0% (however, the percentage and the ratio are indicated by the number of repeating units).
~ 2000 parts by weight Hydroxyl-containing acrylate or methacrylate 100
0.05 to 50 parts by weight of an active hydrogen group-containing alkoxysilane, an organic polyisocyanate containing an isocyanate group in an amount equivalent to 70 to 100 mol% based on the total number of moles of active hydrogen atoms contained in And a reactive diluent (II), wherein (II) is (I)
An aromatic polycarbonate laminate, which is a urethane acrylate-based adhesive which is blended in an amount of 10 to 500% by weight based on the weight of the urethane acrylate adhesive.